Title of Invention	PERFUMING COMPOSITION
Abstract	Perfuming composition or perfumed article comprising, together with perfuming ingredients, solvents or adjuvants of the kind such as herein described in the preparation of perfume formulations, at least 0.01% of a 2-benzoyl benzoate or a 2-alkanoyl benzoate of formula or in which Ri represents hydrogen or a group of formula —CH—X in which X and Y can be identical or different and represent, independently from each other, hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group or a group of formula >1 + R2 can be identical to R1 or different from it and represents hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group, a group of formula or a polyalcohol or polyether group R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or branched, a OH group or a NH2 group; R4 and R5, taken separately, have the meaning given above for R1 and can be identical to or different from R1 or from each other ; or R4 and R5, taken together, form a bridging group between the two aromatic rings which bridging group can be a methylene or a keto group m is an integer from 0 to 3 and n is an integer from 0 to 2; R6 and R7, taken separately, each represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C12, or a phenyl group, or, R6 and R7, taken together with the nitrogen atom form a 5-membered or six- membered ring possibly containing another hetero atom R8 represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C12 or a phenyl group; M represents hydrogen or an alkali metal; and R* is the organic part derived from a primary or secondary fragrant alcohol R*OH.

Title of Invention

PERFUMING COMPOSITION

Abstract

Perfuming composition or perfumed article comprising, together with perfuming ingredients, solvents or adjuvants of the kind such as herein described in the preparation of perfume formulations, at least 0.01% of a 2-benzoyl benzoate or a 2-alkanoyl benzoate of formula or in which Ri represents hydrogen or a group of formula —CH—X in which X and Y can be identical or different and represent, independently from each other, hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group or a group of formula >1 + R2 can be identical to R1 or different from it and represents hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group, a group of formula or a polyalcohol or polyether group R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or branched, a OH group or a NH2 group; R4 and R5, taken separately, have the meaning given above for R1 and can be identical to or different from R1 or from each other ; or R4 and R5, taken together, form a bridging group between the two aromatic rings which bridging group can be a methylene or a keto group m is an integer from 0 to 3 and n is an integer from 0 to 2; R6 and R7, taken separately, each represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C12, or a phenyl group, or, R6 and R7, taken together with the nitrogen atom form a 5-membered or six- membered ring possibly containing another hetero atom R8 represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C12 or a phenyl group; M represents hydrogen or an alkali metal; and R* is the organic part derived from a primary or secondary fragrant alcohol R*OH.

Full Text	FORM 2 THE PATENTS ACT 1970 [39 OF 1970] COMPLETE SPECIFICATION [See Section 10] "Perfuming compostion" FIRMENICH SA, of 1, route des Jeunes, P.O. Box 239, 1211 Geneva 8, Switzerland, The following specification particularly describes the nature of the invention and the manner in which it is to be performed:- 17-04-2000 IB 009900890 Slow release of fragrant compounds in perfumery using 2-benzoyl benzoates, 2-alkanoyl benzoates or a-keto esters 5 1 echnical Field and Prior Art The present invention relates to the field of perfumery. It relates, more particularly, to perfuming compositions or perfumed products containing a class of aliphatic or aromatic keto esters of fragrant alcohols, as defined below, which are 10 capable of releasing said fragrant alcohol upon exposure to light, more particularly daylight. The present invention also relates to a-keto esters, as defined below, of alcohols which are precursors of fragrant aldehydes and ketones and which are capable of releasing said fragrant ketone or aldehyde upon exposure to light, more particularly daylight. Said a-keto esters may furthermore contain, in a-position to the keto group, an 15 alkyl group which may contain various substituents and which alkyl group is derived from a fragrant molecule possessing an olefinic unsaturation. The unsaturated molecule and/or the aldehyde or ketone are released upon exposure to light, in particular daylight, of the a-keto ester. Some compounds of the invention, namely some 2-benzoylbenzoate esters 20 as well as some a-keto esters are known to be photolabile compounds. Therefore, it has been suggested in the prior art to use 2-benzoylbentoate esters as protective groups for alcohols in organic synthesis and subsequently release the alcohol present in the ester function by photolysis (see Porter et al., J. Org. Chem 1996, 67, 9455-9461). The authors conducted experiments with different alcohols, and they described the 25 elimination of geraniol from the geranyl 2-benzoyl benzoate (R1=R2=R3=R4=R5=H). Moreover, S. Hu and D.C.Neckers in J. Org. Chem. 1997, 62, 6820-6826, and G.A. Kraus and Y. Wu in J.Am. Chem. Soc. 1992, 114, 8705-8707 disclose some a-keto ester derivatives within the scope of photolysis studies. On the other hand, some pyruvate esters are known to be active ingredients to enable the removal of amine and 30 mercaptan type odors (Patent Abstracts of Japan, 1994, 18, 410). However, it has not been described or suggested in the prior art to use the said esters in perfumery, as fragrance delivery systems capable of releasing the fragrant alcohol over a prolonged period of time and thus provide a slow release fragrance effect. IB 009900890 There exists, in perfumery, a particular interest in compounds which are capable of "fixing" fragrant molecules, for example by chemical bonding or intramolecular forces like absorption, and releasing said fragrant molecules over a 5 prolonged period of time, for example by the action of heat, enzymes, or even sunlight. Fragrant molecules have to be volatile in order to be perceived. Although many fragrant compounds are known which show a good substantivity, i.e. they will remain on a surface to which they have been applied for several days and can hence be perceived over such a period of time, a great number of fragrant compounds are very volatile, and 10 their characteristic smell can no longer be perceived several hours after their application. It is thus desirable to dispose of fragrance delivery systems which are capable of releasing the fragrant compound or compounds in a controlled manner, maintaining a desired smell over a prolonged period of time. Accordingly, the present invention relates to a perfuming composition or perfumed article comprising, together with perfuming ingredients, solvents or adjuvants of the kind such as herein described in the preparation of perfume formulations, at least 0.01% of a 2-benzoyl benzoate or a 2-alkanoyl benzoate of formula (R2), (R2)n or (I) (H) in which Ri represents hydrogen or a group of formula —CH—X in which X and Y can be identical or different and represent, independently from each other, hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group or a group of formula + or a polyalcohol or polyether group R2 can be identical to R1 or different from it and represents hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group, a group of formula R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or branched, a OH group or a NH2 group; R4 and R5, taken separately, have the meaning given above for Ri and can be identical to or different from R1 or from each other ; or R4 and R5, taken together, form a bridging group between the two aromatic rings which bridging group can be a methylene or a keto group m is an integer from 0 to 3 and n is an integer from 0 to 2; R6 and R7, taken separately, each represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C12, or a phenyl group, or, R4 and R7, taken together with the nitrogen atom form a 5-membered or six- membered ring possibly containing another hetero atom Rs represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1to C12 or a phenyl group; M represents hydrogen or an alkali metal; and R* is the organic part derived from a primary or secondary fragrant alcohol ROH. WO 99/60990 R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or branched, a OH group or a NH2 group ; R4 and R5, taken separately, have the meaning given above for R, and can be identical to or different from R1 or from each other ; or 5 R4 and R5, taken together, form a bridging group between the two aromatic rings, which bridging group can be a methylene or a keto group ; m is an integer from 0 to 3 and n is an integer from 0 to 2 ; R6 and R7, taken separately, each represent hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C,12, or a phenyl group, or, R6 and R7 taken together with the nitrogen 10 atom form a 5-membered or six-membered ring possibly containing another hetero atom; R8 represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C,2 or a phenyl group ; M represents hydrogen or an alkali metal; and 15 R is the organic part derived from a primary or secondary fragrant alcohol ROH. In the above definition, when reference is made to a fragrant alcohol, there is always meant an alcohol which not only has an odor, but which is also known to a person skilled in the art as being useful as perfuming ingredient for the formulation of perfumes or perfumed articles. The criteria a useful perfuming ingredient has to fulfil 20 are known to a person skilled in the art and include, amongst others, a certain originality of the odoriferous note, stability and a certain price/performance ratio. Non-limiting examples for fragrant alcohols which can be used with the benzoates of the invention will be mentioned below. From the above, it is clear that when reference is made to the organic part 25 R of a fragrant alcohol ROH, R is the hydrocarbyl rest of said alcohol, e.g. a geranyl radical in case ROH is geraniol. The advantage of the fragrance delivery system of the present invention lies in its capacity to slowly release the fragrant alcohols ROH from which the benzoyl benzoate esters of formula (I) or the alkanoyl benzoate esters of formula (II) are derived. 30 The release occurs when said esters are exposed to daylight in particular. Upon absorption of energy from said light, the ester undergoes a photoreaction in the course of which the fragrant alcohol is released from the molecule into the surroundings. Said WO 99/60990 PCT/IB99/00890 release occurs in a controlled manner, i.e. a more or less constant amount of alcohol ROH is formed over a period of time, without an initial burst of very intense odor which becomes rapidly imperceptible as is the case with volatile alcohols. Because the release of the alcohol ROH can occur over several days or weeks, the use of the system 5 of the present invention obviates the drawbacks of many fragrant alcohols ROH which are of pleasant smell but also very volatile. Good examples are citronellol and geraniol which can only be perceived over a short period of, say, one or two hours, when applied to the surface of, for example, tiles and windows in the course of a cleaning procedure using liquid cleaners ; even in solution, the typical smell of said alcohols disappears 10 within several hours. It goes without saying that the concentration of the alcohols in the application plays an important role in the time during which the fragrant molecules can be perceived. With the system of the present invention, the typical odor of the alcohol ROH is perceived over a considerably prolonged period of time, as the 2-benzoyl 15 benzoate or the 2-alkanoyl benzoate of the fragrance delivery system, which are not or few volatile, remain as such on the surface to which they are applied or in the solution into which they are incorporated, and it is only upon exposure to light, that the fragrant alcohol ROH is released. It is clear that this reaction can provide perceptible amounts of the alcohol over days or weeks, depending, amongst others, on the amount or the 20 concentration of the fragrance delivery system, the time of exposure to light, its intensity and its wavelength. 2-Benzoyl benzoate esters of the above formula (I) which can carry various substituents in positions R1 R2, R3, R4 and R5 are known to be photolabile compounds. It was suggested to use these esters as protective groups for alcohols in organic 25 synthesis and subsequently release the alcohol present in the ester function by photolysis (see Porter et al., J. Org. Chem 1996, 61, 9455-9461). The authors conducted experiments with different alcohols, and they described the elimination of geraniol from the geranyl 2-benzoyl benzoate (R,=R2=R3=R4=R5=H). However, it has not been described or suggested to use the said esters in perfumery, as a fragrance delivery 30 system which is capable of releasing the fragrant alcohol over a prolonged period of time and thus provide a slow release fragrance effect. 04-2000 IB 009900890 release occurs in a controlled manner, i.e. a more or less constant amount of alcohol ROH is formed over a period of time, without an initial burst of very intense odor which becomes rapidly imperceptible as is the case with volatile alcohols. Because the release of the alcohol ROH can occur over several days or weeks, the use of the system 5 of the present invention obviates the drawbacks of many fragrant alcohols ROH which are of pleasant smell but also very volatile. Good examples are citronellol and geraniol which can only be perceived over a short period of, say, one or two hours, when applied to the surface of, for example, tiles and windows in the course of a cleaning procedure using liquid cleaners; even in solution, the typical smell of said alcohols disappears 10 within several hours. It goes without saying that the concentration of the alcohols in the application plays an important role in the time during which the fragrant molecules can be perceived. With the system of the present invention, the typical odor of the alcohol ROH is perceived over a considerably prolonged period of time, as the 2-benzoyl 15 benzoate or the 2-alkanoyl benzoate of the fragrance delivery system, which are not a few volatile, remain as such on the surface to which they are applied or in the solution into which they are incorporated, and it is only upon exposure to light, that the fragrant alcohol ROH is released. It is clear that this reaction can provide perceptible amounts of the alcohol over days or weeks, depending, amongst others, on the amount or the 20 concentration of the fragrance delivery system, the time of exposure to light, its intensity and its wavelength. WO 99/60990 PCT/IB99/00890 As fragrant alcohol ROH derived radical R in the above formula (I), in principle a group derived from any fragrant alcohol which is known in the art can be used. Primary and secondary alcohols are shown to be useful in the present invention as they are liberated when exposed to daylight. 5 As non-limiting examples of alcohols which can be used in the present invention in the form of the 2-benzoyl benzoate esters, one can cite anisic alcohol, cinnamic alcohol, fenchylic alcohol, 9-decen-l-ol, phenethylol, citronellol, 3-methyl-5-phenyl-1-pentanol (origin: Firmenich SA, Geneva, Switzerland), Mayol ® (7-p-menthan-1-ol; origin : Firmenich SA, Geneva, Switzerland), geraniol (3,7-dimethyl- 10 2,6-octadien-l-ol), (Z)-3-hexen-l-ol, 1-hexanol, 2-hexanol, 5-ethyl-2-nonanol, 2,6-nonadien-1-ol, borneol, 1-octen-3-ol, cyclomethyl citronellol, decanol, dihydroeugenol, 8-p-menthanol, 3,7-dimethyl-l-octanol, dodecanol, eugenol, isoeugenol, Tarragol ® (2-methoxy-4-propyl-l-cylohexanol; origin: Firmenich SA, Geneva, Switzerland), Polysantol ® [(E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-l'-yl)-4-penten-2-ol; 15 origin : Firmenich SA, Geneva, Switzerland] and Limbanol ® [l-(2',2',3',6'-tetramethyl-cyclohex-l-yl)-3-hexanol; origin : Firmenich SA, Geneva, Switzerland]. It is quite obvious, however, that the process of the invention is perfectly general and can relate to many other alcohols which the skilled person is quite able to choose from the general knowledge in the art and as a function of the olfactive effect it 20 is desired to achieve. The above list therefore is more illustrative for fragrant alcohols which are known to a person skilled in the art, and whose delivery can be improved, but it is clearly quite impossible to cite in an exhaustive manner all alcohols of formula ROH which have a pleasant odor and the 2-benzoyl or 2-alkanoyl benzoate esters of which can be used in the fragrance delivery system of the present invention. 25 From the foregoing, it is evident that the fragrance delivery system is particularly appropriate for delivering fragrant alcohols ROH which are very volatile, or which have a low perception threshold, like geraniol, citronellol or phenethylol. The benzoyl and alkanoyl benzoate esters (I) of the latter are thus preferred according to the present invention. 30 The chemical reaction which releases the fragrant alcohol can only occur when a source of a hydrogen radical He is present in the fragrance delivery system. It is believed that in the first reaction step, said hydrogen radical is transferred to the oxygen WO 99/60990 PCT/IB99/00890 of the keto-function. Such a source can be intramolecular, i.e. the hydrogen radical comes from the 2-benzoyl benzoates of formula (I) or the 2-alkanoyl benzoates of formula (II) themselves, or intermolecular, i.e. the hydrogen radical comes from another, different source which is present in the medium in which the ester is 5 incorporated. The intramolecular pathway or mechanism is a universal mechanism which can occur in every possible application medium, thus in the liquid or solid state. The intermolecular mechanism, however, is only possible in solution, but not in the solid state. Non-limiting examples of liquid state application media are liquid air-fresheners which release the fragrant alcohol upon exposure to light. Examples of 10 release of the fragrant alcohol in the solid state are surfaces, like those of tiles or windows, which are cleaned with a cleaner containing the fragrance delivery system of the invention, the system being thus deposited on the surface after cleaning and remaining on it as a solid film after evaporation of the liquids present in the cleaner. However, it has to be understood that the term "solid" as used beforehand is used to 15 designate the benzoates in the neat state in which they may be a real solid, crystalline or non-crystalline, or be in the form of a more or less viscous oil. For the 2-benzoyl benzoates of the above formula (I) or the 2-alkanoyl benzoates of the above formula (II) in which R1, R4 and R5 are hydrogen, an external hydrogen radical source is necessary. In general, the hydrogen radical will be abstracted 20 from the solvent in which the 2-benzoyl or the 2-alkanoyl benzoate is dissolved or provided by a solvent which is added to the solution containing the said compound. Suitable sources are known to a person skilled in the art. The most important criterion a suitable hydrogen radical source has to fulfil is that a stable radical is formed after abstraction of the hydrogen. For a given compound, and independently from other 25 functional groups or structural elements present in the same, the presence of hydrocarbon groups which are not methyl or tert-butyl is very favorable towards the formation of a stable radical after hydrogen abstraction. Suitable groups include ethyl or n-propyl. Even better are branched secondary alkyl groups, like isopropyl or sec-butyl. It is preferred when the solvent contains an isopropyl group or is a primary or secondary 30 alcohol. Non-limiting examples for classes of solvents are the following: aliphatic and aromatic alcohols, like methanol, ethanol, propanol, decanol or benzyl alcohol, in particular isopropanol ; diols and polyols, like ethyleneglycol, glycerol, WO 99/60990 PCT/IB99/00890 polyethyleneglycol, propyleneglycol or polypropyleneglycol ; ketones, such as diisopropylketone; esters, such as isopropylacetate; aromatic solvents, such as ethylbenzene, cyclohexylbenzene or isopropylbenzene (cumene), di- or triisopropylbenzene; ethers, such as diisopropylether, tetrahydrofxjran, mono-, di- or 5 triethyleneglycoldimethylether, diethyleneglycolmonoether or polyethyleneglycol-dimethylether ; aminoalcohols, such as mono-, di- or triethanolamine ; hydrocarbons, in particular branched hydrocarbons, including limonene. Preferred solvents include primary and secondary alcohols, in particular isopropanol, 1-dodecanol, 2-tridecanol, butanol or amyl alcohol. 10 All the above-mentioned solvents can, of course, also be used for benzoyl and alkanoyl benzoate esters which react in an intramolecular pathway to release the fragrant alcohol. In such case, R1, R4 or R5 are the intramolecular hydrogen radical source, as will be described below. The mentioned solvents will be chosen according to their ability to release 15 hydrogen radicals. We have found that the intramolecular pathway for the release of the fragrant alcohol only occurs when at least one of the groups R1 R4 or R5 of formula (I) or (II),which is in 2-position relative to the keto function, is a group of formula —CH-x 20 Y from which the hydrogen radical is easily transferred to the keto function, due to the vicinity of the group R, to the keto function by which an energetically favorable transition state is possible. X and Y are chosen to stabilize the resulting radical 25 • —C—X I Y which remains after abstraction of the hydrogen radical and its transfer to the keto function. Suitable groups X and Y which can stabilize radicals are known to a person 30 skilled in the art, and X and Y, which can be the same or different, will be chosen according to the respective benzoyl benzoate and the fragrant alcohol ROH used in a given fragrance delivery system in order to give the best results, i.e. the desired release WO 99/60990 PCT/IB99/00890 rate for the fragrant alcohol. Preferably X and Y are, independently from each other, a group as defined above with respect to formulae (I) and (II). The compounds of formula (I) can contain, in addition to the substituent R, in 2-position of the cycle relative to the keto function, a further substituent R4 in 5 6-position. It is evident that this substituent R4 can also function as a hydrogen radical source, after a rotation around the single bond between the keto function and the phenyl ring. Moreover, the same applies to the group R5 of the above formula (I) or (II), which is optionally present in the phenyl ring which carries the ester function. R5, after a rotation of the phenyl group, can also serve as a hydrogen radical source. R4 and R5 thus 10 have the same meaning as R1, which has-been defined above, and R4 and R5 can be identical to R1, or they can be different from R1, and, respectively, from each other. The two phenyl groups of the 2-benzoyl benzoates or formula (I) can furthermore be bridged by a methylene or keto group. We have furthermore found that it can be advantageous with respect to the 15 release of the fragrant alcohol when the respective benzoyl benzoate of formula (I) or the respective alkanoyl benzoate of formula (II) carries a substituent R3 other than hydrogen in the ortho-position to the -COOR- function. The purpose of this substituent is to establish a favorable conformation of the -COOR- function relative to the keto group, or respectively to the reduced keto-group, in order to facilitate the cyclization to 20 the lactone which occurs after release of the alcohol. This reaction leads to the release of the fragrant alcohol ROH. Practically, any group which is inert towards the -COOR-function can be used, and they are known to a person skilled in the art. The groups defined in the above formula (I) and (II), namely linear or branched alkyl or alkoxy from C1, to C4, OH or NH2 have revealed themselves as being appropriate from the point 25 of view of effectiveness, and, of course, synthetic access. The benzoyl benzoates of formula (I) and the alkanoyl benzoate of formula (II) can furthermore carry one or more substituents R2 in the positions indicated and defined above. Substituents R2, however, seem to be of less importance to the reactivity and the performance of the fragrance delivery system of the present invention, 30 although it is often preferred, for reasons of easy accessibility of the corresponding 2-benzoyl and 2 -alkanoyl benzoates of the invention, to use an ester wherein R, is a group other than hydrogen. It is however possible to adapt e.g. the stability of the WO 99/60990 PCT/IB99/008902-benzoyl and 2 -alkanoyl benzoates of the present invention to the respective application desired. The 2-benzoyl benzoates can e.g. be rendered more hydrophilic by one or more groups R2 which are a quaternary amine group, a polyalcohol group or a polyether group. Specific examples for said functional groups are known to a person 5 skilled in the art, and the groups will be chosen according to the effect desired. Preferred 2-benzoyl benzoate esters of the present invention are those of formula (I') 10 in which R1, is a branched alkyl group from C3 to C4 containing a secondary hydrocarbon group ; R2 is a branched alkyl group from C3, to C4, and is identical to R1 ; R3 is hydrogen or a linear or branched alkyl group from C1, to C4; R4 is hydrogen or a linear or branched alkyl group from C1, to C4; 15 R5 is hydrogen or a linear or branched alkyl group from C1, to C4; R is the organic part derived from a primary or secondary fragrant alcohol ROH. Generally, with respect to the above formulae (I) and (T), it can be said that it is preferred when R1 R4 or R5 which are responsible for the transfer of the hydrogen radical towards the keto function, is an isopropyl group, irrespective of the other 20 substituents which may be present in the molecule. The isopropyl group was found to be the substituent which is most easily available, from a synthetic point of view, and which readily transfers hydrogen to the keto function, which we attribute to its ability to form a stable radical after abstraction of hydrogen. The most preferred compounds according to the above formula (I') are 25 geranyl 2-(2'-isopropylbenzoyl)benzoate, geranyl 2-(2',4'-diisopropyl-benzoyl)benzoate and 3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-l '-y!)-4-penten-2-yl 2-(2',4'- diisopropylbenzoyl)benzoate [(E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1 '- yl)-4-penten-2-ol is a secondary alcohol sold under the name Polysantol ® by Firmenich SA, Geneva, Switzerland]. WO 99/60990 PCT/1B99/00890 The 2-benzoyl and 2-alkanoyl benzoates of the present invention are synthesized by esterification of the respective 2-benzoyl and 2-alkanoyl benzoic acids with the desired alcohol, in a way known to a person skilled in the art, preferably using 4-dimethylaminopyridine in pyridine and 1,3-dicyclohexylcarbodiimide. The above-5 mentioned benzoic acids are obtained from the respective phthalic anhydride. This latter is brought to reaction, for example, with the desired substituted or unsubstituted benzene in a Friedel-Crafts reaction. If necessary, the respective phthalic anhydride can also be reacted with the Grignard reagent, the organolithium compound or another appropriate organometallic compound of the desired substituted or unsubstituted 10 benzene or alkane, respectively. A further object of the present invention is a fragrance delivery system ά-keto esters of formula comprising (III) 15 in which R' is hydrogen or a linear or branched, unsubstituted or substituted alkyl group or alkylene group from C1 to C35, an unsubstituted or substituted cycloalkyl group from C3, to C8, an unsubstituted or substituted phenyl group, wherein said alkyl, alkylene, 20 cycloalkyl and phenyl groups may comprise one or several hetero atoms not directly linked to the a-keto group and selected from the group consisting of oxygen, nitrogen, phosphorous and sulfur, or R'* is a substituted or unsubstituted, linear or branched alkyl group carrying an abstractable hydrogen in y-position relative to the a-keto function and comprising a 25 moiety from which is derived a fragrant compound containing an olefin function, such that said fragrant compound containing an olefin function is eliminated after abstraction of said γ-hydrogen atom ; R"* is hydrogen or a methyl, ethyl or tert-butyl group or is the organic part of a primary or secondary alcohol from which is derived a fragrant aldehyde or ketone, and 30 at least one of the groups R'* and R"* being a group which is derived from a fragrant compound. WO 99/60990 PCT/IB99/00890 In the above definition, when reference is made to a fragrant compound, aldehyde or ketone, it is always meant a compound which not only has an odor, but which is also known to a person skilled in the art as being useful as a perfuming ingredient for the formulation of perfumes or perfumed articles. The criteria a useful 5 perfuming ingredient has to fulfil are known to a person skilled in the art and include, amongst others, a certain originality of the odoriferous note, stability and a certain price/performance ratio. Non-limiting examples for fragrant compounds which can be used with the a-keto esters of the invention will be mentioned below. Like the above-described 2-benzoyl benzoates and 2-alkanoyl benzoates, the 10 a-keto esters of the above formula (III) release fragrant compounds upon exposure to light, in particular daylight. The a-keto esters of formula (III), however, are capable of releasing a fragrant compound containing an olefin function from the group R'* in 1-position relative to the keto function, or a fragrant aldehyde or ketone which is derived from the alcohol R"OH from which the organic part R" is present in the ester function 15 of the keto esters of the present invention, or even both. From the above, it is clear that when reference is made to the organic part R"* of a fragrant alcohol R"OH, R" is the hydrocarbyl rest of said alcohol, e.g. a menthyl radical in case R"OH is menthol. The release of the fragrant compound from the keto esters occurs in an 20 elimination reaction after an intramolecular transfer of an abstractable hydrogen radical, in γ-position to the a-keto function, to said keto function. The respective part of the molecule from which the hydrogen radical has been abstracted is subsequently released from the reduced keto ester, with concomitant formation of a double bond. The above is illustrated in the scheme below in which possible substituents in the respective parts of 25 the molecules have been omitted for reasons of clarity. The double bonds which will be formed after elimination are indicated by dotted lines. WO 99/60990 PCT/1B99/00890It is to be understood that the a-keto esters of the present invention can release only one or both molecules of fragrant compound per molecule of a-keto ester. When the hydrogen transfer to the a-keto function is able to occur from the one or the other side of said function, as illustrated above, a certain part of the molecules will 5 release a ketone or aldehyde and a certain part will release the olefin compound. The proportions of the two products released depend on the relative rate of each hydrogen transfer reaction. According to the effect desired, the a-keto esters of the invention can be tailored to release exclusively a fragrant ketone or aldehyde, or exclusively a fragrant compound containing an olefin group, or both. When only one of the two classes of 10 fragrant compounds is to be released from the a-keto esters of the invention, the part of the molecule from which no release shall occur does not contain an abstractable hydrogen atom in y-position to the keto function, i.e. either no hydrogen atom at all is present in the said position, or it is one which is not abstracted. It is also clear that the a-keto esters according to the invention can, in a first 15 step, release the olefin compound under formation of a molecule which does not any longer contain an abstractable hydrogen atom in y-position to the keto function (left side of the molecule as designed above); in a second step, this molecule can then release the ketone or aldehyde from the ester function. It is evident that a fragrance delivery system which contains the a-keto 20 esters of the above formula (III) has all the advantages described above for the 2-benzoyl and 2-alkanoyl benzoates of formula (I) and (II), i.e. the release of the fragrant compound occurs in a more or less constant amount. No initial burst of very intensive odor which becomes imperceptible after a relatively short period of time occurs, as is often observed with volatile aldehydes or ketones or fragrant compounds containing an 25 olefin group. With the a-keto esters of the present invention, such disadvantages are obviated because the esters will remain on a surface to which they have been applied or in the solution into which they have been incorporated. Upon exposure to light, the fragrant compound or compounds are released, and this reaction can provide perceptible amounts of the compound over days or weeks, depending, amongst others, on the 30 amount or the concentration of the a-keto esters, the time of exposure to light and its intensity. WO 99/60990 PCT/IB99/00890 A further advantage of the a-keto esters according to formula (III) is the protection of the reactive, unstable aldehyde or keto function in the molecules to be released against degradation which may occur during storage. Additionally, the a-keto esters of the present invention allow for the 5 generation of mixtures of two different fragrant compounds, and in different proportions, if desired. In principle, any fragrant aldehyde or ketone which is known in the art can be released from the a-keto esters of the invention in which they are chemically bound in the form of the ester of their corresponding secondary or primary alcohol. 10 Non-limiting examples for fragrant aldehydes which can be released from the a-keto esters include saturated and unsaturated linear and branched aldehydes from C6 to Ct3, citral, citronellal, campholenic aldehyde, cinnamic aldehyde, hexylcinnamic aldehyde, formyl pinane, hydroxycitronellal, cuminic aldehyde, vanillin, ethylvanillin, Lilial ® [3-(4-tert-butylphenyl)-2-methylpropanal; origin: Givaudan-Roure SA, 15 Vernier, Switzerland], Lyral ® [4- and 3-(4-hydroxy-4-methylpentyI)-3-cyclohexene-l-carbaldehyde ; origin : International Flavors and Fragrances, USA], Bourgeonal ® [3-(4-tert-butylphenyl)propanal; origin: Quest International, Naarden, Netherlands], heliopropanal [3-(l,3-benzodioxol-5-yl)-2-methylpropanal; origin: Firmenich SA, Geneva, Switzerland], Zestover (2,4-dimethyl-3-cyclohexene-1-carbaldehyde; origin: 20 Firmenich SA, Geneva, Switzerland), Trifernal ® (3-phenylbutanal; origin : Firmenich SA, Geneva, Switzerland), a-sinensal, (4-methylphenoxy)acetaldehyde, 1,3-benzodioxol-5-carboxaldehyde (heliotropine), Scentenal ® [8(9)-methoxy-tricydo[5.2.1.0.(2,6)]decane-3(4)-carbaIdehyde; origin: Firmenich SA, Geneva, Switzerland], Liminal [(4R)-l-p-menthene-9-carbaldehyde; origin: Firmenich SA, 25 Geneva, Switzerland], Cyclosal [3-(4-isopropylphenyl)-2-methylpropanal; origin: Firmenich SA, Geneva, Switzerland], ortho- and para-anisaldehyde, 3-methyl-5-phenylpentanal, Acropal ® [4-(4-methyI-3-pentenyl)-3-cyclohexene-l-carbaldehyde ; origin : Givaudan-Roure SA., Vernier, Switzerland], Intreleven ® aldehyde (mixture of 10-undecenal and 9-undecenal; origin : International Flavors & Fragrances, USA), 30 muguet aldehyde l(3,7-dimethyl-6-octenyl)acetaldehyde ; origin : International Flavors & Fragrances, USA], 2,6-dimethyi-5-heptanal, Precyclemone ® B f l-methyl-4-(4- WO 99/60990 PCT/IB99/008 methyl-3-pentenyl)-3-cyclohexen-l-carbaldehyde; origin: International Flavors & Fragrances, USA] and Isocyclocitral ® (2,4,6-trimethyl-3-cyclohexene-l-carbaldehyde ; origin : International Flavors & Fragrances, USA). Non-limiting examples for ketones which can be released from the a-keto 5 esters include camphor, carvone, menthone, ionones, irones, damascenones and damacones, benzyl acetone (4-phenyl-2-butanone), 1-carvone, 4-(4-hydroxy-l-phenyI)-2-butanone (raspberry ketone), Hedione ® (methyl dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland), Neobutenone [l-(5,5-dimethyl-l-cyclohexen-l-yl)-4-penten-l-one ; origin : Firmenich SA, Geneva, Switzerland], Calone ® (7-methyl- 10 2H,4H-l,5-benzodioxepin-3-one ; origin : C.A.L. SA, Grasse, France), Sulfox [(1R,4R)-8-mercapto-3-p-menthanone; origin : Firmenich SA, Geneva, Switzerland], Orivone ® [4-(l,l-dimethylpropyl)-l-cyclohexanone; origin: International Flavors & Fragrances, USA], Delphone (2-pentyl-l-cyclopentanone; origin: Firmenich SA, Geneva, Switzerland), 2-naphthalenyl-l-ethanone, Veloutone (2,2,5-trimethyl-5-pentyl-l- 15 cyclopentanone; origin: Firmenich SA, Geneva, Switzerland), 4-isopropyl-2-cyclohexen-1-one, Iso E Super® [isomer mixture of l-(octahydro-2,3,8,8-tetrame-2-naphthalenyl)-l-ethanone ; origin : International Flavors & Fragrances, USA], Plicatone [5-methyl-exo-tricyclo[6.2.1.0(2,7)]undecan-4-one ; origin: Firmenich SA, Geneva, Switzerland]; and macrocyclic ketones such as, for example Exaltone 20 (cyclopentadecanone), Delta Muscenone (mixture of 3-methyl-4-cyclopentadecen-l-one and 3-methyl-5-cyclopentadecen-l-one) and Muscone (3-methyl-l- cyclopentadecanone), all from Firmenich SA, Geneva, Switzerland. With respect to the fragrant compounds carrying an olefin group, in principle any compound containing such olefin group and, in addition, any osmophoric 25 group known in perfumery can be used. As non-limiting examples for osmophoric groups, one can cite alcohol, ether, ester, aldehyde and keto groups, the thio analogues of the said groups, nitrile, nitro and olefin groups. As non-limiting examples for fragrant compounds which carry an olefin group, there can be cited linalool, 1,3,5-undecatrienes, myrcene, myrcenol, 30 dihydromyrcenol, nerolidol, sinensals, limonene, carvone, farnesenes, isopentyrate (1,3-dimethyI-3-butenyl isobutyrate ; origin : Firmenich SA, Geneva, Switzerland), ally I 3- WO 99/60990 PCT/IB99/00890 methylbutoxyacetate, eugenol, Rosalva ® (9-decen-l-ol; origin : International Flavors & Fragrances, USA), and allyl heptanoate. It is quite obvious, however, that the invention is perfectly general and can relate to many other aldehydes, ketones and olefins which are useful as fragrant 5 compounds. The person skilled in the art is quite able to choose these compounds from the general knowledge in the art and from the olfactive effect it is desired to achieve. The above list is therefore more illustrative for the compounds which are known to a person skilled in the art, and whose delivery can be improved. It is clearly quite impossible to cite in an exhaustive manner all aldehydes, ketones and olefins which 10 have a pleasant odor and which can be used in the form of derivatives in the a-keto esters of formula (III) from which they are released upon exposure to light. The a-keto esters of the present invention are in particular appropriate for delivering fragrant aldehydes, ketones and fragrant compounds containing an olefin group which are very volatile or which have a low perception threshold. Preferred 15 aldehydes and ketones include citronellal, citral, hydroxycitronellal, Hedione ®, Lilial ®, raspberry ketone, anisaldehyde, menthone, Delphone, Orivone®, 2-naphthalenyl-l- ethanone, and aldehydes from C6 to C!3, saturated or unsaturated linear or branched. Preferred fragrant compounds containing an olefin group include linalool, myrcene, myrcenol and Rosalva ®. In case the a-keto esters of the present invention are used to release exclusively aldehydes or ketones, the group R'* is hydrogen, phenyl, cyclohexyl or cyclopentyl, methyl, ethyl, n-propyl, isopropyl, sec-butyl, isobutyl or tert-butyl, i.e. groups which do not provide an abstractable hydrogen atom in y-position to the a-keto function or which do not form a stable radical when a hydrogen radical is abstracted 25 from them. In the latter case, small amounts of olefin may be formed which however do not interfere with the aldehyde or ketone released. Likewise, when the a-keto esters of the present invention are used to release a fragrant compound containing an olefin group only, then the group R"* will be hydrogen or a methyl, ethyl or tert-butyl group, thus a group which does not provide an 30 abstractable proton in y-position to the a-keto function or which do not form a stable radical when a hydrogen radical is abstracted from them. WO 99/60990 PCT/IB99/00890 It is preferred when the fragrance delivery system of the present invention contains a-keto esters of formula (III) in which R"* is the organic part of a primary or secondary alcohol from which is derived a fragrant aldehyde or ketone and in which R'* is a phenyl, cyclohexyl or cyclopentyl group or a linear or branched alkyl group from C1, 5 to C4. A fragrance delivery system containing the a-keto esters of formula (III) does not need an external hydrogen radical source. A fragrance delivery system containing a-keto esters of the present invention may thus comprise a solvent the choice of which is not supposed to be critical. Suitable classes of solvents include alcohols, 10 ethers, esters, ketones, amines and aminoalcohols. Depending on the general application conditions or on the product into which the a-keto esters according to the present invention are incorporated, one can sometimes also observe the release of alcohols R"OH, due to saponification of the ester function, or due to reduction of the aldehyde or ketone formed by irradiation. 15 The a-keto esters of formula (III) can be prepared, on the one hand, by esterification of the respective a-ketoacids with the primary or secondary alcohols which are the precursors of the fragrant aldehydes and ketones to be releasead. Another way for the preparation of the a-keto esters of the present invention is the reaction of the bis(oxalyl) ester of the primary or secondary precursor alcohol R"OH with the 20 Grignard compound of the appropriate group R'* as defined in formula (III). The reaction is illustrated in the scheme I below. Scheme I 25 The bis(oxalyl) ester is prepared from oxalyl chloride and the desired alcohol, see Synth. Commun. 1981, (11), 943-946 and Org. Synth. Coll. Vol. II 1943, 425-427. WO 99/60990 PCT/IB99/0089 Another synthetic route leading to the desired a-keto esters of formula (III) is the Grignard reaction of the readily available bis(oxalyl)esters of lower aliphatic alcohols such as, for example, methanol, ethanol or propanol, with the Grignard compound of the respective group R', resulting in the intermediate ester (IV). This said ester (IV) is then submitted to a transesterification reaction with the respective precursor alcohol R"OH, to give the desired a-keto ester. This reaction is outlined in the following scheme II in which R'* and R"* have the meaning defined in formula (III). Hal is CI, Br or I and R is a lower alkyl group such as, for example, methyl, ethyl, propyl or butyl. Scheme II Various a-keto esters of formula (III) in which R'* is hydrogen or a phenyl or methyl group and R"* is derived from the alcohol precursor of a fragrant aldehyde are described in the literature. Also known is hexyl (cyclohexyl)oxoacetate (see DE-OS 29 09 951 to Bayer AG, describing the use of the said compound as starting product for the synthesis 20 of catalysts for the polymerisation of olefins), which would release n-hexanal upon irradiation. In Biochem. Z. 1935, (277), p 426-436, there is described the synthesis of the (-)-bornyl ester of (4-methylphenyI)oxoacetic acid, i.e. (-) (IS,2R), 1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl (4-methylphenyl)oxoacetate. The compound is 25 characterized by its physical data. There are furthermore known, from the chemical literature, various compounds according to the above formula (III) wherein OR"* is a menthyl or a benzyl group, with the groups R'* being various alkyl, alkenyl, cycloalkyl or phenyl groups as defined above. WO 99/60990 PCT/IB99/00890 There is nowhere found, however, any description or hint concerning the value of the compounds according to formula (III) in perfumery as a photosensitive molecule which will release a fragrant compound upon irradiation. In the book of S. Arctander, Perfume and Flavors Chemicals, 1969, 5 Montclair, New Jersey, USA, there are mentioned decyl 2-oxopropanoate, (Z)-3- hexenyl 2-oxopropanoate and 2-ethyl-3-methylbutyl 2-oxopropanoate, with a short description of their odor and their synthesis. It is not mentioned that the said molecules release fragrant compounds upon irradiation. The release of the above-mentioned fragrant compounds from the delivery 10 system occurs upon the exposure to light, e.g. the normal daylight which can penetrate through ordinary windows in houses and which is not particularly rich in UV-radiation. It goes without saying that upon exposure to bright sunlight, in particular outdoors, the release of the fragrant alcohol, aldehyde, ketone or alkene will occur faster and to a greater extent than upon exposure to the light in a room inside a building. Of course, the 15 reaction which releases the fragrant compound from the delivery system can also be initiated by an appropriate artificial lamp. The fragrance delivery systems of the present invention can be used in any application in which a prolonged, defined release of the above-mentioned fragrant compounds is desired. They therefore mostly find use in functional perfumery, in 20 articles which are exposed to daylight when in use or which are applied to other articles which thereafter are exposed to daylight. Suitable examples include air-fresheners in liquid and solid form which, with the delivery system of the present invention, still can release a fragrance when conventional air-fresheners, i.e. those not containing the system of the present invention, are exhausted. Other examples are various cleaners for 25 the cleaning of surfaces of all kinds, e.g. window and household cleaners, all purpose-cleaners and furniture polish. The surfaces which have been cleaned with such cleaners will diffuse the smell of the perfume much longer than when cleaned with conventional cleaners. Other representative examples include detergents for fabric wash, fabric conditioners and fabric softeners which can also contain the delivery system of the 30 present invention and which products can be in the form of powders, liquids or tablets. The fabrics and clothes washed or treated with such detergents or softeners will diffuse WO 99/60990 PCT/IB99/00890 the fragrant compound even after having been stored for weeks or even months, in a dark place, like a wardrobe. The release of the fragrant compound occurs in all the above-mentioned application examples. All possible types of window, household, all-purpose cleaners, 5 air-fresheners, detergent, fabric wash and fabric softeners can be used with the fragrance delivery system of the present invention, which has revealed itself to be useful in all types of these above-mentioned application examples. In the field of body care, the delivery systems according to the present invention have shown themselves to be particularly appropriate for an application in the 10 hair care area, and specific examples include shampoos, hair conditioners, in particular leave- in conditioners, hairspray and other hair care products. It can be said that generally all products which can be applied to a surface which is exposable to light may contain the system of the present invention. Examples include surfaces which belong to the human body, like skin or hair, surfaces in buildings 15 and apartments, like floors, windows, tiles or furniture, or surfaces of fabrics, e.g. clothes. It is clear that the system of the invention can also be used to release fragrances from liquids, like in liquid air-fresheners. The possible applications of this type, however, appear to be less general than the application on the various surfaces mentioned. 20 Of course, the above examples are only illustrative and non-limiting as referring to preferred embodiments. All other current articles in functional and fine perfumery may contain the system of the present invention, and these articles include soaps, bath or shower gels, cosmetic preparations, body deodorants, and even perfumes or colognes. 25 In the above-cited applications, the device of the present invention can be used alone or with other perfuming ingredients, solvents and adjuvants of current use in the art. The nature and variety of these co-ingredients does not require a detailed description which, moreover could not be exhaustive, and a person skilled in the art will be able to choose said coingredients by his general knowledge and in function of the 30 nature of the product to be perfumed and the olfactive effect sought. These perfuming ingredients belong to such varied chemical classes as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogen- or sulfur- containing WO 99/60990 PCT/IB99/00890 heterocyclic compounds, as well as essential oils of natural or synthetic origin. By way of example, embodiments of compounds can be found in standard reference works, such as the book of S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or more recent versions thereof, or in other works of similar nature. 5 The proportions in which the system of the present invention can be incorporated in the various above-mentioned products vary within a wide range of values. These values depend on the nature of the fragrant compound to be released, the nature of the article or product which is to be perfumed and the desired olfactive effect, as well as on the nature of the co-ingredients in a given composition when the system of 10 the present invention is used in admixture with perfuming co-ingredients, solvents or adjuvants of current use in the art. By way of example, one can cite typical concentrations of the order of 0.01 to 5%, or even 10% by weight relative to the weight of the consumer products cited above into which it is incorporated. Higher concentrations than those mentioned above 15 can be used when the system is applied in perfuming compositions, perfumes or colognes. The invention will now be described in greater detail in the following examples in which the temperatures are indicated in degrees centigrade and the abbreviations have the usual meaning in the art. 20 Embodiments of the invention General 25 The following chemicals were obtained from commercial sources : geraniol, Polysantol ®, 2-benzoylbenzoate, dicyclohexylcarbodiimide (DCC), diisopropyl- carbodiimide (DIC), 4-dimethylamino-pyridine, magnesium turnings, 2-iodoisopropyl benzene, 1,3-diisopropylbenzene, A1C1,, 1,2-dichloroethane, 1,2-dibromoethane, 2- 30 norbornyl bromide, bromocyclopentane, citronellol, decanol, 4-methoxybenzyl alcohol, Lilial ®, (-)-menthol, 2-pentylcyclopentanol, 4-(l,l-dimethylpropyl)-l-cyclohexanol, 1- (2-naphthalenyl)ethanol, oxalyl chloride, diethyl oxalate, 3-methyl-2-oxo-pentanoic acid, 2-oxopropionic acid, 2-oxobutanoic acid, bromocyclohexane, bromobenzene, 2- WO 99/60990 PCT/IB99/00890 oxo-pentanoic acid, 4-bromo acetophenone, ethylene glycol, 2-bromo-tetradecane, 1-bromo-tetradecane. Geranyl 2-benzoylbenzoate (1) was prepared as described by Porter et al., J. Org, Chem. 1996,67,9455-9461. 5 A. Execution of photorelease assays and analysis for 2-benzoyl benzoates and 2-alkanoyl benzoates B. Photorelease Assays 10 Photorelease assays were conducted on solutions (typical concentrations = 0.005 to 0.01 M) or films of the respective esters in 10 ml borosilicate glass volumetric flasks (Pyrex ®) unless otherwise stated. The films were prepared by dissolving the ester in a small ( 15 drying under a stream of nitrogen or reduced pressure while rotating the flask to evenly disperse the ester on the surface of the glass. The samples were not degassed. The Fadeometer assays were done using an Atlas Ci35 Fadeometer, equipped with a borosilicate glass inner filter and a soda lime outer filter, set at 0.35 W/m2 at 340 nm. Natural light assays were done by putting the samples in a metal rack outdoors during 20 daylight hours. Natural light conditions could also be mimicked by using a 8W 366 nm UV lamp with an intensity of 500 μW/cm2 (VWR Scientific Products). Analysis 25 After photolysis, the quantity of alcohol released was measured by GC analysis of duplicate samples using the alcohol as the external standard. The presence of photoreleased alcohol was checked using GC retention times, GC-MS and also by smelling the samples. The ester solutions were injected neat while the solid films were dissolved and diluted volumetrically to 10 ml in acetone. Samples (1 (μl, split 54:1, 30 injector at 250°C) were injected as acetone solutions. Gas chromatography-flame ionization detection (GC-FID) was carried out using an SPB-1 capillary column (30 m, 250 μm id. 0,25 μm film. Me carrier gas, 1.0 ml/min). WO 99/60990 PCT/IB99/00890 Gas chromatography-mass spectrometry (GC-MS) was performed using an HP-5890 GC coupled to an HP 5989A mass spectrometer. The GC separation utilized an SPB-1 capillary column (30 m, 0,25 urn id, 0.25 μm film, He carrier gas, 1 ml/min). An SPB-1 column (30 m, 0,32 u.m id, 0.25 μm film, He carrier gas, 1.3 ml/min) was used 5 for the GC separation with the same temperature program used for the GC-MS. The samples (1 μ1, split 16:1, injector at 250°C) were injected as acetone solutions. B. Execution of photorelease assays and analysis for a-keto esters 10 Photorelease Assays Photorelease assays were conducted on solutions or on films of the respective ester and will be described below in each of the examples referring to the respective mode of irradiation. 15 All samples were irradiated using a xenon lamp (Heraeus Suntest CPS at 460W/m2), a UV lamp (UVP Model UVL-28, 8W at 360 nm) or exposed to outdoor sunlight, as will be indicated for each sample in the respective examples. Analysis 20 The mode of analysis for each sample which had been irradiated will be indicated in each respective example. Analytical HPLC was carried out on a Spectra Physics instrument composed from a SP 8800 ternary pump, a SP 5750 injection valve, a SP 8780 autosampler, a Waters 490E 25 UV detector and a Spectra Physics ChromJet integratorMacherey-Nagel Nucleosil 5 Cjs reversed phase column (125 x4 mm i.d.) eluted with a gradient from acetonitrile/water 1:1 to pure acetonitrile during 20 min. The injection volume was 50 μl and the UV detector wavelength fixed at 220 nm. Analytical GC for analysis of all-purpose/window cleaner applications : the on-column 30 injections were carried out on a Carlo Erba MFC 500 using a precolumn (30 cm) and a Suppelco SPB-l capillary column (30 m) at 115°C for 8 min, then to 280°C, helium pressure 75 kPa, injection volume 2 μl. All other GC analyses were carried out on the WO 99/60990 PCT/IB99/00890 same instrument equiped with a Fisons AS 800 autosampler using a J& W Scientific DB1 capillary column (15 m) at 70 or 80°C for lOmin, then to 260°C, helium pressure 50 kPa, injection volume 0.5 μl. Analytical GC for dynamic headspace analysis : Tenax cartridges were thermally desorbed 5 in a PE ATD400 or a TDAS 5000 desorber. The volatiles were then analysed either with a Carlo Erba HRGC 5300 gas chromatograph coupled to Finnigan ITD-800 mass spectrometers using a Supelco SPB-1 capillary column (60 m, 0.75 mm i.d., film 1 micron) at 60°C for 5 min then to 120°C (3°C/min) and 280°C (5°C/min) for the citronellal analysis, and at 100°C then to 250°C (5°C/min) for the menthone quantification or, 10 alternatively, with a Carlo Erba Vega 6000 gas chromatograph using a Supelco SPB-1 capillary column (30 m, 0.53 mm i.d., film 1.5 micron) from 110°C to 200°C (6°C/min) using He as carrier gas in both cases. Example 1 Preparation of substituted 2-benzoyl benzoates a) Geranyl 2-(2'-isopropylbenzoyl)benzoate (2) 20 Magnesium (0.46 g, 19 mmol) and a crystal of iodine were placed in a dry round bottom flask which was heated to activate the magnesium. Diethyl ether was added to cover the magnesium (50 ml) and several drops of 2-iodoisopropyl benzene in diethyl ether were added to start the preparation of the Grignard reagent. When the latter was underway, a solution of 2-iodoisopropyl benzene (4.18 g, 17 mmol) in 25 diethyl ether (20 ml) was added over 20 minutes. The reaction mixture was stirred for another 15 minutes and then refluxed for 20 minutes. Phthalic anhydride (3.11 g, 21 mmol) in toluene (50 ml) was added dropwise to the Grignard reagent at room temperature. The reaction temperature was raised to 60°C and the diethyl ether removed by evaporation. The reaction was allowed to stir at 60°C for 6 hours. 30 The reaction mixture was poured on ice and 10% HC1 (100 ml) and extracted twice with diethyl ether. The organic phase was washed twice with a 10% Na2CO3 solution (200 ml). The aqueous phase was acidified with acetic acid (120 ml) and WO 99/60990 PCT/IB99/00890 extracted twice with diethyl ether (200 ml). The organic phase was washed three times with NaHCO3(100 ml) and then twice with water. The ether phase was dried over Na2S04, filtered and concentrated. The yield was 1.43 g (purity: 94.6%, isolated yield : 31%) of 2-(2-isopropylbenzoyl)benzoic acid. 5 For esterification, a solution of the thus obtained acid (3.77 g, 10 mmol), geraniol (1.4 g, 9 mmol) and 4-dimethylaminopyridine (DMAP, 0.244 g, 2 mmol) in pyridine (15 ml) was prepared under anhydrous conditions. 1,3- Dicyclohexylcarbodiimide (DCC, 2.06 g, 10 mmol) was added and the reaction was stirred under a stream of nitrogen gas for 52 hours. The reaction mixture was 10 partitioned between IM HCl and ethyl acetate. The organic extract was dried over Na2S04, filtered and concentrated under vacuum. The ester product was purified by flash column chromatography (Si02, 7:1 cyclohexane:ethyl acetate ; isolated yield : 0.7 g, 48%) to give the following analytical data : UV (cyclohexane) 240 (ε 13 000), 280 (ε 5 000); 'H-NMR (360MHz, CDC13) 8 (ppm) : 7.85 (m, 1H); 7.49 (m, 4H); 7.38 (m, 1H); 7.23 (dd, 1H, J=l, 8Hz); 7.12 (m, 1H); 5.21 (1H, m); 5.05 (1H, m); 4.65 (1H, d, J=7Hz); 3.70 (1H, m); 2.00 (4H, m); 1.66 (3H, br s); 1.63 (3H, br s); 1.58 (3H, br s); 1.28 (6H, d, J=7Hz) 20 13C NMR (90MHz, CDC13) 5 (ppm) : 198.7(s), 167.2(s), 150.1(s), 142.5(s), 142.1(s), 136.7(s), 131.6(d), 131.1(d), 130.6(d), 130.3(d), 129.5(d), 129.0(d), 126.4(d), 124.9(d), 123.8(d), 117.8(d), 62.4(t), 39.5(t), 29.3(d), 26.3(t), 24.1(q), 17.7(q), 16.5(q). 25 b) Geranyl 2-(2',4'-diisopropylbenzoyl)benzoate (3) Phthalic anhydride (19.3 g, 0.13 mol) was placed in a flame-dried three-neck round- bottom flask under nitrogen. 1,2-Dibromoethane (100 ml) and aluminum chloride (36.0 g, 0.27 mol) were added. The reaction solution was stirred at room 30 temperature while 1,3-diisopropylbenzene (20.4 g, 0.126 mol) was added dropwise over the space of an hour. The reaction mixture was stirred at 100°C for two hours. Upon completion, the reaction mixture was cooled to room temperature and poured WO 99/60990 PCT/IB99/00890 over ice/hydrochloric acid (1:1). The solution was extracted twice with dichloromethane. The organic extract was washed with saturated aqueous sodium chloride solution to neutrality, dried over anhydrous sodium sulfate, filtered and concentrated under vacuum to yield a heavy brown oil of 80% purity (isolated 5 yield = 36 g, % yield = 74%). The thus obtained 2-(2',4'-diisopropylbenzoyl) benzoic acid showed the following analytical characteristics : lR: (neat), 2965, 1695, 1670, 1605 cm1lH NMR (360 MHz, CDC13) 5 ppm : 7.98 (1H, dd, J= 1, 8 Hz), 7.59 (1H, m), 7.52 10 (1H, m), 7.37 (1H, dd,J= 1,8 Hz), 7.31 (1H, d,J = 1.2 Hz), 7.09 (1H, d,J= 8 Hz), 6.94 (1H, dd,J= 2, 8 Hz), 3.82 (1H, m), 2.91 (1H, m), 1.25 (12H, m); 13C NMR (90 MHz, CDCI3) 8ppm : 198.6 (s), 170.9 (s), 153.2 (s), 151.0 (s), 143.8 (s), 133.9 (s), 132.3 (d), 131.7 (d), 130.6(d), 129.8 (d), 128.9 (s), 128.7 (d), 125.0 (d), 122.7 (d), 34.3 (d), 29.0 (d), 24.1 (q), 24.1 (q), 23.7 (q), 23.7 (q); 15 LREIMS: m/z (relative abundance) 310 (5, M+), 265 (43), 249 (45), 221 (100), 149 (32), 84 (41), 49 (35). The thus obtained product (1.15 g, 3.7 mmol) was dissolved in dry pyridine (10 ml) in a flame-dried three-neck round-bottom flask. To the solution were added geraniol 20 (freshly distilled, 0.55 g, 3.6 mmol), 4-dimethylaminopyridine (DMAP, 0.10 g, 0.8 mmol) and 1,3-dicyclohexylcarbodiimide (DCC, 0.76 g, 3.7 mmol). The reaction mixture was stirred at room temperature overnight. When complete, the reaction mixture was poured onto shaved ice (20 g), 32% hydrochloric acid (24 g) and ethyl acetate (30 ml) and stirred vigorously for 10 minutes. The solution was 25 extracted twice with diethyl ether and the organic phase was washed twice with saturated aqueous sodium bicarbonate solution and twice with water. The organic phase was dried over anhydrous sodium sulfate and concentrated under vacuum. The product was purified by redissolving in pentane, crystallizing at 4°C, and filtering through Celite. The filtered solution was concentrated under vacuum and 30 purified further by normal phase silica gel chromatography (20% diethyl ether/heptane). Geranyl 2-(2'-4'-diisopropylbenzoyl)benzoate was isolated as a pale WO 99/60990 PCT/IB99/00890 yellow oil (isolated yield = 1.08 g, % yield =74.5%), having the following analytical data: 1H NMR (360 MHz, CDC13) 5 ppm : 7.76 (1H, dd, J= 3, 6 Hz), 7.51 (2H, m), 7.37 5 (1H, dd, J- 3, 6 Hz), 7.31 (1H, d, J = 2 Hz), 7.18 (1H, d, J= 8 Hz), 6.97 (1H, dd, J= 2, 8 Hz), 5.22 (1H, m), 5.04 (1H, m), 4.64 (2H, d,J= 7 Hz), 3.79 (1H, m), 2.92 (1H, m), 2.1-1.9 (4H, m), 1.74 (3H, br s), 1.62 (3H, br s), 1.58 (3H, br s), 1.28 (6H, d, J= 7 Hz), 1.25 (6H, d, J= 7 Hz); l3C NMR (90 MHz, CDCI3) 5 ppm : 198.5 (s), 167.2 (s), 152.9 (s), 150.6 (s), 10 142.7 (s), 142.4 (s), 134.1 (s), 131.7 (s), 131.2 (s), 131.6 (d), 131.1 (d), 129.9 (d), 129.6 (d), 128.7 (d), 124.7 (d), 123.8 (d), 122.8 (d), 117.9 (d), 62.3 (t), 39.5 (t), 34.3 (d), 29.2 (d), 26.3 (t), 25.7 (q), 24.1 (q), 24.1 (q), 23.7 (q), 23.7 (q), 17.7 (q), 16.4 (q); LREIMS: m/z (relative abundance) 446 (M+, 15 231 (28), 221 (49), 149 (52), 93 (34), 69 (55), 41 (53). c) (E)-3,3-dimethyl-5-(2,,2,,3'-trimethyl-3'-cyclopenten-l,-yl)-4-penten-2-yl 2-(2',4'-diisopropylbenzoyl)benzoate (4) 20 2-(2',4'-Diisopropylbenzoyl)benzoic acid (0.3114 g, 1.0 mmol) was dissolved in dry pyridine (2 ml) in a flame-dried round bottom flask. To the solution were added Polysantol® (0.2113 g, 0.95 mmol), 4-dimethylaminopyridine (DMAP) on polystyrene resin (0,168 g, 0.34 mmol) and 1,3-diisopropylcarbodiimide (DIC, 120 ul, 1.4 mmol). The reaction mixture was stirred at room temperature under an 25 atmosphere of dry nitrogen for 68 hours. The reaction mixture was filtered, and partitioned between 0.5M aqueous hydrochloric acid and ethyl acetate. The organic phase was washed a second time with 0.5M hydrochloric acid, then once with 10% aqueous sodium carbonate solution. The ethyl acetate solution was washed with saturated, aqueous sodium bicarbonate solution and finally with water. The organic 30 phase was dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The resulting ester was purified by normal phase silica gel chromatography (2% ethyl acctate/cyclohexane) to yield a 1:1 mixture of two WO 99/60990 PCT/IB99/00890 stereoisomers in the form of an oil (isolated yield = 0.14 g, % yield = 27%) which showed the following analytical data : IR: (neat) 2960, 1720, 1675 cm"1, 5 'H NMR (360 MHz, CDC13) 8ppm : 7.83 (m, 1H), 7.52 (m, 2H), 7.39 (m, 1H), 7.30 (d, 1H, J = 1 Hz), 7.12 (dd, 1H, J = 2, 8 Hz), 6.94 (dd, 1H, J = 2, 8 Hz), 5.39 (2H, m), 5.21 (1H, m), 4.82 (1H, m), 3.83 (1H, m), 2.90 (1H, m), 2.26 (1H, m), 2.17 (1H, m), 2.03 (1H, m)J.59 (3H, br d, J- 1 Hz), 1.30 (6H, d,J = 7 Hz), 1.24 (6H, d, J= 7 Hz), 0.99, 0.99 (311, d, J= 6 Hz), 0.97, 0.95 (6H, br 10 s), 0.90, 0.87 (3H, s), 0.69, 0.69 (3H, s); 13C NMR (90 MHz, CDCI3) 5 ppm : 198.5 (s), 166.5 (s), 152.8 (s), 150.8 (s), 148.1 (s), 143.0 (s), 136.7 (s), 136.6 (s), 134.3 (s), 131.9 (s), 131.5 (d), 131.0 (d), 129.8 (d), 129.5 (d), 129.5 (d), 129.3 (d), 128.8 (d), 124.8 (d), 122.6 (d), 121.5 (d), 78.3 (d), 78.2 (d), 54.3 (d), 48.1 (s), 48.1 (s), 39.9 (s), 35.5 (t), 34.4 (d), 15 29.1 (d), 25.4 (q), 24.2 (q), 24.2 (q), 23.7 (q), 23.7 (q), 23.4 (q), 23.2 (q), 20.5 (q), 14.8 (q), 14.7 (q), 12.7 (q); Nanospray MS: m/z (relative abundance) 537.4 ([M + Na]+, 100), 515.2 ([M + H]+, 2). 20 Example 2 Preparation of ά -keto esters 25 The bis(3,7-dimethyl-6-octenyl)oxalate which was used for the synthesis of some of the ά -keto esters described below was prepared as follows. Oxalyl chloride (10 ml, 116 mmol) was added dropwise to a stirred solution of 36.37 g (233 mmol) of citronellol in 300 ml of pyridine at 0°C over a period of 30 min. The formation of a white precipitate was observed. The solution was allowed to warm up at 30 room temperature over night and was quenched with water, extracted with diethyl ether (2x), H2S04 (10%) (2x), NaHC03 (10%) and saturated NaCl. The organic layer was dried over NUTS04, concentrated at reduced pressure and filtered over a short plug WO 99/60990 PCT/IB99/0089 (SiO2, heptane/diethyl ether). Column chromatography (SiO2, heptane/diethyl ether) gave 18.55 g (43%) of a colorless oil. IR (neat): 2965s, 2925$, 2873m, 2856m, 1770s, 1745s, 1457m, 1380m, \347w, 1312m, 5 1250w, 1170s, 1122w, 1044w, 941m, 886w, 83\w, 792w, 756w, 742w. 'H NMR (360 MHz, CDC13): 5.13-5.04 (m, 1 H); 4.40-4.23 (m, 2 H); 2.08-1.87 (m, 2 H); 1.85-1.71 (m, 1 H); 1.70-1.50 (m, 2 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43-1.29 (m, 1 H); 1.29-1.13 (m, 1 H); 0.94 (d, J =6.3, 3 H). 13C NMR (90.6 MHz, CDC13): 158.04 (s); 131.45 (s); 124.42 (d); 65.59 (/); 36.91 (/); io 35.08 (0; 29.42 (d); 25.70 (q); 25.36 (/); 19.36 (q); 17.65 (q). MS (EI): 336 (M+, 0.1); 228 (0.1); 183 (0.1); 165 (0.1); 138 (18); 123 (30); 109 (16); 95 (38); 81 (51); 69 (100); 55 (30); 41 (46); 29 (5). a) 3,7-Dimethyl-6-octenyl-2-oxopropanoate (5) 15 A stirred solution of 5.56 g (63 mmol) of 2-oxo propionic acid and 19.68 g (126 mmol) of citronellol in 150 ml of toluene was heated for 35 h under reflux with azeotropic removal of water. After cooling to room temperature the reaction mixture was extracted with diethyl ether (2x), 10% NaHC03, sat. NaCl, dried (Na2S04) and concentrated in vacuo. Column chromatography (SiCO2, pentane/ether 20 9:1) afforded 2.81 g (20%) of a colorless oil. UV/Vis (hexane): 388 (sh, 3); 378 (sh, 5); 369 (sh, 8); 360 (sh, 10); 345 (14); 334 (14);319(sh, 12); 284 (sh, 9). IR (neat): 2961m, 2915m, 2873m, 2856m, 1728s, 1454m, 1378m, 1357m, 1297m, 251266m, 1203w, 1134s, 1051m, 1024w, 982m, 937m, 830m, 771w, 720m, 663w. 'H NMR (360 MHz, CDC13): 5.15-5.03 (m, 1 H); 4.37-4.18 (m, 2 H); 2.47 (s, 3 H); 2.10-1.88 (m, 2 H); 1.87-1.71 (m, 1 H); 1.71-1.47 (m, 2 H); 1.68 (s, 3 H); 1.60 (s, 3H); 1.46-1.28 (m, 1 H); 1.28-1.12 (m, 1 H); 0.94 (d, J= 6.3, 3 H). I3C NMR (90.6 MHz, CDC13): 191.96 (s); 160.92 (s); 131.52 (s); 124.37 {d)\ 65.06 30(/); 36.89 (/); 35.14 (0; 29.39 (d); 26.73 (4); 25.71 (q); 25.33 (0; 19.36 (q); 17.66 (^). WO 99/60990 PCT/IB99/00890 MS (EI): 226 (M+, 3); 209 (1); 208 (5); 198 (1), 184 81); 183 (9); 165 (2); 156 (1); 155 (14); 139 (1); 138 (15); 137 (20); 136 (1); 124 (3); 123 (29); 121 (3); 111 (1); 110 (5); 109 (20); 99 (1); 97 (2); 96 (8); 95 (45); 94 (2); 93 (1); 91 (1); 90 (1); 84 (1); 83 (15); 82 (28); 81 (51); 80 (2); 79 (2); 77 (1); 71 (1); 70 (10); 69 5 (100); 68 (14); 67 (23); 66 (1); 65 (2); 57 (5); 56 (8); 55 (34); 54 (2); 53 (7); 44 (1); 43 (41); 42 (5); 41 (40); 40 (2); 39 (6); 29 (4); 27 (3). b) 3,7-Dimethyl-6-octenyl-2-oxobutanoate (6) The synthesis was carried out as described above under a) with 6.43 g (63 mmol) of 10 2-oxo butyric acid, 19.68 g (126 mmol) of citronellol and 150 ml of toluene (24 h). Column chromatography (SiO2, pentane/ether 9:1) afforded 7.80 g (52%) of a colorless oil. UV/Vis (hexane): 397 (sh, 1); 383 (sh, 3); 373 (sh, 6); 356 (sh, 12); 341 (16); 330 15 (16); 318 (sh, 14); 268 (sh, 12). IR (neat): 2961m, 2914m, 2879m, 2857m, 1725s, 1456m, 1404w, 1379m, 1351w, 1273m, 1242m, 1173w, 1144m, 1097s, 1041m, 982m, 946w, 88 lw, 830m, 760w, 737w, 700m, 678m. >H NMR (360 MHz, CDC13): 5.14-5.02 (m, 1 H); 4.40-4.20 (m, 2 H); 2.86 (q, J = 20 7.3, 2 H); 2.09-1.88 (m, 2 H); 1.87-1.68 (m, 1 H); 1.68 (s, 3 H); 1.68-1.45 (m, 2 H); 1.60 (s, 3 H); 1.45-1.29 (m, 1 H); 1.29-1.15 (m, 1 H); 1.13 (/, J= 7.1, 3 H); 0.94 (4 J= 6.3, 3 H). '3C NMR (90.6 MHz, CDC13): 195.09 (s); 161.32(5); 131.51 (s); 124.40 (d); 64.87 (0; 36.90 (/); 35.17 (/); 32.89 (t); 29.40 (d); 25.71 (q); 25.34 (/); 19.37 (?); 25 17.66(g); 6.97 (q). MS (EI): 240 (MM); 222 (3); 212 (2); 184(1); 183(8); 165(1); 156(1); 155(12); 139(3); 138(20); 137(15); 136(1); 124(3); 123 (31); 121 (3); 111 (2); 110 (4); 109 (16); 104 (2); 99 (1); 97 (3); 96 (9); 95 (43); 94 (3); 93 (2); 91 (1); 85 (1); 84 (2); 83 (17); 82 (31); 81 (51); 80 (3); 79 (2); 77 (1), 71 (1); 70 (8); 69 30 (100); 68 (13); 67 (19); 66 (1); 65 (2); 58 (2); 57 (63); 56 (7); 55 (30); 54 (2); 53 (6); 43 (6); 42 (4); 41 (38); 40 (1); 39 (5); 29 (17); 28 (2); 27 (5). WO 99/60990 PCT/IB99/00890 c) 3,7-Dimethyl-6-octenyl 3-methyl-2-oxopentanoate (7) The synthesis was carried out as described above under a), using 4.85 g (38 mmol) of 3-methyl-2-oxo pentanoic acid and 11.66 g (74 mmol) of citronellol in 130 ml of toluene, for 72 h. Column chromatography (Si02, toluene/EtOAc) afforded 10 g of 5 crude product, which was fractionally distilled to give 3.65 g (36%) of a colorless oil. B.p. 94°C/2xlO'Pa. UV/Vis (hexane): 394 (sh, 4), 382 (sh, 10), 374 (sh, 10), 365 (sh, 10), 350 (sh, 20), 10 336 (20), 268 (sh, 30), 241 (sh, 180). 1R (neat): 2966s, 2929s, 2877m, 1749m, 1728s, 1460m, 1380m, 1267m, 1254m, 1165m, 1115w, 1087w, 1051m, lOOlw, 961w, 829w. 1H NMR (360 MHz, CDC13): 5.12-5.04 (m, 1 H); 4.36-4.24 (m, 2 H); 3.18-3.06 (m, 1 H); 2.08-1.88 (m, 2 H); 1.86-1.67 (m, 2 H); 1.68 (s, 3 H); 1.65-1.10 (m, 5 H); 15 1.60 (s, 3 H); 1.28 (d,J= 6.8, 3 H); 0.94 (d,J= 6.4, 3 H); 0.92 (/, J= 7.6, 3 H). I3C NMR (90.6 MHz, CDC13): 198.22 (s); 162.21 (s); 131.51 (s); 124.40 (d); 64.74 (0; 43.64 (d); 36.92 (0; 35.23 (/); 29.43 (d); 25.71 (q); 25.36 (/); 24.93 (/); 19.35 (q); 17.66 (q); 14.55 (q); 11.35 (q). MS (EI): 268 (M+, 1); 250 (1); 240 (1); 207 (1); 183 (2); 155 (2); 138 (10); 123 20 (14); 109 (7); 95 (18); 85 (32); 81 (26); 69 (51); 57 (100); 41 (53); 29 (18). d) 3,7-Dimethyl-6-octenyl 2-oxopentanoate (8) The synthesis was carried out as described above under a), using 4.33 g (37 mmol) of 2-oxo pentanoic acid and 11.65 g (75 mmol) of citronellol. Column 25 chromatography (SiCO2, toluene/EtOAc and SiCO2, heptane/diethyl ether) afforded 3.79 g of crude product, which was distilled (Kugelrohr) to give 2.52 g (27%) of a colorless oil. UV/Vis (hexane): 398 (sh, 1), 376 (sh, 10), 357 (sh, 10), 342 (sh, 20), 331 (20), 281 30 (sh, 20), 268 (sh, 30), 241 (sh, 280). IR (neat): 2965.V, 2931s, 2877m, 1750m, 1728s, 1457m, 1380m, 1287w, 1261m. 1 178»v, 1 146M\ 1118m, 1055m, 1037iv, 943vr, 832vr. WO 99/60990 PCT/IB99/00890 1H NMR (360 MHz, CDC13): 5.13-5.03 (m, 1 H); 4.36-4.21 (m, 2 H); 2.80 (t,J = 7.1, 2 H); 2.10-1.89 (m, 2 H); 1.83-1.70 (m, 1 H); 1.68 (s, 3 H); 1.67 (q,J= 7.3, 2H); 1.63-1.47 (m, 2 H); 1.60 (s, 3 H); 1.45-1.29 (m, 1 H); 1.28-1.12 (m, 1 H); 0.96 (t,J= 6.9, 3 H); 0.94 (d, J= 6.3, 3 H). 5 13C NMR (90.6 MHz, CDC13): 194.63 (s); 161.44 (s); 131.52 (s); 124.40 (d); 64.88 (/); 41.21 (0; 36.91 (0; 35.19 (/); 29.43 (d); 25.71 (q); 25.35 (/); 19.37 (q); 17.67 (q); 16.54(0; 13.52 (q). MS (EI): 254 (M+, 1); 236 (2); 226 (1); 193 (1); 183 (6); 165 (1); 155 (7); 138 (15); 137 (10); 123 (26); 118 (3); 109 (17); 95 (41); 83 (15); 82 (32); 81 (54); 71 10 (87); 69 (100); 67 (23); 55 (34); 43 (66); 41 (72); 27 (14). e) 3,7-Dimethyl-6-octenyl oxo(phenyl)acetate (9) A Grignard reagent prepared from 3.14 g of 1-bromobenzene (20 mmol) and 0.55 g of magnesium (22 mmol) in THF was added dropwise to a stirred solution of 8.0 g 15 (22 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate in 50 ml of THF at -78°C. The mixture was slowly warmed to -10°C, quenched with 25-30 ml of a saturated solution of NH4CI and left stirring for 30 min. The reaction mixture was extracted with diethyl ether and water (3x) and the organic phase dried over Na2S04. MPLC on a Lobar column (Si02 Merck, heptane/diethyl ether) afforded 3.5 g (61%) of the 20 pure product as a bright yellow oil. UV/Vis (hexane): 370 (sh, 30), 352 (40), 340 (sh, 40), 294 (sh, 1020), 252 (10350), 248 (10360). 1R (neat): 3065w, 2962s, 2926s, 2872m, 2855m, 1738s, 1693s, 1597m, 1581m, 25 1451m, 1379m, 1322m, 1313m, 1300m, 1246w, 1198s, 1175s, 1122w, 1042w, 1030w, 1003m, 998m, 94 lw, 83 lw. 1H NMR (360 MHz, CDC13): 8.04-7.97 (m, 2 H); 7.69.7.62 (m, 1 H); 7.55-7.45 (m, 2 H); 5.12-5.03 (m, 1 H); 4.50-4.36 (m, 2 H); 2.15-1.90 (m, 2 H); 1.90-1.75 (m, 1 H); 1.75-1.50 (m, 2 H); 1.66 (s, 3 H); 1.59 (s. 3 H); 1.45-1.32 (m, 1 H); 1.32- 30 1.15 (m, 1 H); 0.96 (d, J =6.3, 3 H). WO 99/60990 PCT/1B99/00890 l3C NMR (90.6 MHz, CDC13): 186.50 (s); 164.02 (s); 134.87 {d)\ 132.56 (s); 131.51 (s); 130.02 {d); 128.90 {d)\ 124.40 (rf); 64.85 (/); 36.93 (0; 35.30 (0; 29.44 id); 25.69 (q); 25.38 (/); 19.38 (q); 17.66 (q). MS (EI): 288 (M+, 1); 270 (4); 260 (1); 227 (1); 215 (1); 187 (1); 183 (1); 174 (1); 5 165 (1); 155 (4); 152 (3); 138 (9); 137 (10); 134 (2); 123 (11); 109 (8); 106 (10); 105 (100); 96 (3); 95 (20); 83 (3); 82 (12); 81 (24); 80 (2); 78 (3); 77 (36); 70 (3); 69 (26); 68 (5); 67 (10); 57 (3); 56 (3); 55 (11); 53 (3); 51 (10); 43 (4); 42 (3); 41 (28); 39 (5); 29 (4); 27 (4). 10 f) 3,7-Dimethyl-6-octenyl (4-acetylphenyl)oxoacetate (10) In the first step, 2-(4-bromomethyl)-2-mefhyl-l,3-dioxolane was prepared as follows. 10.0 g (50 mmol) of 4-bromo acetophenone, 7.0 g (112 mmol) of ethylene glycol and a few crystals of p-toluene sulphonic acid were dissolved in 100 ml of toluene and heated overnight under reflux with azeotropic removal of water. After 15 cooling to room temperature the reaction mixture was concentrated in vacuo. Column chromatography (SiC>2, heptane/diethyl ether) afforded 11.4 g (93%) of a colorless oil which easily crystallized. UV/Vis (hexane): 287 (sh, 400), 274 (sh, 1300), 270 (sh, 1800), 259 (sh, 6700), 252 20 (7800), 227 (sh, 61800), 220 (75600), 217 (sh, 75000). IR (neat): 3084w, 3060w, 2990m, 2957s, 2928s, 2890s, 2856m, 2670w, 191 lw, 1691m, 1657w, 1591m, 1575w, 1482m, 1470w, 1443m, 1393m, 1373m, 1249m, 1222w, 1196s, 1144m, 1118m, 1092m, 1079m, 1040s, 1010s, 947m, 873s, 826s. 25 lH NMR (360 MHz, CDC13): 7.49-7.42 (m, 2 H); 7.39-7.32 (m, 2 H); 4.08-3.96 (m, 2 H); 3.80-3.69 (m, 2 H); 1.62 (s, 3 H). 13C NMR (90.6 MHz, CDC13): 142.49 (s); 131.30 (d); 127.17 (d); 121.86 (s); 108.43 (s); 64.47(/); 27.52 {q). MS (EI): 244, 242 (M\ 1, 1); 230 (14); 229 (97); 227 (100); 213 (5); 211 (5); 186 30 (4); 185, 183 (51, 53); 171 (2); 169 (2); 157, 155 (14, 14); 148 (4); 133 (5); 105 (2); 104 (8); 103 (9); 102 (8); 101 (2); 89 (3); 87 (26); 78 (2); 77 (12); 76 (16); 75 (14); 74 (7); 73 (2); 63 (4); 62 (2); 51 (7); 50 (13); 43 (41); 39 (3); 29 (7). WO 99/60990 PCT/IB99/00890 The thus obtained compound was then used as starting product for the synthesis of 3,7-dimethyl-6-octenyl [4-(2-methyl-l ,3-dioxolan-2-yl)phenyl]oxoacetate. The synthesis was carried out as described above under e), using 4.66 g (20 mmol) of 5 the above-prepared dioxolane, 0.54 g (22 mmol) of magnesium and 8.0 g (22 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate. Column chromatography (Si02, heptane/diethyl ether) afforded 4.35 g (58%) of the product as a slightly yellow oil. UV/Vis (hexane): 370 (sh, 40), 353 (60), 340 (sh, 60), 296 (sh, 1300), 258 (13890). 10 1R (neat): 2963s, 2926s, 1736s, 1690s, 1607s, 1573m, 1505vv, 1455m, 1407m, 1374m, 1347w, 1314m, 1294w, 1250m, 1199s, 1175s, 1146w, 1122w, 1100w, 1078m, 1039m, 1018w, 989m, 948w, 890w, 876m, 861m, 833w. 1H NMR (360 MHz, CDC13): 7.98 (d,J= 8.3, 2 H); 7.62 {d, J = 8.7, 2 H); 5.12- 5.04 (m, 1 H); 4.50-4.36 (m, 2 H); 4.13-4.00 (m, 2 H); 3.82-3.70 (m, 2 H); 2.10- 15 1.90 (m, 2 H); 1.90-1.75 (w, 1 H); 1.72-1.54 (m, 2 H); 1.67 (s, 3 H); 1.65 (s, 3 H); 1.60 (s, 3 H); 1.45-1.32 (m, 1 H); 1.30-1.16 (m, 1 H); 0.96 (d, J= 6.3, 3 H). 13c NMR (90.6 MHz, CDCI3): 186.04 (s); 163.97 (s); 150.64 (s); 132.12 (s); 131.53 (s); 130.15 (d)\ 125.97 (d); 124.39 (d); 108.39 (s); 64.89 (0; 64.65 (2x) (0; 36.93 (0; 35.30 (/); 29.44 (d); 27.38 (q); 25.70 (q); 25.37 (0; 19.38 (q); 20 17.66 (q). MS (EI): 374 (M+, 7); 359 (8); 356 (3); 289 (1); 220 (2); 205 (1); 192 (32); 191 (100); 176 (2); 160 (2); 155 (2); 148 (24); 138 (16); 133 (6); 123 (14); 119 (76); 109 (9); 104 (15); 95 (22); 91 (8); 87 (18); 81 (30); 69 (26); 55 (10); 43 (12); 41 (21); 29 (3). 25 3,7-Dimethyl-6-octenyl (4-acetylphenyl)oxoacetate (10) 5 ml of H2SO4 (50%) were added to a solution of 4.2 g (13 mmol) of the product obtained in the above step in 30 ml of THF. The reaction mixture was heated at 40°C for 5 h, then extracted with diethyl ether (2x), and saturated solutions of 30 NaHC03 (2x) and NaCl (2x). The organic layer was dried over Na2S04 and concentrated. Column chromatography (SiO2, heptane/diethyl ether) yielded 2.0 g (47%) ofa yellow oil. WO 99/60990 PCT/IB99/00890 UV/Vis (hexane): 384 (sh, 60), 367 (sh, 100), 343 (sh, 150), 310 (sh, 1230), 301 (sh, 1660), 266 (17910), 260 (18440). IR (neat): 305 lw, 2964s, 2926s, 2872m, 2856m, 1736s, 1693s, 1607w, 1570m, 5 1500m, 1457m, 1434m, 1407m, 1379m, 1359m, 1318m, 1307m, 1260s, 1199s, 1176s, 1117w, 1075m, 992s, 959m, 861m, 832m. 1H NMR (360 MHz, CDC13): 8.17-8.02 (m, 4 H); 5.12-5.04 (m, 1 H); 4.53-4.37 (m, 2 H); 2.66 (s, 3 H); 2.14-1.90 (m, 2 H); 1.90-1.75 (m, 1 H); 1.73-1.53 (m, 2 H); 1.67 (s, 3 H); 1.60 (s, 3 H); 1.46-1.32 (m, 1 H); 1.32-1.12 (m, 1 H); 0.96 (d,J = 10 6.3, 3 H). 13C NMR (90.6 MHz, CDC13): 197.19 (s); 185.55 (s); 163.25 (s); 141.33 (s); 135.67 (s); 131.57 (s); 130.28 (d); 128.56 (d); 124.34 (d); 65.19 (0; 36.91 (t); 35.26 (0; 29.43 (d); 26.94 (9); 25.70 (q); 25.35 (/); 19.37 (q); 17.67 (q). MS (EI): 330 (M+, 4); 312 (1); 302 (1); 281 (1); 269 (1); 194 (4); 193 (2); 183 (1); 15 176 (2); 165 (1); 161 (1); 155 (2); 149 (5); 148 (43); 147 (100); 138 (4); 137 (11); 133(1); 132(2); 123 (10); 120(4); 119(11); 110(2); 109 (10);105 (2); 104 (12); 96 (4); 95 (21); 91 (15); 83 (5); 82 (13); 81 (29); 77 (6); 76 (8); 69 (38); 68 (5); 67 (11); 65 (3); 57 (3); 56 (3); 55 (12); 53 (3); 50 (3); 43 (15); 41 (30); 39 (5); 29 (4); 27 (3). 20 g) 3,7-Dimethyl-6-octenyl 3-methyI-2-oxopentadecanoate (11) The compound was prepared as described above under e), using 5.0 g (18 mmol) of 2-bromotetradecane, 0.58 g (24 mmol) of magnesium and 7.32 g (20 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate. Column chromatography (SiCO2, heptane/ 25 diethyl ether) afforded 2.52 g (34%) of a colorless oil. UV/Vis (hexane): 394 (sh, 4), 383 (sh, 10), 373 (sh, 10), 365 (sh, 20), 349 (sh, 20), 336 (20), 284 (sh, 10), 269 (sh, 20), 241 (sh, 140). IR (neat): 3440w, 2958s, 2924s, 2854s, 2730w, 1749s, 1725s, 1460m, 1378m, 30 1350w, 1266m, 1173w, 1146w, 11 \2w, 1053m, 1032m, 943w, 887w, 830w. ]H NMR (360 MHz, CDCI3): 5.13-5.04 (m, 1 II); 4.36-4.23 (m, 2 H); 3.23-3.10 (m, 1 H); 2.10-1.87 (/», 2 H); 1.87-1.64 (m, 1 H); 1.68 (.v, 3 H); 1.64-1.47 (m. 2 H); WO 99/60990 PCT/IB99/00890 1.60 (s, 3 H); 1.46-1.16 (m, 24 H); 1.13 (d,J = 6.7, 3 H); 0.94 (d,J=6.3, 3 H); 0.88 (t,.J= 6.9, 3 H). 13C NMR (90.6 MHz, CDC13): 198.33 (s); 162.20 (s); 131.50 (s); 124.40 (d); 64.75 (t); 42.21 (d); 36.93 (t); 35.23 (t); 31.92 (t); 29.68 (t); 29.66 (2x) (0; 5 29.59 (2x) (0; 29.45 (2x) (t); 29.37 (t); 27.01 (0; 25.71 (q); 25.37 (0; 22.70 (0; 19.35 (q); 17.66 (q); 15.01 (q); 14.12 (q). MS (EI): 408 (M+, 1); 390 (1); 380 (1); 347 (1); 294 (1); 272 (1); 255 (4); 205 (1); 197 (3); 184 (2); 183 (12); 165 (1); 155 (8); 141 (4); 139 (9); 138 (76); 137 (21); 127 (7); 123 (46); 113 (9); 109 (19); 99 (15); 96 (15); 95 (57); 94 (8); 85 10 (47); 83 (25); 82 (52); 81 (89); 80 (14); 71 (65); 70 (10); 69 (100); 68 (10); 67 (18); 57 (94);56 (17); 55 (51); 43 (61); 41 (69); 39 (7); 29 (15); 27 (6). h) 3,7-Dimethyl-6-octenyl 2-oxohexadecanoate (12) The compound was prepared as described above under e), using 5.54 g (20 mmol) 15 of 1-bromotetradecane, 0.54 g (22.5 mmol) of magnesium and 8.0 g (22 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate. Column chromatography (SiO2, heptane/ diethyl ether) afforded 3.21 g (39%) of a colorless oil. UV/Vis (hexane): 376 (sh, 10), 359 (sh, 20), 343 (sh, 20), 279 (260), 272 (sh, 250), 20 242 (530). IR (neat): 2958m, 2924s, 28545, 1728s, 1465m, 1458m, 1400w, 1378m, 1271m, 1128w, 1088w, 1062m, 945w, 831 w. »H NMR (360 MHz, CDC13): 5.12-5.03 (m, 1 H); 4.35-4.21 (m, 2 H); 2.81 (t, J = 7.3, 2 H); 2.09-1.88 (m, 2 H); 1.87-1.69 (m, 1 H); 1.68 (s, 3 H); 1.69-1.47 (m, 2 25 H); 1.60 (s, 3 H); 1.45-1.14 (m, 26 H); 0.94 (d, J= 6.3, 3 H); 0.88 (/, J= 6.9, 3 H). 13C NMR (90.6 MHz, CDCI3): 194.77 (s); 161.48 (s); 131.49(5); 124.41 (J); 64.86 (t); 39.38 (/); 36.93 (t/); 35.20 (t); 31.96 (0; 29.68 (3x) (t); 29.61 (t); 29.45 (2x) (t); 29.39 (t); 29.33 (t); 29.01 (t); 25.71 (q); 25.37 (t); 23.05 (0; 22.71 (t); 19.38 30 (q); 17.66 fa); 14.12 (q). MS (EI): 390(1), 225(11), 183(14), 165(1), 155(8), 139(7), 138(55), 137(28), 124(6), 123 (52), 121 (5), 111 (4), 110(7), 109 (27), 97 (9), 96 (16), 95 (70), WO 99/60990 PCT/IB99/0089094 (8), 85 (16), 83 (28), 82 (50), 81 (97), 80 (10), 71 (26), 70 (11), 69 (100), 68 (11), 67 (21), 57 (54), 56 (12), 55 (47), 43 (48), 42 (10), 41 (55), 39 (7), 29 (12). 5 i) 3,7-Dimethyl-6-octenyl (cyclohexyl)oxoacctate (13) The compound was prepared as described above under e), using 3.24 g (20 mmol) of freshly distilled 1-bromocyclohexane, 0.55 g (22 mmol) of magnesium and 8.0 g (22 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate. MPLC on a Lobar column (SiCO2 Merck, heptane/diethyl ether) finally afforded 1.69 g (29%) of the pure product as a 10 colorless oil. UV/Vis (hexane): 394 (sh, 4), 375 (sh, 11), 366 (sh, 14), 350 (sh, 18), 338 (19). IR (neat): 2932s, 2856m, 1747m, 17275, 1451m, 1379m, 131 \w, 1276m, 1230m, 1183w, 1173w, 1140m, 1118w, 1082m, 1067m, 1050w, 1029w, 997m, 942w, 15 895w, 837w. 'H NMR (360 MHz, CDC13): 5.12-5.04 (m, 1 H); 4.36-4.22 (m, 2 H); 3.07-2.95 (m, 1H); 2.09-1.85 (m,4 H); 1.85-1.64 (m, 3 H); 1.68 (s, 3 H); 1.64-1.47 (m, 2 H); 1.60 (s, 3 H); 1.43-1.13 (m, 8 H); 0.93 (d, J = 6.3, 3 H). 13C NMR (90.6 MHz, CDC13): 197.65 (s); 162.17 (s); 131.51 (s); 124.39 (d); 64.71 20 (t); 46.34 (d); 36.91 (t); 35.21 (t); 29A4(d); 27.46 (0; 25.72 (t); 25.36 (t); 25.30 (t);19.35(q); 17.66(q). MS (EI): 294 (M+, 1); 276 (1); 266 (1); 233 (1); 193 (1); 183 (4); 165 (1); 155 (2); 139 (2); 138 (13); 137 (4); 123 (14); 112 (2); 111 (16); 110 (3); 109 (6); 96 (4); 95 (16); 94 (2); 84 (7); 83 (100); 82 (15); 81 (22); 80 (3); 70 (2); 69 (29); 68 25 (4); 67 (11); 56 (4); 55 (42); 54 (3); 53 (5); 43 (4); 42 (4); 41 (38); 39 (8); 29 (6); 27 (4). k) (E)-3,7-Dimethyl-2,6-octadienyl (cyclohexyl)oxoacetate (14) In the first step, ethyl (cyclohexyl)oxoacetate was prepared as follows. 30 A Grignard reagent prepared from 24.45 g of 1-bromocyclohexane (0.18 mol) and 4.32 g of magnesium (0.15 mol) in 70 ml THF was added dropwisc (during a period of 40 min) to a stirred solution of 14.6 g (0.10 mol) of diethyl oxalate in 150 ml of 04-2000 IB 009900890 THF at -70°C. The formation of a precipitate was observed and another 100 ml of THF were added. The mixture was slowly warmed to -10°C and poured onto ice, saturated with NaCl, extracted with, diethyl ether (2x) and washed with a sat. solution of NH4CI (2x) and water (pH ≈ 7). The organic phase was dried over 5 Na2S04 and concentrated. Fractional distillation gave 9.86 g (54%) of a colorless oil. B.p. 54°C/0.1-150Pa. UV/Vis (hexane).-394 (sh, 5); 375 (sh, 10); 366 (sh, 15); 350 (sh, 20); 337 (20); 285 10 (sh, 7). IR (neat): 2982w, 2930m, 2854m, 1722s, 1449m, 1366w, 1272m, 1229m, 1184w, 1140m, 1112w, 1081m, 1066s, 1014m, 991m, 923w, 894w, 855w. 1H NMR (360 MHz, CDC13): 4.32 (q, J= 7.1, 2 H); 3.1-2.97 (m, 1 H); 1.97-1.85 (m, 2 H); 1.85-1.74 (m, 2 H); 1.74-1.64 (m, 1 H); 1.45-1.13 (m, 5 H): 1.37 (t, J 15 =7.1,3H). 13C NMR (90.6 MHz, CDC13): 197.65 (s); 162.03 (s); 62.19 (f); 46.29 {d)\ 27.51 (0; 25.73 (/); 25.32 (/); 14.06 (q). MS (EI): 184 (M+, 2); 112 (3); 111 (33); 110 (3); 84 (6); 83 (100); 81 (3); 79 (2); 77 (1); 68 (1); 67 (5); 65 (1); 56 (3); 55 (54); 54(5); 53 (5); 51 (1); 43 (2); 42 20 (3); 41 (23); 40 (2); 39 (12); 30 (1); 29 (20); 28 (3); 27 (13); 26 (1). (E)-3,7-Dimethyl-2,6-octadienyl (cyclohexyl)oxoacetate (14) A solution of 25.20 g (137mmol) of the product obtained above, 25.56 g (166mmol) of geraniol and 1 ml of NaOCH3 (30% in methanol) in 150 ml of •25 cyclohexane was heated under reflux overnight. After cooling to room temperature the reaction mixture was taken up in ether, washed with a sat. solution of NaCI (pH ≈ 7), dried (Na2S04), filtered and concentrated. Column chromatography (SiO2, heptane/ether 9:1) and fractional distillation afforded 23.36 g (58%) of a colorless oil. 30 04-2000 IB 009900890 B.p. 130°C/10 Pa. UV/Vis (hexane): 394 (sh, 5); 384 (sh, 8); 375 (sh, 14); 366 (sh, 17); 358 (sh, 20); 350 (sh, 22); 336 (24). IR (neat): 2926m, 2853m, 1743m, 1721, 1670w, 1449m, 1376m, 1341 w, 1331w, 5 1309w, 1273m, 1267m, 1227m, 1183w, 1139m, llllw, 1080m, 1063.?, 1027w, 993s, 915m, 895w, 830w, 805w, 787w, 739w, 729w, 718w. H NMR (360 MHz, CDCI3): 5.45-5.35 (m, 1 H); 5.12-5.03 (m, 1 H); 4.76 (d, J = 7.1, 2 H); 3.09-2.95 (m, 1 H); 2.17-1.98 (m, 4 H); 1.98-1.85 (m, 2 H); 1.84-1.75 (m, 2 H); 1.74 (s, 3 H); 1.73-1.62 (m, 1 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43- 10 1.14 (m, 5 H). 13C NMR (90.6 MHz, CDCI3): 197.70 (s); 162.08 (s); 143.97 (j); 131.97 (s); 123.59 (rf); 117.16 (d); 62.90 (t); 46.38 (d); 39.55 (r); 27.49 (f); 26.23 (); 25.73 (t); 25.67 (q); 25.31 (t); 17.69 (?); 16.58 (?). MS (EI): 292 (M+, 1); 205 (1); 179 (1); 138 (3); 137 (24); 136 (4); 135 (3); 123 (1): 15 122 (1); 121 (2); 112 (1); 111 (9); 107 (2); 105 (1); 96 (1); 95 (9); 94 (1), 93 (9); 92 (2); 91 (3); 84 (4); 83 (54); 82 (4); 81 (55); 80 (2); 79 (4); 77 (3); 70 (6); 69 (100); 68 (12); 67 (12); 65 (1); 56 (1); 55 (24); 54(2); 53 (6); 43 (2); 42 (2); 41 (25); 40(1); 39 (5); 29 (2); 27 (2). 20 1) Decyl (cyclohexyl)oxoacetate (15) The synthesis was carried out as described above under k), using 6.21 g (33.4 mmol) of ethyl (cyclohexyl)oxoacetate, 5.75 g (36.4 mmol) of decanol, 0.5 ml of NaOCHj (30% in methanol) and 50 ml of cyclohexane. Fractional distillation afforded 3.85 g (39%) of a colorless oil. 25. B.p. 118-126°C/20Pa. UV/Vis (hexane): 394 (sh, 4); 382 (sh, 8); 376 (sh, 11); 367 (sh, 14); 358 (sh, 17); 350 (sh, 19); 336 (19); 314 (sh, 17); 302 (sh, 15). IR (neat): 2924. 2852m, 1745m, 1723, 1466m, 1450m, 1377w, 1330w, 1310w, 30 1290w, 1274m, 1229m, 1183w, 1139m, U17w, 1082m, 1065m, 1028w, 995m, 929w, 895w, 867w, 802w, 785w, 720m, 662w. WO 99/60990 PCT/IB99/00890 1H NMR (360 MHz, CDC13): 4.24 (t, .J= 6.7, 2 H); 3.07-2.96 (m, 1 H); 1.98-1.85 (m,2H); 1.85-1.60 (m, 5 H); 1.44-1.14 (m, 19 H); 0.88 (t,.J= 6.9, 3 H). 13C NMR (90.6 MHz, CDC13): 197.70 (s); 162.22 (s); 66.27 (t); 46.37 (d); 31.90 (t); 29.51 (/); 29.49 (/); 29.30 (/); 29.17 (/); 28.42 (/); 27.48 (/); 25.80 (t); 25.74 5 (t); 25.32 (r); 22.69 (0; 14.11 (q). MS (EI): 296 (M+, 2); 185(1); 158(1); 156(1); 112(7); 111 (88); 110 (3); 85 (2); 84 (7); 83 (100); 81 (1); 79 (I); 71 82); 70 (1); 69 (2); 68 (1); 67 (3); 57 (5); 56 (3); 55 (23); 54 (1); 53 (1); 43 (7); 42 (2); 41 (10); 39 (2); 29 (2); 27 (1). 10 m) 4-Methoxybenzyl (cyclohexyl)oxoacetate (16) The synthesis was carried out as described above under k), using 6.62 g (35.9 mmol) of ethyl (cyclohexyl)oxoacetate, 6.06 g (43.9 mmol) of 4-methoxybenzyl alcohol, 0.5 ml of NaOCH3 (30% in methanol) and 50 ml of cyclohexane. Column chromatography (SiO2, heptane/ether 7:3) afforded one 15 fraction of the pure product together with another fraction of lower purity. The latter was rechromatographed (SiO2, heptane/ether 8:2) to yield a total of 1.15 g (12%) of pure product as a slightly yellow oil. UV/Vis (hexane): 395 (sh, 5); 375 (sh, 15); 367 (sh, 18); 360 (sh, 21); 352 (sh, 24); 20 337 (26); 324 (sh, 25); 312 (sh, 24); 288 (sh, 230); 280 (1520); 274 (1790); 268 (sh, 1590); 265 (sh, 1520); 259 (sh, 1170). IR (neat): 3001w, 2929m, 2853m, 1806w, 1721s, 1612m, 1586m, 1514s, 1461m, 1449m, 1424w, \369w, 1303m, 1271m, 1246s, 1225s, 1174s, 1138s, 1112m, 1080m, 1063s, 1031s, 996s, 984s, 946w, 916w, 895m, 849w, 821s, 755w, 25 719w. 1H NMR (360 MHz, CDC13): 7.38-7.30 (m, 2 H); 6.94-6.85 (m, 2 H); 5.21 (s, 2 H); 3.81 (s, 3 H); 3.08-2.94 (m, 1 H); 1.98-1.83 (m, 2 H); 1.83-1.71 (m, 2 H); 1.71- 1.56 (m, 1 H); 1.41-1.10 (m, 5 H). 13C NMR (90.6 MHz, CDCI3): 197.39 (s); 161.94 (s); 160.04 (s); 130.51 (d); 30 126.81 (s); 114.08 (d); 67.58 (0; 55.31 (9); 46.41 (d); 27.46 (/); 25.70 (t): 25.27 (t)- WO 99/60990 PCT/IB99/00890 MS (EI): 276 (M+ 1); 135 (1); 123 (1); 122 (10); 121 (100); 111 (2); 107 (1); 106 (2); 94 (1); 92 (1); 91 (3); 90 (1); 89 (1); 83 (7); 78 (5); 77 (4); 65 (1); 55 (9); 53(1); 52(1); 51(1); 41 (3); 39 (2). 5 n) 3-(4-tert-Butylphenyl)-2-methylpropyl cyclohexyl(oxo)acetate (17) The synthesis was carried out as described above under k), using 4.8 g (26.1 mmol) of ethyl (cyclohexyl)oxoacetate, 4.0 g (21.5 mmol) of 3-(4-tert-butylphenyl)-2-methylpropanol (obtained by reduction of (±)-3-(4-tert-butylphenyl)-2-methylpropanal (Liliaf) with LiAlH4 in ether), 0.5 ml of NaOCH, (30% in 10 methanol) and 40 ml of cyclohexane. Column chromatography (Si02, heptane/ether 8:2) afforded 3.43 g (46%) of a colorless oil. UV/Vis (hexane): 393 (sh, 4); 384 (sh, 7); 375 (sh, 12); 366 (sh, 15); 357 (sh, 18); 351 (sh, 20); 336 (22); 322 (sh, 20); 271 (270); 263 (330); 257 (280); 251 15 (240); 244 (sh, 240). IR (neat): 3089w, 3055w, 3021w, 2953m, 2928m, 2855m, 1723, 1512m, 1450m, 1410w, 1387w, 1364w, 1310>v, 1270m, 1226m, 1183w, 1139m, 1112w, 1079m, 1064m, 998m, 963w, 954M', 91 9W, 892w, 843w, 800w, 718w, 674w. 1H NMR (360 MHz, CDC13): 7.35-7.27 (m, 2 H); 7.12-7.05 (m, 2 H); 4.14 (ABX, J 20 = 10.7, 5.6, 1 H); 4.07 (ABX, J = 10.7, 6.7, 1 H); 3.06-2.95 (m, 1 H); 2.70 (ABX, J= 13.7, 6.5, 1 H); 2.48 (ABX, J = 13.7, 7.7, 1 H); 2.28-2.12 (m, 1 H); 1.97-1.86 (m, 2 H); 1.86-1.74 (m, 2 H); 1.74-1.63 (m, 1 H); 1.45-1-15 (m, 5 H); 1.31 (s, 9 H); 0.98 (d,J/=6.7, 3 H). I3C NMR (90.6 MHz, CDC13): 197.52 (s); 162.24 (s); 149.01 (s); 136.34 (s); 25 128.75 (d); 125.27 (d); 70.11 (t); 46.44 (d); 39.08 (t); 34.43 (d); 34.38 (s); 31.39 (q); 27.44(0; 25.71 (t); 25.30 (t); 16.77 (q). MS (EI): 345 ([M+H]+, 1); 344 (M+, 6); 330 (1); 329 (6); 234 (9); 233 (52); 231 (4); 217 (2); 190 (1); 189 (10); 188 (27); 178 (2); 177 (13); 175 (2); 174 (7); 173 (31); 161 (1); 160 (1); 159 (5); 148 (6); 147 (45); 146 (1); 145 (8); 133 (3); 30 132 (23); 131 (29); 130 (1); 129 (2); 128 (2); 127 (1); 119 (4); 118 (3); 117 (19); 116 (3); 115 (5); 112 (3); 111 (40); 110(1); 105 (5); 104 (2); 103 (1); 91 17-04-2000 IB 009900890 (9); 84 (7); 83 (100); 81 (1); 79 (1); 77 (1); 67 (1); 65 (1); 57 (14); 55 (20); 54 (1); 53(1); 41 (9); 39 (2); 29 (2). o) (lR,3R,4S)-3-p-Menthanyl (cyclohexyl)oxoacetate (18) 5 The synthesis was carried out as described above under k), using 25.03 g (136mmol) of ethyl (cyclohexyl)oxoacetate, 25.70 g (165mmol) of (-)-menthol and 1 ml of NaOCH3 (30% in methanol) in 150 ml of cyclohexane. Fractional distillation afforded 23.14 g (58%) of a colorless oil. 10 B.p. 122°C/33 Pa. UV/Vis (hexane): 394 (sh, 5); 383 (sh, 8); 375 (sh, 12); 366 (sh, 16); 360 (sh, 18); 351 (sh, 20); 337 (22). IR (neat): 2949m, 2928m, 2854m, 1717.T, 1450m, 1387w, 1370m, 1332w, 131 Iw, 1274m, 1230m, 1181w, 1139m, llllw, 1081m, 1064m, 1037w, 1027w, 1006w, 15 995^, 980m, 951m, 912m, 894m, 869w, 844m, 802w, 787w, 717m. 1H NMR (360 MHz, CDC13): 4.83 (td,J = 10.9, 4.36, 1 H); 3.05-2.94 (m, 1 H); 2.08-1.99 (m, 1 H); 1.96-1.62 (m, 8 H); 1.59-1.45 (m, 2 H); 1.44-0.99 (m, 7 H); 0.93 (d, J= 6.7,3 H); 0.90 (d, J= 7.1,3 H); 0.77 (d, J = 7.1, 3 H). 13C NMR (90.6 MHz, CDC13): 198.09 (J); 162.16 (s); 76.71 (d); 46.79 (d); 46.32 20 (d); 40.49 (t); 34.10 (t); 31.50 (d); 27.37 (t); 26.25 (d)\ 25.76 (0; 25.32 (t); 25.26 (0; 23.38 (t); 21.95 (q); 20.67 (q); 16.17 (g). MS (EI): 294 (M+, 1); 250 (1); 167 (1); 154 (4); 140 (4); 139 (33); 138 (8); 137 (1); 123 (2); 112 (1); 111 (9); 110 (1); 109 (1); 98 (1); 97 (16); 96 (1); 95 (5); 84 (7); 83 (100); 82 (2); 81 (12); 80 (1); 79 (2); 71 (3); 70 (1); 69 (19); 68 (1); 67 25 . (5); 57 (13); 56 (2); 55 (33); 54 (2); 53 (2); 43 (5); 42 (1); 41 (11); 39 (2); 29 (2); 27 (1). p) 2-PentyM-cyclopentyl (cyclohexyl)oxoacetate (19) The synthesis was carried out as described above under k), using 6.62 g (36 mmol) 30 of ethyl (cyclohexyl)oxoacetate, 6.80 g (44 mmol) of 2-pentyl cyclopentanol and 1 ml of NaOCHj (30% in methanol) in 50 ml of cyclohexane for 24 h. Column chromatography (Si02, heptane/ether 8:2) afforded 5.91 g (55%) of a yellow oil WO 99/60990 PCT/IB99/00890 (9); 84 (7); 83 (100); 81 (1); 79 (1); 77 (1); 67 (1); 65 (1); 57 (14); 55 (20); 54 (1); 53(1); 41 (9); 39 (2); 29 (2). (lR,3R,4S)-3-p-Menthanyl (cyclohexyl)oxoacetate (18) 5 The synthesis was carried out as described above under k), using 25.03 g (136mmol) of ethyl (cyclohexyl)oxoacetate, 25.70 g (165mmol) of (-)-menthol and 1 ml of NaOCH, (30% in methanol) in 150 ml of cyclohexane. Fractional distillation afforded 23.14 g (58%) of a colorless oil. 10 B.p. 122°C/0.33 mbar. UV/Vis (hexane): 394 (sh, 5); 383 (sh, 8); 375 (sh, 12); 366 (sh, 16); 360 (sh, 18); 351 (sh, 20); 337 (22). IR (neat): 2949m, 2928m, 2854m, 1717s, 1450m, 1387M', 1370m, 1332w, 131 1W, 1274m, 1230m, 1181w, 1139m, 111 lw, 1081m, 1064m, 1037M/, 1027W, 1006w, 15 995s, 980m, 951m, 912m, 894m, 869w, 844m, 802w, 787w, 717m. 'H NMR (360 MHz, CDC13): 4.83 (td, J= 10.9, 4.36, 1 H); 3.05-2.94 (m, 1 H); 2.08-1.99 (m, 1 H); 1.96-1.62 (m, 8 H); 1.59-1.45 (m, 2 H); 1.44-0.99 (m, 7 H); 0.93 (d, J = 6.7, 3 H); 0.90 (d, J = 7.1, 3 H); 0.77 (d, J = 7.1, 3 H). 13C NMR (90.6 MHz, CDC13): 198.09 (s); 162.16 (s); 76.71 (d); 46.79 (d); 46.32 20 (d); 40.49 (0; 34.10 (t); 31.50 (d); 27.37 (t); 26.25 (d); 25.76 (t); 25.32 t); 25.26 (0; 23.38 (t); 21.95 (g); 20.67 (q); 16.17 (q). MS (EI): 294 (M+, 1); 250 (1); 167 (1); 154 (4); 140 (4); 139 (33); 138 (8); 137 (1); 123 (2); 112 (1); 111 (9); 110 (1); 109 (1); 98 (1); 97 (16); 96 (1); 95 (5); 84 (7); 83 (100); 82 (2); 81 (12); 80 (1); 79 (2); 71 (3); 70 (1); 69 (19); 68 (1); 67 25 (5); 57 (13); 56 (2); 55 (33); 54 (2); 53 (2); 43 (5); 42 (1); 41 (11); 39 (2); 29 (2); 27(1). 2-Pentyl-l-cyclopentyl (cyclohcxyl)oxoacetate (19) The synthesis was carried out as described above under k), using 6.62 g (36 mmol) 30 of ethyl (cyclohexyl)oxoacetate, 6.80 g (44 mmol) of 2-pentyl cyclopentanol and 1 ml of NaOCH., (30% in methanol) in 50 ml of cyclohexane for 24 h. Column chromatography (Si03, heptane/ether 8:2) afforded 5.91 g (55%) of a yellow oil WO 99/60990 PCT/1B99/00890 (mixture of diastereoisomers). The UV/Vis spectrum indicated the presence of a colored impurity. UV/Vis (hexane): 395 (sh, 4); 383 (sh, 7); 374 (sh, 11); 366 "(sh, 14); 358 (sh, 16); 5 349 (sh, 19); 320 (sh, 23); 303 (sh, 34); 289 (sh, 43). IR (neat): 2924m, 2853m, 1806w, 1719s, 146lw, 1449m, 1376w, 131 lw, 1275m, 1254w, 1229m, 1183w, 1139m, 1116w, 1081m, 1064m, 1028w, 996m, 968w, 925w, 894w, 844w, 724W. •H NMR (360 MHz, CDC13): 5.35-5.28 (m, 1 H); 4.96-4.89 (m, 1 H); 3.05-2.88 (m, 10 2 H); 2.10-1.55 (m, 10 H); 1.53-1.10 (m, 13 H); 0.93-0.80 (m, 3 H). 13C NMR (90.6 MHz, CDC13): 197.99 (s); 162.29 (s); 162.26 (j); 83.72 (d); 80.36 (d); 46.58 (d); 46.42 (d); 45.39 (d); 44.81 (d); 33.49 (/); 32.53 (/); 32.07 (t); 31.94 (t); 31.80 (t); 30.20 (t); 29.61 (t); 29.12 (t); 28.18 (/); 27.60 (t); 27.46 (t); 27.38 (t); 25.32 (t); 22.76 (0; 22.59 (t); 22.03 (t); 14.05 (q). 15 MS (EI): 167(1); 140(1); 139 (8); 138 (7); 123 (1); 112 (1); 111 (11); 110(1); 109 (1); 98 (2); 97 (25); 96 (2); 95 (3); 84 (7); 83 (100); 82 (5); 81 (4); 79 (2); 71 (4); 70 (2); 69 (22); 68 (2); 67 (9); 66 (1); 65 (1); 57 (11); 56 (2); 55 (29); 54 (3); 53 (2); 43 (4); 42 (1); 41 (12); 39 (3); 29 (3); 27 (1). 20 q) 4-( 1,1 -Dimethylpropyl)-1 -cyclohexyl (cyclohexyl)oxoacetate (20) The synthesis was carried out as described above under k), using 6.62 g (36 mmol) of ethyl (cyclohexyl)oxoacetate, 7.40 g (43.5 mmol) of 4-( 1,1-dimethylpropyl)-1-cyclohexanol and 1 ml of NaOCH3 (30% in methanol) in 50 ml of cyclohexane. Column chromatography (Si02, heptane/ether 8:2) afforded 4.78 g (43%) of a 25 slightly yellow oil as a mixture of cisltrans isomers (≈ 38:62). UV/Vis (hexane): 394 (sh, 4); 385 (sh, 7); 375 (sh, 12); 367 (sh, 15); 339 (sh, 35); 326 (40); 312 (sh, 38); 297 (sh, 34); 283 (33); 272 (sh, 36). IR (neat): 2929s, 2855m, 1800w, 1719s, 1462w, H48/w, 1387w, 1377w, 1364w, 30 1323w, 1309w, 1274m, 1254w, 1228m, 1182w\ 1160w, 1140m, 1108w, 1081m, 1064m, 1047w, 1005w, 995s, 948w, 928M, 906W, 894W, 875W, 830W, 805W, 780M-, 745w, l\9w. WO 99/60990 PCT/IB99/00890 'HNMR(360MHz,CDCl3):5.21-5.14(w, 1 H (cis)); 4.85-4.72 (tt,J= 11.3, 4.6, 1 H (trans)); 3.07-2.91 (m, 1 H); 2.17-1.04 (m, 21 H); 0.83-0.77 (m, 9 H). 13C NMR (90.6 MHz, CDC13): 198.07 (s); 161.85 (s); 76.16 (d); 72.28 (d); 46.81 (d); 46.35 (d); 44.58 (d); 44.21 (d); 34.82 (s); 34.60 (5); 32.75 (/); 32.49 (/); 5 31.90 (t); 30.49.(0; 27.47 (0; 25.75 (/); 25.38 (0; 25.31 (t); 24.97 (t); 24.27 (q); 24.17(g); 21.22(0; 8.10 (q). MS (EI): 264 (1); 193 (1); 181 (1); 153 (4); 152 (3); 137 (4); 124 (1); 6); 112 (1); 111 (14); 110 (2); 109 (1); 98 (4); 97 (55); 95 (5); 85 (2); 84 (4); 83 (60); 81 (12); 80 (1); 79 (2); 72 (6); 71 (100); 69 (13); 68 (1); 67 (11); 57 (15); 56 (3); 10 55 (51); 54 (4); 53 (3); 43 (32); 41 (22); 39 (4); 29 (7); 27 (4). r) l-(2-Naphthalenyl)ethyl (cyclohexyl)oxoacetate (21) The synthesis was carried out as described above under k), using 6.62 g (24 mmol) of ethyl (cyclohexyl)oxoacetate, 7.5 g (29 mmol) of 1 -(2-naphthalenyl)ethanol and 15 1 ml of NaOCH3 (30% in methanol) in 70 ml of cyclohexane for 28 h. Column cliromatography (Si02, heptane/ether 8:2) afforded 2.67 g of a colorless oil still containing about 30% of ethyl (cyclohexyl)oxoacetate. 1H NMR (360 MHz, CDC13): 7.88-7.78 (w, 4 H); 7.54-7.44 (m, 3 H); 6.16 (q, J = 20 6.6, 1 H); 3.08-2.93 (m, 1 H); 1.97-1.60 (m, 5 H); 1.72 (d,J= 6.7, 3 H); 1.44- 1.12 (mi, 5 H). 13C NMR (90.6 MHz, CDC13): 197.53 (s); 161.49 (s); 137.73 (s); 133.21 (s); 133.13 (s); 128.60 (d); 128.09 (d); 127.71 (d); 126.40 (d); 126.34 (d); 125.38 (d); 123.85 (d); 74.76 (d); 46.41 (d); 27.38 (0; 25.70 (0; 25.26 (0; 22.08 (q). 25 MS (EI): 310 (M+, 1); 157 (2); 156 (14); 155 (100); 154 (22); 153 (16); 152 (8); 151 (2); 141 (2); 139(1); 129(3); 128(9); 127(9); 126(2); 115(4); 111 (3); 101 (1); 84 (1); 83 (17); 77 (4); 76 (4); 75 (2); 64 (1); 63 (2); 56 (1); 55 (16); 51 (2); 50 (1); 43 (2); 41 (9); 39 (4); 29 (3); 27 (3). 30 s) 3,7-Dimethyl-6-octenyl (cyclopentyl)oxoacetate (22) In the first step, ethyl (cyclopentyl)oxoacctate was prepared as follows. WO 99/60990 PCT/IB99/00890 A Grignard reagent prepared from 64.0 g of freshly distilled bromocyclopentane (0.43 mol) and 11.0 g of magnesium (0.45 mol) in 360 ml of dry ether and filtered under N2 was added dropwise to a stirred solution of 48.2 g (0.33 mol) of diethyl oxalate in 300 ml of dry ether at -40°C. The mixture was slowly warmed to 0°C and 5 poured onto a sat. solution of NH4CI, extracted with ether and washed with water (pH ≈ 7). The organic phase was dried over Na2S04 and concentrated. Fractional distillation gave 27.1 g (48%) of a colorless oil in sufficient purity for further derivatization. Column chromatography (Si02, heptane/ether 8:2) of 2.50 g afforded 2.04 g of product at high purity. 10 B.p. 42°C/0.1 mbar. UV/Vis (hexane): 389 (sh, 3); 371 (sh, 9); 359 (sh, 13); 345 (sh, 15); 336 (15). IR (neat): 3483W, 2956m, 2869m, \723s, 1684m, 1469w, 1449m, 1399w, 1372w, 1318w, 1296m, 12545, 1194m, 1159m, 1140m, 1091S, 1043s, 1029s, 952m, 15 906m, 858m, 780m, 708w. 1H NMR (360 MHz, CDC13): 4.32 {q,J= 7.1,2 H); 3.56-3.44 (m, 1 H); 1.98-1.75 (m, 4 H); 1.75-1.57 (m, 4 H); 1.37 (t, J = 7.1, 3 H). 13C NMR (90.6 MHz, CDC13): 196.73 (s); 161.98 (s); 62.24 (t); 47.42 (d); 28.32 (0; 26.05(0; 14.05 (q). 20 MS (EI): 170 (M+, 5); 114 (1); 101 (1); 98 (4); 97 (48); 96 (4); 95 (1); 70 (6); 69 (100); 68 (3); 67 (6); 66 (1); 65 (1); 55 (4); 54 (1); 53 (2); 51 (1); 43 (1); 42 (2); 41 (22); 40 (2); 39 (7); 29 (5); 28 (1); 27 (4). 3,7-Dimethyl-6-octenyl (cyclopentyl)oxoacetate (22) 25 The synthesis was carried out as described above under k), using 6,07 g (35.6 mmol) of the product obtained above, 6.80 g (43.6 mmol) of citronellol and 0.5 ml of NaOCH, (30% in methanol) in 50 ml of cyclohexane. Column chromatography (SiO,, heptane/ether 7:3) afforded 5.28 g (53%) of a yellow oil. 30 UV/Vis (hexane): 389 (sh, 4); 366 (sh, 12); 345 (sh, 17); 336 (17). 04-2000 IB 009900890 A Grignard reagent prepared from 64.0 g of freshly distilled bromocyclopentane (0.43 mol) and 11.0 g of magnesium (0.45 mol) in 360 ml of dry ether and filtered under N2 was added dropwise to a stirred solution of 48.2 g (0.33 mol) of diethyl oxalate in 300 ml of dry ether at -40°C. The mixture was slowly warmed to 0°C and poured onto a sat. solution of NH4CI, extracted with ether and washed with water (pH ≈ 7). The organic phase was dried over Na2SO4 and concentrated. Fractional distillation gave 27.1 g (48%) of a colorless oil in sufficient purity for further derivatization. Column chromatography (Si02, heptane/ether 8:2) of 2.50 g afforded 2.04 g of product at high purity. 10 B.p. 42°C/10 Pa. UV/Vis (hexane): 389 (sh, 3); 371 (sh, 9); 359 (sh, 13); 345 (sh, 15); 336 (15). IR (neat): 3483w, 2956m, 2869m, 1723s, 1684m, 1469w, 1449m, 1399w, 1372w, 1318vf, 1296m, 1254J, 1194m, 1159m, 1140m, 109ls, 1042s, 1029J, 952m, 15 906m, 858m, 780m, 708w. 1H NMR (360 MHz, CDC13): 4.32 (q, J = 7.1, 2 H); 3.56-3.44 (m, 1 H); 1.98-1.75 (m, 4 H); 1.75-1.57 (m, 4 H); 1.37 (t, J= 7.1, 3 H). 13C NMR (90.6 MHz, CDC13): 196.73 (s); 161.98 (s); 62.24 (t); MAI (d) 28.32 (0; 26.05 (0; 14.05 for). 20 MS (EI): 170 (M+, 5); 114 (1); 101 (1); 98 (4); 97 (48); 96 (4); 95 (1); 70 (6); 69 (100); 68 (3); 67 (6); 66 (1); 65 (1); 55 (4); 54 (1); 53 (2); 51 (1); 43 (1); 42 (2); 41 (22); 40 (2); 39 (7); 29 (5); 28 (1); 27 (4). 3,7-Dimethyl-6-octenyl (cyclopentyl)oxoacetate (22) 25 The synthesis was carried out as described above under k), using 6.07 g (35.6 mmol) of the product obtained above, 6.80 g (43.6 mmol) of citronellol and 0.5 ml of NaOCH3 (30% in methanol) in 50 ml of cyclohexane. Column chromatography (Si02, heptane/ether 7:3) afforded 5.28 g (53%) of a yellow oil. 30 UV/Vis (hexane): 389 (sh,); 366 (sh, 12); 345 (sh, 17); 336 (17).. 04-2000 IB 009900890 IR (neat): 3493w, 2951m, 2916m, 2869m, 1798w, 17245, 1687m, 1451/ra, 1377m, 1354w, 1259m, 1190m, 1164m, 1144m, 1091m, 1047m, 1027m, 984w, 945m, 829m, 782w, 73 9w, 717w. 1H MMR (360 MHz, CDC13): 5.13-5.03 (m, 1 H); 4.40-4.20 (m, 2 H); 3.54-3.42 (m, 5 1 H); 2.10-1.71 (m, 7 H); 1.71-1.45 (m, 6 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43- 1.30 (m, 1 H); 1.29-1.13 (m, 1 H); 0.94 (d,J= 6.3,3 H). 13CNMR (90.6 MHz, CDC13): 196.66 (s); 162.11 (s); 131.51 (s); 124.40 (d); 64.75 (0; 47.48 (d); 36.90 (/); 35.22 (0; 29.40 (d); 28.27 (0; 26.05 (t); 25.71 (q); 25.35(0; 19.35 (q); 17.66 (q). 10 MS (EI): 280 (M+, 1); 262 (2); 252 (1); 184 (1); 183 (6); 165 (1); 155 (3); 144 (2); 142 (1); 139 (2); 138 (20); 137 (6); 126 (1); 125 (1); 124 (2); 123 (22); 121 (1); 111 (1); 110 (2); 109 (9); 98 (3); 97 (39); 96 (7); 95 (21); 94 (2); 83 (6); 82 (15); 81 (23); 80 (2); 79 (1); 70 (7); 69 (100); 68 (5); 67 (9); 65 (1); 57 (2); 56 (2); 55 (10); 54 (1); 53 (3); 43 (2); 42 (2); 41 (25); 40 (1); 39 (4); 29 (2); 27 (2\ 15 t) (E)-3,7-Dimethyl-2,6-octadienyl 3-methyl-2-oxopentanoate (23) The synthesis was caried out as described above under a),"using 4.85 g (38 mmol) of 3-methyl-2-oxo pentanoic acid and 11.5 g (75 mmol) of geraniol in 130 ml of toluene for 24 h. Column chromatography (SiO2, heptane/EtOAc 95:5) afforded 20 7.68 g of crude product, which was fractionally distilled to give 4.04 g (40%) of a colorless oil. B.p. 82°C/20 Pa. UV/Vis (hexane): 393 (sh, 5); 382 (sh, 9); 374 (sh, 13); 364 (sh, 17); 357 (sh, 19); 25 350 (sh, 21); 335 (23). IR (neat): 2966m, 2929m, 2878m, 1746m, 1723s, I670w, 1454m, 1377m, 1338w5 1274m, 1244m, 1163m, 1107w, 1085w, 1039, 999m, 959m, 913m, 827w, 796w, 772w, 742w, 705w. 1H NMR (360 MHz, CDC13): 5.46-5.35 (m, 1 H); 5.14-5.04 (m, 2 H); 4.77 (d, J = 30 7.1, 2 H); 3.20-3.07 (m, 1 H); 2.20-2.00 (m, 4 H); 1.83-1.66 (m, 1 H); 1.74 (s, 3 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.52-1.36 (m, 1 H); 1.13 (d, J= 7.1, 3 H); 0.92 (t,J=7.5,3H). WO 99/60990 PCT7IB99/00890 IR (neat): 3493M-, 2957m, 2916m, 2869m, 1798w, 1724s, 1687m, 1451m, 1377m, 1354w, 1259m, 1190m, 1164m, 1144m, 1091m, 1047m, 1027m, 984w, 945m, 829m, 782 w, 73 9 w, 717w. 1H NMR (360 MHz, CDC13): 5.13-5.03 (m, 1 H); 4.40-4.20 (m, 2 H); 3.54-3.42 (m, 5 1 H); 2.10-1.71 (m, 7 H); 1.71-1.45 (m, 6 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43- 1.30 (m, 1H); 1.29-1.13 (m, 1 H); 0.94 (d, J= 6.3, 3 H). 13C NMR (90.6 MHz, CDC13): 196.66 (s); 162.11 (5); 131.51 (s); 124.40 (d); 64.75 (t); 47.48 (d); 36.90 (/); 35.22 (0; 29.40 (d); 28.27 (/); 26.05 (/); 25.71 (q); 25.35(/); 19.35 (4); 17.66 (q). 10 MS (EI): 280 (M+, 1); 262 (2); 252 (1); 184 (1); 183 (6); 165 (1); 155 (3); 144 (2); 142 (1); 139 (2); 138 (20); 137 (6); 126 (1); 125 (1); 124 (2); 123 (22); 121 (1); 111 (1); 110 (2); 109 (9); 98 (3); 97 (39); 96 (7); 95 (21); 94 (2); 83 (6); 82 (15); 81 (23); 80 (2); 79 (1); 70 (7); 69 (100); 68 (5); 67 (9); 65 (1); 57 (2); 56 (2); 55 (10); 54 (1); 53 (3); 43 (2); 42 (2); 41 (25); 40 (1); 39 (4); 29 (2); 27 (2). 15 t) (E)-3,7-Dimethyl-2,6-octadienyl 3-methyl-2-oxopentanoate (23) The synthesis was caried out as described above under a), using 4.85 g (38 mmol) of 3-methyl-2-oxo pentanoic acid and 11.5 g (75 mmol) of geraniol in 130 ml of toluene for 24 h. Column chromatography (Si02, heptane/EtOAc 95:5) afforded 20 7.68 g of crude product, which was fractionally distilled to give 4.04 g (40%) of a colorless oil. B.p. 82°C/0.2 mbar. UV/Vis (hexane): 393 (sh, 5); 382 (sh, 9); 374 (sh, 13); 364 (sh, 17); 357 (sh, 19); 25 350 (sh, 21); 335 (23). IR (neat): 2966m, 2929m, 2878m, 1746m, 1723s, 1670w, 1454m, 1377m, 1338w, 1274m, 1244m, 1163m, 1107w, 1085w, 1039s, 999m, 959m, 913m, 827w, 796w, 772w, 742w, 705M'. 'II NMR (360 MHz, CDC13): 5.46-5.35 (m, 1 H); 5.14-5.04 (m, 2 H); 4.77 (d, J = 30 7.1, 2 H); 3.20-3.07 (m, 1 H); 2.20-2.00 (m, 4 II); 1.83-1.66 (m, 1 H); 1.74 (s, 3 H); 1.68 (s, 3 H); 1.60 (.9,3 H); 1.52-1.36 (m, 1 H); 1.13 {d, J = 7.1, 3 H); 0.92 (t,J= 7.5, 3 H). WO 99/60990 PCT/IB99/00890 13C NMR (90.6 MHz, CDC13): 198.29 (.9); 162.10 (s); 144.01 (s); 131.97 (s); 123.58 (d); 117.13 (d); 62.94 (t); 43.66 (d); 39.53 (t); 26.22 (t); 25.66 (q); 24.92 (0; 17.69 (9); 16.57 (q); 14.46 for); 11.35 (9). MS (EI): 266 (M+, 1); 181 (1); 179 (1); 153 (1); 138 (3); 137 (28); 136 (6); 135 (5); 5 123 (1); 122 (1); 121 (2); 109 (1); 107 82); 96 (2); 95 (10); 94 (2); 93 (6); 92 (2); 91 (3); 85 (9); 83 (1); 82 (4); 81 (52); 80 (2); 79 (3); 78 (1); 77 (3); 71 (1); 70 (6); 69 (100); 68 (12); 67 (12); 66 (1); 65 (2); 58 (2); 57 (30); 56 (1); 55 (5); 54 (1); 53 (6); 51 (1); 43 (1); 42 (2); 41 (26); 40 (2); 39 (5) 29 (5); 28 (1); 27 (2). 10 u) 3,7-Dimethyl-6-octenyl (bicyclo[2.2.1]hept-2-yl)oxoacetate (24) A Grignard reagent prepared from 4.00 g of 2-norbornyl bromide (23 mmol) and 0.59 g of magnesium (24 mmol) in 30 ml THF was, after filtration under N2, added dropwise (during 45 min) to a stirred solution of 3.00 g (8 mmol) of bis(3,7- 15 dimethyl-6-octenyl) oxalate in 40 ml of THF at -40°C. The mixture was slowly warmed to 0°C, quenched with 30 ml of a sat. solution of NH4C1. The reaction mixture was extracted with diethyl ether and water (2x) and the organic phase dried over Na2S04. Repetitive column chromatography (Si02, heptane/ether 9:1 and heptane/ether 95:5) followed by MPLC on a Lobar column (Si02 Merck, 20 heptane/ether 85:15) finally afforded 0.188 g (3%) of the pure product as a colorless oil. 1H NMR (360 MHz, CDC13): 5.13-5.04 (m, 1 H); 4.37-4.22 (m, 2 H); 3.06 (in, 1 H); 2.59-2.48 (m, 1 H); 2.36-2.27 (m, 1 H); 2.09-1.84 (m, 3 H); 1.84-1.69 (m,1 25 H); 1.68 (s, 3 H); 1.66-1.45 (m, 4 H); 1.60 (s, 3 H); 1.45-1.30 (m, 3 H); 1.30-1.08 (m, 4 H); 0.94 (d, J = 6.3, 3 H). 13C NMR (90.6 MHz, CDC13): 195.33 (s); 162.08 (s); 131.50 (s); 124.39 (d); 64.75 (0; 50.37 (d); 39.82 (d); 36.91 (t); 36.28 (d); 35.84 (t); 35.23 (t); 31.86 (t); 29.64 (0; 29.43 (d); 28.78 (t); 25.71 (q); 25.36 (t); 19.34 (qr); 17.66 (q). 30 MS (EI): 288 (1); 183 (4); 168 (1); 155 (1); 139 (2); 138 (15); 137 (2); 124 (3); 123 (30); 122(2); 121 (1); 110(1); 109(5); 97 (1); 96 (11); 95 (100); 93 (4); 91 (1); 83 (4); 82 (19); 81 (21); 80 (5); 79 (3); 77 (2); 70 (2); 69 (23); 68 (5); 67 WO 99/60990 PCT/IB99/00890 (22); 66 (3); 65 (3); 57 (3); 56 (3); 55 (15); 54 (2); 53 (5); 43 (4); 42 (3); 41 (33); 39 (6); 29 (5); 28(1); 27 (5). Example 3 Release of geraniol from solutions of geranyl 2-benzoyl benzoate Geranyl 2-benzoyl benzoate was dissolved in a concentration of 3.68g/l in the solvents 10 indicated in Table 1. The samples were then irradiated using a Fadeometer and under the conditions indicated in Table 1, and the amount of released geraniol was measured. The values indicated are the average of duplicate samples. Table 1 : Release of geraniol from geranyl 2-benzoyl benzoate in solution upon irradiation 15 with a Fadeometer Run Solvent Irradiation intensity (KJ/m2) % of geraniol released 1 Isopropanol/benzene 1:1 33.7 24.4 2 Isopropanol/benzene 1:1 3.4 30.4 3 Isopropanol/benzene 1:1 0 0 4 Dodecanol/benzene 1:1 33.7 26.8 5 Isopropanol/acetonitrile 3.4 22.6 6 Isopropanol/ acetonitrile Q 0 * calculated as weight % of theoretically possible geraniol release ** indicates a control run in which the flask was wrapped with aluminum foil before irradiation The following Table 2 indicates the amount of geraniol released from the same ester, but upon exposure to sunlight (New Jersey, USA, typical sunny day of June). WO 99/60990 PCT/1B99/00890 Table 2 : Release of geraniol from geranyl 2-benzoyl benzoate in solution upon exposure to sunlight Run Solvent Hours of sun exposure % of geraniol released * 1 Isopropanol/benzene 1:1 5 71.3 2 Isopropanol/benzene 1:1 Q** 0 5 * calculated as weight % of theoretically possible geraniol release ** indicates a control run in which the flask was wrapped with aluminum foil before irradiation The above results show that it is possible to release geraniol in solution upon exposure to a 10 Fadeometer or to sunlight, while no release occurs when the sample is not exposed to radiation. Example 4 15 Release of geraniol from geranyl 2-(2,-isopropylbenzoyl)benzoate (solution and film) Geranyl 2-(2-isopropylbenzoyl)benzoate was dissolved in a concentration of 4.05g/l in benzene and subsequently irradiated, or was deposited as a thin film, by evaporation of the solvent, on the walls of the flask before irradiation. After irradiation, the amount of 20 released geraniol was measured. The results are shown in Table 3. The values indicated are the average of duplicate samples. Table 3 : Release of geraniol from geranyl 2-(2'-isopropylbenzoyl)benzoate in solution and as a film upon irradiation with a Fadeometer 25 Run Solvent/film Irradiation intensity (KJ/m2) % of geraniol released * 1 Benzene 3.4 11.2 2 Benzene o 0 3 Film (33.5mg) 3.4 9.5 4 Film (32.5mg) 0 0 / WO 99/60990 PCT/IB99/00890 * calculated as weight % of theoretically possible geraniol release ** indicates a control run in which the flask was wrapped with aluminum foil before irradiation 5 Table 4 indicates the results of analogous experiments in which the solutions and films of geranyl 2-(2'-isopropylbenzoyl)benzoate were exposed to sunlight (New Jersey, USA, typical sunny day of June). The values indicated are the average of duplicate samples. 10 Table 4 : Release of geraniol from geranyl 2-(2'-isopropylbenzoyl)benzoate (solution and film) upon exposure to sunlight Run Solvent/film Hours of sun exposure % of geraniol released * 1 Isopropanol/benzene 1:1 5 71.3 2 Isopropanol/benzene 1:1 Q 0 3 Film (14.2mg) 5 27.0 4 Film (14.2mg) 0 0 * calculated as weight % of theoretically possible geraniol release 15 ** indicates a control run in which the flask was wrapped with aluminum foil before irradiation The above results show that the introduction of an isopropyl substituent into the geranyl ester allows the release of geraniol from solution and from a solid film, upon exposure to a 20 Fadeometer radiation and to natural sunlight. Example 5 25 Release of geraniol from geranyl 2-(2',4'-diisopropylbenzoyl)benzoate (solutionjmd film) Geranyl 2-(2',4'-diisopropylbenzoyl)benzoate was dissolved in benzene in a concentration of 4.48 g/1 in benzene and subsequently irradiated, using a Fadeometer. The samples were WO 99/60990 PCT/IB99/00890 irradiated with 31.1 KJ/m2, and 50 weight% of the theoretical value of geraniol was released. Similar experiments were conducted in which benzene solutions with the same content in geranyl 2-(2',4'-diisopropylbenzoyl)benzoate and films which were obtained by 5 evaporation of the solvent, were exposed to daylight outdoors (New Jersey, USA, cloudy day in August). Table 5 shows the results of the experiments. The values indicated are the average of duplicate samples. Table 5 : Release of geraniol from geranyl 2-(2',4'-diisopropylbenzoyl)benzoate in 10 solution and as film, upon exposure to sunlight Run Solvent/film Hours of sun exposure % of geraniol released * 1 Benzene 6 13 2 Film 6 18 calculated as weight % of theoretically possible geraniol release 15 Example 6 Release of geraniol from geranyl 2-(2',4'-diisopropylbenzoyl)benzoate in an all-purpose cleaner 20 An all-purpose cleaner of the Fabuloso ® (registered trademark of Colgate-Palmolive, USA) type containing 0.3% of geranyl 2-(2',4'-diisopropylbenzoyl)benzoate was prepared. The all-purpose cleaner solution thus obtained was added to borosilicate flasks which were then irradiated for 3 hours in outdoor sunlight. The resulting solutions were then compared 25 to the unperfumed all-purpose cleaner base, on a triangular blind test by a panel composed of 15 non-experts. The odd sample was the one containing the above precursor molecule. The evaluation was carried out by sniffing on the flask. From the 15 test persons, 14 correctly distinguished the perfumed sample from the unperfumed sample. They found that the odor note of the irradiated sample was floral. WO 99/60990 PCT/IB99/00890 geraniol, citrus or citronellal, whereas the non-irradiated sample was found to be neutral, odorless or slightly oily. When the odd sample was the one containing the unperfumed cleaner base, 10 of 15 panelists correctly distinguished the samples. 5 The release of geraniol from the 2-benzoyl benzoate used in the present embodiment and from the other benzoates synthesized occurrred in all types of all-purpose cleaners and is therefore not restricted to one type of these. 10 Example 7 Release of Polysantol ® from (E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-l-yl)-4-penten-2-yl 2-(2',4'-diisopropylbenzoyl)benzoate 15 The above-identified compound was dissolved in toluene in a concentration of 2.35 g/1 and irradiated for 6 hours with a UV lamp. The amount of released Polysantol was measured by GC, and it was found that 35% of the theoretical amount of Polysantol had been released. 20 Example 8 Release of geraniol from a film of 2-(2',4'-diisopropylbenzoyl)benzoate deposed on tiles 0.8 G of an all-purpose cleaner of the Fabuloso ® type containing 0.3% of the title 25 compound were evenly deposed on tiles of the size 10x10 cm. The liquid was allowed to evaporate, and the tiles were exposed to sunlight for 7 h in a covered petri dish. The tiles were then olfactively compared to tiles treated in the same way with the unperfumed cleaner base and exposed to sunlight on the same day and the same hours, on a triangular blind test by a panel composed of 15 non-experts, by sniffing on the petri dish. 30 When the odd sample was the one containing the title compound. 14 of 15 panelists correctly distinguished the perfumed sample from the unperfumed sample. When the odd WO 99/60990 PCT/IB99/00890 sample was the one containing the unperfumed base, the correct attribution was made by 9 of 15 panelists. Example 9 Release of fragrant aldehydes and ketones from various citronellyl a-keto esters in solution or in the neat state 10 0.01 M solutions (5 ml) of the a-keto esters prepared as described in example 2, in toluene, acetonitrile or isopropanol, were prepared and irradiated with a xenon or a UV lamp or exposed to outdoor sunlight in 10 ml volumetric flasks. Samples in the neat state were also irradiated under the same conditions. Before irradiation in solution, 1 ml of a 0.01 M solution of decanol was added which served as internal standard for GC analysis. The 15 results are found in the Table 6 below. Table 6 indicates the amount of released aldehyde or ketone in mol%, the amount of remaining starting material is indicated in brackets. It was also observed that olefins were released, from compounds (11) and (12) of example 2, together with release of citronellal. 20 Table 6 : Results of the photoirradiations of different a-keto esters in solution and in their neat state Structure of Compounds N° Light Source Yield of Perfume (Remaining Starting Material3) in mol-% Toluene 2-Propanol Acetonitrile Neat 3h 3h 3h 3.5 h 0 ' 5 Xenon UV sunlight 27 44 (10) ( 30 (15) (45) WO 99/60990 PCT/IB99/00890 6 Xenon UV sunlight 33 50 ( 7 Xenon UV sunlight 55 ' 19 23 ( (60) ( ( 23 Xenon UV sunlight 15/26' 17/21f ( 8 Xenon UV sunlight 38 13 21 ( ( 7 21 (10)b (95) ( 11 Xenon UV sunlight 11 2/6d (30)b (85) 0/3d (-----)C l/6d (80) 2/11d (30) 12 Xenon UV sunlight 8 0/5e 7/42e (50)b (85) (35) 0/5e 3/2 le (70) (55) 0/5e 0/3 T (95) (25) l/10e 0/6e (35) (75) 22 Xenon UV sunlight 24 37 ( 22 (5) (15) WO 99/60990 PCT/IB99/00890 24 Xenon UV sunlight 26 (10) 13 Xenon UV sunlight ≈45 25 38 ( 35 (90) (15) 13 18 (70) ( 14 Xenon UV sunlight 26/43' 19/25f ( (5) 10/33* 10/48f (30) (30) 11/19' ll/17f (20) (30) 15 Xenon UV sunlight 52 52 (0) ( 16 Xenon UV sunlight 81 86 ( 17 Xenon UV sunlight 69 63 ( (5) 18 Xenon UV sunlight quant, quant. ( (10) 53 44 (10) (10) 91 86 ( (5) 75 21 (40) (50) All numbers are average values of 2 or 3 samples. a) amount of remaining starting material rounded to ± 5%, b) amount of starting material estimated from blank sample, 5 c) yield not or only approximatively determined due to transesterification, d) mol-% of citronellal/dodecene liberated by hydrogen abstraction from the alkyl chain, c) mol-% of citronellal/tridecene liberated by hydrogen abstraction of the alkyl chain, f) mol-% of trans/cis citral. WO 99/60990 PCT/1B99/00890 Example 10 Release of citronellal from various citronellyl a-keto esters in after-shave lotions 5 Compounds (7) and (8) of example 2 were each dissolved in an amount of 0.29 g in 19.54 g of a standard after-shave lotion base, under addition of a standard solubilizer (Cremophor RH40, BASF AG). For each of the compounds, three samples of 6 ml (one of which was wrapped in aluminium foil to serve as reference) were irradiated in 10 ml volumetric flasks for 3h with a xenon lamp. The irradiated samples were analyzed by 10 HPLC using citronellal and the corresponding starting materials as external standards. The reference experiment (aluminium foil wrapped) showed no release of citronellal. The results obtained with the other samples are summarized in Table 7. Table 7 : Results of the photoirradiations of a-keto esters in after-shave lotion Compound N° mol-% of citronellal liberated mol-% of remaining * starting material 7 12 36 8 2 53 * average of 2 samples 20 Example 11 Release of citronellal or menthone from various citronellyl a-keto esters in a window cleaner and in an all-purpose cleaner 25 10-15 mg of the respective a-keto ester as specified in Table 8 below were weighed into 10 ml volumetric flasks. A solubilizer was added (Cremophor RH40, BASF AG for window cleaner, Triton XI00 (Rohm & Haas) for all-purpose cleaner), before adding WO 99/60990 PCT/IB99/00890 6 ml of the respective base, i.e. a standard type window cleaner, or a Fabuloso® (registered trademark of Colgate-Palmolive, USA) type all-purpose cleaner, and agitating until the solution became clear. For each irradiation series four samples were prepared for each compound, one of which, wrapped in aluminium foil, served as reference. All the samples were irradiated for 3, 6, or 15 h with either the Xenon or the UV lamp or exposed to outdoor sunlight. In all cases the formation of citronellal or menthone could be smelled after the photolysis. In order to quantify the amount of aldehyde or ketone (and of the remaining starting material) in the application base, the irradiated samples were subjected to GC analysis (extraction and on-column injection). For analysis, 1 g of NaCI was added and the samples were extracted with 3 ml of a 0.35 mM (50 mg/1) solution of undecane (used as internal standard) in iso-octane. The aqueous layer was re-extracted with 2 ml of the wo-octane solution and the two organic phases were combined and injected directly onto a GC column. The results obtained for the different bases are summarized in Table 8. Table 8 : Results of the photoirradiations of different a-keto esters in different household application bases WO 99/60990 PCT/IB99/00890 All numbers are average values of 2 or 3 samples. a) citronellal was released from compounds 7, 13 and 9, respectively, menthone was liberated from compound 18. 5 b) amount of remaining starting material rounded to ±5%. WO 99/60990 PCT/1B99/00890 Example 12 Dynamic headspace analysis in all purpose cleaners (APC) 5 In order to follow the perfume release under more realistic application conditions, quantitative dynamic headspace analyses were carried out. The formation of citronellal from its precursor in an APC application was compared to the behaviour of free citronellal in the same base. Solutions of a base of the Fabuloso ® type containing either 0.3 mass-% of citronellal precursor 13 or 0.3 mass-% of pure citronellal (≈ 2 molar 10 equivalents) were prepared and deposed in self-built 3.5 1 Pyrex® glass containers covered with a thin window glass plate. The chambers were exposed to outdoor sunlight for 6 h and continuously flushed with an air stream. Every hour the volatiles contained in the air stream were adsorbed on a Tenax cartridge (during 15 min) and the light intensity was measured. The amount of citronellal trapped on the cartridges was 15 desorbed and quantified by GC analysis and are summarized in Table 9. 20 The amount of citronellal released increases with increasing light intensity and decreases when the intensity decreases, with the maximum of release being obtained shortly after the maximum of irradiation was measured. The amount of free citronellal, however, was found to decrease steadily with increasing time and, no dependency on the light intensity was observed. Time Free citronellal in base Citronellal released from Sunlight [h] (0.3 mass-%) precursor 13 in base intensity [ngl1] (0.3 mass-%) [ng 1"'] [lux] 1 154086 1579 38500 2 117735 4752 53500 3 67015 7475 64500 4 50632 7829 63000 5 33215 7297 52500 6 19757 5919 35000 25 Table 9 : Comparison of the dynamic headspace of free citronellal and citronellal released from precursor 13 in a Fabuloso ® type APC irradiated with outdoor sunlight. WO 99/60990 PCT/IB99/00890 The above described experiment was repeated using 0.3 mass-% of menthone precursor 18 or 0.15 mass-% of pure menthone (≈ 1 molar equivalent) in an APC application of the Fabuloso ® type. Again a dependency of perfume release of the irradiation intensity could be observed, see Table 10, whereas the amount of unprotected menthone decreased continuously over time. Working with molar equivalents instead of mass equivalents shows that the perfume concentration of both systems are in the same order of magnitude. At the beginning of the experiment the concentration of unprotected menthone is about three times stronger than the concentration of the perfume released from the precursor. At the end of the experiment the perfume released from the keto ester contributes more strongly than the free menthone. Table 10 : Comparison of the dynamic headspace of free menthone and menthone released from precursor 18 in a Fabuloso ® type APC irradiated with outdoor sunlight. Time Free menthone in base Menthone released from Sunlight M (0. 15 mass- %) precursor 18 in base intensity [μg 1-1] (0.3 mass-%) [μg l"1] [lux] 0.5 94.6 33.1 53000 1.5 86.4 59.7 71000 2.5 81.5 70.0 86750 3.5 76.7 68.9 88500 4.5 64.2 63.3 80500 5.5 47.4 60.5 69250 6.5 39.1 48.1 53000 Example 13 Dynamic headspace analysis for the slow release on hair In order to test the performance of the controlled photochemical release of perfumes in typical body care applications, 0.2 mass-% of precursor 13 dissolved in a leave-in hair WO 99/60990 PCT/IB99/00890 conditioner of the standard type was sprayed four times on a hair curl (≈ 5 g weight) and irradiated in a glass tube for 3 h with a Xenon lamp. The hair curl had been washed beforehand with an unperfumed shampoo base and the amount of conditioner deposed on the hair was weighed precisely. A comparison experiment with 0.1 mass-% (≈ 1 5 molar equivalent) of unprotected citronellal in the same base was carried out under identical conditions. During irradiation, the glass tube was connected to a charcoal filter (for air decontamination) and a Tenax cartridge and continuously flushed with an air stream 10 (80 ml/min, corresponding to 4 renewals of air/sampling). The diffusion of citronellal was monitored over a period of three hours and four samplings at t = 0, 1,2 and 3 h were carried out. At each sampling, the citronellal diffusing from the hair was adsorbed onto a Tenax cartridge during 15 min, respectively. The cartridges were then thermally desorbed and the concentration of citronellal precisely quantified by GC (Table 11). 15 Table 11 : Comparison of the dynamic headspace of free citronellal and citronellal released from precursor 13 in a leave-in hair conditioner irradiated with a Xenon lamp. Time Free citronellal in hair Citronellal released from Xenon light [h] conditioner precursor 13 in hair conditioner intensity (0.1 mass-%) [ng 1-1'] (0.2 mass-%) [ng 1-1] [lux] 0 20700 284 78000 1 435 394 86000 2 127 237 86500 3 39 151 87500 Table 11 illustrates that the concentration of unprotected citronellal decreases rapidly with time whereas the citronellal released from the precursor remains almost constant during the experiment with constant light intensity. After only one hour of irradiation the concentration of citronellal released from the precursor is as high as the 25 concentration of the unprotected aldehyde, and thereafter remains higher than the concentration of the unprotected aldehyde. WO 99/60990 PCT/1B99/00890 Example 14 Dynamic headspace analysis for the slow release on cotton fabric 5 The release of citronellal from precursor 13 was compared to the diffusion of unprotected aldehyde on cotton fabric. For the study, precisely determined amounts of ethanolic solutions containing either 0.2 mass-% of 13 or 0.1 mass-% (≈ 1 molar equivalent) of unprotected citronellal, respectively, were sprayed four times on 10 4 x 20 cm cotton sheets, which had been washed beforehand with an unperfumed detergent base. The irradiation was carried out in a Pyrex ® glass tube for 3 h with a Xenon lamp as described above. Again a rapid decrease of the released amount unprotected citronellal over time was 15 observed, whereas the release of citronellal from the precursor remained constant with respect to the irradiation intensity, as illustrated in Table 12. The light dependence of the controlled perfume release was verified in a blank experiment. After only 3 h of irradiation comparable concentrations of citronellal were obtained either from the experiment with the free perfume or from release of the precursor compound. 20 Table 12 : Comparison of the dynamic headspace of free citronellal and citronellal released from precursor 13 on cotton sheets irradiated with a Xenon lamp. Time Free citronellal on cotton Citronellal released from Xenon light [h] (0.1 mass-% in EtOH) precursor 13 on cotton intensity . [ng 1'] (0.2 mass-% in EtOH) [ng 1'] [lux] 0-0.25 3022 71 92500 1 - 1.25 1590 168 89250 2-2.25 469 150 80750 3-3.25 116 115 81750 WO 99/60990 PCT/IB99/00890 Example 15 Slow release from cotton sheets treated with fabric softener 5 In a typical experiment, ten cotton towels were washed with an unperfumed, lipase free detergent powder and a fabric softener containing either 0.8 mass-% of keto ester 13 or 0.23 equivalents of the theoretically releasable unprotected aldehyde, respectively. The towels were washed at 40°C without prewashing cycle and dried in the dark overnight. Two towels of each type were irradiated with the above described UV lamp in one 10 covered Pyrex ® crystallizing dish with an approximative volume of 3.5 1 and compared to a set of non irradiated samples. After 3 h of irradiation the towels were analyzed by nine panelists. In all cases the irradiated towels with precursor 13 were characterized to give a fresh, floral, citrus type odor, and the average intensity was given the value 3 on an increasing scale starting at 0 and ending at 10. In the case of the unprotected 15 citronellal or the two blank samples, the panelists detected only a weak odor with an intensity of 1 on the scale from 0 to 10. The photoperfume precursor can therefore sucessfully be deposed on fabrics in a normal washing cycle, and the release of the desired perfume is detected in perceptible amounts 20 upon irradiation of the dry fabric. Example 16 Release of menthone from an all-purpose cleaner An all-purpose cleaner of the Fabuloso ® type containing 0.3% of the compound 18 was prepared. This cleaner and the same cleaner without any perfume were placed into trapezoid flashes which were exposed to sunlight for 3 h (see also Example 11). The 30 thus-obtained samples were then compared on a blind test by a panel of 15 non-experts. When the sample containing the photoperfume was the odd sample. 14 of the panelists WO 99/60990 PCT/IB99/00890 correctly distinguished the samples. When the odd sample was the one containing the unperfumed base, 13 of the panelists correctly attributed the samples. 5 Example 17 Release of menthone from a window cleaner A window cleaner of the type described in Example 11 containing 0.3% of the 10 compound 18 was prepared. This cleaner and the same cleaner without any perfume were placed into trapezoid flashes which were exposed to sunlight for 3 h. The thus-obtained samples were then compared on a blind test by a panel of 15 non-experts. When the sample containing the photoperfume was the odd sample, 12 of the panelists correctly distinguished the samples. When the odd sample was the one containing the 15 unperfumed base, 10 of the panelists correctly attributed the samples. WE CLAIM: 1. Perfuming composition or perfumed article comprising, together with perfuming ingredients, solvents or adjuvants of the kind such as herein described in the preparation of perfume formulations, at least 0.01% of a 2-benzoyl benzoate or a 2-alkanoyl benzoate of formula or in which Ri represents hydrogen or a group of formula —CH—X in which X and Y can be identical or different and represent, independently from each other, hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group or a group of formula >1 + R2 can be identical to R1 or different from it and represents hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group, a group of formula or a polyalcohol or polyether group R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or branched, a OH group or a NH2 group; R4 and R5, taken separately, have the meaning given above for R1 and can be identical to or different from R1 or from each other ; or R4 and R5, taken together, form a bridging group between the two aromatic rings which bridging group can be a methylene or a keto group m is an integer from 0 to 3 and n is an integer from 0 to 2; R6 and R7, taken separately, each represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C12, or a phenyl group, or, R6 and R7, taken together with the nitrogen atom form a 5-membered or six- membered ring possibly containing another hetero atom R8 represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl chain from C1 to C12 or a phenyl group; M represents hydrogen or an alkali metal; and R* is the organic part derived from a primary or secondary fragrant alcohol ROH. 2. Perfuming composition or perfumed article as claimed in claim 1, wherein the 2-benzoyl benzoate is of formula (D in which R1 is a branched alkyl group from C3 to C4 containing a secondary hydrocarbon group; R2 is a branched alkyl group from C3 to C4 and is identical to R1; R3 is hydrogen or a linear or branched alkyl group from C1 to C4; R4is hydrogen or a linear or branched alkyl group from C1 to C4; R5is hydrogen or a linear or branched alkyl group from C1 to C4; R is the organic part derived from a primary or secondary fragrant alcohol ROH. 3. Perfuming composition or perfumed article as claimed in claim 1, wherein Ri is an isopropyl group. 4. Perfuming composition or perfumed article as claimed in any of claims 1 to 3, wherein the fragrant alcohol ROH from which is derived R* is geraniol, (E)-3,3-dimethyl-5-(2',2', 3'-trimethyl-3'-cyclopenten- 1 '-yl)-4-penten-2-ol or phenethylol. 5. Perfuming composition or perfumed article as claimed in claim 1, wherein the 2-benzoyl benzoate is geranyl 2-benzoyl benzoate, geranyl 2-(2-isopropylbenzyl)benzoate, geranyl 2-(2',4'-diisopropylbenzoyl)benzoate or (E)-3 ,3-dimethyl-5-(2\2',3' -trimethyl-3'-cyclopenten- 1' -yl)-4-penten- 1-yl 2-(2',4'-diiso-propyl-benzoyl)benzoate. 6. Perfuming composition or perfumed article as claimed in any of the preceding claims, wherein there is added to the said composition or article a hydrogen radical source which is a solvent selected from the group consisting of primary or secondary aliphatic alcohols, aromatic alcohols, diols and polyols, ketones, esters, alkyl-substituted aromatic compounds, ethers, aminoalcohols and linear and branched hydrocarbons, provided that said solvents contain a linear alkyl group higher than ethyl or a branched secondary alkyl group. 7. Perfuming composition or perfumed article as claimed in claim 6, wherein the solvent is isopropanol, 1-dodecanol 2-tridecenol, butanol or amyl alcohol. 8. Perfuming composition or perfumed article as claimed in claim 1 in the form of a perfume or a cologne, a bath or shower gel, a hair-care product, a cosmetic preparation, a body deodorant, a solid or liquid air-freshener, a detergent or a fabric softener, or a household product. Dated this 24th day of October, 2000. [RANJNA MEHTA-DUTT] OF REMFRY & SAGAR ATTORNEYS FOR THE APPLICANTS

Full Text

FORM 2
THE PATENTS ACT 1970 [39 OF 1970]
COMPLETE SPECIFICATION [See Section 10]
"Perfuming compostion"
FIRMENICH SA, of 1, route des Jeunes, P.O. Box 239, 1211 Geneva 8, Switzerland,
The following specification particularly describes the nature of the invention and the manner in which it is to be performed:-

17-04-2000 IB 009900890

Slow release of fragrant compounds in perfumery using 2-benzoyl benzoates, 2-alkanoyl benzoates or a-keto esters
5 1 echnical Field and Prior Art
The present invention relates to the field of perfumery. It relates, more particularly, to perfuming compositions or perfumed products containing a class of aliphatic or aromatic keto esters of fragrant alcohols, as defined below, which are 10 capable of releasing said fragrant alcohol upon exposure to light, more particularly daylight. The present invention also relates to a-keto esters, as defined below, of alcohols which are precursors of fragrant aldehydes and ketones and which are capable of releasing said fragrant ketone or aldehyde upon exposure to light, more particularly daylight. Said a-keto esters may furthermore contain, in a-position to the keto group, an 15 alkyl group which may contain various substituents and which alkyl group is derived from a fragrant molecule possessing an olefinic unsaturation. The unsaturated molecule and/or the aldehyde or ketone are released upon exposure to light, in particular daylight, of the a-keto ester.
Some compounds of the invention, namely some 2-benzoylbenzoate esters
20 as well as some a-keto esters are known to be photolabile compounds. Therefore, it has
been suggested in the prior art to use 2-benzoylbentoate esters as protective groups for
alcohols in organic synthesis and subsequently release the alcohol present in the ester
function by photolysis (see Porter et al., J. Org. Chem 1996, 67, 9455-9461). The
authors conducted experiments with different alcohols, and they described the
25 elimination of geraniol from the geranyl 2-benzoyl benzoate (R1=R2=R3=R4=R5=H).
Moreover, S. Hu and D.C.Neckers in J. Org. Chem. 1997, 62, 6820-6826, and
G.A. Kraus and Y. Wu in J.Am. Chem. Soc. 1992, 114, 8705-8707 disclose some
a-keto ester derivatives within the scope of photolysis studies. On the other hand, some
pyruvate esters are known to be active ingredients to enable the removal of amine and
30 mercaptan type odors (Patent Abstracts of Japan, 1994, 18, 410). However, it has not
been described or suggested in the prior art to use the said esters in perfumery, as
fragrance delivery systems capable of releasing the fragrant alcohol over a prolonged
period of time and thus provide a slow release fragrance effect.

IB 009900890

There exists, in perfumery, a particular interest in compounds which are
capable of "fixing" fragrant molecules, for example by chemical bonding or
intramolecular forces like absorption, and releasing said fragrant molecules over a
5 prolonged period of time, for example by the action of heat, enzymes, or even sunlight.
Fragrant molecules have to be volatile in order to be perceived. Although many fragrant
compounds are known which show a good substantivity, i.e. they will remain on a
surface to which they have been applied for several days and can hence be perceived
over such a period of time, a great number of fragrant compounds are very volatile, and
10 their characteristic smell can no longer be perceived several hours after their application.
It is thus desirable to dispose of fragrance delivery systems which are
capable of releasing the fragrant compound or compounds in a controlled manner,
maintaining a desired smell over a prolonged period of time.

Accordingly, the present invention relates to a perfuming composition or perfumed article comprising, together with perfuming ingredients, solvents or adjuvants of the kind such as herein described in the preparation of perfume formulations, at least 0.01% of a 2-benzoyl benzoate or a 2-alkanoyl benzoate of formula

(R2),

(R2)n

or

(I)

(H)

in which Ri represents hydrogen or a group of formula

—CH—X
in which X and Y can be identical or different and represent, independently from each other, hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group or a group of formula
+

or a polyalcohol or polyether group

R2 can be identical to R1 or different from it and represents hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group, a group of formula

R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or
branched, a OH group or a NH2 group;
R4 and R5, taken separately, have the meaning given above for Ri and can be
identical to or different from R1 or from each other ; or
R4 and R5, taken together, form a bridging group between the two aromatic
rings which bridging group can be a methylene or a keto group
m is an integer from 0 to 3 and n is an integer from 0 to 2; R6 and R7, taken
separately, each represents hydrogen, an alkyl group from C1 to C4, an
alcohol group having an alkyl chain from C1 to C12, or a phenyl group, or, R4
and R7, taken together with the nitrogen atom form a 5-membered or six-
membered ring possibly containing another hetero atom
Rs represents hydrogen, an alkyl group from C1 to C4, an alcohol group
having an alkyl chain from C1to C12 or a phenyl group;
M represents hydrogen or an alkali metal; and
R* is the organic part derived from a primary or secondary fragrant alcohol
R*OH.

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R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or branched, a
OH group or a NH2 group ;
R4 and R5, taken separately, have the meaning given above for R, and can be identical to
or different from R1 or from each other ; or 5 R4 and R5, taken together, form a bridging group between the two aromatic rings, which
bridging group can be a methylene or a keto group ;
m is an integer from 0 to 3 and n is an integer from 0 to 2 ; R6 and R7, taken separately,
each represent hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl
chain from C1 to C,12, or a phenyl group, or, R6 and R7 taken together with the nitrogen 10 atom form a 5-membered or six-membered ring possibly containing another hetero
atom;
R8 represents hydrogen, an alkyl group from C1 to C4, an alcohol group having an alkyl
chain from C1 to C,2 or a phenyl group ;
M represents hydrogen or an alkali metal; and 15 R* is the organic part derived from a primary or secondary fragrant alcohol R*OH.
In the above definition, when reference is made to a fragrant alcohol, there
is always meant an alcohol which not only has an odor, but which is also known to a
person skilled in the art as being useful as perfuming ingredient for the formulation of
perfumes or perfumed articles. The criteria a useful perfuming ingredient has to fulfil 20 are known to a person skilled in the art and include, amongst others, a certain originality
of the odoriferous note, stability and a certain price/performance ratio. Non-limiting
examples for fragrant alcohols which can be used with the benzoates of the invention
will be mentioned below.
From the above, it is clear that when reference is made to the organic part 25 R* of a fragrant alcohol R*OH, R* is the hydrocarbyl rest of said alcohol, e.g. a geranyl
radical in case R*OH is geraniol.
The advantage of the fragrance delivery system of the present invention lies
in its capacity to slowly release the fragrant alcohols R*OH from which the benzoyl
benzoate esters of formula (I) or the alkanoyl benzoate esters of formula (II) are derived. 30 The release occurs when said esters are exposed to daylight in particular. Upon
absorption of energy from said light, the ester undergoes a photoreaction in the course
of which the fragrant alcohol is released from the molecule into the surroundings. Said

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release occurs in a controlled manner, i.e. a more or less constant amount of alcohol R*OH is formed over a period of time, without an initial burst of very intense odor which becomes rapidly imperceptible as is the case with volatile alcohols. Because the release of the alcohol R*OH can occur over several days or weeks, the use of the system 5 of the present invention obviates the drawbacks of many fragrant alcohols R*OH which are of pleasant smell but also very volatile. Good examples are citronellol and geraniol which can only be perceived over a short period of, say, one or two hours, when applied to the surface of, for example, tiles and windows in the course of a cleaning procedure using liquid cleaners ; even in solution, the typical smell of said alcohols disappears
10 within several hours. It goes without saying that the concentration of the alcohols in the application plays an important role in the time during which the fragrant molecules can be perceived.
With the system of the present invention, the typical odor of the alcohol R*OH is perceived over a considerably prolonged period of time, as the 2-benzoyl
15 benzoate or the 2-alkanoyl benzoate of the fragrance delivery system, which are not or few volatile, remain as such on the surface to which they are applied or in the solution into which they are incorporated, and it is only upon exposure to light, that the fragrant alcohol R*OH is released. It is clear that this reaction can provide perceptible amounts of the alcohol over days or weeks, depending, amongst others, on the amount or the
20 concentration of the fragrance delivery system, the time of exposure to light, its intensity and its wavelength.
2-Benzoyl benzoate esters of the above formula (I) which can carry various substituents in positions R1 R2, R3, R4 and R5 are known to be photolabile compounds. It was suggested to use these esters as protective groups for alcohols in organic
25 synthesis and subsequently release the alcohol present in the ester function by photolysis (see Porter et al., J. Org. Chem 1996, 61, 9455-9461). The authors conducted experiments with different alcohols, and they described the elimination of geraniol from the geranyl 2-benzoyl benzoate (R,=R2=R3=R4=R5=H). However, it has not been described or suggested to use the said esters in perfumery, as a fragrance delivery
30 system which is capable of releasing the fragrant alcohol over a prolonged period of time and thus provide a slow release fragrance effect.

04-2000 IB 009900890
release occurs in a controlled manner, i.e. a more or less constant amount of alcohol R*OH is formed over a period of time, without an initial burst of very intense odor which becomes rapidly imperceptible as is the case with volatile alcohols. Because the release of the alcohol R*OH can occur over several days or weeks, the use of the system 5 of the present invention obviates the drawbacks of many fragrant alcohols R*OH which are of pleasant smell but also very volatile. Good examples are citronellol and geraniol which can only be perceived over a short period of, say, one or two hours, when applied to the surface of, for example, tiles and windows in the course of a cleaning procedure using liquid cleaners; even in solution, the typical smell of said alcohols disappears
10 within several hours. It goes without saying that the concentration of the alcohols in the application plays an important role in the time during which the fragrant molecules can be perceived.
With the system of the present invention, the typical odor of the alcohol R*OH is perceived over a considerably prolonged period of time, as the 2-benzoyl
15 benzoate or the 2-alkanoyl benzoate of the fragrance delivery system, which are not a few volatile, remain as such on the surface to which they are applied or in the solution into which they are incorporated, and it is only upon exposure to light, that the fragrant alcohol R*OH is released. It is clear that this reaction can provide perceptible amounts of the alcohol over days or weeks, depending, amongst others, on the amount or the
20 concentration of the fragrance delivery system, the time of exposure to light, its intensity and its wavelength.

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As fragrant alcohol R*OH derived radical R* in the above formula (I), in
principle a group derived from any fragrant alcohol which is known in the art can be
used. Primary and secondary alcohols are shown to be useful in the present invention as
they are liberated when exposed to daylight.
5 As non-limiting examples of alcohols which can be used in the present
invention in the form of the 2-benzoyl benzoate esters, one can cite anisic alcohol, cinnamic alcohol, fenchylic alcohol, 9-decen-l-ol, phenethylol, citronellol, 3-methyl-5-phenyl-1-pentanol (origin: Firmenich SA, Geneva, Switzerland), Mayol ® (7-p-menthan-1-ol; origin : Firmenich SA, Geneva, Switzerland), geraniol (3,7-dimethyl-
10 2,6-octadien-l-ol), (Z)-3-hexen-l-ol, 1-hexanol, 2-hexanol, 5-ethyl-2-nonanol, 2,6-nonadien-1-ol, borneol, 1-octen-3-ol, cyclomethyl citronellol, decanol, dihydroeugenol, 8-p-menthanol, 3,7-dimethyl-l-octanol, dodecanol, eugenol, isoeugenol, Tarragol ® (2-methoxy-4-propyl-l-cylohexanol; origin: Firmenich SA, Geneva, Switzerland), Polysantol ® [(E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-l'-yl)-4-penten-2-ol;
15 origin : Firmenich SA, Geneva, Switzerland] and Limbanol ® [l-(2',2',3',6'-tetramethyl-cyclohex-l-yl)-3-hexanol; origin : Firmenich SA, Geneva, Switzerland].
It is quite obvious, however, that the process of the invention is perfectly general and can relate to many other alcohols which the skilled person is quite able to choose from the general knowledge in the art and as a function of the olfactive effect it
20 is desired to achieve. The above list therefore is more illustrative for fragrant alcohols which are known to a person skilled in the art, and whose delivery can be improved, but it is clearly quite impossible to cite in an exhaustive manner all alcohols of formula R*OH which have a pleasant odor and the 2-benzoyl or 2-alkanoyl benzoate esters of which can be used in the fragrance delivery system of the present invention.
25 From the foregoing, it is evident that the fragrance delivery system is
particularly appropriate for delivering fragrant alcohols R*OH which are very volatile, or which have a low perception threshold, like geraniol, citronellol or phenethylol. The benzoyl and alkanoyl benzoate esters (I) of the latter are thus preferred according to the present invention.
30 The chemical reaction which releases the fragrant alcohol can only occur
when a source of a hydrogen radical He is present in the fragrance delivery system. It is believed that in the first reaction step, said hydrogen radical is transferred to the oxygen

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of the keto-function. Such a source can be intramolecular, i.e. the hydrogen radical comes from the 2-benzoyl benzoates of formula (I) or the 2-alkanoyl benzoates of formula (II) themselves, or intermolecular, i.e. the hydrogen radical comes from another, different source which is present in the medium in which the ester is 5 incorporated. The intramolecular pathway or mechanism is a universal mechanism which can occur in every possible application medium, thus in the liquid or solid state. The intermolecular mechanism, however, is only possible in solution, but not in the solid state. Non-limiting examples of liquid state application media are liquid air-fresheners which release the fragrant alcohol upon exposure to light. Examples of
10 release of the fragrant alcohol in the solid state are surfaces, like those of tiles or windows, which are cleaned with a cleaner containing the fragrance delivery system of the invention, the system being thus deposited on the surface after cleaning and remaining on it as a solid film after evaporation of the liquids present in the cleaner. However, it has to be understood that the term "solid" as used beforehand is used to
15 designate the benzoates in the neat state in which they may be a real solid, crystalline or non-crystalline, or be in the form of a more or less viscous oil.
For the 2-benzoyl benzoates of the above formula (I) or the 2-alkanoyl benzoates of the above formula (II) in which R1, R4 and R5 are hydrogen, an external hydrogen radical source is necessary. In general, the hydrogen radical will be abstracted
20 from the solvent in which the 2-benzoyl or the 2-alkanoyl benzoate is dissolved or provided by a solvent which is added to the solution containing the said compound. Suitable sources are known to a person skilled in the art. The most important criterion a suitable hydrogen radical source has to fulfil is that a stable radical is formed after abstraction of the hydrogen. For a given compound, and independently from other
25 functional groups or structural elements present in the same, the presence of hydrocarbon groups which are not methyl or tert-butyl is very favorable towards the formation of a stable radical after hydrogen abstraction. Suitable groups include ethyl or n-propyl. Even better are branched secondary alkyl groups, like isopropyl or sec-butyl. It is preferred when the solvent contains an isopropyl group or is a primary or secondary
30 alcohol. Non-limiting examples for classes of solvents are the following: aliphatic and aromatic alcohols, like methanol, ethanol, propanol, decanol or benzyl alcohol, in particular isopropanol ; diols and polyols, like ethyleneglycol, glycerol,

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polyethyleneglycol, propyleneglycol or polypropyleneglycol ; ketones, such as diisopropylketone; esters, such as isopropylacetate; aromatic solvents, such as ethylbenzene, cyclohexylbenzene or isopropylbenzene (cumene), di- or triisopropylbenzene; ethers, such as diisopropylether, tetrahydrofxjran, mono-, di- or 5 triethyleneglycoldimethylether, diethyleneglycolmonoether or polyethyleneglycol-dimethylether ; aminoalcohols, such as mono-, di- or triethanolamine ; hydrocarbons, in particular branched hydrocarbons, including limonene.
Preferred solvents include primary and secondary alcohols, in particular
isopropanol, 1-dodecanol, 2-tridecanol, butanol or amyl alcohol.
10 All the above-mentioned solvents can, of course, also be used for benzoyl
and alkanoyl benzoate esters which react in an intramolecular pathway to release the fragrant alcohol. In such case, R1, R4 or R5 are the intramolecular hydrogen radical source, as will be described below.
The mentioned solvents will be chosen according to their ability to release 15 hydrogen radicals.
We have found that the intramolecular pathway for the release of the fragrant alcohol only occurs when at least one of the groups R1 R4 or R5 of formula (I) or (II),which is in 2-position relative to the keto function, is a group of formula

—CH-x
20 Y
from which the hydrogen radical is easily transferred to the keto function, due to the vicinity of the group R, to the keto function by which an energetically favorable
transition state is possible. X and Y are chosen to stabilize the resulting radical
25
•
—C—X
I
Y
which remains after abstraction of the hydrogen radical and its transfer to the keto function. Suitable groups X and Y which can stabilize radicals are known to a person 30 skilled in the art, and X and Y, which can be the same or different, will be chosen according to the respective benzoyl benzoate and the fragrant alcohol R*OH used in a given fragrance delivery system in order to give the best results, i.e. the desired release

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rate for the fragrant alcohol. Preferably X and Y are, independently from each other, a group as defined above with respect to formulae (I) and (II).
The compounds of formula (I) can contain, in addition to the substituent R, in 2-position of the cycle relative to the keto function, a further substituent R4 in 5 6-position. It is evident that this substituent R4 can also function as a hydrogen radical source, after a rotation around the single bond between the keto function and the phenyl ring. Moreover, the same applies to the group R5 of the above formula (I) or (II), which is optionally present in the phenyl ring which carries the ester function. R5, after a rotation of the phenyl group, can also serve as a hydrogen radical source. R4 and R5 thus
10 have the same meaning as R1, which has-been defined above, and R4 and R5 can be identical to R1, or they can be different from R1, and, respectively, from each other.
The two phenyl groups of the 2-benzoyl benzoates or formula (I) can furthermore be bridged by a methylene or keto group.
We have furthermore found that it can be advantageous with respect to the
15 release of the fragrant alcohol when the respective benzoyl benzoate of formula (I) or the respective alkanoyl benzoate of formula (II) carries a substituent R3 other than hydrogen in the ortho-position to the -COOR*- function. The purpose of this substituent is to establish a favorable conformation of the -COOR*- function relative to the keto group, or respectively to the reduced keto-group, in order to facilitate the cyclization to
20 the lactone which occurs after release of the alcohol. This reaction leads to the release of the fragrant alcohol R*OH. Practically, any group which is inert towards the -COOR*-function can be used, and they are known to a person skilled in the art. The groups defined in the above formula (I) and (II), namely linear or branched alkyl or alkoxy from C1, to C4, OH or NH2 have revealed themselves as being appropriate from the point
25 of view of effectiveness, and, of course, synthetic access.
The benzoyl benzoates of formula (I) and the alkanoyl benzoate of formula (II) can furthermore carry one or more substituents R2 in the positions indicated and defined above. Substituents R2, however, seem to be of less importance to the reactivity and the performance of the fragrance delivery system of the present invention,
30 although it is often preferred, for reasons of easy accessibility of the corresponding 2-benzoyl and 2 -alkanoyl benzoates of the invention, to use an ester wherein R, is a group other than hydrogen. It is however possible to adapt e.g. the stability of the

WO 99/60990 PCT/IB99/008902-benzoyl and 2 -alkanoyl benzoates of the present invention to the respective application desired. The 2-benzoyl benzoates can e.g. be rendered more hydrophilic by one or more groups R2 which are a quaternary amine group, a polyalcohol group or a polyether group. Specific examples for said functional groups are known to a person 5 skilled in the art, and the groups will be chosen according to the effect desired.
Preferred 2-benzoyl benzoate esters of the present invention are those of formula
(I')
10 in which
R1, is a branched alkyl group from C3 to C4 containing a secondary hydrocarbon group ;
R2 is a branched alkyl group from C3, to C4, and is identical to R1 ;
R3 is hydrogen or a linear or branched alkyl group from C1, to C4;
R4 is hydrogen or a linear or branched alkyl group from C1, to C4; 15 R5 is hydrogen or a linear or branched alkyl group from C1, to C4;
R* is the organic part derived from a primary or secondary fragrant alcohol R*OH.
Generally, with respect to the above formulae (I) and (T), it can be said that
it is preferred when R1 R4 or R5 which are responsible for the transfer of the hydrogen
radical towards the keto function, is an isopropyl group, irrespective of the other 20 substituents which may be present in the molecule. The isopropyl group was found to be
the substituent which is most easily available, from a synthetic point of view, and which
readily transfers hydrogen to the keto function, which we attribute to its ability to form a
stable radical after abstraction of hydrogen.
The most preferred compounds according to the above formula (I') are 25 geranyl 2-(2'-isopropylbenzoyl)benzoate, geranyl 2-(2',4'-diisopropyl-benzoyl)benzoate
and 3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-l '-y!)-4-penten-2-yl 2-(2',4'-
diisopropylbenzoyl)benzoate [(E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1 '-
yl)-4-penten-2-ol is a secondary alcohol sold under the name Polysantol ® by
Firmenich SA, Geneva, Switzerland].

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The 2-benzoyl and 2-alkanoyl benzoates of the present invention are synthesized by esterification of the respective 2-benzoyl and 2-alkanoyl benzoic acids with the desired alcohol, in a way known to a person skilled in the art, preferably using 4-dimethylaminopyridine in pyridine and 1,3-dicyclohexylcarbodiimide. The above-5 mentioned benzoic acids are obtained from the respective phthalic anhydride. This latter is brought to reaction, for example, with the desired substituted or unsubstituted benzene in a Friedel-Crafts reaction. If necessary, the respective phthalic anhydride can also be reacted with the Grignard reagent, the organolithium compound or another appropriate organometallic compound of the desired substituted or unsubstituted 10 benzene or alkane, respectively.
A further object of the present invention is a fragrance delivery system

ά-keto esters of formula
comprising
(III) 15
in which
R'* is hydrogen or a linear or branched, unsubstituted or substituted alkyl group or
alkylene group from C1 to C35, an unsubstituted or substituted cycloalkyl group from C3,
to C8, an unsubstituted or substituted phenyl group, wherein said alkyl, alkylene, 20 cycloalkyl and phenyl groups may comprise one or several hetero atoms not directly
linked to the a-keto group and selected from the group consisting of oxygen, nitrogen,
phosphorous and sulfur, or
R'* is a substituted or unsubstituted, linear or branched alkyl group carrying an
abstractable hydrogen in y-position relative to the a-keto function and comprising a 25 moiety from which is derived a fragrant compound containing an olefin function, such
that said fragrant compound containing an olefin function is eliminated after abstraction
of said γ-hydrogen atom ;
R"* is hydrogen or a methyl, ethyl or tert-butyl group or is the organic part of a primary
or secondary alcohol from which is derived a fragrant aldehyde or ketone, and 30 at least one of the groups R'* and R"* being a group which is derived from a fragrant
compound.

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In the above definition, when reference is made to a fragrant compound, aldehyde or ketone, it is always meant a compound which not only has an odor, but which is also known to a person skilled in the art as being useful as a perfuming ingredient for the formulation of perfumes or perfumed articles. The criteria a useful 5 perfuming ingredient has to fulfil are known to a person skilled in the art and include, amongst others, a certain originality of the odoriferous note, stability and a certain price/performance ratio. Non-limiting examples for fragrant compounds which can be used with the a-keto esters of the invention will be mentioned below.
Like the above-described 2-benzoyl benzoates and 2-alkanoyl benzoates, the
10 a-keto esters of the above formula (III) release fragrant compounds upon exposure to light, in particular daylight. The a-keto esters of formula (III), however, are capable of releasing a fragrant compound containing an olefin function from the group R'* in 1-position relative to the keto function, or a fragrant aldehyde or ketone which is derived from the alcohol R"*OH from which the organic part R"* is present in the ester function
15 of the keto esters of the present invention, or even both.
From the above, it is clear that when reference is made to the organic part R"* of a fragrant alcohol R"*OH, R"* is the hydrocarbyl rest of said alcohol, e.g. a menthyl radical in case R"*OH is menthol.
The release of the fragrant compound from the keto esters occurs in an
20 elimination reaction after an intramolecular transfer of an abstractable hydrogen radical, in γ-position to the a-keto function, to said keto function. The respective part of the molecule from which the hydrogen radical has been abstracted is subsequently released from the reduced keto ester, with concomitant formation of a double bond. The above is illustrated in the scheme below in which possible substituents in the respective parts of
25 the molecules have been omitted for reasons of clarity. The double bonds which will be formed after elimination are indicated by dotted lines.

WO 99/60990 PCT/1B99/00890It is to be understood that the a-keto esters of the present invention can release only one or both molecules of fragrant compound per molecule of a-keto ester. When the hydrogen transfer to the a-keto function is able to occur from the one or the other side of said function, as illustrated above, a certain part of the molecules will 5 release a ketone or aldehyde and a certain part will release the olefin compound. The proportions of the two products released depend on the relative rate of each hydrogen transfer reaction. According to the effect desired, the a-keto esters of the invention can be tailored to release exclusively a fragrant ketone or aldehyde, or exclusively a fragrant compound containing an olefin group, or both. When only one of the two classes of
10 fragrant compounds is to be released from the a-keto esters of the invention, the part of the molecule from which no release shall occur does not contain an abstractable hydrogen atom in y-position to the keto function, i.e. either no hydrogen atom at all is present in the said position, or it is one which is not abstracted.
It is also clear that the a-keto esters according to the invention can, in a first
15 step, release the olefin compound under formation of a molecule which does not any longer contain an abstractable hydrogen atom in y-position to the keto function (left side of the molecule as designed above); in a second step, this molecule can then release the ketone or aldehyde from the ester function.
It is evident that a fragrance delivery system which contains the a-keto
20 esters of the above formula (III) has all the advantages described above for the 2-benzoyl and 2-alkanoyl benzoates of formula (I) and (II), i.e. the release of the fragrant compound occurs in a more or less constant amount. No initial burst of very intensive odor which becomes imperceptible after a relatively short period of time occurs, as is often observed with volatile aldehydes or ketones or fragrant compounds containing an
25 olefin group. With the a-keto esters of the present invention, such disadvantages are obviated because the esters will remain on a surface to which they have been applied or in the solution into which they have been incorporated. Upon exposure to light, the fragrant compound or compounds are released, and this reaction can provide perceptible amounts of the compound over days or weeks, depending, amongst others, on the
30 amount or the concentration of the a-keto esters, the time of exposure to light and its intensity.

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A further advantage of the a-keto esters according to formula (III) is the protection of the reactive, unstable aldehyde or keto function in the molecules to be released against degradation which may occur during storage.
Additionally, the a-keto esters of the present invention allow for the 5 generation of mixtures of two different fragrant compounds, and in different proportions, if desired.
In principle, any fragrant aldehyde or ketone which is known in the art can be released from the a-keto esters of the invention in which they are chemically bound in the form of the ester of their corresponding secondary or primary alcohol.
10 Non-limiting examples for fragrant aldehydes which can be released from
the a-keto esters include saturated and unsaturated linear and branched aldehydes from C6 to Ct3, citral, citronellal, campholenic aldehyde, cinnamic aldehyde, hexylcinnamic aldehyde, formyl pinane, hydroxycitronellal, cuminic aldehyde, vanillin, ethylvanillin, Lilial ® [3-(4-tert-butylphenyl)-2-methylpropanal; origin: Givaudan-Roure SA,
15 Vernier, Switzerland], Lyral ® [4- and 3-(4-hydroxy-4-methylpentyI)-3-cyclohexene-l-carbaldehyde ; origin : International Flavors and Fragrances, USA], Bourgeonal ® [3-(4-tert-butylphenyl)propanal; origin: Quest International, Naarden, Netherlands], heliopropanal [3-(l,3-benzodioxol-5-yl)-2-methylpropanal; origin: Firmenich SA, Geneva, Switzerland], Zestover (2,4-dimethyl-3-cyclohexene-1-carbaldehyde; origin:
20 Firmenich SA, Geneva, Switzerland), Trifernal ® (3-phenylbutanal; origin : Firmenich SA, Geneva, Switzerland), a-sinensal, (4-methylphenoxy)acetaldehyde, 1,3-benzodioxol-5-carboxaldehyde (heliotropine), Scentenal ® [8(9)-methoxy-tricydo[5.2.1.0.(2,6)]decane-3(4)-carbaIdehyde; origin: Firmenich SA, Geneva, Switzerland], Liminal * [(4R)-l-p-menthene-9-carbaldehyde; origin: Firmenich SA,
25 Geneva, Switzerland], Cyclosal [3-(4-isopropylphenyl)-2-methylpropanal; origin: Firmenich SA, Geneva, Switzerland], ortho- and para-anisaldehyde, 3-methyl-5-phenylpentanal, Acropal ® [4-(4-methyI-3-pentenyl)-3-cyclohexene-l-carbaldehyde ; origin : Givaudan-Roure SA., Vernier, Switzerland], Intreleven ® aldehyde (mixture of 10-undecenal and 9-undecenal; origin : International Flavors & Fragrances, USA),
30 muguet aldehyde l(3,7-dimethyl-6-octenyl)acetaldehyde ; origin : International Flavors & Fragrances, USA], 2,6-dimethyi-5-heptanal, Precyclemone ® B f l-methyl-4-(4-

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methyl-3-pentenyl)-3-cyclohexen-l-carbaldehyde; origin: International Flavors & Fragrances, USA] and Isocyclocitral ® (2,4,6-trimethyl-3-cyclohexene-l-carbaldehyde ; origin : International Flavors & Fragrances, USA).
Non-limiting examples for ketones which can be released from the a-keto 5 esters include camphor, carvone, menthone, ionones, irones, damascenones and damacones, benzyl acetone (4-phenyl-2-butanone), 1-carvone, 4-(4-hydroxy-l-phenyI)-2-butanone (raspberry ketone), Hedione ® (methyl dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland), Neobutenone [l-(5,5-dimethyl-l-cyclohexen-l-yl)-4-penten-l-one ; origin : Firmenich SA, Geneva, Switzerland], Calone ® (7-methyl-
10 2H,4H-l,5-benzodioxepin-3-one ; origin : C.A.L. SA, Grasse, France), Sulfox [(1R,4R)-8-mercapto-3-p-menthanone; origin : Firmenich SA, Geneva, Switzerland], Orivone ® [4-(l,l-dimethylpropyl)-l-cyclohexanone; origin: International Flavors & Fragrances, USA], Delphone (2-pentyl-l-cyclopentanone; origin: Firmenich SA, Geneva, Switzerland), 2-naphthalenyl-l-ethanone, Veloutone (2,2,5-trimethyl-5-pentyl-l-
15 cyclopentanone; origin: Firmenich SA, Geneva, Switzerland), 4-isopropyl-2-cyclohexen-1-one, Iso E Super® [isomer mixture of l-(octahydro-2,3,8,8-tetrame-2-naphthalenyl)-l-ethanone ; origin : International Flavors & Fragrances, USA], Plicatone [5-methyl-exo-tricyclo[6.2.1.0(2,7)]undecan-4-one ; origin: Firmenich SA, Geneva, Switzerland]; and macrocyclic ketones such as, for example Exaltone
20 (cyclopentadecanone), Delta Muscenone (mixture of 3-methyl-4-cyclopentadecen-l-one
and 3-methyl-5-cyclopentadecen-l-one) and Muscone (3-methyl-l-
cyclopentadecanone), all from Firmenich SA, Geneva, Switzerland.
With respect to the fragrant compounds carrying an olefin group, in principle any compound containing such olefin group and, in addition, any osmophoric
25 group known in perfumery can be used. As non-limiting examples for osmophoric groups, one can cite alcohol, ether, ester, aldehyde and keto groups, the thio analogues of the said groups, nitrile, nitro and olefin groups.
As non-limiting examples for fragrant compounds which carry an olefin group, there can be cited linalool, 1,3,5-undecatrienes, myrcene, myrcenol,
30 dihydromyrcenol, nerolidol, sinensals, limonene, carvone, farnesenes, isopentyrate (1,3-dimethyI-3-butenyl isobutyrate ; origin : Firmenich SA, Geneva, Switzerland), ally I 3-

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methylbutoxyacetate, eugenol, Rosalva ® (9-decen-l-ol; origin : International Flavors &
Fragrances, USA), and allyl heptanoate.
It is quite obvious, however, that the invention is perfectly general and can
relate to many other aldehydes, ketones and olefins which are useful as fragrant 5 compounds. The person skilled in the art is quite able to choose these compounds from
the general knowledge in the art and from the olfactive effect it is desired to achieve.
The above list is therefore more illustrative for the compounds which are known to a
person skilled in the art, and whose delivery can be improved. It is clearly quite
impossible to cite in an exhaustive manner all aldehydes, ketones and olefins which 10 have a pleasant odor and which can be used in the form of derivatives in the a-keto
esters of formula (III) from which they are released upon exposure to light.
The a-keto esters of the present invention are in particular appropriate for
delivering fragrant aldehydes, ketones and fragrant compounds containing an olefin
group which are very volatile or which have a low perception threshold. Preferred 15 aldehydes and ketones include citronellal, citral, hydroxycitronellal, Hedione ®, Lilial ®,
raspberry ketone, anisaldehyde, menthone, Delphone, Orivone®, 2-naphthalenyl-l-
ethanone, and aldehydes from C6 to C!3, saturated or unsaturated linear or branched.
Preferred fragrant compounds containing an olefin group include linalool, myrcene,
myrcenol and Rosalva ®.
In case the a-keto esters of the present invention are used to release
exclusively aldehydes or ketones, the group R'* is hydrogen, phenyl, cyclohexyl or
cyclopentyl, methyl, ethyl, n-propyl, isopropyl, sec-butyl, isobutyl or tert-butyl, i.e.
groups which do not provide an abstractable hydrogen atom in y-position to the a-keto
function or which do not form a stable radical when a hydrogen radical is abstracted 25 from them. In the latter case, small amounts of olefin may be formed which however do
not interfere with the aldehyde or ketone released.
Likewise, when the a-keto esters of the present invention are used to release
a fragrant compound containing an olefin group only, then the group R"* will be
hydrogen or a methyl, ethyl or tert-butyl group, thus a group which does not provide an 30 abstractable proton in y-position to the a-keto function or which do not form a stable
radical when a hydrogen radical is abstracted from them.

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It is preferred when the fragrance delivery system of the present invention
contains a-keto esters of formula (III) in which R"* is the organic part of a primary or
secondary alcohol from which is derived a fragrant aldehyde or ketone and in which R'*
is a phenyl, cyclohexyl or cyclopentyl group or a linear or branched alkyl group from C1,
5 to C4.
A fragrance delivery system containing the a-keto esters of formula (III)
does not need an external hydrogen radical source. A fragrance delivery system
containing a-keto esters of the present invention may thus comprise a solvent the choice
of which is not supposed to be critical. Suitable classes of solvents include alcohols,
10 ethers, esters, ketones, amines and aminoalcohols.
Depending on the general application conditions or on the product into
which the a-keto esters according to the present invention are incorporated, one can
sometimes also observe the release of alcohols R"*OH, due to saponification of the
ester function, or due to reduction of the aldehyde or ketone formed by irradiation.
15 The a-keto esters of formula (III) can be prepared, on the one hand, by
esterification of the respective a-ketoacids with the primary or secondary alcohols which are the precursors of the fragrant aldehydes and ketones to be releasead. Another way for the preparation of the a-keto esters of the present invention is the reaction of the bis(oxalyl) ester of the primary or secondary precursor alcohol R"*OH with the 20 Grignard compound of the appropriate group R'* as defined in formula (III). The reaction is illustrated in the scheme I below.
Scheme I
25 The bis(oxalyl) ester is prepared from oxalyl chloride and the desired alcohol, see Synth. Commun. 1981, (11), 943-946 and Org. Synth. Coll. Vol. II 1943,
425-427.

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Another synthetic route leading to the desired a-keto esters of formula (III) is the Grignard reaction of the readily available bis(oxalyl)esters of lower aliphatic alcohols such as, for example, methanol, ethanol or propanol, with the Grignard compound of the respective group R'*, resulting in the intermediate ester (IV). This said ester (IV) is then submitted to a transesterification reaction with the respective precursor alcohol R"*OH, to give the desired a-keto ester. This reaction is outlined in the following scheme II in which R'* and R"* have the meaning defined in formula (III). Hal is CI, Br or I and R is a lower alkyl group such as, for example, methyl, ethyl, propyl or butyl.
Scheme II

Various a-keto esters of formula (III) in which R'* is hydrogen or a phenyl
or methyl group and R"* is derived from the alcohol precursor of a fragrant aldehyde are described in the literature.
Also known is hexyl (cyclohexyl)oxoacetate (see DE-OS 29 09 951 to Bayer AG, describing the use of the said compound as starting product for the synthesis
20 of catalysts for the polymerisation of olefins), which would release n-hexanal upon irradiation.
In Biochem. Z. 1935, (277), p 426-436, there is described the synthesis of the (-)-bornyl ester of (4-methylphenyI)oxoacetic acid, i.e. (-) (IS,2R), 1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl (4-methylphenyl)oxoacetate. The compound is
25 characterized by its physical data.
There are furthermore known, from the chemical literature, various compounds according to the above formula (III) wherein OR"* is a menthyl or a benzyl group, with the groups R'* being various alkyl, alkenyl, cycloalkyl or phenyl groups as defined above.

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There is nowhere found, however, any description or hint concerning the value of the compounds according to formula (III) in perfumery as a photosensitive molecule which will release a fragrant compound upon irradiation.
In the book of S. Arctander, Perfume and Flavors Chemicals, 1969,
5 Montclair, New Jersey, USA, there are mentioned decyl 2-oxopropanoate, (Z)-3-
hexenyl 2-oxopropanoate and 2-ethyl-3-methylbutyl 2-oxopropanoate, with a short
description of their odor and their synthesis. It is not mentioned that the said molecules
release fragrant compounds upon irradiation.
The release of the above-mentioned fragrant compounds from the delivery
10 system occurs upon the exposure to light, e.g. the normal daylight which can penetrate through ordinary windows in houses and which is not particularly rich in UV-radiation. It goes without saying that upon exposure to bright sunlight, in particular outdoors, the release of the fragrant alcohol, aldehyde, ketone or alkene will occur faster and to a greater extent than upon exposure to the light in a room inside a building. Of course, the
15 reaction which releases the fragrant compound from the delivery system can also be initiated by an appropriate artificial lamp.
The fragrance delivery systems of the present invention can be used in any application in which a prolonged, defined release of the above-mentioned fragrant compounds is desired. They therefore mostly find use in functional perfumery, in
20 articles which are exposed to daylight when in use or which are applied to other articles which thereafter are exposed to daylight. Suitable examples include air-fresheners in liquid and solid form which, with the delivery system of the present invention, still can release a fragrance when conventional air-fresheners, i.e. those not containing the system of the present invention, are exhausted. Other examples are various cleaners for
25 the cleaning of surfaces of all kinds, e.g. window and household cleaners, all purpose-cleaners and furniture polish. The surfaces which have been cleaned with such cleaners will diffuse the smell of the perfume much longer than when cleaned with conventional cleaners. Other representative examples include detergents for fabric wash, fabric conditioners and fabric softeners which can also contain the delivery system of the
30 present invention and which products can be in the form of powders, liquids or tablets. The fabrics and clothes washed or treated with such detergents or softeners will diffuse

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the fragrant compound even after having been stored for weeks or even months, in a dark place, like a wardrobe.
The release of the fragrant compound occurs in all the above-mentioned
application examples. All possible types of window, household, all-purpose cleaners,
5 air-fresheners, detergent, fabric wash and fabric softeners can be used with the fragrance
delivery system of the present invention, which has revealed itself to be useful in all
types of these above-mentioned application examples.
In the field of body care, the delivery systems according to the present invention have shown themselves to be particularly appropriate for an application in the
10 hair care area, and specific examples include shampoos, hair conditioners, in particular leave- in conditioners, hairspray and other hair care products.
It can be said that generally all products which can be applied to a surface which is exposable to light may contain the system of the present invention. Examples include surfaces which belong to the human body, like skin or hair, surfaces in buildings
15 and apartments, like floors, windows, tiles or furniture, or surfaces of fabrics, e.g. clothes. It is clear that the system of the invention can also be used to release fragrances from liquids, like in liquid air-fresheners. The possible applications of this type, however, appear to be less general than the application on the various surfaces mentioned.
20 Of course, the above examples are only illustrative and non-limiting as
referring to preferred embodiments. All other current articles in functional and fine perfumery may contain the system of the present invention, and these articles include soaps, bath or shower gels, cosmetic preparations, body deodorants, and even perfumes or colognes.
25 In the above-cited applications, the device of the present invention can be
used alone or with other perfuming ingredients, solvents and adjuvants of current use in the art. The nature and variety of these co-ingredients does not require a detailed description which, moreover could not be exhaustive, and a person skilled in the art will be able to choose said coingredients by his general knowledge and in function of the
30 nature of the product to be perfumed and the olfactive effect sought. These perfuming ingredients belong to such varied chemical classes as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogen- or sulfur- containing

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heterocyclic compounds, as well as essential oils of natural or synthetic origin. By way
of example, embodiments of compounds can be found in standard reference works, such
as the book of S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New
Jersey, USA, or more recent versions thereof, or in other works of similar nature.
5 The proportions in which the system of the present invention can be
incorporated in the various above-mentioned products vary within a wide range of values. These values depend on the nature of the fragrant compound to be released, the nature of the article or product which is to be perfumed and the desired olfactive effect, as well as on the nature of the co-ingredients in a given composition when the system of 10 the present invention is used in admixture with perfuming co-ingredients, solvents or adjuvants of current use in the art.
By way of example, one can cite typical concentrations of the order of 0.01
to 5%, or even 10% by weight relative to the weight of the consumer products cited
above into which it is incorporated. Higher concentrations than those mentioned above
15 can be used when the system is applied in perfuming compositions, perfumes or
colognes.
The invention will now be described in greater detail in the following
examples in which the temperatures are indicated in degrees centigrade and the
abbreviations have the usual meaning in the art. 20 Embodiments of the invention
General 25
The following chemicals were obtained from commercial sources : geraniol,
Polysantol ®, 2-benzoylbenzoate, dicyclohexylcarbodiimide (DCC), diisopropyl-
carbodiimide (DIC), 4-dimethylamino-pyridine, magnesium turnings, 2-iodoisopropyl
benzene, 1,3-diisopropylbenzene, A1C1,, 1,2-dichloroethane, 1,2-dibromoethane, 2-
30 norbornyl bromide, bromocyclopentane, citronellol, decanol, 4-methoxybenzyl alcohol,
Lilial ®, (-)-menthol, 2-pentylcyclopentanol, 4-(l,l-dimethylpropyl)-l-cyclohexanol, 1-
(2-naphthalenyl)ethanol, oxalyl chloride, diethyl oxalate, 3-methyl-2-oxo-pentanoic
acid, 2-oxopropionic acid, 2-oxobutanoic acid, bromocyclohexane, bromobenzene, 2-

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oxo-pentanoic acid, 4-bromo acetophenone, ethylene glycol, 2-bromo-tetradecane, 1-bromo-tetradecane.
Geranyl 2-benzoylbenzoate (1) was prepared as described by Porter et al., J. Org, Chem. 1996,67,9455-9461. 5
A. Execution of photorelease assays and analysis for 2-benzoyl benzoates and 2-alkanoyl benzoates
B. Photorelease Assays
10
Photorelease assays were conducted on solutions (typical concentrations = 0.005 to 0.01 M) or films of the respective esters in 10 ml borosilicate glass volumetric flasks (Pyrex ®) unless otherwise stated. The films were prepared by dissolving the ester in a small ( 15 drying under a stream of nitrogen or reduced pressure while rotating the flask to evenly disperse the ester on the surface of the glass. The samples were not degassed. The Fadeometer assays were done using an Atlas Ci35 Fadeometer, equipped with a borosilicate glass inner filter and a soda lime outer filter, set at 0.35 W/m2 at 340 nm. Natural light assays were done by putting the samples in a metal rack outdoors during
20 daylight hours. Natural light conditions could also be mimicked by using a 8W 366 nm UV lamp with an intensity of 500 μW/cm2 (VWR Scientific Products).
Analysis
25 After photolysis, the quantity of alcohol released was measured by GC analysis of duplicate samples using the alcohol as the external standard. The presence of photoreleased alcohol was checked using GC retention times, GC-MS and also by smelling the samples. The ester solutions were injected neat while the solid films were dissolved and diluted volumetrically to 10 ml in acetone. Samples (1 (μl, split 54:1,
30 injector at 250°C) were injected as acetone solutions. Gas chromatography-flame ionization detection (GC-FID) was carried out using an SPB-1 capillary column (30 m, 250 μm id. 0,25 μm film. Me carrier gas, 1.0 ml/min).

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Gas chromatography-mass spectrometry (GC-MS) was performed using an HP-5890 GC coupled to an HP 5989A mass spectrometer. The GC separation utilized an SPB-1 capillary column (30 m, 0,25 urn id, 0.25 μm film, He carrier gas, 1 ml/min). An SPB-1 column (30 m, 0,32 u.m id, 0.25 μm film, He carrier gas, 1.3 ml/min) was used 5 for the GC separation with the same temperature program used for the GC-MS. The samples (1 μ1, split 16:1, injector at 250°C) were injected as acetone solutions.
B. Execution of photorelease assays and analysis for a-keto esters
10 Photorelease Assays
Photorelease assays were conducted on solutions or on films of the respective ester and will be described below in each of the examples referring to the respective mode of irradiation. 15 All samples were irradiated using a xenon lamp (Heraeus Suntest CPS at 460W/m2), a UV lamp (UVP Model UVL-28, 8W at 360 nm) or exposed to outdoor sunlight, as will be indicated for each sample in the respective examples.
Analysis 20
The mode of analysis for each sample which had been irradiated will be indicated in
each respective example.
Analytical HPLC was carried out on a Spectra Physics instrument composed from a SP
8800 ternary pump, a SP 5750 injection valve, a SP 8780 autosampler, a Waters 490E 25 UV detector and a Spectra Physics ChromJet integratorMacherey-Nagel Nucleosil 5
Cjs reversed phase column (125 x4 mm i.d.) eluted with a gradient from
acetonitrile/water 1:1 to pure acetonitrile during 20 min. The injection volume was 50 μl
and the UV detector wavelength fixed at 220 nm.
Analytical GC for analysis of all-purpose/window cleaner applications : the on-column 30 injections were carried out on a Carlo Erba MFC 500 using a precolumn (30 cm) and a
Suppelco SPB-l capillary column (30 m) at 115°C for 8 min, then to 280°C, helium
pressure 75 kPa, injection volume 2 μl. All other GC analyses were carried out on the

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same instrument equiped with a Fisons AS 800 autosampler using a J& W Scientific DB1 capillary column (15 m) at 70 or 80°C for lOmin, then to 260°C, helium pressure 50 kPa, injection volume 0.5 μl. Analytical GC for dynamic headspace analysis : Tenax cartridges were thermally desorbed
5 in a PE ATD400 or a TDAS 5000 desorber. The volatiles were then analysed either with a Carlo Erba HRGC 5300 gas chromatograph coupled to Finnigan ITD-800 mass spectrometers using a Supelco SPB-1 capillary column (60 m, 0.75 mm i.d., film 1 micron) at 60°C for 5 min then to 120°C (3°C/min) and 280°C (5°C/min) for the citronellal analysis, and at 100°C then to 250°C (5°C/min) for the menthone quantification or,
10 alternatively, with a Carlo Erba Vega 6000 gas chromatograph using a Supelco SPB-1 capillary column (30 m, 0.53 mm i.d., film 1.5 micron) from 110°C to 200°C (6°C/min) using He as carrier gas in both cases.
Example 1
Preparation of substituted 2-benzoyl benzoates
a) Geranyl 2-(2'-isopropylbenzoyl)benzoate (2)
20 Magnesium (0.46 g, 19 mmol) and a crystal of iodine were placed in a dry round
bottom flask which was heated to activate the magnesium. Diethyl ether was added to cover the magnesium (50 ml) and several drops of 2-iodoisopropyl benzene in diethyl ether were added to start the preparation of the Grignard reagent. When the latter was underway, a solution of 2-iodoisopropyl benzene (4.18 g, 17 mmol) in
25 diethyl ether (20 ml) was added over 20 minutes. The reaction mixture was stirred
for another 15 minutes and then refluxed for 20 minutes. Phthalic anhydride (3.11 g, 21 mmol) in toluene (50 ml) was added dropwise to the Grignard reagent at room temperature. The reaction temperature was raised to 60°C and the diethyl ether removed by evaporation. The reaction was allowed to stir at 60°C for 6 hours.
30 The reaction mixture was poured on ice and 10% HC1 (100 ml) and extracted twice
with diethyl ether. The organic phase was washed twice with a 10% Na2CO3 solution (200 ml). The aqueous phase was acidified with acetic acid (120 ml) and

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extracted twice with diethyl ether (200 ml). The organic phase was washed three
times with NaHCO3(100 ml) and then twice with water. The ether phase was dried
over Na2S04, filtered and concentrated. The yield was 1.43 g (purity: 94.6%,
isolated yield : 31%) of 2-(2-isopropylbenzoyl)benzoic acid.
5 For esterification, a solution of the thus obtained acid (3.77 g, 10 mmol), geraniol
(1.4 g, 9 mmol) and 4-dimethylaminopyridine (DMAP, 0.244 g, 2 mmol) in
pyridine (15 ml) was prepared under anhydrous conditions. 1,3-
Dicyclohexylcarbodiimide (DCC, 2.06 g, 10 mmol) was added and the reaction was
stirred under a stream of nitrogen gas for 52 hours. The reaction mixture was
10 partitioned between IM HCl and ethyl acetate. The organic extract was dried over
Na2S04, filtered and concentrated under vacuum. The ester product was purified by flash column chromatography (Si02, 7:1 cyclohexane:ethyl acetate ; isolated yield : 0.7 g, 48%) to give the following analytical data :
UV (cyclohexane) 240 (ε 13 000), 280 (ε 5 000);
'H-NMR (360MHz, CDC13) 8 (ppm) : 7.85 (m, 1H); 7.49 (m, 4H); 7.38 (m, 1H); 7.23 (dd, 1H, J=l, 8Hz); 7.12 (m, 1H); 5.21 (1H, m); 5.05 (1H, m); 4.65 (1H, d, J=7Hz); 3.70 (1H, m); 2.00 (4H, m); 1.66 (3H, br s); 1.63 (3H, br s); 1.58 (3H, br s); 1.28 (6H, d, J=7Hz)
20 13C NMR (90MHz, CDC13) 5 (ppm) : 198.7(s), 167.2(s), 150.1(s), 142.5(s),
142.1(s), 136.7(s), 131.6(d), 131.1(d), 130.6(d), 130.3(d), 129.5(d), 129.0(d), 126.4(d), 124.9(d), 123.8(d), 117.8(d), 62.4(t), 39.5(t), 29.3(d), 26.3(t), 24.1(q), 17.7(q), 16.5(q).
25 b) Geranyl 2-(2',4'-diisopropylbenzoyl)benzoate (3)
Phthalic anhydride (19.3 g, 0.13 mol) was placed in a flame-dried three-neck round-
bottom flask under nitrogen. 1,2-Dibromoethane (100 ml) and aluminum chloride
(36.0 g, 0.27 mol) were added. The reaction solution was stirred at room
30 temperature while 1,3-diisopropylbenzene (20.4 g, 0.126 mol) was added dropwise
over the space of an hour. The reaction mixture was stirred at 100°C for two hours. Upon completion, the reaction mixture was cooled to room temperature and poured

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over ice/hydrochloric acid (1:1). The solution was extracted twice with
dichloromethane. The organic extract was washed with saturated aqueous sodium
chloride solution to neutrality, dried over anhydrous sodium sulfate, filtered and
concentrated under vacuum to yield a heavy brown oil of 80% purity (isolated
5 yield = 36 g, % yield = 74%). The thus obtained 2-(2',4'-diisopropylbenzoyl)
benzoic acid showed the following analytical characteristics :
lR: (neat), 2965, 1695, 1670, 1605 cm1lH NMR (360 MHz, CDC13) 5 ppm : 7.98 (1H, dd, J= 1, 8 Hz), 7.59 (1H, m), 7.52
10 (1H, m), 7.37 (1H, dd,J= 1,8 Hz), 7.31 (1H, d,J = 1.2 Hz), 7.09 (1H, d,J= 8
Hz), 6.94 (1H, dd,J= 2, 8 Hz), 3.82 (1H, m), 2.91 (1H, m), 1.25 (12H, m);
13C NMR (90 MHz, CDCI3) 8ppm : 198.6 (s), 170.9 (s), 153.2 (s), 151.0 (s),
143.8 (s), 133.9 (s), 132.3 (d), 131.7 (d), 130.6(d), 129.8 (d), 128.9 (s), 128.7
(d), 125.0 (d), 122.7 (d), 34.3 (d), 29.0 (d), 24.1 (q), 24.1 (q), 23.7 (q), 23.7 (q);
15 LREIMS: m/z (relative abundance) 310 (5, M+), 265 (43), 249 (45), 221 (100), 149
(32), 84 (41), 49 (35).
The thus obtained product (1.15 g, 3.7 mmol) was dissolved in dry pyridine (10 ml) in a flame-dried three-neck round-bottom flask. To the solution were added geraniol
20 (freshly distilled, 0.55 g, 3.6 mmol), 4-dimethylaminopyridine (DMAP, 0.10 g,
0.8 mmol) and 1,3-dicyclohexylcarbodiimide (DCC, 0.76 g, 3.7 mmol). The reaction mixture was stirred at room temperature overnight. When complete, the reaction mixture was poured onto shaved ice (20 g), 32% hydrochloric acid (24 g) and ethyl acetate (30 ml) and stirred vigorously for 10 minutes. The solution was
25 extracted twice with diethyl ether and the organic phase was washed twice with
saturated aqueous sodium bicarbonate solution and twice with water. The organic phase was dried over anhydrous sodium sulfate and concentrated under vacuum. The product was purified by redissolving in pentane, crystallizing at 4°C, and filtering through Celite. The filtered solution was concentrated under vacuum and
30 purified further by normal phase silica gel chromatography (20% diethyl
ether/heptane). Geranyl 2-(2'-4'-diisopropylbenzoyl)benzoate was isolated as a pale

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yellow oil (isolated yield = 1.08 g, % yield =74.5%), having the following analytical data:
1H NMR (360 MHz, CDC13) 5 ppm : 7.76 (1H, dd, J= 3, 6 Hz), 7.51 (2H, m), 7.37
5 (1H, dd, J- 3, 6 Hz), 7.31 (1H, d, J = 2 Hz), 7.18 (1H, d, J= 8 Hz), 6.97 (1H,
dd, J= 2, 8 Hz), 5.22 (1H, m), 5.04 (1H, m), 4.64 (2H, d,J= 7 Hz), 3.79 (1H,
m), 2.92 (1H, m), 2.1-1.9 (4H, m), 1.74 (3H, br s), 1.62 (3H, br s), 1.58 (3H, br
s), 1.28 (6H, d, J= 7 Hz), 1.25 (6H, d, J= 7 Hz);
l3C NMR (90 MHz, CDCI3) 5 ppm : 198.5 (s), 167.2 (s), 152.9 (s), 150.6 (s),
10 142.7 (s), 142.4 (s), 134.1 (s), 131.7 (s), 131.2 (s), 131.6 (d), 131.1 (d), 129.9
(d), 129.6 (d), 128.7 (d), 124.7 (d), 123.8 (d), 122.8 (d), 117.9 (d), 62.3 (t), 39.5
(t), 34.3 (d), 29.2 (d), 26.3 (t), 25.7 (q), 24.1 (q), 24.1 (q), 23.7 (q), 23.7 (q),
17.7 (q), 16.4 (q);
LREIMS: m/z (relative abundance) 446 (M+, 15 231 (28), 221 (49), 149 (52), 93 (34), 69 (55), 41 (53).
c) (E)-3,3-dimethyl-5-(2,,2,,3'-trimethyl-3'-cyclopenten-l,-yl)-4-penten-2-yl 2-(2',4'-diisopropylbenzoyl)benzoate (4)
20 2-(2',4'-Diisopropylbenzoyl)benzoic acid (0.3114 g, 1.0 mmol) was dissolved in dry
pyridine (2 ml) in a flame-dried round bottom flask. To the solution were added Polysantol® (0.2113 g, 0.95 mmol), 4-dimethylaminopyridine (DMAP) on polystyrene resin (0,168 g, 0.34 mmol) and 1,3-diisopropylcarbodiimide (DIC, 120 ul, 1.4 mmol). The reaction mixture was stirred at room temperature under an
25 atmosphere of dry nitrogen for 68 hours. The reaction mixture was filtered, and
partitioned between 0.5M aqueous hydrochloric acid and ethyl acetate. The organic phase was washed a second time with 0.5M hydrochloric acid, then once with 10% aqueous sodium carbonate solution. The ethyl acetate solution was washed with saturated, aqueous sodium bicarbonate solution and finally with water. The organic
30 phase was dried over anhydrous sodium sulfate, filtered and concentrated under
vacuum. The resulting ester was purified by normal phase silica gel chromatography (2% ethyl acctate/cyclohexane) to yield a 1:1 mixture of two

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stereoisomers in the form of an oil (isolated yield = 0.14 g, % yield = 27%) which showed the following analytical data :
IR: (neat) 2960, 1720, 1675 cm"1,
5 'H NMR (360 MHz, CDC13) 8ppm : 7.83 (m, 1H), 7.52 (m, 2H), 7.39 (m, 1H),
7.30 (d, 1H, J = 1 Hz), 7.12 (dd, 1H, J = 2, 8 Hz), 6.94 (dd, 1H, J = 2, 8 Hz),
5.39 (2H, m), 5.21 (1H, m), 4.82 (1H, m), 3.83 (1H, m), 2.90 (1H, m), 2.26
(1H, m), 2.17 (1H, m), 2.03 (1H, m)J.59 (3H, br d, J- 1 Hz), 1.30 (6H, d,J =
7 Hz), 1.24 (6H, d, J= 7 Hz), 0.99, 0.99 (311, d, J= 6 Hz), 0.97, 0.95 (6H, br
10 s), 0.90, 0.87 (3H, s), 0.69, 0.69 (3H, s);
13C NMR (90 MHz, CDCI3) 5 ppm : 198.5 (s), 166.5 (s), 152.8 (s), 150.8 (s), 148.1
(s), 143.0 (s), 136.7 (s), 136.6 (s), 134.3 (s), 131.9 (s), 131.5 (d), 131.0 (d),
129.8 (d), 129.5 (d), 129.5 (d), 129.3 (d), 128.8 (d), 124.8 (d), 122.6 (d), 121.5
(d), 78.3 (d), 78.2 (d), 54.3 (d), 48.1 (s), 48.1 (s), 39.9 (s), 35.5 (t), 34.4 (d),
15 29.1 (d), 25.4 (q), 24.2 (q), 24.2 (q), 23.7 (q), 23.7 (q), 23.4 (q), 23.2 (q), 20.5
(q), 14.8 (q), 14.7 (q), 12.7 (q);
Nanospray MS: m/z (relative abundance) 537.4 ([M + Na]+, 100), 515.2 ([M + H]+, 2).
20 Example 2
Preparation of ά -keto esters
25 The bis(3,7-dimethyl-6-octenyl)oxalate which was used for the synthesis of some of the ά -keto esters described below was prepared as follows.
Oxalyl chloride (10 ml, 116 mmol) was added dropwise to a stirred solution of 36.37 g (233 mmol) of citronellol in 300 ml of pyridine at 0°C over a period of 30 min. The formation of a white precipitate was observed. The solution was allowed to warm up at
30 room temperature over night and was quenched with water, extracted with diethyl ether (2x), H2S04 (10%) (2x), NaHC03 (10%) and saturated NaCl. The organic layer was dried over NUTS04, concentrated at reduced pressure and filtered over a short plug

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(SiO2, heptane/diethyl ether). Column chromatography (SiO2, heptane/diethyl ether) gave 18.55 g (43%) of a colorless oil.
IR (neat): 2965s, 2925$, 2873m, 2856m, 1770s, 1745s, 1457m, 1380m, \347w, 1312m,
5 1250w, 1170s, 1122w, 1044w, 941m, 886w, 83\w, 792w, 756w, 742w.
'H NMR (360 MHz, CDC13): 5.13-5.04 (m, 1 H); 4.40-4.23 (m, 2 H); 2.08-1.87 (m, 2
H); 1.85-1.71 (m, 1 H); 1.70-1.50 (m, 2 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43-1.29
(m, 1 H); 1.29-1.13 (m, 1 H); 0.94 (d, J =6.3, 3 H).
13C NMR (90.6 MHz, CDC13): 158.04 (s); 131.45 (s); 124.42 (d); 65.59 (/); 36.91 (/);
io 35.08 (0; 29.42 (d); 25.70 (q); 25.36 (/); 19.36 (q); 17.65 (q).
MS (EI): 336 (M+, 0.1); 228 (0.1); 183 (0.1); 165 (0.1); 138 (18); 123 (30); 109 (16); 95 (38); 81 (51); 69 (100); 55 (30); 41 (46); 29 (5).
a) 3,7-Dimethyl-6-octenyl-2-oxopropanoate (5)
15 A stirred solution of 5.56 g (63 mmol) of 2-oxo propionic acid and 19.68 g
(126 mmol) of citronellol in 150 ml of toluene was heated for 35 h under reflux with azeotropic removal of water. After cooling to room temperature the reaction mixture was extracted with diethyl ether (2x), 10% NaHC03, sat. NaCl, dried (Na2S04) and concentrated in vacuo. Column chromatography (SiCO2, pentane/ether
20 9:1) afforded 2.81 g (20%) of a colorless oil.
UV/Vis (hexane): 388 (sh, 3); 378 (sh, 5); 369 (sh, 8); 360 (sh, 10); 345 (14); 334
(14);319(sh, 12); 284 (sh, 9).
IR (neat): 2961m, 2915m, 2873m, 2856m, 1728s, 1454m, 1378m, 1357m, 1297m,
251266m, 1203w, 1134s, 1051m, 1024w, 982m, 937m, 830m, 771w, 720m, 663w.
'H NMR (360 MHz, CDC13): 5.15-5.03 (m, 1 H); 4.37-4.18 (m, 2 H); 2.47 (s, 3 H);
2.10-1.88 (m, 2 H); 1.87-1.71 (m, 1 H); 1.71-1.47 (m, 2 H); 1.68 (s, 3 H); 1.60
(s, 3H); 1.46-1.28 (m, 1 H); 1.28-1.12 (m, 1 H); 0.94 (d, J= 6.3, 3 H).
I3C NMR (90.6 MHz, CDC13): 191.96 (s); 160.92 (s); 131.52 (s); 124.37 {d)\ 65.06
30(/); 36.89 (/); 35.14 (0; 29.39 (d); 26.73 (4); 25.71 (q); 25.33 (0; 19.36 (q);
17.66 (^).

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MS (EI): 226 (M+, 3); 209 (1); 208 (5); 198 (1), 184 81); 183 (9); 165 (2); 156 (1);
155 (14); 139 (1); 138 (15); 137 (20); 136 (1); 124 (3); 123 (29); 121 (3); 111
(1); 110 (5); 109 (20); 99 (1); 97 (2); 96 (8); 95 (45); 94 (2); 93 (1); 91 (1); 90
(1); 84 (1); 83 (15); 82 (28); 81 (51); 80 (2); 79 (2); 77 (1); 71 (1); 70 (10); 69
5 (100); 68 (14); 67 (23); 66 (1); 65 (2); 57 (5); 56 (8); 55 (34); 54 (2); 53 (7); 44
(1); 43 (41); 42 (5); 41 (40); 40 (2); 39 (6); 29 (4); 27 (3).
b) 3,7-Dimethyl-6-octenyl-2-oxobutanoate (6)
The synthesis was carried out as described above under a) with 6.43 g (63 mmol) of
10 2-oxo butyric acid, 19.68 g (126 mmol) of citronellol and 150 ml of toluene (24 h).
Column chromatography (SiO2, pentane/ether 9:1) afforded 7.80 g (52%) of a colorless oil.
UV/Vis (hexane): 397 (sh, 1); 383 (sh, 3); 373 (sh, 6); 356 (sh, 12); 341 (16); 330
15 (16); 318 (sh, 14); 268 (sh, 12).
IR (neat): 2961m, 2914m, 2879m, 2857m, 1725s, 1456m, 1404w, 1379m, 1351w,
1273m, 1242m, 1173w, 1144m, 1097s, 1041m, 982m, 946w, 88 lw, 830m,
760w, 737w, 700m, 678m.
>H NMR (360 MHz, CDC13): 5.14-5.02 (m, 1 H); 4.40-4.20 (m, 2 H); 2.86 (q, J =
20 7.3, 2 H); 2.09-1.88 (m, 2 H); 1.87-1.68 (m, 1 H); 1.68 (s, 3 H); 1.68-1.45 (m, 2
H); 1.60 (s, 3 H); 1.45-1.29 (m, 1 H); 1.29-1.15 (m, 1 H); 1.13 (/, J= 7.1, 3 H);
0.94 (4 J= 6.3, 3 H).
'3C NMR (90.6 MHz, CDC13): 195.09 (s); 161.32(5); 131.51 (s); 124.40 (d); 64.87
(0; 36.90 (/); 35.17 (/); 32.89 (t); 29.40 (d); 25.71 (q); 25.34 (/); 19.37 (?);
25 17.66(g); 6.97 (q).
MS (EI): 240 (MM); 222 (3); 212 (2); 184(1); 183(8); 165(1); 156(1); 155(12);
139(3); 138(20); 137(15); 136(1); 124(3); 123 (31); 121 (3); 111 (2); 110
(4); 109 (16); 104 (2); 99 (1); 97 (3); 96 (9); 95 (43); 94 (3); 93 (2); 91 (1); 85
(1); 84 (2); 83 (17); 82 (31); 81 (51); 80 (3); 79 (2); 77 (1), 71 (1); 70 (8); 69
30 (100); 68 (13); 67 (19); 66 (1); 65 (2); 58 (2); 57 (63); 56 (7); 55 (30); 54 (2);
53 (6); 43 (6); 42 (4); 41 (38); 40 (1); 39 (5); 29 (17); 28 (2); 27 (5).

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c) 3,7-Dimethyl-6-octenyl 3-methyl-2-oxopentanoate (7)
The synthesis was carried out as described above under a), using 4.85 g (38 mmol)
of 3-methyl-2-oxo pentanoic acid and 11.66 g (74 mmol) of citronellol in 130 ml of
toluene, for 72 h. Column chromatography (Si02, toluene/EtOAc) afforded 10 g of
5 crude product, which was fractionally distilled to give 3.65 g (36%) of a colorless
oil.
B.p. 94°C/2xlO'Pa.
UV/Vis (hexane): 394 (sh, 4), 382 (sh, 10), 374 (sh, 10), 365 (sh, 10), 350 (sh, 20),
10 336 (20), 268 (sh, 30), 241 (sh, 180).
1R (neat): 2966s, 2929s, 2877m, 1749m, 1728s, 1460m, 1380m, 1267m, 1254m,
1165m, 1115w, 1087w, 1051m, lOOlw, 961w, 829w.
1H NMR (360 MHz, CDC13): 5.12-5.04 (m, 1 H); 4.36-4.24 (m, 2 H); 3.18-3.06 (m,
1 H); 2.08-1.88 (m, 2 H); 1.86-1.67 (m, 2 H); 1.68 (s, 3 H); 1.65-1.10 (m, 5 H);
15 1.60 (s, 3 H); 1.28 (d,J= 6.8, 3 H); 0.94 (d,J= 6.4, 3 H); 0.92 (/, J= 7.6, 3 H).
I3C NMR (90.6 MHz, CDC13): 198.22 (s); 162.21 (s); 131.51 (s); 124.40 (d); 64.74
(0; 43.64 (d); 36.92 (0; 35.23 (/); 29.43 (d); 25.71 (q); 25.36 (/); 24.93 (/);
19.35 (q); 17.66 (q); 14.55 (q); 11.35 (q).
MS (EI): 268 (M+, 1); 250 (1); 240 (1); 207 (1); 183 (2); 155 (2); 138 (10); 123
20 (14); 109 (7); 95 (18); 85 (32); 81 (26); 69 (51); 57 (100); 41 (53); 29 (18).
d) 3,7-Dimethyl-6-octenyl 2-oxopentanoate (8)
The synthesis was carried out as described above under a), using 4.33 g (37 mmol)
of 2-oxo pentanoic acid and 11.65 g (75 mmol) of citronellol. Column
25 chromatography (SiCO2, toluene/EtOAc and SiCO2, heptane/diethyl ether) afforded
3.79 g of crude product, which was distilled (Kugelrohr) to give 2.52 g (27%) of a colorless oil.
UV/Vis (hexane): 398 (sh, 1), 376 (sh, 10), 357 (sh, 10), 342 (sh, 20), 331 (20), 281
30 (sh, 20), 268 (sh, 30), 241 (sh, 280).
IR (neat): 2965.V, 2931s, 2877m, 1750m, 1728s, 1457m, 1380m, 1287w, 1261m. 1 178»v, 1 146M\ 1118m, 1055m, 1037iv, 943vr, 832vr.

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1H NMR (360 MHz, CDC13): 5.13-5.03 (m, 1 H); 4.36-4.21 (m, 2 H); 2.80 (t,J = 7.1, 2 H); 2.10-1.89 (m, 2 H); 1.83-1.70 (m, 1 H); 1.68 (s, 3 H); 1.67 (q,J= 7.3, 2H); 1.63-1.47 (m, 2 H); 1.60 (s, 3 H); 1.45-1.29 (m, 1 H); 1.28-1.12 (m, 1 H); 0.96 (t,J= 6.9, 3 H); 0.94 (d, J= 6.3, 3 H).
5 13C NMR (90.6 MHz, CDC13): 194.63 (s); 161.44 (s); 131.52 (s); 124.40 (d); 64.88
(/); 41.21 (0; 36.91 (0; 35.19 (/); 29.43 (d); 25.71 (q); 25.35 (/); 19.37 (q);
17.67 (q); 16.54(0; 13.52 (q).
MS (EI): 254 (M+, 1); 236 (2); 226 (1); 193 (1); 183 (6); 165 (1); 155 (7); 138 (15);
137 (10); 123 (26); 118 (3); 109 (17); 95 (41); 83 (15); 82 (32); 81 (54); 71
10 (87); 69 (100); 67 (23); 55 (34); 43 (66); 41 (72); 27 (14).
e) 3,7-Dimethyl-6-octenyl oxo(phenyl)acetate (9)
A Grignard reagent prepared from 3.14 g of 1-bromobenzene (20 mmol) and 0.55 g of magnesium (22 mmol) in THF was added dropwise to a stirred solution of 8.0 g
15 (22 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate in 50 ml of THF at -78°C. The
mixture was slowly warmed to -10°C, quenched with 25-30 ml of a saturated solution of NH4CI and left stirring for 30 min. The reaction mixture was extracted with diethyl ether and water (3x) and the organic phase dried over Na2S04. MPLC on a Lobar column (Si02 Merck, heptane/diethyl ether) afforded 3.5 g (61%) of the
20 pure product as a bright yellow oil.
UV/Vis (hexane): 370 (sh, 30), 352 (40), 340 (sh, 40), 294 (sh, 1020), 252 (10350),
248 (10360).
1R (neat): 3065w, 2962s, 2926s, 2872m, 2855m, 1738s, 1693s, 1597m, 1581m,
25 1451m, 1379m, 1322m, 1313m, 1300m, 1246w, 1198s, 1175s, 1122w, 1042w,
1030w, 1003m, 998m, 94 lw, 83 lw.
1H NMR (360 MHz, CDC13): 8.04-7.97 (m, 2 H); 7.69.7.62 (m, 1 H); 7.55-7.45 (m,
2 H); 5.12-5.03 (m, 1 H); 4.50-4.36 (m, 2 H); 2.15-1.90 (m, 2 H); 1.90-1.75 (m,
1 H); 1.75-1.50 (m, 2 H); 1.66 (s, 3 H); 1.59 (s. 3 H); 1.45-1.32 (m, 1 H); 1.32-
30 1.15 (m, 1 H); 0.96 (d, J =6.3, 3 H).

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l3C NMR (90.6 MHz, CDC13): 186.50 (s); 164.02 (s); 134.87 {d)\ 132.56 (s);
131.51 (s); 130.02 {d); 128.90 {d)\ 124.40 (rf); 64.85 (/); 36.93 (0; 35.30 (0;
29.44 id); 25.69 (q); 25.38 (/); 19.38 (q); 17.66 (q).
MS (EI): 288 (M+, 1); 270 (4); 260 (1); 227 (1); 215 (1); 187 (1); 183 (1); 174 (1);
5 165 (1); 155 (4); 152 (3); 138 (9); 137 (10); 134 (2); 123 (11); 109 (8); 106
(10); 105 (100); 96 (3); 95 (20); 83 (3); 82 (12); 81 (24); 80 (2); 78 (3); 77 (36); 70 (3); 69 (26); 68 (5); 67 (10); 57 (3); 56 (3); 55 (11); 53 (3); 51 (10); 43 (4); 42 (3); 41 (28); 39 (5); 29 (4); 27 (4).
10 f) 3,7-Dimethyl-6-octenyl (4-acetylphenyl)oxoacetate (10)
In the first step, 2-(4-bromomethyl)-2-mefhyl-l,3-dioxolane was prepared as follows. 10.0 g (50 mmol) of 4-bromo acetophenone, 7.0 g (112 mmol) of ethylene glycol and a few crystals of p-toluene sulphonic acid were dissolved in 100 ml of toluene and heated overnight under reflux with azeotropic removal of water. After
15 cooling to room temperature the reaction mixture was concentrated in vacuo.
Column chromatography (SiC>2, heptane/diethyl ether) afforded 11.4 g (93%) of a colorless oil which easily crystallized.
UV/Vis (hexane): 287 (sh, 400), 274 (sh, 1300), 270 (sh, 1800), 259 (sh, 6700), 252
20 (7800), 227 (sh, 61800), 220 (75600), 217 (sh, 75000).
IR (neat): 3084w, 3060w, 2990m, 2957s, 2928s, 2890s, 2856m, 2670w, 191 lw,
1691m, 1657w, 1591m, 1575w, 1482m, 1470w, 1443m, 1393m, 1373m, 1249m,
1222w, 1196s, 1144m, 1118m, 1092m, 1079m, 1040s, 1010s, 947m, 873s,
826s.
25 lH NMR (360 MHz, CDC13): 7.49-7.42 (m, 2 H); 7.39-7.32 (m, 2 H); 4.08-3.96 (m,
2 H); 3.80-3.69 (m, 2 H); 1.62 (s, 3 H). 13C NMR (90.6 MHz, CDC13): 142.49 (s); 131.30 (d); 127.17 (d); 121.86 (s);
108.43 (s); 64.47(/); 27.52 {q).
MS (EI): 244, 242 (M\ 1, 1); 230 (14); 229 (97); 227 (100); 213 (5); 211 (5); 186
30 (4); 185, 183 (51, 53); 171 (2); 169 (2); 157, 155 (14, 14); 148 (4); 133 (5); 105
(2); 104 (8); 103 (9); 102 (8); 101 (2); 89 (3); 87 (26); 78 (2); 77 (12); 76 (16); 75 (14); 74 (7); 73 (2); 63 (4); 62 (2); 51 (7); 50 (13); 43 (41); 39 (3); 29 (7).

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The thus obtained compound was then used as starting product for the synthesis of
3,7-dimethyl-6-octenyl [4-(2-methyl-l ,3-dioxolan-2-yl)phenyl]oxoacetate. The
synthesis was carried out as described above under e), using 4.66 g (20 mmol) of
5 the above-prepared dioxolane, 0.54 g (22 mmol) of magnesium and 8.0 g
(22 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate. Column chromatography (Si02, heptane/diethyl ether) afforded 4.35 g (58%) of the product as a slightly yellow oil.
UV/Vis (hexane): 370 (sh, 40), 353 (60), 340 (sh, 60), 296 (sh, 1300), 258 (13890).
10 1R (neat): 2963s, 2926s, 1736s, 1690s, 1607s, 1573m, 1505vv, 1455m, 1407m,
1374m, 1347w, 1314m, 1294w, 1250m, 1199s, 1175s, 1146w, 1122w, 1100w,
1078m, 1039m, 1018w, 989m, 948w, 890w, 876m, 861m, 833w.
1H NMR (360 MHz, CDC13): 7.98 (d,J= 8.3, 2 H); 7.62 {d, J = 8.7, 2 H); 5.12-
5.04 (m, 1 H); 4.50-4.36 (m, 2 H); 4.13-4.00 (m, 2 H); 3.82-3.70 (m, 2 H); 2.10-
15 1.90 (m, 2 H); 1.90-1.75 (w, 1 H); 1.72-1.54 (m, 2 H); 1.67 (s, 3 H); 1.65 (s, 3
H); 1.60 (s, 3 H); 1.45-1.32 (m, 1 H); 1.30-1.16 (m, 1 H); 0.96 (d, J= 6.3, 3 H).
13c NMR (90.6 MHz, CDCI3): 186.04 (s); 163.97 (s); 150.64 (s); 132.12 (s);
131.53 (s); 130.15 (d)\ 125.97 (d); 124.39 (d); 108.39 (s); 64.89 (0; 64.65 (2x)
(0; 36.93 (0; 35.30 (/); 29.44 (d); 27.38 (q); 25.70 (q); 25.37 (0; 19.38 (q);
20 17.66 (q).
MS (EI): 374 (M+, 7); 359 (8); 356 (3); 289 (1); 220 (2); 205 (1); 192 (32); 191 (100); 176 (2); 160 (2); 155 (2); 148 (24); 138 (16); 133 (6); 123 (14); 119 (76); 109 (9); 104 (15); 95 (22); 91 (8); 87 (18); 81 (30); 69 (26); 55 (10); 43 (12); 41 (21); 29 (3). 25
3,7-Dimethyl-6-octenyl (4-acetylphenyl)oxoacetate (10)
5 ml of H2SO4 (50%) were added to a solution of 4.2 g (13 mmol) of the product
obtained in the above step in 30 ml of THF. The reaction mixture was heated at
40°C for 5 h, then extracted with diethyl ether (2x), and saturated solutions of
30 NaHC03 (2x) and NaCl (2x). The organic layer was dried over Na2S04 and
concentrated. Column chromatography (SiO2, heptane/diethyl ether) yielded 2.0 g (47%) ofa yellow oil.

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UV/Vis (hexane): 384 (sh, 60), 367 (sh, 100), 343 (sh, 150), 310 (sh, 1230), 301
(sh, 1660), 266 (17910), 260 (18440).
IR (neat): 305 lw, 2964s, 2926s, 2872m, 2856m, 1736s, 1693s, 1607w, 1570m,
5 1500m, 1457m, 1434m, 1407m, 1379m, 1359m, 1318m, 1307m, 1260s, 1199s,
1176s, 1117w, 1075m, 992s, 959m, 861m, 832m.
1H NMR (360 MHz, CDC13): 8.17-8.02 (m, 4 H); 5.12-5.04 (m, 1 H); 4.53-4.37 (m,
2 H); 2.66 (s, 3 H); 2.14-1.90 (m, 2 H); 1.90-1.75 (m, 1 H); 1.73-1.53 (m, 2 H);
1.67 (s, 3 H); 1.60 (s, 3 H); 1.46-1.32 (m, 1 H); 1.32-1.12 (m, 1 H); 0.96 (d,J =
10 6.3, 3 H).
13C NMR (90.6 MHz, CDC13): 197.19 (s); 185.55 (s); 163.25 (s); 141.33 (s);
135.67 (s); 131.57 (s); 130.28 (d); 128.56 (d); 124.34 (d); 65.19 (0; 36.91 (t);
35.26 (0; 29.43 (d); 26.94 (9); 25.70 (q); 25.35 (/); 19.37 (q); 17.67 (q).
MS (EI): 330 (M+, 4); 312 (1); 302 (1); 281 (1); 269 (1); 194 (4); 193 (2); 183 (1);
15 176 (2); 165 (1); 161 (1); 155 (2); 149 (5); 148 (43); 147 (100); 138 (4); 137
(11); 133(1); 132(2); 123 (10); 120(4); 119(11); 110(2); 109 (10);105 (2); 104 (12); 96 (4); 95 (21); 91 (15); 83 (5); 82 (13); 81 (29); 77 (6); 76 (8); 69 (38); 68 (5); 67 (11); 65 (3); 57 (3); 56 (3); 55 (12); 53 (3); 50 (3); 43 (15); 41 (30); 39 (5); 29 (4); 27 (3). 20
g) 3,7-Dimethyl-6-octenyl 3-methyI-2-oxopentadecanoate (11)
The compound was prepared as described above under e), using 5.0 g (18 mmol) of
2-bromotetradecane, 0.58 g (24 mmol) of magnesium and 7.32 g (20 mmol) of
bis(3,7-dimethyl-6-octenyl)oxalate. Column chromatography (SiCO2, heptane/
25 diethyl ether) afforded 2.52 g (34%) of a colorless oil.
UV/Vis (hexane): 394 (sh, 4), 383 (sh, 10), 373 (sh, 10), 365 (sh, 20), 349 (sh, 20),
336 (20), 284 (sh, 10), 269 (sh, 20), 241 (sh, 140).
IR (neat): 3440w, 2958s, 2924s, 2854s, 2730w, 1749s, 1725s, 1460m, 1378m,
30 1350w, 1266m, 1173w, 1146w, 11 \2w, 1053m, 1032m, 943w, 887w, 830w.
]H NMR (360 MHz, CDCI3): 5.13-5.04 (m, 1 II); 4.36-4.23 (m, 2 H); 3.23-3.10 (m, 1 H); 2.10-1.87 (/», 2 H); 1.87-1.64 (m, 1 H); 1.68 (.v, 3 H); 1.64-1.47 (m. 2 H);

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1.60 (s, 3 H); 1.46-1.16 (m, 24 H); 1.13 (d,J = 6.7, 3 H); 0.94 (d,J=6.3, 3 H);
0.88 (t,.J= 6.9, 3 H). 13C NMR (90.6 MHz, CDC13): 198.33 (s); 162.20 (s); 131.50 (s); 124.40 (d);
64.75 (t); 42.21 (d); 36.93 (t); 35.23 (t); 31.92 (t); 29.68 (t); 29.66 (2x) (0; 5 29.59 (2x) (0; 29.45 (2x) (t); 29.37 (t); 27.01 (0; 25.71 (q); 25.37 (0; 22.70 (0;
19.35 (q); 17.66 (q); 15.01 (q); 14.12 (q). MS (EI): 408 (M+, 1); 390 (1); 380 (1); 347 (1); 294 (1); 272 (1); 255 (4); 205 (1);
197 (3); 184 (2); 183 (12); 165 (1); 155 (8); 141 (4); 139 (9); 138 (76); 137
(21); 127 (7); 123 (46); 113 (9); 109 (19); 99 (15); 96 (15); 95 (57); 94 (8); 85 10 (47); 83 (25); 82 (52); 81 (89); 80 (14); 71 (65); 70 (10); 69 (100); 68 (10); 67
(18); 57 (94);56 (17); 55 (51); 43 (61); 41 (69); 39 (7); 29 (15); 27 (6).
h) 3,7-Dimethyl-6-octenyl 2-oxohexadecanoate (12)
The compound was prepared as described above under e), using 5.54 g (20 mmol)
15 of 1-bromotetradecane, 0.54 g (22.5 mmol) of magnesium and 8.0 g (22 mmol) of
bis(3,7-dimethyl-6-octenyl)oxalate. Column chromatography (SiO2, heptane/ diethyl ether) afforded 3.21 g (39%) of a colorless oil.
UV/Vis (hexane): 376 (sh, 10), 359 (sh, 20), 343 (sh, 20), 279 (260), 272 (sh, 250),
20 242 (530).
IR (neat): 2958m, 2924s, 28545, 1728s, 1465m, 1458m, 1400w, 1378m, 1271m,
1128w, 1088w, 1062m, 945w, 831 w.
»H NMR (360 MHz, CDC13): 5.12-5.03 (m, 1 H); 4.35-4.21 (m, 2 H); 2.81 (t, J =
7.3, 2 H); 2.09-1.88 (m, 2 H); 1.87-1.69 (m, 1 H); 1.68 (s, 3 H); 1.69-1.47 (m, 2
25 H); 1.60 (s, 3 H); 1.45-1.14 (m, 26 H); 0.94 (d, J= 6.3, 3 H); 0.88 (/, J= 6.9, 3
H). 13C NMR (90.6 MHz, CDCI3): 194.77 (s); 161.48 (s); 131.49(5); 124.41 (J); 64.86
(t); 39.38 (/); 36.93 (t/); 35.20 (t); 31.96 (0; 29.68 (3x) (t); 29.61 (t); 29.45 (2x)
(t); 29.39 (t); 29.33 (t); 29.01 (t); 25.71 (q); 25.37 (t); 23.05 (0; 22.71 (t); 19.38
30 (q); 17.66 fa); 14.12 (q).
MS (EI): 390(1), 225(11), 183(14), 165(1), 155(8), 139(7), 138(55), 137(28),
124(6), 123 (52), 121 (5), 111 (4), 110(7), 109 (27), 97 (9), 96 (16), 95 (70),

WO 99/60990 PCT/IB99/0089094 (8), 85 (16), 83 (28), 82 (50), 81 (97), 80 (10), 71 (26), 70 (11), 69 (100), 68
(11), 67 (21), 57 (54), 56 (12), 55 (47), 43 (48), 42 (10), 41 (55), 39 (7), 29
(12).
5 i) 3,7-Dimethyl-6-octenyl (cyclohexyl)oxoacctate (13)
The compound was prepared as described above under e), using 3.24 g (20 mmol) of freshly distilled 1-bromocyclohexane, 0.55 g (22 mmol) of magnesium and 8.0 g (22 mmol) of bis(3,7-dimethyl-6-octenyl)oxalate. MPLC on a Lobar column (SiCO2 Merck, heptane/diethyl ether) finally afforded 1.69 g (29%) of the pure product as a
10 colorless oil.
UV/Vis (hexane): 394 (sh, 4), 375 (sh, 11), 366 (sh, 14), 350 (sh, 18), 338 (19). IR (neat): 2932s, 2856m, 1747m, 17275, 1451m, 1379m, 131 \w, 1276m, 1230m,
1183w, 1173w, 1140m, 1118w, 1082m, 1067m, 1050w, 1029w, 997m, 942w,
15 895w, 837w.
'H NMR (360 MHz, CDC13): 5.12-5.04 (m, 1 H); 4.36-4.22 (m, 2 H); 3.07-2.95 (m,
1H); 2.09-1.85 (m,4 H); 1.85-1.64 (m, 3 H); 1.68 (s, 3 H); 1.64-1.47 (m, 2 H);
1.60 (s, 3 H); 1.43-1.13 (m, 8 H); 0.93 (d, J = 6.3, 3 H). 13C NMR (90.6 MHz, CDC13): 197.65 (s); 162.17 (s); 131.51 (s); 124.39 (d); 64.71 20 (t); 46.34 (d); 36.91 (t); 35.21 (t); 29A4(d); 27.46 (0; 25.72 (t); 25.36 (t); 25.30
(t);19.35(q); 17.66(q). MS (EI): 294 (M+, 1); 276 (1); 266 (1); 233 (1); 193 (1); 183 (4); 165 (1); 155 (2);
139 (2); 138 (13); 137 (4); 123 (14); 112 (2); 111 (16); 110 (3); 109 (6); 96 (4);
95 (16); 94 (2); 84 (7); 83 (100); 82 (15); 81 (22); 80 (3); 70 (2); 69 (29); 68
25 (4); 67 (11); 56 (4); 55 (42); 54 (3); 53 (5); 43 (4); 42 (4); 41 (38); 39 (8); 29
(6); 27 (4).
k) (E)-3,7-Dimethyl-2,6-octadienyl (cyclohexyl)oxoacetate (14)
In the first step, ethyl (cyclohexyl)oxoacetate was prepared as follows.
30 A Grignard reagent prepared from 24.45 g of 1-bromocyclohexane (0.18 mol) and
4.32 g of magnesium (0.15 mol) in 70 ml THF was added dropwisc (during a period of 40 min) to a stirred solution of 14.6 g (0.10 mol) of diethyl oxalate in 150 ml of

04-2000 IB 009900890
THF at -70°C. The formation of a precipitate was observed and another 100 ml of THF were added. The mixture was slowly warmed to -10°C and poured onto ice, saturated with NaCl, extracted with, diethyl ether (2x) and washed with a sat.
solution of NH4CI (2x) and water (pH ≈ 7). The organic phase was dried over
5 Na2S04 and concentrated. Fractional distillation gave 9.86 g (54%) of a colorless
oil.
B.p. 54°C/0.1-150Pa.
UV/Vis (hexane).-394 (sh, 5); 375 (sh, 10); 366 (sh, 15); 350 (sh, 20); 337 (20); 285
10 (sh, 7).
IR (neat): 2982w, 2930m, 2854m, 1722s, 1449m, 1366w, 1272m, 1229m, 1184w,
1140m, 1112w, 1081m, 1066s, 1014m, 991m, 923w, 894w, 855w.
1H NMR (360 MHz, CDC13): 4.32 (q, J= 7.1, 2 H); 3.1-2.97 (m, 1 H); 1.97-1.85
(m, 2 H); 1.85-1.74 (m, 2 H); 1.74-1.64 (m, 1 H); 1.45-1.13 (m, 5 H): 1.37 (t, J
15 =7.1,3H).
13C NMR (90.6 MHz, CDC13): 197.65 (s); 162.03 (s); 62.19 (f); 46.29 {d)\ 27.51
(0; 25.73 (/); 25.32 (/); 14.06 (q).
MS (EI): 184 (M+, 2); 112 (3); 111 (33); 110 (3); 84 (6); 83 (100); 81 (3); 79 (2);
77 (1); 68 (1); 67 (5); 65 (1); 56 (3); 55 (54); 54(5); 53 (5); 51 (1); 43 (2); 42
20 (3); 41 (23); 40 (2); 39 (12); 30 (1); 29 (20); 28 (3); 27 (13); 26 (1).
(E)-3,7-Dimethyl-2,6-octadienyl (cyclohexyl)oxoacetate (14)
A solution of 25.20 g (137mmol) of the product obtained above, 25.56 g
(166mmol) of geraniol and 1 ml of NaOCH3 (30% in methanol) in 150 ml of
•25 cyclohexane was heated under reflux overnight. After cooling to room temperature
the reaction mixture was taken up in ether, washed with a sat. solution of NaCI (pH ≈ 7), dried (Na2S04), filtered and concentrated. Column chromatography (SiO2, heptane/ether 9:1) and fractional distillation afforded 23.36 g (58%) of a colorless oil.
30

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IB 009900890

B.p. 130°C/10 Pa.
UV/Vis (hexane): 394 (sh, 5); 384 (sh, 8); 375 (sh, 14); 366 (sh, 17); 358 (sh, 20);
350 (sh, 22); 336 (24).
IR (neat): 2926m, 2853m, 1743m, 1721*, 1670w, 1449m, 1376m, 1341 w, 1331w,
5 1309w, 1273m, 1267m, 1227m, 1183w, 1139m, llllw, 1080m, 1063.?, 1027w,
993s, 915m, 895w, 830w, 805w, 787w, 739w, 729w, 718w. *H NMR (360 MHz, CDCI3): 5.45-5.35 (m, 1 H); 5.12-5.03 (m, 1 H); 4.76 (d, J =
7.1, 2 H); 3.09-2.95 (m, 1 H); 2.17-1.98 (m, 4 H); 1.98-1.85 (m, 2 H); 1.84-1.75
(m, 2 H); 1.74 (s, 3 H); 1.73-1.62 (m, 1 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43-
10 1.14 (m, 5 H).
13C NMR (90.6 MHz, CDCI3): 197.70 (s); 162.08 (s); 143.97 (j); 131.97 (s);
123.59 (rf); 117.16 (d); 62.90 (t); 46.38 (d); 39.55 (r); 27.49 (f); 26.23 (*); 25.73
(t); 25.67 (q); 25.31 (t); 17.69 (?); 16.58 (?). MS (EI): 292 (M+, 1); 205 (1); 179 (1); 138 (3); 137 (24); 136 (4); 135 (3); 123 (1): 15 122 (1); 121 (2); 112 (1); 111 (9); 107 (2); 105 (1); 96 (1); 95 (9); 94 (1), 93
(9); 92 (2); 91 (3); 84 (4); 83 (54); 82 (4); 81 (55); 80 (2); 79 (4); 77 (3); 70 (6);
69 (100); 68 (12); 67 (12); 65 (1); 56 (1); 55 (24); 54(2); 53 (6); 43 (2); 42 (2);
41 (25); 40(1); 39 (5); 29 (2); 27 (2).
20 1) Decyl (cyclohexyl)oxoacetate (15)
The synthesis was carried out as described above under k), using 6.21 g
(33.4 mmol) of ethyl (cyclohexyl)oxoacetate, 5.75 g (36.4 mmol) of decanol, 0.5 ml
of NaOCHj (30% in methanol) and 50 ml of cyclohexane. Fractional distillation
afforded 3.85 g (39%) of a colorless oil. 25.
B.p. 118-126°C/20Pa.
UV/Vis (hexane): 394 (sh, 4); 382 (sh, 8); 376 (sh, 11); 367 (sh, 14); 358 (sh, 17); 350 (sh, 19); 336 (19); 314 (sh, 17); 302 (sh, 15).
IR (neat): 2924*. 2852m, 1745m, 1723*, 1466m, 1450m, 1377w, 1330w, 1310w,
30 1290w, 1274m, 1229m, 1183w, 1139m, U17w, 1082m, 1065m, 1028w, 995m,
929w, 895w, 867w, 802w, 785w, 720m, 662w.

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1H NMR (360 MHz, CDC13): 4.24 (t, .J= 6.7, 2 H); 3.07-2.96 (m, 1 H); 1.98-1.85
(m,2H); 1.85-1.60 (m, 5 H); 1.44-1.14 (m, 19 H); 0.88 (t,.J= 6.9, 3 H).
13C NMR (90.6 MHz, CDC13): 197.70 (s); 162.22 (s); 66.27 (t); 46.37 (d); 31.90
(t); 29.51 (/); 29.49 (/); 29.30 (/); 29.17 (/); 28.42 (/); 27.48 (/); 25.80 (t); 25.74
5 (t); 25.32 (r); 22.69 (0; 14.11 (q).
MS (EI): 296 (M+, 2); 185(1); 158(1); 156(1); 112(7); 111 (88); 110 (3); 85 (2); 84 (7); 83 (100); 81 (1); 79 (I); 71 82); 70 (1); 69 (2); 68 (1); 67 (3); 57 (5); 56 (3); 55 (23); 54 (1); 53 (1); 43 (7); 42 (2); 41 (10); 39 (2); 29 (2); 27 (1).
10 m) 4-Methoxybenzyl (cyclohexyl)oxoacetate (16)
The synthesis was carried out as described above under k), using 6.62 g (35.9 mmol) of ethyl (cyclohexyl)oxoacetate, 6.06 g (43.9 mmol) of 4-methoxybenzyl alcohol, 0.5 ml of NaOCH3 (30% in methanol) and 50 ml of cyclohexane. Column chromatography (SiO2, heptane/ether 7:3) afforded one
15 fraction of the pure product together with another fraction of lower purity. The
latter was rechromatographed (SiO2, heptane/ether 8:2) to yield a total of 1.15 g (12%) of pure product as a slightly yellow oil.
UV/Vis (hexane): 395 (sh, 5); 375 (sh, 15); 367 (sh, 18); 360 (sh, 21); 352 (sh, 24);
20 337 (26); 324 (sh, 25); 312 (sh, 24); 288 (sh, 230); 280 (1520); 274 (1790); 268
(sh, 1590); 265 (sh, 1520); 259 (sh, 1170).
IR (neat): 3001w, 2929m, 2853m, 1806w, 1721s, 1612m, 1586m, 1514s, 1461m,
1449m, 1424w, \369w, 1303m, 1271m, 1246s, 1225s, 1174s, 1138s, 1112m,
1080m, 1063s, 1031s, 996s, 984s, 946w, 916w, 895m, 849w, 821s, 755w,
25 719w.
1H NMR (360 MHz, CDC13): 7.38-7.30 (m, 2 H); 6.94-6.85 (m, 2 H); 5.21 (s, 2 H);
3.81 (s, 3 H); 3.08-2.94 (m, 1 H); 1.98-1.83 (m, 2 H); 1.83-1.71 (m, 2 H); 1.71-
1.56 (m, 1 H); 1.41-1.10 (m, 5 H).
13C NMR (90.6 MHz, CDCI3): 197.39 (s); 161.94 (s); 160.04 (s); 130.51 (d);
30 126.81 (s); 114.08 (d); 67.58 (0; 55.31 (9); 46.41 (d); 27.46 (/); 25.70 (t): 25.27
(t)-

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MS (EI): 276 (M+ 1); 135 (1); 123 (1); 122 (10); 121 (100); 111 (2); 107 (1); 106 (2); 94 (1); 92 (1); 91 (3); 90 (1); 89 (1); 83 (7); 78 (5); 77 (4); 65 (1); 55 (9); 53(1); 52(1); 51(1); 41 (3); 39 (2).
5 n) 3-(4-tert-Butylphenyl)-2-methylpropyl cyclohexyl(oxo)acetate (17)
The synthesis was carried out as described above under k), using 4.8 g (26.1 mmol) of ethyl (cyclohexyl)oxoacetate, 4.0 g (21.5 mmol) of 3-(4-tert-butylphenyl)-2-methylpropanol (obtained by reduction of (±)-3-(4-tert-butylphenyl)-2-methylpropanal (Liliaf) with LiAlH4 in ether), 0.5 ml of NaOCH, (30% in
10 methanol) and 40 ml of cyclohexane. Column chromatography (Si02, heptane/ether
8:2) afforded 3.43 g (46%) of a colorless oil.
UV/Vis (hexane): 393 (sh, 4); 384 (sh, 7); 375 (sh, 12); 366 (sh, 15); 357 (sh, 18);
351 (sh, 20); 336 (22); 322 (sh, 20); 271 (270); 263 (330); 257 (280); 251
15 (240); 244 (sh, 240).
IR (neat): 3089w, 3055w, 3021w, 2953m, 2928m, 2855m, 1723*, 1512m, 1450m,
1410w, 1387w, 1364w, 1310>v, 1270m, 1226m, 1183w, 1139m, 1112w, 1079m,
1064m, 998m, 963w, 954M', 91 9W, 892w, 843w, 800w, 718w, 674w.
1H NMR (360 MHz, CDC13): 7.35-7.27 (m, 2 H); 7.12-7.05 (m, 2 H); 4.14 (ABX, J
20 = 10.7, 5.6, 1 H); 4.07 (ABX, J = 10.7, 6.7, 1 H); 3.06-2.95 (m, 1 H); 2.70
(ABX, J= 13.7, 6.5, 1 H); 2.48 (ABX, J = 13.7, 7.7, 1 H); 2.28-2.12 (m, 1 H);
1.97-1.86 (m, 2 H); 1.86-1.74 (m, 2 H); 1.74-1.63 (m, 1 H); 1.45-1-15 (m, 5 H);
1.31 (s, 9 H); 0.98 (d,J/=6.7, 3 H).
I3C NMR (90.6 MHz, CDC13): 197.52 (s); 162.24 (s); 149.01 (s); 136.34 (s);
25 128.75 (d); 125.27 (d); 70.11 (t); 46.44 (d); 39.08 (t); 34.43 (d); 34.38 (s);
31.39 (q); 27.44(0; 25.71 (t); 25.30 (t); 16.77 (q).
MS (EI): 345 ([M+H]+, 1); 344 (M+, 6); 330 (1); 329 (6); 234 (9); 233 (52); 231
(4); 217 (2); 190 (1); 189 (10); 188 (27); 178 (2); 177 (13); 175 (2); 174 (7);
173 (31); 161 (1); 160 (1); 159 (5); 148 (6); 147 (45); 146 (1); 145 (8); 133 (3);
30 132 (23); 131 (29); 130 (1); 129 (2); 128 (2); 127 (1); 119 (4); 118 (3); 117
(19); 116 (3); 115 (5); 112 (3); 111 (40); 110(1); 105 (5); 104 (2); 103 (1); 91

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(9); 84 (7); 83 (100); 81 (1); 79 (1); 77 (1); 67 (1); 65 (1); 57 (14); 55 (20); 54 (1); 53(1); 41 (9); 39 (2); 29 (2).
o) (lR,3R,4S)-3-p-Menthanyl (cyclohexyl)oxoacetate (18)
5 The synthesis was carried out as described above under k), using 25.03 g
(136mmol) of ethyl (cyclohexyl)oxoacetate, 25.70 g (165mmol) of (-)-menthol and 1 ml of NaOCH3 (30% in methanol) in 150 ml of cyclohexane. Fractional distillation afforded 23.14 g (58%) of a colorless oil.
10 B.p. 122°C/33 Pa.
UV/Vis (hexane): 394 (sh, 5); 383 (sh, 8); 375 (sh, 12); 366 (sh, 16); 360 (sh, 18);
351 (sh, 20); 337 (22).
IR (neat): 2949m, 2928m, 2854m, 1717.T, 1450m, 1387w, 1370m, 1332w, 131 Iw,
1274m, 1230m, 1181w, 1139m, llllw, 1081m, 1064m, 1037w, 1027w, 1006w,
15 995^, 980m, 951m, 912m, 894m, 869w, 844m, 802w, 787w, 717m.
1H NMR (360 MHz, CDC13): 4.83 (td,J = 10.9, 4.36, 1 H); 3.05-2.94 (m, 1 H);
2.08-1.99 (m, 1 H); 1.96-1.62 (m, 8 H); 1.59-1.45 (m, 2 H); 1.44-0.99 (m, 7 H);
0.93 (d, J= 6.7,3 H); 0.90 (d, J= 7.1,3 H); 0.77 (d, J = 7.1, 3 H).
13C NMR (90.6 MHz, CDC13): 198.09 (J); 162.16 (s); 76.71 (d); 46.79 (d); 46.32
20 (d); 40.49 (t); 34.10 (t); 31.50 (d); 27.37 (t); 26.25 (d)\ 25.76 (0; 25.32 (t);
25.26 (0; 23.38 (t); 21.95 (q); 20.67 (q); 16.17 (g).
MS (EI): 294 (M+, 1); 250 (1); 167 (1); 154 (4); 140 (4); 139 (33); 138 (8); 137 (1);
123 (2); 112 (1); 111 (9); 110 (1); 109 (1); 98 (1); 97 (16); 96 (1); 95 (5); 84
(7); 83 (100); 82 (2); 81 (12); 80 (1); 79 (2); 71 (3); 70 (1); 69 (19); 68 (1); 67
25 . (5); 57 (13); 56 (2); 55 (33); 54 (2); 53 (2); 43 (5); 42 (1); 41 (11); 39 (2); 29
(2); 27 (1).
p) 2-PentyM-cyclopentyl (cyclohexyl)oxoacetate (19)
The synthesis was carried out as described above under k), using 6.62 g (36 mmol)
30 of ethyl (cyclohexyl)oxoacetate, 6.80 g (44 mmol) of 2-pentyl cyclopentanol and
1 ml of NaOCHj (30% in methanol) in 50 ml of cyclohexane for 24 h. Column
chromatography (Si02, heptane/ether 8:2) afforded 5.91 g (55%) of a yellow oil

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(9); 84 (7); 83 (100); 81 (1); 79 (1); 77 (1); 67 (1); 65 (1); 57 (14); 55 (20); 54 (1); 53(1); 41 (9); 39 (2); 29 (2).
(lR,3R,4S)-3-p-Menthanyl (cyclohexyl)oxoacetate (18)
5 The synthesis was carried out as described above under k), using 25.03 g
(136mmol) of ethyl (cyclohexyl)oxoacetate, 25.70 g (165mmol) of (-)-menthol and 1 ml of NaOCH, (30% in methanol) in 150 ml of cyclohexane. Fractional distillation afforded 23.14 g (58%) of a colorless oil.
10 B.p. 122°C/0.33 mbar.
UV/Vis (hexane): 394 (sh, 5); 383 (sh, 8); 375 (sh, 12); 366 (sh, 16); 360 (sh, 18);
351 (sh, 20); 337 (22).
IR (neat): 2949m, 2928m, 2854m, 1717s, 1450m, 1387M', 1370m, 1332w, 131 1W,
1274m, 1230m, 1181w, 1139m, 111 lw, 1081m, 1064m, 1037M/, 1027W, 1006w,
15 995s, 980m, 951m, 912m, 894m, 869w, 844m, 802w, 787w, 717m.
'H NMR (360 MHz, CDC13): 4.83 (td, J= 10.9, 4.36, 1 H); 3.05-2.94 (m, 1 H);
2.08-1.99 (m, 1 H); 1.96-1.62 (m, 8 H); 1.59-1.45 (m, 2 H); 1.44-0.99 (m, 7 H);
0.93 (d, J = 6.7, 3 H); 0.90 (d, J = 7.1, 3 H); 0.77 (d, J = 7.1, 3 H).
13C NMR (90.6 MHz, CDC13): 198.09 (s); 162.16 (s); 76.71 (d); 46.79 (d); 46.32
20 (d); 40.49 (0; 34.10 (t); 31.50 (d); 27.37 (t); 26.25 (d); 25.76 (t); 25.32 t);
25.26 (0; 23.38 (t); 21.95 (g); 20.67 (q); 16.17 (q).
MS (EI): 294 (M+, 1); 250 (1); 167 (1); 154 (4); 140 (4); 139 (33); 138 (8); 137 (1);
123 (2); 112 (1); 111 (9); 110 (1); 109 (1); 98 (1); 97 (16); 96 (1); 95 (5); 84
(7); 83 (100); 82 (2); 81 (12); 80 (1); 79 (2); 71 (3); 70 (1); 69 (19); 68 (1); 67
25 (5); 57 (13); 56 (2); 55 (33); 54 (2); 53 (2); 43 (5); 42 (1); 41 (11); 39 (2); 29
(2); 27(1).
2-Pentyl-l-cyclopentyl (cyclohcxyl)oxoacetate (19)
The synthesis was carried out as described above under k), using 6.62 g (36 mmol)
30 of ethyl (cyclohexyl)oxoacetate, 6.80 g (44 mmol) of 2-pentyl cyclopentanol and
1 ml of NaOCH., (30% in methanol) in 50 ml of cyclohexane for 24 h. Column
chromatography (Si03, heptane/ether 8:2) afforded 5.91 g (55%) of a yellow oil

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(mixture of diastereoisomers). The UV/Vis spectrum indicated the presence of a colored impurity.
UV/Vis (hexane): 395 (sh, 4); 383 (sh, 7); 374 (sh, 11); 366 "(sh, 14); 358 (sh, 16);
5 349 (sh, 19); 320 (sh, 23); 303 (sh, 34); 289 (sh, 43).
IR (neat): 2924m, 2853m, 1806w, 1719s, 146lw, 1449m, 1376w, 131 lw, 1275m,
1254w, 1229m, 1183w, 1139m, 1116w, 1081m, 1064m, 1028w, 996m, 968w,
925w, 894w, 844w, 724W.
•H NMR (360 MHz, CDC13): 5.35-5.28 (m, 1 H); 4.96-4.89 (m, 1 H); 3.05-2.88 (m,
10 2 H); 2.10-1.55 (m, 10 H); 1.53-1.10 (m, 13 H); 0.93-0.80 (m, 3 H).
13C NMR (90.6 MHz, CDC13): 197.99 (s); 162.29 (s); 162.26 (j); 83.72 (d); 80.36
(d); 46.58 (d); 46.42 (d); 45.39 (d); 44.81 (d); 33.49 (/); 32.53 (/); 32.07 (t);
31.94 (t); 31.80 (t); 30.20 (t); 29.61 (t); 29.12 (t); 28.18 (/); 27.60 (t); 27.46 (t);
27.38 (t); 25.32 (t); 22.76 (0; 22.59 (t); 22.03 (t); 14.05 (q).
15 MS (EI): 167(1); 140(1); 139 (8); 138 (7); 123 (1); 112 (1); 111 (11); 110(1); 109
(1); 98 (2); 97 (25); 96 (2); 95 (3); 84 (7); 83 (100); 82 (5); 81 (4); 79 (2); 71
(4); 70 (2); 69 (22); 68 (2); 67 (9); 66 (1); 65 (1); 57 (11); 56 (2); 55 (29); 54
(3); 53 (2); 43 (4); 42 (1); 41 (12); 39 (3); 29 (3); 27 (1).
20 q) 4-( 1,1 -Dimethylpropyl)-1 -cyclohexyl (cyclohexyl)oxoacetate (20)
The synthesis was carried out as described above under k), using 6.62 g (36 mmol) of ethyl (cyclohexyl)oxoacetate, 7.40 g (43.5 mmol) of 4-( 1,1-dimethylpropyl)-1-cyclohexanol and 1 ml of NaOCH3 (30% in methanol) in 50 ml of cyclohexane. Column chromatography (Si02, heptane/ether 8:2) afforded 4.78 g (43%) of a
25 slightly yellow oil as a mixture of cisltrans isomers (≈ 38:62).
UV/Vis (hexane): 394 (sh, 4); 385 (sh, 7); 375 (sh, 12); 367 (sh, 15); 339 (sh, 35);
326 (40); 312 (sh, 38); 297 (sh, 34); 283 (33); 272 (sh, 36). IR (neat): 2929s, 2855m, 1800w, 1719s, 1462w, H48/w, 1387w, 1377w, 1364w, 30 1323w, 1309w, 1274m, 1254w, 1228m, 1182w\ 1160w, 1140m, 1108w, 1081m,
1064m, 1047w, 1005w, 995s, 948w, 928M, 906W, 894W, 875W, 830W, 805W,
780M-, 745w, l\9w.

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'HNMR(360MHz,CDCl3):5.21-5.14(w, 1 H (cis)); 4.85-4.72 (tt,J= 11.3, 4.6, 1 H (trans)); 3.07-2.91 (m, 1 H); 2.17-1.04 (m, 21 H); 0.83-0.77 (m, 9 H).
13C NMR (90.6 MHz, CDC13): 198.07 (s); 161.85 (s); 76.16 (d); 72.28 (d); 46.81
(d); 46.35 (d); 44.58 (d); 44.21 (d); 34.82 (s); 34.60 (5); 32.75 (/); 32.49 (/);
5 31.90 (t); 30.49.(0; 27.47 (0; 25.75 (/); 25.38 (0; 25.31 (t); 24.97 (t); 24.27 (q);
24.17(g); 21.22(0; 8.10 (q).
MS (EI): 264 (1); 193 (1); 181 (1); 153 (4); 152 (3); 137 (4); 124 (1); 6); 112 (1);
111 (14); 110 (2); 109 (1); 98 (4); 97 (55); 95 (5); 85 (2); 84 (4); 83 (60); 81
(12); 80 (1); 79 (2); 72 (6); 71 (100); 69 (13); 68 (1); 67 (11); 57 (15); 56 (3);
10 55 (51); 54 (4); 53 (3); 43 (32); 41 (22); 39 (4); 29 (7); 27 (4).
r) l-(2-Naphthalenyl)ethyl (cyclohexyl)oxoacetate (21)
The synthesis was carried out as described above under k), using 6.62 g (24 mmol)
of ethyl (cyclohexyl)oxoacetate, 7.5 g (29 mmol) of 1 -(2-naphthalenyl)ethanol and
15 1 ml of NaOCH3 (30% in methanol) in 70 ml of cyclohexane for 28 h. Column
cliromatography (Si02, heptane/ether 8:2) afforded 2.67 g of a colorless oil still containing about 30% of ethyl (cyclohexyl)oxoacetate.
1H NMR (360 MHz, CDC13): 7.88-7.78 (w, 4 H); 7.54-7.44 (m, 3 H); 6.16 (q, J =
20 6.6, 1 H); 3.08-2.93 (m, 1 H); 1.97-1.60 (m, 5 H); 1.72 (d,J= 6.7, 3 H); 1.44-
1.12 (mi, 5 H). 13C NMR (90.6 MHz, CDC13): 197.53 (s); 161.49 (s); 137.73 (s); 133.21 (s);
133.13 (s); 128.60 (d); 128.09 (d); 127.71 (d); 126.40 (d); 126.34 (d); 125.38
(d); 123.85 (d); 74.76 (d); 46.41 (d); 27.38 (0; 25.70 (0; 25.26 (0; 22.08 (q). 25 MS (EI): 310 (M+, 1); 157 (2); 156 (14); 155 (100); 154 (22); 153 (16); 152 (8);
151 (2); 141 (2); 139(1); 129(3); 128(9); 127(9); 126(2); 115(4); 111 (3);
101 (1); 84 (1); 83 (17); 77 (4); 76 (4); 75 (2); 64 (1); 63 (2); 56 (1); 55 (16);
51 (2); 50 (1); 43 (2); 41 (9); 39 (4); 29 (3); 27 (3).
30 s) 3,7-Dimethyl-6-octenyl (cyclopentyl)oxoacetate (22)
In the first step, ethyl (cyclopentyl)oxoacctate was prepared as follows.

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A Grignard reagent prepared from 64.0 g of freshly distilled bromocyclopentane
(0.43 mol) and 11.0 g of magnesium (0.45 mol) in 360 ml of dry ether and filtered
under N2 was added dropwise to a stirred solution of 48.2 g (0.33 mol) of diethyl
oxalate in 300 ml of dry ether at -40°C. The mixture was slowly warmed to 0°C and
5 poured onto a sat. solution of NH4CI, extracted with ether and washed with water
(pH ≈ 7). The organic phase was dried over Na2S04 and concentrated. Fractional distillation gave 27.1 g (48%) of a colorless oil in sufficient purity for further derivatization. Column chromatography (Si02, heptane/ether 8:2) of 2.50 g afforded 2.04 g of product at high purity. 10
B.p. 42°C/0.1 mbar.
UV/Vis (hexane): 389 (sh, 3); 371 (sh, 9); 359 (sh, 13); 345 (sh, 15); 336 (15).
IR (neat): 3483W, 2956m, 2869m, \723s, 1684m, 1469w, 1449m, 1399w, 1372w,
1318w, 1296m, 12545, 1194m, 1159m, 1140m, 1091S, 1043s, 1029s, 952m,
15 906m, 858m, 780m, 708w.
1H NMR (360 MHz, CDC13): 4.32 {q,J= 7.1,2 H); 3.56-3.44 (m, 1 H); 1.98-1.75
(m, 4 H); 1.75-1.57 (m, 4 H); 1.37 (t, J = 7.1, 3 H). 13C NMR (90.6 MHz, CDC13): 196.73 (s); 161.98 (s); 62.24 (t); 47.42 (d); 28.32
(0; 26.05(0; 14.05 (q). 20 MS (EI): 170 (M+, 5); 114 (1); 101 (1); 98 (4); 97 (48); 96 (4); 95 (1); 70 (6); 69
(100); 68 (3); 67 (6); 66 (1); 65 (1); 55 (4); 54 (1); 53 (2); 51 (1); 43 (1); 42 (2);
41 (22); 40 (2); 39 (7); 29 (5); 28 (1); 27 (4).
3,7-Dimethyl-6-octenyl (cyclopentyl)oxoacetate (22)
25 The synthesis was carried out as described above under k), using 6,07 g
(35.6 mmol) of the product obtained above, 6.80 g (43.6 mmol) of citronellol and 0.5 ml of NaOCH, (30% in methanol) in 50 ml of cyclohexane. Column chromatography (SiO,, heptane/ether 7:3) afforded 5.28 g (53%) of a yellow oil.
30 UV/Vis (hexane): 389 (sh, 4); 366 (sh, 12); 345 (sh, 17); 336 (17).

04-2000 IB 009900890

A Grignard reagent prepared from 64.0 g of freshly distilled bromocyclopentane (0.43 mol) and 11.0 g of magnesium (0.45 mol) in 360 ml of dry ether and filtered under N2 was added dropwise to a stirred solution of 48.2 g (0.33 mol) of diethyl oxalate in 300 ml of dry ether at -40°C. The mixture was slowly warmed to 0°C and poured onto a sat. solution of NH4CI, extracted with ether and washed with water (pH ≈ 7). The organic phase was dried over Na2SO4 and concentrated. Fractional distillation gave 27.1 g (48%) of a colorless oil in sufficient purity for further derivatization. Column chromatography (Si02, heptane/ether 8:2) of 2.50 g afforded 2.04 g of product at high purity.
10
B.p. 42°C/10 Pa.
UV/Vis (hexane): 389 (sh, 3); 371 (sh, 9); 359 (sh, 13); 345 (sh, 15); 336 (15).
IR (neat): 3483w, 2956m, 2869m, 1723s, 1684m, 1469w, 1449m, 1399w, 1372w,
1318vf, 1296m, 1254J, 1194m, 1159m, 1140m, 109ls, 1042s, 1029J, 952m,
15 906m, 858m, 780m, 708w.
1H NMR (360 MHz, CDC13): 4.32 (q, J = 7.1, 2 H); 3.56-3.44 (m, 1 H); 1.98-1.75
(m, 4 H); 1.75-1.57 (m, 4 H); 1.37 (t, J= 7.1, 3 H). 13C NMR (90.6 MHz, CDC13): 196.73 (s); 161.98 (s); 62.24 (t); MAI (d) 28.32
(0; 26.05 (0; 14.05 for). 20 MS (EI): 170 (M+, 5); 114 (1); 101 (1); 98 (4); 97 (48); 96 (4); 95 (1); 70 (6); 69
(100); 68 (3); 67 (6); 66 (1); 65 (1); 55 (4); 54 (1); 53 (2); 51 (1); 43 (1); 42 (2);
41 (22); 40 (2); 39 (7); 29 (5); 28 (1); 27 (4).
3,7-Dimethyl-6-octenyl (cyclopentyl)oxoacetate (22)
25 The synthesis was carried out as described above under k), using 6.07 g
(35.6 mmol) of the product obtained above, 6.80 g (43.6 mmol) of citronellol and 0.5 ml of NaOCH3 (30% in methanol) in 50 ml of cyclohexane. Column chromatography (Si02, heptane/ether 7:3) afforded 5.28 g (53%) of a yellow oil.
30 UV/Vis (hexane): 389 (sh,); 366 (sh, 12); 345 (sh, 17); 336 (17)..
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IB 009900890

IR (neat): 3493w, 2951m, 2916m, 2869m, 1798w, 17245, 1687m, 1451/ra, 1377m,
1354w, 1259m, 1190m, 1164m, 1144m, 1091m, 1047m, 1027m, 984w, 945m,
829m, 782w, 73 9w, 717w.
1H MMR (360 MHz, CDC13): 5.13-5.03 (m, 1 H); 4.40-4.20 (m, 2 H); 3.54-3.42 (m,
5 1 H); 2.10-1.71 (m, 7 H); 1.71-1.45 (m, 6 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43-
1.30 (m, 1 H); 1.29-1.13 (m, 1 H); 0.94 (d,J= 6.3,3 H).
13CNMR (90.6 MHz, CDC13): 196.66 (s); 162.11 (s); 131.51 (s); 124.40 (d); 64.75
(0; 47.48 (d); 36.90 (/); 35.22 (0; 29.40 (d); 28.27 (0; 26.05 (t); 25.71 (q);
25.35(0; 19.35 (q); 17.66 (q).
10 MS (EI): 280 (M+, 1); 262 (2); 252 (1); 184 (1); 183 (6); 165 (1); 155 (3); 144 (2);
142 (1); 139 (2); 138 (20); 137 (6); 126 (1); 125 (1); 124 (2); 123 (22); 121 (1); 111 (1); 110 (2); 109 (9); 98 (3); 97 (39); 96 (7); 95 (21); 94 (2); 83 (6); 82 (15); 81 (23); 80 (2); 79 (1); 70 (7); 69 (100); 68 (5); 67 (9); 65 (1); 57 (2); 56 (2); 55 (10); 54 (1); 53 (3); 43 (2); 42 (2); 41 (25); 40 (1); 39 (4); 29 (2); 27 (2\ 15
t) (E)-3,7-Dimethyl-2,6-octadienyl 3-methyl-2-oxopentanoate (23)
The synthesis was caried out as described above under a),"using 4.85 g (38 mmol)
of 3-methyl-2-oxo pentanoic acid and 11.5 g (75 mmol) of geraniol in 130 ml of
toluene for 24 h. Column chromatography (SiO2, heptane/EtOAc 95:5) afforded
20 7.68 g of crude product, which was fractionally distilled to give 4.04 g (40%) of a
colorless oil.
B.p. 82°C/20 Pa.
UV/Vis (hexane): 393 (sh, 5); 382 (sh, 9); 374 (sh, 13); 364 (sh, 17); 357 (sh, 19);
25 350 (sh, 21); 335 (23).
IR (neat): 2966m, 2929m, 2878m, 1746m, 1723s, I670w, 1454m, 1377m, 1338w5
1274m, 1244m, 1163m, 1107w, 1085w, 1039*, 999m, 959m, 913m, 827w,
796w, 772w, 742w, 705w.
1H NMR (360 MHz, CDC13): 5.46-5.35 (m, 1 H); 5.14-5.04 (m, 2 H); 4.77 (d, J =
30 7.1, 2 H); 3.20-3.07 (m, 1 H); 2.20-2.00 (m, 4 H); 1.83-1.66 (m, 1 H); 1.74 (s, 3
H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.52-1.36 (m, 1 H); 1.13 (d, J= 7.1, 3 H); 0.92
(t,J=7.5,3H).

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IR (neat): 3493M-, 2957m, 2916m, 2869m, 1798w, 1724s, 1687m, 1451m, 1377m,
1354w, 1259m, 1190m, 1164m, 1144m, 1091m, 1047m, 1027m, 984w, 945m,
829m, 782 w, 73 9 w, 717w.
1H NMR (360 MHz, CDC13): 5.13-5.03 (m, 1 H); 4.40-4.20 (m, 2 H); 3.54-3.42 (m,
5 1 H); 2.10-1.71 (m, 7 H); 1.71-1.45 (m, 6 H); 1.68 (s, 3 H); 1.60 (s, 3 H); 1.43-
1.30 (m, 1H); 1.29-1.13 (m, 1 H); 0.94 (d, J= 6.3, 3 H).
13C NMR (90.6 MHz, CDC13): 196.66 (s); 162.11 (5); 131.51 (s); 124.40 (d); 64.75
(t); 47.48 (d); 36.90 (/); 35.22 (0; 29.40 (d); 28.27 (/); 26.05 (/); 25.71 (q);
25.35(/); 19.35 (4); 17.66 (q).
10 MS (EI): 280 (M+, 1); 262 (2); 252 (1); 184 (1); 183 (6); 165 (1); 155 (3); 144 (2);
142 (1); 139 (2); 138 (20); 137 (6); 126 (1); 125 (1); 124 (2); 123 (22); 121 (1); 111 (1); 110 (2); 109 (9); 98 (3); 97 (39); 96 (7); 95 (21); 94 (2); 83 (6); 82 (15); 81 (23); 80 (2); 79 (1); 70 (7); 69 (100); 68 (5); 67 (9); 65 (1); 57 (2); 56 (2); 55 (10); 54 (1); 53 (3); 43 (2); 42 (2); 41 (25); 40 (1); 39 (4); 29 (2); 27 (2). 15
t) (E)-3,7-Dimethyl-2,6-octadienyl 3-methyl-2-oxopentanoate (23)
The synthesis was caried out as described above under a), using 4.85 g (38 mmol)
of 3-methyl-2-oxo pentanoic acid and 11.5 g (75 mmol) of geraniol in 130 ml of
toluene for 24 h. Column chromatography (Si02, heptane/EtOAc 95:5) afforded
20 7.68 g of crude product, which was fractionally distilled to give 4.04 g (40%) of a
colorless oil.
B.p. 82°C/0.2 mbar.
UV/Vis (hexane): 393 (sh, 5); 382 (sh, 9); 374 (sh, 13); 364 (sh, 17); 357 (sh, 19);
25 350 (sh, 21); 335 (23).
IR (neat): 2966m, 2929m, 2878m, 1746m, 1723s, 1670w, 1454m, 1377m, 1338w,
1274m, 1244m, 1163m, 1107w, 1085w, 1039s, 999m, 959m, 913m, 827w,
796w, 772w, 742w, 705M'.
'II NMR (360 MHz, CDC13): 5.46-5.35 (m, 1 H); 5.14-5.04 (m, 2 H); 4.77 (d, J =
30 7.1, 2 H); 3.20-3.07 (m, 1 H); 2.20-2.00 (m, 4 II); 1.83-1.66 (m, 1 H); 1.74 (s, 3
H); 1.68 (s, 3 H); 1.60 (.9,3 H); 1.52-1.36 (m, 1 H); 1.13 {d, J = 7.1, 3 H); 0.92 (t,J= 7.5, 3 H).

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13C NMR (90.6 MHz, CDC13): 198.29 (.9); 162.10 (s); 144.01 (s); 131.97 (s);
123.58 (d); 117.13 (d); 62.94 (t); 43.66 (d); 39.53 (t); 26.22 (t); 25.66 (q);
24.92 (0; 17.69 (9); 16.57 (q); 14.46 for); 11.35 (9). MS (EI): 266 (M+, 1); 181 (1); 179 (1); 153 (1); 138 (3); 137 (28); 136 (6); 135 (5); 5 123 (1); 122 (1); 121 (2); 109 (1); 107 82); 96 (2); 95 (10); 94 (2); 93 (6); 92
(2); 91 (3); 85 (9); 83 (1); 82 (4); 81 (52); 80 (2); 79 (3); 78 (1); 77 (3); 71 (1);
70 (6); 69 (100); 68 (12); 67 (12); 66 (1); 65 (2); 58 (2); 57 (30); 56 (1); 55 (5);
54 (1); 53 (6); 51 (1); 43 (1); 42 (2); 41 (26); 40 (2); 39 (5) 29 (5); 28 (1); 27
(2).
10
u) 3,7-Dimethyl-6-octenyl (bicyclo[2.2.1]hept-2-yl)oxoacetate (24)
A Grignard reagent prepared from 4.00 g of 2-norbornyl bromide (23 mmol) and 0.59 g of magnesium (24 mmol) in 30 ml THF was, after filtration under N2, added dropwise (during 45 min) to a stirred solution of 3.00 g (8 mmol) of bis(3,7-
15 dimethyl-6-octenyl) oxalate in 40 ml of THF at -40°C. The mixture was slowly
warmed to 0°C, quenched with 30 ml of a sat. solution of NH4C1. The reaction mixture was extracted with diethyl ether and water (2x) and the organic phase dried over Na2S04. Repetitive column chromatography (Si02, heptane/ether 9:1 and heptane/ether 95:5) followed by MPLC on a Lobar column (Si02 Merck,
20 heptane/ether 85:15) finally afforded 0.188 g (3%) of the pure product as a colorless
oil.
1H NMR (360 MHz, CDC13): 5.13-5.04 (m, 1 H); 4.37-4.22 (m, 2 H); 3.06 (in, 1 H); 2.59-2.48 (m, 1 H); 2.36-2.27 (m, 1 H); 2.09-1.84 (m, 3 H); 1.84-1.69 (m,1
25 H); 1.68 (s, 3 H); 1.66-1.45 (m, 4 H); 1.60 (s, 3 H); 1.45-1.30 (m, 3 H); 1.30-1.08 (m, 4 H); 0.94 (d, J = 6.3, 3 H). 13C NMR (90.6 MHz, CDC13): 195.33 (s); 162.08 (s); 131.50 (s); 124.39 (d); 64.75 (0; 50.37 (d); 39.82 (d); 36.91 (t); 36.28 (d); 35.84 (t); 35.23 (t); 31.86 (t); 29.64 (0; 29.43 (d); 28.78 (t); 25.71 (q); 25.36 (t); 19.34 (qr); 17.66 (q).
30 MS (EI): 288 (1); 183 (4); 168 (1); 155 (1); 139 (2); 138 (15); 137 (2); 124 (3); 123 (30); 122(2); 121 (1); 110(1); 109(5); 97 (1); 96 (11); 95 (100); 93 (4); 91 (1); 83 (4); 82 (19); 81 (21); 80 (5); 79 (3); 77 (2); 70 (2); 69 (23); 68 (5); 67

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(22); 66 (3); 65 (3); 57 (3); 56 (3); 55 (15); 54 (2); 53 (5); 43 (4); 42 (3); 41 (33); 39 (6); 29 (5); 28(1); 27 (5).
Example 3
Release of geraniol from solutions of geranyl 2-benzoyl benzoate
Geranyl 2-benzoyl benzoate was dissolved in a concentration of 3.68g/l in the solvents 10 indicated in Table 1. The samples were then irradiated using a Fadeometer and under the conditions indicated in Table 1, and the amount of released geraniol was measured. The values indicated are the average of duplicate samples.
Table 1 : Release of geraniol from geranyl 2-benzoyl benzoate in solution upon irradiation
15 with a Fadeometer

Run Solvent Irradiation intensity (KJ/m2) % of geraniol released *
1 Isopropanol/benzene 1:1 33.7 24.4
2 Isopropanol/benzene 1:1 3.4 30.4
3 Isopropanol/benzene 1:1 0 ** 0
4 Dodecanol/benzene 1:1 33.7 26.8
5 Isopropanol/acetonitrile 3.4 22.6
6 Isopropanol/ acetonitrile Q ** 0
* calculated as weight % of theoretically possible geraniol release
** indicates a control run in which the flask was wrapped with aluminum foil before irradiation
The following Table 2 indicates the amount of geraniol released from the same ester, but upon exposure to sunlight (New Jersey, USA, typical sunny day of June).

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Table 2 : Release of geraniol from geranyl 2-benzoyl benzoate in solution upon exposure to sunlight

Run Solvent Hours of sun exposure % of geraniol released *
1 Isopropanol/benzene 1:1 5 71.3
2 Isopropanol/benzene 1:1 Q** 0
5 * calculated as weight % of theoretically possible geraniol release
** indicates a control run in which the flask was wrapped with aluminum foil before irradiation
The above results show that it is possible to release geraniol in solution upon exposure to a 10 Fadeometer or to sunlight, while no release occurs when the sample is not exposed to radiation.
Example 4
15 Release of geraniol from geranyl 2-(2,-isopropylbenzoyl)benzoate (solution and film)
Geranyl 2-(2-isopropylbenzoyl)benzoate was dissolved in a concentration of 4.05g/l in benzene and subsequently irradiated, or was deposited as a thin film, by evaporation of the solvent, on the walls of the flask before irradiation. After irradiation, the amount of 20 released geraniol was measured. The results are shown in Table 3. The values indicated are the average of duplicate samples.
Table 3 : Release of geraniol from geranyl 2-(2'-isopropylbenzoyl)benzoate in solution and as a film upon irradiation with a Fadeometer
25

Run Solvent/film Irradiation intensity (KJ/m2) % of geraniol released *
1 Benzene 3.4 11.2
2 Benzene o ** 0
3 Film (33.5mg) 3.4 9.5
4 Film (32.5mg) 0 ** 0

/

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* calculated as weight % of theoretically possible geraniol release
** indicates a control run in which the flask was wrapped with aluminum foil before irradiation
5
Table 4 indicates the results of analogous experiments in which the solutions and films of geranyl 2-(2'-isopropylbenzoyl)benzoate were exposed to sunlight (New Jersey, USA, typical sunny day of June). The values indicated are the average of duplicate samples.
10 Table 4 : Release of geraniol from geranyl 2-(2'-isopropylbenzoyl)benzoate (solution and film) upon exposure to sunlight

Run Solvent/film Hours of sun exposure % of geraniol released *
1 Isopropanol/benzene 1:1 5 71.3
2 Isopropanol/benzene 1:1 Q ** 0
3 Film (14.2mg) 5 27.0
4 Film (14.2mg) 0 ** 0
* calculated as weight % of theoretically possible geraniol release 15 ** indicates a control run in which the flask was wrapped with aluminum foil before irradiation
The above results show that the introduction of an isopropyl substituent into the geranyl ester allows the release of geraniol from solution and from a solid film, upon exposure to a 20 Fadeometer radiation and to natural sunlight.
Example 5
25 Release of geraniol from geranyl 2-(2',4'-diisopropylbenzoyl)benzoate (solutionjmd film)
Geranyl 2-(2',4'-diisopropylbenzoyl)benzoate was dissolved in benzene in a concentration of 4.48 g/1 in benzene and subsequently irradiated, using a Fadeometer. The samples were

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irradiated with 31.1 KJ/m2, and 50 weight% of the theoretical value of geraniol was released.
Similar experiments were conducted in which benzene solutions with the same content in geranyl 2-(2',4'-diisopropylbenzoyl)benzoate and films which were obtained by 5 evaporation of the solvent, were exposed to daylight outdoors (New Jersey, USA, cloudy day in August). Table 5 shows the results of the experiments. The values indicated are the average of duplicate samples.
Table 5 : Release of geraniol from geranyl 2-(2',4'-diisopropylbenzoyl)benzoate in
10 solution and as film, upon exposure to sunlight

Run Solvent/film Hours of sun exposure % of geraniol released *
1 Benzene 6 13
2 Film 6 18
calculated as weight % of theoretically possible geraniol release
15
Example 6
Release of geraniol from geranyl 2-(2',4'-diisopropylbenzoyl)benzoate in an all-purpose
cleaner 20
An all-purpose cleaner of the Fabuloso ® (registered trademark of Colgate-Palmolive,
USA) type containing 0.3% of geranyl 2-(2',4'-diisopropylbenzoyl)benzoate was prepared.
The all-purpose cleaner solution thus obtained was added to borosilicate flasks which were
then irradiated for 3 hours in outdoor sunlight. The resulting solutions were then compared 25 to the unperfumed all-purpose cleaner base, on a triangular blind test by a panel composed
of 15 non-experts. The odd sample was the one containing the above precursor molecule.
The evaluation was carried out by sniffing on the flask.
From the 15 test persons, 14 correctly distinguished the perfumed sample from the
unperfumed sample. They found that the odor note of the irradiated sample was floral.

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geraniol, citrus or citronellal, whereas the non-irradiated sample was found to be neutral, odorless or slightly oily.
When the odd sample was the one containing the unperfumed cleaner base, 10 of 15 panelists correctly distinguished the samples. 5 The release of geraniol from the 2-benzoyl benzoate used in the present embodiment and from the other benzoates synthesized occurrred in all types of all-purpose cleaners and is therefore not restricted to one type of these.
10 Example 7
Release of Polysantol ® from (E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-l-yl)-4-penten-2-yl 2-(2',4'-diisopropylbenzoyl)benzoate
15 The above-identified compound was dissolved in toluene in a concentration of 2.35 g/1 and irradiated for 6 hours with a UV lamp. The amount of released Polysantol was measured by GC, and it was found that 35% of the theoretical amount of Polysantol had been released.
20 Example 8
Release of geraniol from a film of 2-(2',4'-diisopropylbenzoyl)benzoate deposed on tiles
0.8 G of an all-purpose cleaner of the Fabuloso ® type containing 0.3% of the title 25 compound were evenly deposed on tiles of the size 10x10 cm. The liquid was allowed to evaporate, and the tiles were exposed to sunlight for 7 h in a covered petri dish. The tiles were then olfactively compared to tiles treated in the same way with the unperfumed cleaner base and exposed to sunlight on the same day and the same hours, on a triangular blind test by a panel composed of 15 non-experts, by sniffing on the petri dish. 30 When the odd sample was the one containing the title compound. 14 of 15 panelists correctly distinguished the perfumed sample from the unperfumed sample. When the odd

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sample was the one containing the unperfumed base, the correct attribution was made by 9 of 15 panelists.
Example 9
Release of fragrant aldehydes and ketones from various citronellyl a-keto esters in solution or in the neat state
10 0.01 M solutions (5 ml) of the a-keto esters prepared as described in example 2, in toluene, acetonitrile or isopropanol, were prepared and irradiated with a xenon or a UV lamp or exposed to outdoor sunlight in 10 ml volumetric flasks. Samples in the neat state were also irradiated under the same conditions. Before irradiation in solution, 1 ml of a 0.01 M solution of decanol was added which served as internal standard for GC analysis. The
15 results are found in the Table 6 below. Table 6 indicates the amount of released aldehyde or ketone in mol%, the amount of remaining starting material is indicated in brackets. It was also observed that olefins were released, from compounds (11) and (12) of example 2, together with release of citronellal.
20 Table 6 : Results of the photoirradiations of different a-keto esters in solution and in their neat state

Structure of Compounds N° Light Source Yield of Perfume (Remaining Starting Material3) in
mol-%

Toluene 2-Propanol Acetonitrile Neat

3h 3h 3h 3.5 h
0 ' 5 Xenon
UV sunlight 27 44 (10) ( 30 (15) (45)

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6 Xenon
UV sunlight 33 50 ( 7 Xenon
UV sunlight 55 '
19
23 ( (60)
( ( 23 Xenon
UV sunlight 15/26' 17/21f ( 8 Xenon
UV sunlight 38 13 21 ( ( 7
21 (10)b (95) ( 11 Xenon
UV sunlight 11 2/6d (30)b (85) 0/3d (-----)C l/6d (80) 2/11d (30)
12 Xenon
UV sunlight 8
0/5e 7/42e (50)b (85) (35) 0/5e 3/2 le (70) (55) 0/5e 0/3 T (95) (25) l/10e 0/6e (35) (75)
22 Xenon
UV sunlight 24 37 ( 22 (5) (15)

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24 Xenon
UV sunlight 26 (10)
13 Xenon
UV sunlight ≈45 25 38 ( 35 (90) (15) 13 18 (70) ( 14 Xenon
UV sunlight 26/43' 19/25f ( (5) 10/33* 10/48f (30) (30) 11/19' ll/17f (20) (30) 15 Xenon
UV sunlight 52
52 (0) ( 16 Xenon
UV sunlight 81 86 ( 17 Xenon
UV sunlight 69 63 ( (5)
18 Xenon
UV sunlight quant, quant. ( (10) 53 44 (10) (10) 91 86 ( (5) 75
21 (40) (50)

All numbers are average values of 2 or 3 samples.
a) amount of remaining starting material rounded to ± 5%,
b) amount of starting material estimated from blank sample,
5 c) yield not or only approximatively determined due to transesterification,
d) mol-% of citronellal/dodecene liberated by hydrogen abstraction from the alkyl chain,
c) mol-% of citronellal/tridecene liberated by hydrogen abstraction of the alkyl chain,
f) mol-% of trans/cis citral.

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Example 10 Release of citronellal from various citronellyl a-keto esters in after-shave lotions
5 Compounds (7) and (8) of example 2 were each dissolved in an amount of 0.29 g in 19.54 g of a standard after-shave lotion base, under addition of a standard solubilizer (Cremophor RH40, BASF AG). For each of the compounds, three samples of 6 ml (one of which was wrapped in aluminium foil to serve as reference) were irradiated in 10 ml volumetric flasks for 3h with a xenon lamp. The irradiated samples were analyzed by
10 HPLC using citronellal and the corresponding starting materials as external standards. The reference experiment (aluminium foil wrapped) showed no release of citronellal. The results obtained with the other samples are summarized in Table 7.
Table 7 : Results of the photoirradiations of a-keto esters in after-shave lotion

Compound N° mol-% of citronellal liberated mol-% of remaining * starting material
7 12 36
8 2 53
* average of 2 samples
20 Example 11
Release of citronellal or menthone from various citronellyl a-keto esters in a window cleaner and in an all-purpose cleaner
25 10-15 mg of the respective a-keto ester as specified in Table 8 below were weighed into 10 ml volumetric flasks. A solubilizer was added (Cremophor RH40, BASF AG for window cleaner, Triton XI00 (Rohm & Haas) for all-purpose cleaner), before adding

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6 ml of the respective base, i.e. a standard type window cleaner, or a Fabuloso® (registered trademark of Colgate-Palmolive, USA) type all-purpose cleaner, and agitating until the solution became clear. For each irradiation series four samples were prepared for each compound, one of which, wrapped in aluminium foil, served as reference. All the samples were irradiated for 3, 6, or 15 h with either the Xenon or the UV lamp or exposed to outdoor sunlight. In all cases the formation of citronellal or menthone could be smelled after the photolysis. In order to quantify the amount of aldehyde or ketone (and of the remaining starting material) in the application base, the irradiated samples were subjected to GC analysis (extraction and on-column injection). For analysis, 1 g of NaCI was added and the samples were extracted with 3 ml of a 0.35 mM (50 mg/1) solution of undecane (used as internal standard) in iso-octane. The aqueous layer was re-extracted with 2 ml of the wo-octane solution and the two organic phases were combined and injected directly onto a GC column. The results obtained for the different bases are summarized in Table 8.
Table 8 : Results of the photoirradiations of different a-keto esters in different household application bases

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All numbers are average values of 2 or 3 samples.
a) citronellal was released from compounds 7, 13 and 9, respectively, menthone was liberated from compound 18. 5 b) amount of remaining starting material rounded to ±5%.

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Example 12
Dynamic headspace analysis in all purpose cleaners (APC)
5 In order to follow the perfume release under more realistic application conditions, quantitative dynamic headspace analyses were carried out. The formation of citronellal from its precursor in an APC application was compared to the behaviour of free citronellal in the same base. Solutions of a base of the Fabuloso ® type containing either 0.3 mass-% of citronellal precursor 13 or 0.3 mass-% of pure citronellal (≈ 2 molar
10 equivalents) were prepared and deposed in self-built 3.5 1 Pyrex® glass containers covered with a thin window glass plate. The chambers were exposed to outdoor sunlight for 6 h and continuously flushed with an air stream. Every hour the volatiles contained in the air stream were adsorbed on a Tenax cartridge (during 15 min) and the light intensity was measured. The amount of citronellal trapped on the cartridges was
15 desorbed and quantified by GC analysis and are summarized in Table 9.

20

The amount of citronellal released increases with increasing light intensity and decreases when the intensity decreases, with the maximum of release being obtained shortly after the maximum of irradiation was measured. The amount of free citronellal, however, was found to decrease steadily with increasing time and, no dependency on the light intensity was observed.

Time Free citronellal in base Citronellal released from Sunlight
[h] (0.3 mass-%) precursor 13 in base intensity
[ngl1] (0.3 mass-%) [ng 1"'] [lux]
1 154086 1579 38500
2 117735 4752 53500
3 67015 7475 64500
4 50632 7829 63000
5 33215 7297 52500
6 19757 5919 35000
25

Table 9 : Comparison of the dynamic headspace of free citronellal and citronellal released from precursor 13 in a Fabuloso ® type APC irradiated with outdoor sunlight.

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The above described experiment was repeated using 0.3 mass-% of menthone precursor 18 or 0.15 mass-% of pure menthone (≈ 1 molar equivalent) in an APC application of the Fabuloso ® type. Again a dependency of perfume release of the irradiation intensity could be observed, see Table 10, whereas the amount of unprotected menthone decreased continuously over time. Working with molar equivalents instead of mass equivalents shows that the perfume concentration of both systems are in the same order of magnitude. At the beginning of the experiment the concentration of unprotected menthone is about three times stronger than the concentration of the perfume released from the precursor. At the end of the experiment the perfume released from the keto ester contributes more strongly than the free menthone.
Table 10 : Comparison of the dynamic headspace of free menthone and menthone released from precursor 18 in a Fabuloso ® type APC irradiated with outdoor sunlight.
Time Free menthone in base Menthone released from Sunlight
M (0. 15 mass- %) precursor 18 in base intensity
[μg 1-1] (0.3 mass-%) [μg l"1] [lux]
0.5 94.6 33.1 53000
1.5 86.4 59.7 71000
2.5 81.5 70.0 86750
3.5 76.7 68.9 88500
4.5 64.2 63.3 80500
5.5 47.4 60.5 69250
6.5 39.1 48.1 53000
Example 13
Dynamic headspace analysis for the slow release on hair
In order to test the performance of the controlled photochemical release of perfumes in typical body care applications, 0.2 mass-% of precursor 13 dissolved in a leave-in hair

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conditioner of the standard type was sprayed four times on a hair curl (≈ 5 g weight) and irradiated in a glass tube for 3 h with a Xenon lamp. The hair curl had been washed beforehand with an unperfumed shampoo base and the amount of conditioner deposed on the hair was weighed precisely. A comparison experiment with 0.1 mass-% (≈ 1 5 molar equivalent) of unprotected citronellal in the same base was carried out under identical conditions.
During irradiation, the glass tube was connected to a charcoal filter (for air decontamination) and a Tenax cartridge and continuously flushed with an air stream
10 (80 ml/min, corresponding to 4 renewals of air/sampling). The diffusion of citronellal was monitored over a period of three hours and four samplings at t = 0, 1,2 and 3 h were carried out. At each sampling, the citronellal diffusing from the hair was adsorbed onto a Tenax cartridge during 15 min, respectively. The cartridges were then thermally desorbed and the concentration of citronellal precisely quantified by GC (Table 11).
15
Table 11 : Comparison of the dynamic headspace of free citronellal and citronellal released from precursor 13 in a leave-in hair conditioner irradiated with a Xenon lamp.

Time Free citronellal in hair Citronellal released from Xenon light
[h] conditioner precursor 13 in hair conditioner intensity
(0.1 mass-%) [ng 1-1'] (0.2 mass-%) [ng 1-1] [lux]
0 20700 284 78000
1 435 394 86000
2 127 237 86500
3 39 151 87500
Table 11 illustrates that the concentration of unprotected citronellal decreases rapidly with time whereas the citronellal released from the precursor remains almost constant during the experiment with constant light intensity. After only one hour of irradiation the concentration of citronellal released from the precursor is as high as the 25 concentration of the unprotected aldehyde, and thereafter remains higher than the concentration of the unprotected aldehyde.

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Example 14
Dynamic headspace analysis for the slow release on cotton fabric
5
The release of citronellal from precursor 13 was compared to the diffusion of unprotected aldehyde on cotton fabric. For the study, precisely determined amounts of ethanolic solutions containing either 0.2 mass-% of 13 or 0.1 mass-% (≈ 1 molar equivalent) of unprotected citronellal, respectively, were sprayed four times on
10 4 x 20 cm cotton sheets, which had been washed beforehand with an unperfumed detergent base. The irradiation was carried out in a Pyrex ® glass tube for 3 h with a Xenon lamp as described above.
Again a rapid decrease of the released amount unprotected citronellal over time was 15 observed, whereas the release of citronellal from the precursor remained constant with respect to the irradiation intensity, as illustrated in Table 12. The light dependence of the controlled perfume release was verified in a blank experiment. After only 3 h of irradiation comparable concentrations of citronellal were obtained either from the experiment with the free perfume or from release of the precursor compound. 20
Table 12 : Comparison of the dynamic headspace of free citronellal and citronellal released from precursor 13 on cotton sheets irradiated with a Xenon lamp.
Time Free citronellal on cotton Citronellal released from Xenon light
[h] (0.1 mass-% in EtOH) precursor 13 on cotton intensity
. [ng 1'] (0.2 mass-% in EtOH) [ng 1'] [lux]
0-0.25 3022 71 92500
1 - 1.25 1590 168 89250
2-2.25 469 150 80750
3-3.25 116 115 81750

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Example 15 Slow release from cotton sheets treated with fabric softener
5 In a typical experiment, ten cotton towels were washed with an unperfumed, lipase free detergent powder and a fabric softener containing either 0.8 mass-% of keto ester 13 or 0.23 equivalents of the theoretically releasable unprotected aldehyde, respectively. The towels were washed at 40°C without prewashing cycle and dried in the dark overnight. Two towels of each type were irradiated with the above described UV lamp in one
10 covered Pyrex ® crystallizing dish with an approximative volume of 3.5 1 and compared to a set of non irradiated samples. After 3 h of irradiation the towels were analyzed by nine panelists. In all cases the irradiated towels with precursor 13 were characterized to give a fresh, floral, citrus type odor, and the average intensity was given the value 3 on an increasing scale starting at 0 and ending at 10. In the case of the unprotected
15 citronellal or the two blank samples, the panelists detected only a weak odor with an intensity of 1 on the scale from 0 to 10.
The photoperfume precursor can therefore sucessfully be deposed on fabrics in a normal washing cycle, and the release of the desired perfume is detected in perceptible amounts 20 upon irradiation of the dry fabric.
Example 16
Release of menthone from an all-purpose cleaner
An all-purpose cleaner of the Fabuloso ® type containing 0.3% of the compound 18 was prepared. This cleaner and the same cleaner without any perfume were placed into trapezoid flashes which were exposed to sunlight for 3 h (see also Example 11). The 30 thus-obtained samples were then compared on a blind test by a panel of 15 non-experts. When the sample containing the photoperfume was the odd sample. 14 of the panelists

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correctly distinguished the samples. When the odd sample was the one containing the unperfumed base, 13 of the panelists correctly attributed the samples.
5 Example 17
Release of menthone from a window cleaner
A window cleaner of the type described in Example 11 containing 0.3% of the 10 compound 18 was prepared. This cleaner and the same cleaner without any perfume were placed into trapezoid flashes which were exposed to sunlight for 3 h. The thus-obtained samples were then compared on a blind test by a panel of 15 non-experts. When the sample containing the photoperfume was the odd sample, 12 of the panelists correctly distinguished the samples. When the odd sample was the one containing the 15 unperfumed base, 10 of the panelists correctly attributed the samples.

WE CLAIM:
1. Perfuming composition or perfumed article comprising, together with perfuming ingredients, solvents or adjuvants of the kind such as herein described in the preparation of perfume formulations, at least 0.01% of a 2-benzoyl benzoate or a 2-alkanoyl benzoate of formula

or

in which Ri represents hydrogen or a group of formula
—CH—X

in which X and Y can be identical or different and represent, independently from each other, hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group or a group of formula

>1 +

R2 can be identical to R1 or different from it and represents hydrogen, a linear or branched alkyl or alkoxy group from C1 to C12, a phenyl group which is optionally substituted, an olefinic group from C2 to C12, an alcohol group, a CO2M group, a -NR6R7 group, a group of formula

or a polyalcohol or polyether group
R3 represents hydrogen, an alkyl or alkoxy group from C1 to C4, linear or
branched, a OH group or a NH2 group;
R4 and R5, taken separately, have the meaning given above for R1 and can be
identical to or different from R1 or from each other ; or
R4 and R5, taken together, form a bridging group between the two aromatic
rings which bridging group can be a methylene or a keto group
m is an integer from 0 to 3 and n is an integer from 0 to 2; R6 and R7, taken
separately, each represents hydrogen, an alkyl group from C1 to C4, an
alcohol group having an alkyl chain from C1 to C12, or a phenyl group, or, R6
and R7, taken together with the nitrogen atom form a 5-membered or six-
membered ring possibly containing another hetero atom
R8 represents hydrogen, an alkyl group from C1 to C4, an alcohol group
having an alkyl chain from C1 to C12 or a phenyl group;
M represents hydrogen or an alkali metal; and
R* is the organic part derived from a primary or secondary fragrant alcohol
R*OH.
2. Perfuming composition or perfumed article as claimed in claim 1, wherein the 2-benzoyl benzoate is of formula

(D

in which R1 is a branched alkyl group from C3 to C4 containing a secondary
hydrocarbon group;
R2 is a branched alkyl group from C3 to C4 and is identical to R1;
R3 is hydrogen or a linear or branched alkyl group from C1 to C4;
R4is hydrogen or a linear or branched alkyl group from C1 to C4;
R5is hydrogen or a linear or branched alkyl group from C1 to C4;
R* is the organic part derived from a primary or secondary fragrant alcohol
R*OH.

3. Perfuming composition or perfumed article as claimed in claim 1, wherein Ri is an isopropyl group.
4. Perfuming composition or perfumed article as claimed in any of claims 1 to 3, wherein the fragrant alcohol R*OH from which is derived R* is geraniol, (E)-3,3-dimethyl-5-(2',2', 3'-trimethyl-3'-cyclopenten- 1 '-yl)-4-penten-2-ol or phenethylol.
5. Perfuming composition or perfumed article as claimed in claim 1, wherein the 2-benzoyl benzoate is geranyl 2-benzoyl benzoate, geranyl 2-(2-isopropylbenzyl)benzoate, geranyl 2-(2',4'-diisopropylbenzoyl)benzoate or (E)-3 ,3-dimethyl-5-(2\2',3' -trimethyl-3'-cyclopenten- 1' -yl)-4-penten- 1-yl 2-(2',4'-diiso-propyl-benzoyl)benzoate.
6. Perfuming composition or perfumed article as claimed in any of the preceding claims, wherein there is added to the said composition or article a hydrogen radical source which is a solvent selected from the group consisting of primary or secondary aliphatic alcohols, aromatic alcohols, diols and polyols, ketones, esters, alkyl-substituted aromatic compounds, ethers, aminoalcohols and linear and branched hydrocarbons, provided that said solvents contain a linear alkyl group higher than ethyl or a branched secondary alkyl group.
7. Perfuming composition or perfumed article as claimed in claim 6, wherein the solvent is isopropanol, 1-dodecanol 2-tridecenol, butanol or amyl alcohol.
8. Perfuming composition or perfumed article as claimed in claim 1 in the form of a perfume or a cologne, a bath or shower gel, a hair-care product, a cosmetic preparation, a body deodorant, a solid or liquid air-freshener, a detergent or a fabric softener, or a household product.
Dated this 24th day of October, 2000.
[RANJNA MEHTA-DUTT]
OF REMFRY & SAGAR
ATTORNEYS FOR THE APPLICANTS

Documents:

IN-PCT-2000-00539-MUM-ABSTRACT(AMENDED)-(16-6-2004).pdf

in-pct-2000-00539-mum-cancelled pages(16-6-2004).pdf

IN-PCT-2000-00539-MUM-CLAIMS(24-10-2000).pdf

in-pct-2000-00539-mum-claims(granted)-(16-6-2004).doc

in-pct-2000-00539-mum-claims(granted)-(16-6-2004).pdf

IN-PCT-2000-00539-MUM-CLAIMS(GRANTED)-(28-2-2007).pdf

in-pct-2000-00539-mum-correspondence(16-6-2004).pdf

IN-PCT-2000-00539-MUM-CORRESPONDENCE(29-9-2006).pdf

IN-PCT-2000-00539-MUM-CORRESPONDENCE(IPO)-(23-4-2007).pdf

in-pct-2000-00539-mum-correspondence(ipo)-(28-2-2007).pdf

IN-PCT-2000-00539-MUM-DESCRIPTION(COMPLETE)-(24-10-2000).pdf

IN-PCT-2000-00539-MUM-DESCRIPTION(GRANTED)-(28-2-2007).pdf

IN-PCT-2000-00539-MUM-FORM 1(13-2-2001).pdf

in-pct-2000-00539-mum-form 1(24-10-2000).pdf

in-pct-2000-00539-mum-form 1a(19-11-2003).pdf

in-pct-2000-00539-mum-form 2(granted)-(16-6-2004).doc

in-pct-2000-00539-mum-form 2(granted)-(16-6-2004).pdf

IN-PCT-2000-00539-MUM-FORM 2(GRANTED)-(28-2-2007).pdf

IN-PCT-2000-00539-MUM-FORM 2(TITLE PAGE)-(GRANTED)-(28-2-2007).pdf

in-pct-2000-00539-mum-form 3(19-11-2003).pdf

in-pct-2000-00539-mum-form 3(24-10-2000).pdf

in-pct-2000-00539-mum-form 4(26-3-2004).pdf

in-pct-2000-00539-mum-form 5(24-10-2000).pdf

in-pct-2000-00539-mum-form-pct-ipea-409(16-6-2004).pdf

in-pct-2000-00539-mum-form-pct-isa-210(16-6-2004).pdf

in-pct-2000-00539-mum-petition under rule 137(16-6-2004).pdf

in-pct-2000-00539-mum-petition under rule 137(19-11-2003).pdf

in-pct-2000-00539-mum-power of authority(10-10-2000).pdf

in-pct-2000-00539-mum-power of authority(16-6-2004).pdf

in-pct-2000-00539-mum-power of authority(17-11-2003).pdf

IN-PCT-2000-00539-MUM-POWER OF AUTHORITY(19-11-2003).pdf

IN-PCT-2000-00539-MUM-POWER OF AUTHORITY(25-5-2001).pdf

IN-PCT-2000-00539-MUM-SPECIFICATION(AMENDED)-(16-6-2004).pdf

IN-PCT-2000-00539-MUM-WO INTERNATIONAL PUBLICATION REPORT(24-10-2000).pdf

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Patent Number

204609

Indian Patent Application Number

IN/PCT/2000/00539/MUM

PG Journal Number

24/2007

Publication Date

15-Jun-2007

Grant Date

28-Feb-2007

Date of Filing

24-Oct-2000

Name of Patentee

FIRMENICH SA

Applicant Address

1, ROUTE DES JEUNES, P.O. BOX 239, 1211 GENEVA 8, SWITZERLAND.

Inventors:

#	Inventor's Name	Inventor's Address
1	ANDREAS HERRMANN	5, RUE HENRI CHRISTINE, 1205 GENEVA, SWITZERLAND.
2	CHRISTIAN VIAL	5, RUE BAULACRE, 1202 GENEVA, SWITZERLAND.
3	JANA PIKA	478 EWING STREET, PRINCETON, NEW JERSEY 08540, USA.

PCT International Classification Number

A 61 K 7/00

PCT International Application Number

PCT/IB99/00890

PCT International Filing date

1999-05-17

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09 / 085,593	1998-05-28	U.S.A.