Title of Invention

"A NORBORNANE COMPOUND AND PROCESS FOR PREPARING THE SAME THEREOF"

Abstract A norbornane compound and a process for preparing the same thereof Derivatives of 2,3-dimethyl-norbornane and -norbornene with various hydroxylated or acylated and optionally unsaturated, groups at position 3 are new. Compounds of formula (I) are new. R1 = (a) -CH(CH3)OH/ -CH(CH3)OCOR, -CH(CH3)XCH2CH(OH)R" or -CH(CH3)OCHR"CH2OH (if the dotted line bond is present) or (b) -CH(CH3)OH, -CH(CH3)OCOR, -COCH3, a group of formula (II), -CH(CH3)XCH2CH(OH)R", -CH2CH2XCH2CH(OH)R, -CH=CH2, -CH=CHCOR", -CH2CH2CHR"OH, CH2CH2CHR"OCOR, -CH=CH-CH(OH)R" or -CH=CH-CHR"OCOR (if the dotted line bond is absent); R = H, methyl, ethyl, n- or iso-propyl, butyl, isobutyl, CH3(CH2)4-, (CH3)2CHCH2-, CH2=CH- or (CH3)2C=CH-; R" = H, methyl or ethyl; X = O, N or S Independent claims are also included for (1) a method for the preparation of (I) from a starting material or intermediate of formula (III);; (2) perfumed products containing (I), especially perfumes, toilet water, cosmetics such as soap, shower or bath gel, shampoo and other hair hygiene products, other care products (for washing and softening) and deodorants for personal use or in the ambient air.
Full Text FIELD OF THE INVENTION
The present invention relates to novel norbornane or
norbornene derivatives, which have a particular fragrance, especially a woody or amber odor, and to their use in the fragrance industry.
BACKGROUND OF THE INVENTION
The term "fragrance industry" is used herein to denote not only perfumery in the strict sense of the word, but also other fields in which the odor of products is important, in particular cosmetics, cleaning products, air fresheners and the like.
It has been sought for a long time to synthesize novel compounds with a given odor, for use in the fragrance industry. The inspirational basis has often been natural products, on which attempts have been made to separate out the molecule(s) with olfactory properties.
In particular, the odor of sandalwood oil has been the subject of much research. After having identified the two main molecules that give natural sandalwood oil its odor, namely a-santalol and p-santalol, attempts were made to discover other molecules that might contribute to this odor. Attempts were also made to synthesize molecules that can reproduce this odor. The history of this research is reviewed in the article "The Chemistry


of Sandalwood Fragrance - a Review of the Last Ten Years" by E.-J. Brunke et al., 15th Journees Int. Huiles Essentielles, Dignes-les-Bains, France, 5-7 September 1996.
Patent US 4,229,600 relates to particular norbornane or norbornene derivatives that have the odor of sandalwood oil.
In the search for novel molecules, inspiration was drawn, of course, from the structures of known molecules, but experience has shown that the result was often random. Mention may be made, for example, of the article mentioned above in which is described a structure/odor correlation model, immediately followed by a counterexample, a molecule synthesized according to this model, but which does not have the expected odor. This same article cites a certain number of molecules of similar structure but whose olfactory properties are different, some having an odor, and others not.
Thus, there is no systematic method for designing a molecule as a function of the desired odor, from known molecules, via the implementation of logical and reproducible steps.
After extensive research, the Applicant Company has discovered a novel family of odoriferous molecules.
DETAILED DESCRIPTION
This family is represented by the following formula:

(Formula Removed)

in which the dotted bond is present or absent, and in
which R1 represents:
when the dotted bond is present
-CHCH3OH or -CHCH3OCGR or -CHCH3XCH2CHOHR' or
-CHCH3OCHR'CH2OH or
(Formula Removed)

when the dotted bond is absent
-CHCH3OH or -CHCH3OCOR or -COCH3 or
(Formula Removed)

or -CHCH3XCH2CHOHR' or -CH2CH2XCH2CHOHR' or -CHCH3OCHR'CH2OH or -CHCHCOR' or -CH2CH2CHR' OH or -CH2CH2CHR'OCOR or -CHCHCHOHR' or -CHCHCHR'OCOR, in which R represents H, Me, Et, Pr, isoPr, But, isoBut, CH3(CH2)4, (CH3)2CHCH2, CH2CH or (CH3)2CCH, R' represents H, Me or Et, and X represents 0, N or S.
Each of the compounds of this family may be synthesized


directly or indirectly from compound (c) below:

This compound, 1-(2,3-dimethylbicyclo[2,2,1]hept-5-en)-ethanone, which has already been described in the literature, and which is referred to in this patent application as Presantone, may be obtained, for example, by condensation of 3-methyl-3-penten-2-one (a) and cyclopentadiene (b) , in a Diels-Alder reaction in aqueous phase, catalyzed with methylrhenium trioxide.

Needless to say, other reactions for preparing Presantone may be used, for example with other catalysts, or a particular solvent.
3-methyl-3-penten-2-one (a) is readily obtained, for example, by condensation of acetaldehyde or paraldehyde with methyl ethyl ketone. This product is commercially available and inexpensive.
Cyclopentadiene (b) may be obtained, for example, via several known methods for the depolymerization of dicyclopentadiene, which is produced by the petroleum industry.

Presantone may be the starting material or an intermediate in the synthesis of the compounds according tc the invention. By way of nonlimiting example, a reaction scheme for the preparation of novel compounds according to the invention is given below.


The abbreviations Me, Et, Pr, isoPr, But and isoBut have the usual meanings known to those skilled in the art, namely methyl, ethyl, propyl, isopropyl, butyl and isobutyl, respectively.
The hydrogenation of Presantone (c) at low temperature (between 20°C and 50°C) in the presence of Raney nickel, palladium-on-charcoal or other suitable catalysts gives the saturated ketone (1). This ketone has a strong resinous woody note, the originality of which is appreciated by fragrance formulators.
According to the invention, the acetal (2) of the ketone (1) with, for example, propylene glycol, obtained via the standard acetalization methods, is hydrogenated in the presence, for example, of pure palladium-on-charcoal or mixed palladium-on-charcoal to open the acetal into the alcohol ethers (3) and (3' ) , which are separable by chromatography. The operation is performed with or without a solvent. The process is preferably performed under 30 kg to 120 kg of hydrogen at temperatures of between 120°C and 180°C. The alcohol ethers (3) and (3') obtained have a strong, woody, long-lasting odor, whence arises their great interest for the fragrance industry, cosmetics, soaps, cleaning products, detergents and other fragranced products. The acetal (2) is itself also a novel compound that is

advantageous on account of its odor.
The reduction of Presantone (c) with sodium borohydride gives the unsaturated alcohol (4), a novel product that is also advantageous.
The standard methods of esterification, for example using the acid anhydrides, allow the esters (5) to be obtained, i.e. the formic, acetic, propionic, butyric, isobutyric, etc. esters especially, from the alcohol (4) . These esters are all novel compounds that may be used in the fragrance industry for their originality in the woody notes.
The hydrogenation of Presantone (c) in the presence of Raney nickel, for example at temperatures of between 100°C and 180°C under 20 kg to 100 kg of hydrogen, gives the saturated alcohol (6), which is also an advantageous compound.
The esterification of this saturated alcohol (6) with acid anhydrides, for example, gives the saturated esters (7), R being a hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, CH3(CH2)4, (CH3)2CHCH2, CH2CH or (CH3)2CCH radical. All these novel esters have odors that are advantageous for the fragrance industry, due to their original fruity woody nature.

A second route was found from the saturated alcohol (6) . Via dehydration of this alcohol via well-known methods, the ethylenic hydrocarbon (8) is obtained.
Acylation, for example with acetic or propionic anhydride in the presence of boron trifluoride etherate or zinc chloride, gives the ethylenic ketones (9) . Any other known acylation method may be used.
Reduction of the ethylenic ketones (9) with sodium borohydride in alcohol is a simple method for obtaining the ethylenic alcohols (12), which are novel compounds that are also very advantageous. The esters (13) of the alcohols (12), obtained via standard methods, for example using the acid anhydrides, develop milder but long-lasting woody notes which are also highly appreciated by fragrance formulators.
The total hydrogenation of the ethylenic ketones (9) via the standard methods gives the saturated alcohols (10), and their esterification via any usual method, for example using the acid anhydrides, gives the esters (11), R being a hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, CH3(CH2)4, (CH3)2CHCH2, CH2CH or (CH3)2CCH radical. These compounds also have advantageous woody odors.

It is also possible to prepare compounds (14) and (14') - which are separable by chromatography - by opening ethylene, propylene or butylene oxide, to give ethylene glycol, propylene glycol or butylene glycol, respectively, with the alkoxide of compound (4):
Another process for preparing compounds (3) and (3') from compound (6) may be mentioned. These compounds may be obtained from the alkoxide of compound (6) via the opening of ethylene, propylene or butylene oxide to give the corresponding glycol:

The invention also relates to another process for preparing compounds (3) and (3'), characterized in that the starting material or an intermediate is the novel compound of formula


in which R' is H, Me or Et.
The acetal (2') may also be the starting material or the intermediate in the synthesis of the compounds of formulae (14) and (14') .
The acetal (2') may be prepared, for example, directly by Diels-Alder reaction catalyzed with FeCl3between cyclopentadiene and the acetal (d).
The acetal (d) (in which R' = CH3) may be obtained by acetalization from the methyl-pentenone (a) and propylene glycol.
In one embodiment, the acetal (2') allows the synthesis of compounds (3) and (3'), for example via a one-step hydrogenation catalyzed with palladium-on-charcoal.
The acetal (2') also allows the synthesis of compounds (14) and (14') via hydrogenation, for example with a hvdri dp..

The invention also relates to other novel compounds, similar to compounds (3) and (14), in which the oxygen atom has been replaced with a sulfur or nitrogen atom. These are the compounds (15) to (18) below:

The sulfur compounds (15) [(15a), (15b) and (15c)] may be obtained from compound (1) according to the following process:

The oxathiolane (d) may be obtained via a standard acetalization method, and the acetal is then opened regiospecifically via methods described in the literature, for example with DIBAL in refluxing

toluene.
The sulfur compounds (17) [(17a), (17b) and (17c)] may be obtained in the same manner as above, starting with Presantone (c).

The nitrogen compounds (16) [(16a), (16b) and (16c)] and the sulfur compounds (15) [(15a), (15b) and (15c)], may be obtained from the alcohol (6), for example via mesylation, tosylation or halogenation, followed by nucleophilic substitution with the corresponding amino alcohol or thiol:

The amino alcohols (18) [(18a), (18b) and (18c)], and the thioethers (17) [(17a), (17b) and (17c)] may be obtained in the same manner as above, starting with the alcohol (4). The ethylenic hydrocarbon (8) also allows the synthesis of analogs containing a heteroatom in the side chain:


The primary alcohol or thiol obtained by hydroboration of the double bond or addition of H2S is then condensed with ethylene, propylene or butylene oxide to give compounds (19) [a to c] and (20) [a to c] . Propylene oxide may optionally be replaced with the corresponding haloacetone to give, after reduction with NaBH4, the expected alcohols (19b) and (20b).
The amino analogs (21) [a to c] may be obtained from the primary alcohol derived from hydrogenation via tosylation (or mesylation), followed by a substitution with the corresponding amino alcohol:

A subject of the invention is the compounds represented

by the general formula (I) in the form of a mixture of diastereoisomers in variable proportions, in particular the racemic mixtures.
Moreover, some of the diastereoisomers or enantiomers have olfactory properties that are as advantageous as the compounds obtained in the form of diastereoisomeric
mixtures.
A subject of the invention is also the pure diastereoisomers or enantiomers of the novel compounds represented by the general formula (I), which may be separated by preparative gas chromatography. They may also be synthesized from optically active compounds, for example R or S propylene glycol and the alcohol (6) derived from the enantioselective reduction of Presantone (1-4), and purified by distillation.
A subject of the invention is also the processes for preparing the novel compounds.
Each of the novel compounds, is advantageous on account of its odor, in particular its woody odor. Compound (3) with R' = Me is particularly advantageous. Moreover, the invention has an obvious economic advantage arising from the: simplicity of the reactions used and the low cost of the starting materials used.

On account of their olfactory qualities, these various compounds thus find very varied use in the fragrance industry for the preparation of fragrancing bases and concentrates, perfumes and eaux de toilette, and also in the fragrancing of various consumer articles, such as soaps, shower gels or bath gels, shampoos and other hair hygiene products, cosmetic preparations, body deodorants, air fresheners, or alternatively textile detergents or softeners and cleaning products.
In these applications, the compounds according to the invention may be used alone or, as is more common in the fragrance industry, as a mixture with other fragrancing ingredients, solvents or adjuvants commonly used in the fragrancing industry, and which a person skilled in the art is capable of selecting as a function of the desired effect and of the nature of the product to be fragranced.
The concentrations in which these compounds and the isomeric mixtures thereof may be used to obtain the desired fragrancing effects vary within a very wide range of values (0.1% to 99%), it being well known that these values depend on the nature of the article to be fragranced, the desired odoriferous effect and the nature of the other ingredients in a given composition.

A subject of the invention is thus also the use of the novel compounds for the preparation of a fragrancing composition or a fragranced article, in the applications described above, in particular in perfumery, in cosmetics, for example for shampoos or soaps, and for cleaning products, such as softeners or detergents.
A subject of the invention is also the fragranced products comprising at least one compound according to the present invention, whether in the field of perfumery, cosmetics or cleaning.
The examples that follow further illustrate the various processes for manufacturing the novel compounds according to the invention and also their use and their advantage. These examples are given merely for the purpose of illustration and cannot be considered as limiting the invention.
Example 1: Diels-Alder reaction (Presantone (c)) 110 g of dry toluene are placed in a 500 ml round-bottomed flask with a magnetic stirrer, a thermometer, an addition funnel, and under nitrogen.
After cooling to 0°C, 4 g of aluminum chloride are added in a single portion, followed by addition, at

about 10°C, of 88 g of 94% 3-methyl-3-penten-2-one (a) over 20 to 30 minutes, while cooling gently. A solution of 66 g of cyclopentadiene (b) in 140 g of dry toluene is then added, at between 12 °C and 14 °C, over 1 hour 10 minutes to 1 hour 20 minutes, while maintaining the temperature by cooling.
After separation of the phases by settling, the organic phase is washed with dilute hydrochloric acid (100 ml) and with a 5% carbonate solution. After concentrating the solvent under vacuum, the product is distilled off under 2 mm of vacuum (b.p.: 56-70°C/2 mm) . 128 g of distillate are obtained. This product is taken up in toluene and treated with triethylamine and with a sodium carbonate solution. After washing and evaporating off the solvent under vacuum, the product is redistilled under a vacuum of 1 mm. 112 g of l-(2,3-dimethylbicyclo[2,2,1]hept-5-en)ethanone are obtained (b.p.: 56-60°C/l mm), yield: 76%.
The mixture is left stirring at 14-15°C for a further 15 minutes and is then cooled to 0°C and a solution of 20 g of 32% hydrochloric acid in 100 g of water is then added rapidly while allowing the temperature to rise. The vapor-phase chromatography analysis shows the presence of two main isomers (32% and 56%). The analyses of the infrared and mass spectra correspond to the structures of the expected compounds.

Example 2: Saturated ketone (1)
The hydrogenation of 50 g of the ethylene ketone (c) in
the presence of 0.5 g of Raney nickel at room
temperature, and at a low pressure of hydrogen (1 to
10 kg) absorbs the theoretical amount of hydrogen over
about 2 hours.
After separating out the catalyst, the product is
distilled under vacuum. The saturated ketone (1) is
obtained virtually quantitatively.
The product distils at 54°C-58°C under 1 mm of vacuum.
The vapor-phase chromatography analysis shows two main
peaks and the infrared and mass spectra correspond to
the structures of the expected compounds.
Example 3: Ethylenic alcohol (4)
Via reduction of 40 g of Presantone (c) in 200 ml of
96% alcohol, by adding 6 g of sodium borohydride
portionwise at 25°C over 2 hours, followed by gradually
bringing the temperature to 40°C over 2 hours and
maintaining the mixture at this temperature for a
further 3 hours, the total reduction of the ketone
function to an alcohol is obtained.
After slow acidification, with 2% hydrochloric acid,
extraction with toluene and washing, the product is
concentrated under vacuum and then distilled.
36 g of ethylenic alcohol (4) are obtained, with a
boiling point of 72-75°C under 1 mm of vacuum, i.e.

90 mol% yield.
The vapor-phase chromatography analysis shows the presence of 3 main isomers that have very similar mass and infrared spectra.
Example 4: Ethylenic esters (5)
By slowly bringing 10 g of ethylenic alcohol (4) in
10 g of acetic anhydride to 115-120°C over 2 hours, the
ethylenic acetate (5) is obtained.
The product obtained is concentrated under a vacuum of
30 mm to distil off the acid and the excess acetic
anhydride through a 25 cm Vigreux column. The vacuum is
slowly increased to 1 mm and the ethylenic acetate (5)
is distilled off.
10 g of ethylenic acid (5) are obtained with a boiling
point of 73-76°C under 1 mm of vacuum.
The vapor-phase chromatography, MS and IR analyses
correspond with the structures of the expected
compounds.
The propionic, butyric and isobutyric esters of the
ethylenic alcohol (4) are obtained by heating the
alcohol (4) with the corresponding anhydrides, in the
presence of a small amount of toluene, to maintain the
reflux temperature at about 125-130°C.
The reflux time is increased to 2 hours to complete the
esterification.
By distillation under vacuum, the acids and the

anhydride esters are separated. By increasing the
vacuum, the esters (5) are obtained.
Propionate of the ethylenic alcohol (5) with a boiling
point of 80-83°C under 1 nun of vacuum.
Butyrate of the ethylenic alcohol (5) , with a boiling
point of 88-91°C under 1 mm of vacuum.
Isobutyrate of the ethylenic alcohol (5), with a
boiling point of 85-88°C under 1 mm of vacuum.
Example 5: Saturated alcohol (6)
100 g of ethylenic ketone (c) are placed in an
autoclave and are stirred and heated in the presence of
2 g of Raney nickel.
After flushing 3 times with 10 kg of hydrogen, the
pressure is brought to 30 kg and the autoclave is
heated to 150-160°C with stirring.
The hydrogenation is performed under 60 kg of hydrogen
until the pressure no longer falls (5 to 6 hours).
The crude saturated product (5) is distilled off under
1 mm of vacuum in an apparatus equipped with a 20 cm
Vigreux column.
97 g of alcohol (5) are obtained, with a boiling point
of 72-75°C under 1 mm of vacuum.
The vapor-phase chromatography analysis shows that
there are 4 main isomers, which have very similar mass
and infrared spectra.

Example 6: Saturated esters (7)
The saturated esters are obtained via the standard
method used to make the unsaturated esters (Example 4),
i.e. heating the saturated alcohol (6) in the presence
of the corresponding acid anhydride.
Among the compounds obtained:
Acetate of the saturated alcohol (7), with a boiling
point of 73-76°C under 1 mm of vacuum,
Propionate of the saturated alcohol (7), with a boiling
point of 80-83°C under 1 mm of vacuum,
Butyrate of the saturated alcohol (7), with a boiling
point of 88-91°C under 1 mm of vacuum,
Isobutyrate of the saturated alcohol (5), with a
boiling point of 85-88°C under 1 mm of vacuum.
Example 7: Alcohol ether (3) 7.1. Acetal (2)
The acetal of the saturated ketone (1) and of propylene glycol may be prepared by refluxing, using a 30 cm Vigreux column and a water separator, propylene glycol (50 g), the ketone (1) (80 g) dissolved in toluene (40 g) and p-toluenesulfonic acid (0.4 g) as acid catalyst. The water is removed azeotropically (refluxing for 18 to 20 hours).
The toluene may also be removed and the water eliminated by distilling it off under vacuum. The reaction mixture is washed with 5% sodium carbonate

solution and then with water to neutral pH.
Fractionation under a strong vacuum in apparatus
equipped with a 50 cm Vigreux column allows the
following to be obtained:
25 g of recovered ketone (1) to be recycled, with a
boiling point of 54-58°C under 1 mm of vacuum,.
65 g of acetal (2), with a boiling point of 64-58°C
under 1 mm of vacuum,
10 g of intermediate fractions to be recycled.
7.2. Alcohol ether (3)
50 g of acetal (2), 100 g of isopropanol and 0.5 g of
palladium-on-charcoal are placed in a stirred
autoclave.
After flushing with hydrogen, the autoclave is
maintained at between 160 and 170°C under 50-60 kg of
hydrogen for 18 to 24 hours.
The reaction progress is monitored by vapor-phase
chromatography and the reaction is stopped when the
percentage of acetal (2) has fallen to 5-6%.
After separating out the catalyst, the product is
distilled off under 1 mm of vacuum in an apparatus
equipped with a 50 cm Vigreux column. 6 g of head
fractions are obtained.
Boiling point 40-50°C, 16 g of ketone (1) + acetal (2),
with a boiling point of 54-68°C under 1 mm of vacuum,
to be recycled, and 25 g of alcohol ether (3), with a

boiling point of 85-92°C under 1 mm of vacuum. The mass and infrared spectra correspond with the structures of the expected compounds.
Example 8: Ethylenic ketone (9)
8.1. Dehydration of the alcohol (6)
150 g of alcohol (6) and 100 g of boric acid are placed
in a 500 ml round-bottomed flask.
The mixture is heated under 4 0 mm of vacuum to remove
the water of boratization and is then brought to a
temperature of 230-250°C to dehydrate. After distilling
off 10 to 80 g of ethylenic compound (8), the
dehydration is continued by introducing the alcohol (6)
gradually as the dehydration proceeds.
Starting with 1 kg of alcohol (6), 880 g of ethylenic
compound (8) containing 7-10% of alcohol (5) are
obtained.
By fractionation on a 30 cm Vigreux column, 800 g of
ethylenic compound (8) are separated out and 70 g of
alcohol (6) to be recycled are recovered.
8.2. Ethylenic ketone (9)
120 g of ethylenic compound (8) and 120 g of acetic anhydride are placed in a 1 liter round-bottomed flask with magnetic stirring, and the mixture is heated to 70-75°C. 16 ml of boron trifluoride etherate are then introduced over 15 minutes at 75-80°C. The temperature

and stirring are maintained for 3 hours at 80-82°C. After cooling to about 60°C, the excess acetic anhydride is decomposed by adding, slowly at the start, 320 g of water while maintaining the temperature at about 60-65°C.
The organic phase is separated out and the aqueous phase is extracted with twice 60 ml of cyclohexane. The combined organic phases are washed with 10% sodium carbonate solution and then with water.
After concentrating the solvent under a gentle vacuum, the crude product (138 g) is fractionated in an apparatus with a 30 cm Vigreux column. Under 5 mm of vacuum, 80 g of starting material (8) to be recycled and 32 g of ethylenic ketone (9) with a boiling point of 75-88°C under 1 mm of vacuum are recovered.
Example 9: Ethylenic alcohol (13)
30 g of ethylenic ketone (9) and 75 g of 96° ethanol are
placed in a 250 ml round-bottomed flask with magnetic
stirring and a thermometer. While cooling slightly, to
maintain 20-25°C, 3 g of sodium borohydride are added
portionwise. After the introduction, the mixture is
stirred for 6 hours at room temperature and is then
gradually heated to 40°C over 2 to 3 hours, and then
maintained at 40-45°C for 4 hours.
A large proportion of the alcohol is concentrated under
a gentle vacuum. 30 g of water are added to the

residue, followed by slow acidification, while maintaining the temperature at 20-25°C, with 16 g of concentrated hydrochloric acid diluted with 50 g of water. 30 ml of toluene are then added, followed by separation of the phases by settling. The organic phase is separated out and the aqueous phases are extracted with twice 20 ml of toluene. After combining the organic phases, they are washed twice with 80 ml of water. The toluene is then concentrated under vacuum and the residue (30 g) is distilled under a strong vacuum in an apparatus equipped with a 15 cm Vigreux column.
25 g of ethylenic acid (12) are thus obtained, with a boiling point of 85-92°C under 1 mm of vacuum, along with 3 g of product to be recycled. The infrared and mass spectra correspond to the structures of the expected compounds.
Example 10: Ethylenic acetate (13)
30 g of ethylenic alcohol (12) and 25 g of acetic
anhydride are placed in a 100 ml round-bottomed flask
equipped with a magnetic stirrer, a thermometer and a
20 cm Vigreux column.
The mixture is heated under a gentle vacuum, such that
the bulk temperature is 115-120°C, for 2 hours. The
vacuum is then increased to distil off the acetic
acid/anhydride mixture. The final bulk temperature is

125-130°C.
Under 1 mm of vacuum, the acetate (14) with a boiling point of 80-88°C under 1 mm of vacuum is then distilled off. 27 g of acetate (13) and 3 g of product to be recycled are obtained. The infrared and mass spectra correspond to the structures of the expected compounds.
Example 11: Saturated alcohol (10)
30 g of ethylenic ketone (9) and 0.6 g of Raney nickel
are placed in a stirred and heated autoclave. After
flushing with hydrogen, the mixture is brought to 150-
160°C under 60 kg of hydrogen.
The reaction is complete after 12 hours. The catalyst
is separated out and the product is distilled off under
a strong vacuum. 27 g of saturated alcohol (11) are
obtained, with a boiling point of 82-90°C under 1 mm of
vacuum.
Example 12: Saturated acetate (12)
By performing the process as for the ethylenic acetate (13) on 25 g of saturated alcohol (10), 26 g of acetate (11), with a boiling point of 78-86°C under 1 mm of vacuum, are obtained by distillation.
Example 13: Alcohol ether (3) via the acetal (2')
4 6.00 g of dichloromethane are placed under nitrogen in
the receiving flask of a distillation apparatus on

which is mounted a 30 cm Vigreux column, and the flask is cooled to 0°C. The oil bath of the distillation apparatus is heated to about 195°C in order to obtain a temperature of 165°C inside the three-necked flask. 13.80 g (0.45 mol) of dicyclopentadiene are introduced dropwise via the top of the column, the cyclopentadiene thus freshly depolyxnerized being recovered in the cooled solvent. 56.00 g of a solution of cyclopentadiene in dichloromethane, i.e. a potential of 10.00 g of cyclopentadiene (0.151 mol) are obtained over 4 hours. Yield: 72.5%. The solution is used directly in the following Diels-Alder reaction. 14.80 g (0.076 mol) of 80.0% 2,4-dimethyl-2-(1-methyl-propenyl) [1,3] dioxalane and 1.5 g of iron (III) chloride silica are introduced into the round-bottomed flask under nitrogen and at room temperature, and the mixture is cooled to 0°C. 56.00 g of the solution of cyclopentadiene in dichloromethane are added dropwise at this temperature over 10 minutes. The mixture is stirred for 2 hours at 0°C and then for 15 hours while allowing the bulk temperature to return to room temperature. The catalyst is filtered off and the solvent is evaporated under reduced pressure (about 35 mmHg = 4.67 x 103 Pa). 23.00 g of a pale yellow oil are obtained, and are transferred into a microdistillation apparatus with a 15 cm Vigreux column. 1.5 g (5.6 mmol) of 83% 2-(2,3-

dimethylbicyclo[2.2.1]hept-5-en-2-yl)-2,4-dimethyl-
[1,3]dioxalane (sum of the isomers) are obtained.
Yield: 7.4%.
Example 14: Olfactory evaluation
In a first stage, the olfactory characteristics of compound (3) when R' is methyl were evaluated by a panel at the same time as the olfactory characteristics of commercially available known compounds. The evaluation panel is composed of several professionals, who evaluate each compound qualitatively and quantitatively. The results of the evaluations are collated in the table below.

Odor: Woody Cedar Amber Vetiver Iris Camphor Leather
Compound (3) XXX XX XX XX
Iso E Super(1) XXX X XXX X
Vertofix(2) XXX XX XX X
Bois-ambrene'31 XXX XX X
(1) 2-Acetyl-l,2,3, 4,5, 6, 7, 8-octahydro-2, 3, 8, 8-tetra-
methylnaphthalene (mixture of isomers); from: Inter
national Flavors & Fragrances, USA.
(2) 4-Acetyl-l, 1, 6-trimethyl-6, 8a-ethano-
1, 2, 3, 4 , 5, 6, 7, 8, 8a-octahydronaphthalene; from: Inter-

national Flavors and Fragrances, USA.
(3) (Ethoxymethyl) cyclododecane; from: Henkel.
These three reference products are very widely used in fragrancing compositions for soaps, detergents and softeners or shampoos. They are also very commonly used in alcohol-based perfumery.
It may be observed that compound (3) has a woody, cedar, amber and camphor nature.
In a second stage, the impact or the olfactory characteristics of compound (3) when it is applied to a support were evaluated. Three different supports were used:
as a 10% solution in 96° alcohol,
in a standard softening base at 0.5%: evaluation
on wet laundry and on dry laundry,
in a standard shampoo base at 0.5%: evaluation of
the base coverage and diffusion in solution in hot
water.
Two base fragrancing compositions were prepared by mixing the ingredients listed below. The tests were performed by adding 50 parts by weight of compound (3) to the base mixture.

COMPOSITION 1 Test in detergent (application at 0.5%)
COMPONENTS GERANIUM RECO VMF(1) BENZYL ACETATE
DIMETHYLBENZYLCARBINYL ACETATE PHENOXYALLYL ACETATE PHENYLETHYL ALCOHOL HEXYLCINNAMALDEHYDE C12 LAURYLALDEHYDE C12 MNA ALDEHYDE GAMMA-UNDECALACTONE CITRONELLOL COUMARIN
DIHYDROFLORIFONNE(2) DIHYDROMYRCENOL VERDYL ACETATE (3) MADAGASCAR CLOVE ESS. LILIAL(4> METHYLIONONE PHENYL OXIDE ROSE OXIDE AMYL SALICYLATE BENZYL SALICYLATE TRIPLAL'51 VERDOX(6)


TEST 1 TEST 2
20 20
60 60
20 20
2 2
100 100
200 200
2 2
3 3
7 7
30 30
15 15
1 1
50 50
15 15
12 12
70 70
55 55
25 25
3 3
95 95
135 135
4 4
20 20

OXYPHENYLON at 10% EDG 6 6
COMPOUND (3) 50
TOTAL 950 1000
(1) V. MANE FILS
(2) 1- (2, 6, 6-trimethyl-3-cyclohexen-l-yl) -2-buten-l-
one
(3! 3a, 4,5,6,7, 7a-hexahydro-4, 7-methano-lH-inden-5
(or 6)-ol acetate - from Givaudan (Switzerland)
(4> p-tert-butyl-alpha-methyl-hydrocinnamaldehyde -
from Givaudan (Switzerland)
2, 4-dimethyl-3-cyclohexene-l-carbaldehyde - from
IFF (International Flavors and Fragrances, United
States)
COMPOSITION 2 Test in fragrance (application at 7%)
COMPONENTS TEST 1 TEST 2
5 5
90 90
25 25
80 80
80 80
10 10
20 20
STYRAX RECO VMF(1)
ISOBORNYLCYCLOHEXANOL to 50% EDG YLANG RECO(1) BENZYL ACETATE PHENYLETHYL ALCOHOL ANISALDEHYDE BACDANOL(2)

CITRONELLOL
COUMARIN
DIHYDROMYRCENOL
ETHYLVANILLIN
GALAXOLIDE(3)
GERANIOL
HELIOTROPINE
PURE IRISONE(4>
LILIAL
METHYLIONONE
BENZYL SALICYLATE
VANILLIN
VERTENEX(5)
CIO CAPRYLALDEHYDE at 10% DPG
C12 LAURYLALDEHYDE at 10% DPG
INDOL at 10% DPG
COMPOUND (3)
TOTAL


55 55
35 35
20 20
7 7
140 140
80 80
10 10
25 25
45 45
25 25
80 80
8 8
80 80
10 10
15 15
5 5
50
950 1000

(1) V. MANE FILS
(2) 4-(2,2,3-trimethyl-3-cyclopentenyl)-2-ethyl-3-
buten-1-ol - from IFF
(3) 1, 3, 4, 6, 7, 8-hexahydro-4, 6, 6, 7, 8, 8-hexamethylcyclo-
penta-(g)-2-benzan - from IFF
(4) mixture of ionones

In each case, the evaluations of the olfactory impact were performed at to, t+48h and t+i68h to evaluate the head note, core note and background note.
In all cases, it is observed that compound (3) gives an advantageous head note and base coverage, with a rich and original woody, camphor nature.
Whether in alcoholic solution (composition 2) or in a softening composition (composition 1) , the rich woody amber note is very perceptible after 48 hours of drying and gives an original touch that is both clean and
cosmetic.
The loss of intensity over time appears to be fairly linear without any appreciable change in olfactory characteristic being noticeable.
The diffusion in hot water in shampoo produces a discreet but sophisticated and very pleasant woody nature.
The results of these evaluations show unequivocally
that compound (3) has advantageous olfactory
characteristics, which will find application in
particular in cosmetics, perfumery and cleaning
products.



We Claim:
1. A norbornane compound of formula:
(Formula Removed)
in which the dotted bond is present or absent, and in which Rl represents: when the dotted bond is present
- CHCH3OH or -CHCH3OCOR or -CHCH3XCH2CHOHR' or -
CHCH3OCHR'CH2OH or
(Formula Removed)
when the dotted bond is absent
(Formula Removed)
- CHCH3OH or -CHCH3OCOR or - COCH3 or -CHCH3XCH2CHOHR' or -
CH2CH2XCH2CHOHR' or -CHCH3OCHR'CH2OH or -CHCHCOR' or -
CH2CH2CHR'OH or -CH2CH2CHR'OCOR or -CHCHCCHOHR' or -
CHCHCHCR'OCOR,
in which R represents H, Me, Et, Pr, isoPr, But, isoBut, CH3(CH2)4, (CH3)2CHCH2, CH2CH or (CH3)2CCH,
R' represents H, Me or Et, and X represents O, N or S.
2. The compound as claimed in claim 1, wherein the dotted bond is absent and Rl represents -CHCH3OCH2CHOHCH3 or -CHCH3OCHR'CH2OH.
3. A process for preparing a compound as claimed in any of the preceding claims, comprising:
a. hydrogenating an unsaturated ketone of formula
(Formula Removed)
b. reacting the compound from (a) with a compound of formula
R'CHOHCH2OH or R'CHOHCH2NH2 or R'CHOHCH2SHor RCOOCOR
or R'COOCOR' or(Formula Removed)
wherein R' represents H, Me or Et, and R
represents H, Me, Et, Pr, isoPr, But, isoBut, CH3(CH2)4, (CH3)2CHCH2, CH2=CH or (CH3)2C=CH, or
c. optionally hydrogenating or reducing the compound resulting from b.
4. A fragrancing composition comprising the compound as claimed in any of the
preceding claims, wherein the concentration of the compound is in the range of
0.1% to 99% optionally alongwith other fragrancing ingredients, solvents or
adjuvants used in a perfume, a soap, shower gel or bath gel, shampoo and other
hygiene product, a cleaning, detergent or softening product, a body deodorizer
or an air freshener.
5. A compound and process for preparing the same substantially as herein described with reference to the foregoing examples.


Documents:

824-delnp-2004-abstract (30-06-2009).pdf

824-delnp-2004-abstract.pdf

824-delnp-2004-claims (30-06-2009).pdf

824-delnp-2004-claims.pdf

824-DELNP-2004-Correspondence Others-(21-09-2011).pdf

824-DELNP-2004-Correspondence Others-(27-10-2011).pdf

824-delnp-2004-correspondence.pdf

824-delnp-2004-description.pdf

824-delnp-2004-form1.pdf

824-delnp-2004-form2.pdf

824-delnp-2004-form3.pdf

824-delnp-2004-form5.pdf

824-DELNP-2004-GPA-(27-10-2011).pdf

824-delnp-2004-pct-feuille separee-409.pdf

824-delnp-2004-pct-ipea-409.pdf

824-delnp-2004-pct-ipea-416.pdf

824-delnp-2004-pct-isa-210.pdf

824-delnp-2004-pct-pamphlt a1.pdf

824-delnp-2004-pct-ro-101.pdf

824-delnp-2004-priority document.pdf


Patent Number 246852
Indian Patent Application Number 824/DELNP/2004
PG Journal Number 12/2011
Publication Date 25-Mar-2011
Grant Date 17-Mar-2011
Date of Filing 31-Mar-2004
Name of Patentee V. MANE FILS
Applicant Address 620, Route de Grasse, 06620 BAR SUR LOUP
Inventors:
# Inventor's Name Inventor's Address
1 LE BORGNE FABRICE 92 Chemin du Muguet, F-06330 ROQUEFORT-LES-PINS
2 SCHROEDER MARTIN 13 Boulevard Victor Hugo, 06130 GRASSE
3 MANE JEAN Domaine Saint-Mathieu, 290 Route de Saint-Mathieu, 06130 Grasse
4 CHANOT JEAN-JACQUES 176 Chemin De la Vieille Fontaine, F-06250 MOUGINS
PCT International Classification Number C07C 43/13
PCT International Application Number PCT/FR02/03629
PCT International Filing date 2002-10-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 01/13,663 2001-10-23 France