Title of Invention	NEW ODOURANT COMPOUNDS
Abstract	ABSTRACT NEW ODOURANT COMPOUNDS This invention relates to unsaturated alicyclic carbonyl compounds of formula (I) wherein R isC1 to C4 alkyl; or R is vinyl or a linear, branched or cyclic C3 to C4 alkenyl; X is carbonyl or a divalent radical -(CMe2)- ; and Y is oxygen or a divalent radical -(CH2)- . The compounds are odourant compounds having musk characteristics.

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Improvements in or relating to organic compounds This invention relates to new odorant compounds having musk characteristics, their manufacture and their use in fragrance compositions. Conventional compounds having musk characteristics have been selected from nitro arêtes, polycyclic aromatics and macro cyclic compounds. However, in recent years there has been great activity to find novel compounds having musk characteristics to replace these conventional musk’s, the use of which is becoming more restricted because of, e.g. environmental concerns. In recent years, research activity has resulted in the development of new classes of compounds with musk characteristics. EP 472966, for example describes a family of compounds exemplified by the product Helvetolide (1) that is described as having musky, amoretto-like characteristics. Further attempts were made to improve on the olfactory properties of Helvetolide (1) and its related compounds by replacing the gem-darkly group in the aliphatic side chain by a carbonyl group, as disclosed in WO 00/14051, exemplified by compound (2) that has been described as having a stronger musky smell than prior art compounds. Surprisingly, we now found certain unsaturated salicylic carbonyl compounds that have musk characteristics and a high impact in perfume formulations. Thus, the present invention refers in a first aspect to a compound of formula (1) wherein R is CIO to C4 alkyl, for example methyl, ethyl, /-propyl, n-propyl, n-butyl, sec-butyl, tert- butyl, cyclopropyl, cyclobutyl; or R is vinyl or a linear, branched or cyclic Ca to C4 alchemy. for example propen-1 -yl, propen-2-yl, or prop-2-en-1-yl, butane, e.g. but-1-en-1-yl, cyclobut-1-en-1-y|, or butadienyl, e.g. buta-2,4-dien-1-yl; X is carbonyl or a divalent radical -(CMe2)-; Y is oxygen or a divalent radical ~(CH2)- ; the bond between C-a and C-b is a single bond and the bond between C-b and C-c together with the dotted line represents a double bond; or the bond between C-a and C-b together with the dotted line represents a double bond and the bond between C-b and C-c is a single bond. The compounds according to the present invention may comprise one or more choral centers and as such may exist as a mixture of stereoisomers, or they may be resolved as isomeric ally pure forms. Resolving stereoisomers adds to the complexity of manufacture and purification of these compounds and so it is preferred to use the compounds as mixtures of their stereoisomers simply for economic reasons. However, if it is desired to prepare individual stereoisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective syntheses. Preferred compounds of formula (I) are propanoic acid 2'-[1 "-(3"',3"'-dimethylcyclohex-1"'-enyl}ethoxy]-2'-methylpropyl ester, cyclopropanecarboxylic acid 2'-[1"-(3"',3"'-dimethylcyclohex-1"'-enyl)ethoxy]-2'-methylpnDpyl ester, propionic acid 2'-[1"-(5"',5"'-dimethylcyclohex-1"'-enyl)ethoxy]-2'-methylpropyl ester, cyclopropanecarboxylic acid 2'-[1"-(5"',5"'-dimethylcyclohex-1"'-enyl)ethoxy]-2'-methylpropyl ester, propionic acid 1 "-(5"',5"'-dimethylcyclohex-1 "'-enyl)ethoxycarbony I methyl ester, and 30067 PCT 19.11.2003 CS cyclopropanecarboxylic acid 1 "-(5"',5"'-dimethylcyclohex-l '-enyijeinoxy-carbonylmethyl ester. Particular preferred are compounds of formula (I) wherein the bond between C-b and C-c together with the dotted line represents a double bond and the bond between C-a and C-b is a single bond, e.g. propanoic acid 2'-[1"-(3"',3"'-dimethytcyclDhex-r"-enyl)ethoxy]-2'-methylpropyl ester and cyclopropanecarboxylic acid 2'-[1"-(3"'.3"'-dlmethylcyclohex-1 "'-enyl)ethoxy]-2'-methylpropyl ester. Compounds of formula (I) having a double bond between C-b and C-c are more powerful and possess more distinct musk notes, while compounds having a double bond between C-a and C-b possess more pronounced fruity, green aspects besides their main must character. The compounds according to the present invention may be used alone or in combination with known odourant molecules selected from the extensive range of natural and synthetic molecules contently available, such as essential oils, alcohols, aldehydes and [ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and/or in admixture with one or more ingredients or percipients conventionally used in conjunction with odourants in fragrance compositions, for example carrier materials, and other auxiliary agents commonly used in the art. The following list comprises examples of town odourant molecules, which may be combined with the compounds of the present invention: - ethereal oils and extracts, e.g, cestrum, costus root oi(, oak moss absolute, geranium oil, jasmin absolute, patchouli oil, rose oil, sandalwood oil or ylang-ylang oil; - alkohols, e.g. citroneiiol, Ebanol^", eugenol, geraniol. Super Muguet^"^, linalool, phenylethyl alcohol, Sandalore™, terpineol or Timberol™. - aldehydes and ketones, e.g. a-amylcinnamaldehyd, Georgywood™, hydroxycitronellal, Iso E Super™, Isoratdeine™, Hedione™, maltol, methyl cedryl ketene, methylionone or vanillin; 500G7PCT 19.11.2003 CS - ether and acetals, e.g. Ambo ,granny( methy( ether, rose oxide or Splrambrene"^. - esters and lactones, e.g. benzyl acetate, cedryl acetates, t^-defalcations, Helvetollde® (1), r-undecalactone or delivery acetate. - macrocycles, e.g. ambrettolide, ethylene brassylate or Exaltolide®. - heterocydes, e.g. Isobutylchinoiine. However, due to their unique character, the compounds of formula (I) are especially well suited for use in fresh musky accords, woody-spicy or floral-hesperidia compositions as is more specifically illustrated in the Example. Reference is also made to our cop ending application no, 1039/CHENP/2005 The compounds of the present invention may be used In a broad range of fragrance applications, e.g. in any field of fine and functional perfumery, such as perfumes, household products, laundry products, body care products and cosmetics. The compounds can be employed in wide ranging amounts depending upon the specific application and on the nature and quantity of other odourant ingredients, that may be for example, from about 0.001 to about 20 weight percent. In one embodiment compounds of the present invention may be employed in a fabric softener in an amount of about 0.001 to 0.05 weight percent. In another embodiment compounds of the present invention may be used in an alcoholic solution in amounts of about 0.1 to 20 weight percent, more preferably between about 0.1 and 5 weight percent. However, these values should not be limiting on the present invention, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations. The compounds of the present invention may be employed into the fragrance application simply by direct mixing the fragrance composition with the fragrance application, or they may, in an earlier step be entrapped with an entrapment material such as for example polymers, capsules, microcapsules and nanocapsules, liposome, film formers, absorbents such as for example by using carbon or elites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bound to substrates which are adapted to release the fragrance molecule upon application of an exogenous stimulus such as light, enzyme, or the (il^e, and then mixed with the application. Compounds of formula {)) may be prepared starting from a corresponding ai)yy)c alcohol, which is accessible either by reduction of Artemone (1-(3',3'-dimethylcyclohex-1'-enyl)ethanone; trademark of Givaudan SA, Switzerland), or by Rupe rearrangements of 1-ethynyl-3,3-dimethylcyclohexanol. By etherification of the corresponding allelic alcohol with isobutylene oxide and subsequent etherification with the corresponding carboxylic acids compounds of formula (I) wherein X Is a divalent radical -(CMe2)-, and Y is oxygen, i.e. oxa esters, may be synthesized. Compounds of formula (1) wherein X is cartonyl and Y oxygen, i.e. diester, may be synthesized by esterification of the corresponding allylic alcohol with chloroacetic acid, followed by further esterification with the con-esponding carboxylic acids. Compounds of formula (I) wherein X is carbony! and Y is a divalent radical -(CH2)-, i.e. 0X0 ester, may be prepared by esterification of the corresponding allylic alcohol with the corresponding ox carboxylic acids, e.g. laevulin acid. Compounds of formula (1) wherein X is a divalent radical -(CMe2)- and Y is a divalent radical -(OHz)-, i.e. oxa ketones may be prepared by etherification of the corresponding allylic alcohol with isobutylene oxide, subsequent oxidation to the aldehyde followed by a Wetting-Horner-Emmons reaction well known in the art and selective hydrogenation of the formed double bond. Further particulars as to reaction conditions are provided in the examples. There now follows a series of examples that illustrate the Invention. Example 1: Propanoic acid 2'-ri"-f3"'.3"'-dimethvlcvclohex-1"'-envnethoxv1-2'-methvl-propvl ester A solution of Artemone [1-(3',3'-dimethylcyclohex-1'-enyl)ethanone, commercial product of Givaudan, 152 g, 1.00 mol] in EtzO (500 ml) was added drop wise with stirring within 3 h at room temp, to a suspension of lithium aluminum hydride (LAH, 10.4 g, 275 mmol) 30067 PCT 19.11.2003 CS in Et20 (1 L). The reaction mixture was heated to reflux for 150 min., and after cooling down to 0° C quenched by careful drop wise addition of water {50 ml). Then 2N aq. HCI (200 ml) was added, and the mixture was poured into water (200 ml). The product was extracted with EtjO (2x 500 ml), and the combined extracts were washed with water (200 ml) and brine (100 ml), dried (Na2S04) and evaporated to dryness. The resulting residue (154 g) was purified by silica-gel FC {pentane/Et20, 4:1) to afford 133 g (87%) of 1-{3',3'-dimethylcyclohex-1'-enyl)ethanol. During a period of 1h, a IMsolutionof MeA(Clz(150ml, 150 mmol) in hexane was added dropwise with stinging at 0 °C to a solution of 1-(3',3'-dimethylcyclohex-1'-enyl)ethanol (46.3 g, 300 mmol) and isobutylene oxide (26.0 g, 360 mmol) in cyclohexane (300 ml). The cooling bath was removed, and stirring was continued at room temp, for 20 h, prior to pouring the reaction mixture into ice/water (1:1, 200 ml). Cone. aq. H3PO4 was added until the slurry dissolved, and the product was extracted with EtaO {2x 200 ml). The combined organic extracts were washed with water (200 ml) and brine (25 ml), dried (Na2S04) and concentrated in a rotary evaporator. The resulting residue (60.5 g) was purified by silica-gel FC (pentane/Et20, 9:1, /?t= 0.14) followed by distillation at 55^ /1.5 mbar to furnish 12.7 (19%) of 2-11 ■-(3",3"-dimethylcyclohex-1 "-enyl)ethoxy]-2-methylpropan-1-ol. At OX under Na, N,W-Dicyclohexylcarbodiimide (DOC, 2.27 g, 11.0 mmol) was added to a stirred solution of 2-(1 '-(3",3"-dimethylcyclohex-1 "-enyl)ethoxy3-2-methylpropan-1-ol (2,26 9,10.0 mmol), propionic acid (740 mg, 10.0 mmol) and 4-(diethyl amino)pyridine (DMAP, 120 mg, 1.00 mmol) in CH2Cl2(15 ml). The cooling bath was removed and the reaction mixture was stirred for 2 h at room temp, prior to vacuum filtration of the precipitate. The precipitate was washed with CH2CI2 (2x), and the combined filtrates were concentrated under reduced pressure. The crude material (3,25 g) was purified by silica-gel FC (pentane/EtaO, 19:1, R, = 0.46) to afford 2.52 g (89%) of the odoriferous title compound. IR (ATR): V = 1741 cm'^ (s, vO=CO). 1168 /1068 cm"' (s, vC-O), 1366 cm"' (m, SCH3).- 'H NMR (CDCI3): 8 = 0.93 / 0.94 (2s, 6H, 3'"-Me2), 1.14 (d, J = 6.5 Hz, 3H, 2"-H3), 1.16 (t, J = 7,5 Hz, 3H, 3-H3), 1.17 /1,18 (2s, 6H, 2'-Me2), 1.37 (mc, 2H, 4'"-H2), 1.60 (mc, 2H, 5"'-H2), 1.81-2.06 (m, 2H, 6'"-H2), 2.37 (q, J = 7.5 Hz, 2H, 2-H2), 3.90 (d, 30067 PCT 19.11,2003 00 J=11.0Hz, 1H, r-Hb), 3.99(q,J=7.5Hz, 1H, 1"-H), 4.01 {d, J =11.0 Hz. 1H, 1'-Ha), 5.30 (s, 1H, 2'"-H). - '^C NMR (CDCI3): 5 = 8.99 (q, C-3), 19.6 {t, C-5'"), 22.4 (q. C-2"), 23.4 (t, C-6'"), 23.5 / 23.6 (2q, 2'-Me2), 27.5 (t,C-2), 29.3 / 29.9 (2q, 3"'-Me2). 31.2 (s, C-3'"), 37.3 {t, C-4'"), 69.7 (t, C-1'), 72.2 (d, C-1"), 74.3 (s, C-2'), 131.3 (d. C-2'"). 139.0 (s, C-1'"). 174.1 (s, C-1). - MS (70 eV); miz = 153 (15) [CioHi70*l, 147 (3) [C7H15O3*], 137 (67) [CioH,7*], 129 (36) [CrHnOil, 121 (29) [CgHig*]. 107 (17) [CaH,/], 95 (28) [C7H11I, 93 (27) [C7H9*], 79 (19) [CeH?*], 57 (100) [C3H5I. Odor description: Musky, powerful, powdery, sliglitly animalist. Example 2: Cvclopropanecarboxvlic acid 2'-ri"-(3"'.3"'-dimethvlcvclohex-1"'-envl)-ethoxv1-2'-methYlpropvl ester Following the same procedure according to Example 1, Atelic esterification of 2-[1'-(3".3"-dimethylcyclohex-1"-enyl)ethoxy]-2-methylpropan-1-ol (2.26 g, 10.0 mmol) with cyclopropanecarboxylic acid (860 mg. 10.0 mmol), and purification by silica-gel FC (pentane/'Et20, 19:1, Rf = 0.33) furnished 2.68 (91%) of cyclopropanecarboxylic acid 2'-[1 "-(3"'.3"'-dimethylcyclohex-1 "'-enyl)ethoxyl-2'-methylpropyl ester. IR{ATR): v=1731 cm'^ (s, vO=CO), 1153/1068 cm"^ (s, vC-0), 1400/1381/1366 cm"^ (m, 5CH3). - ^H NMR (CDCI3): 5 = 0.87 (m^, 2H, 3-,4-Hb), 0.93 / 0.94 (2s, 6H, 3'"-Msa), 1.02 (m„ 2H, 3-.4-Ha). 1.15 (d, J = 6.5 Hz, 3H, 2"-H3), 1.17/1.18 (2s, 6H, 2'-Mez), 1.38 (mc, 2H. 4'"-H2). 1.62 (mc. 2H, 5"'-Hz), 1.81-2.06 (m, 2H, 6"'-H2), 3.89 (d, J = 11.0 Hz, IN, r-Ho), 3.98(q,J = 7.5Hz. 1H, 1"-H),4.00(d, J= 11.0 Hz, IN, 1'-Ha), 5.30 (s. IN, 2"'-H). - ^^C NMR (CDCIg): 8 = 8.18 / 8.19 {2t, C-3.-4), 12.8 (d. C-2), 19,6 (t, C-5'"), 22.4 (q, C-2"), 23.4 (t, C-6'"), 23.5 (2q, 2'-Me2), 29.3 / 29.9 (2q. 3"'-Me2), 31.2 (s, C-3"'). 37.3 (t, C-4"'), 69.8 (t, C-1'), 72.2 (d, C-1"). 74.3 (s, C-2'). 131.3 (d, C-2'"), 139.0 (s, C-1"'). 174.5 (s. C-1). - MS (70 eV); mIz = 294 (1) [M*], 279 (1) [M*- CH3], 159(3)[C8Hi503l, 153(22)[CioHi70l, 141 (30) [Chinos^. 137 (61) [CoHw*], 121 ,. (27) [C9H13I, 107 (17) [CaHn*], 95 (26) IC7H1/], 93 (25) [C7H9I, 81 (27) [CeH/], 79 (17) [C6H7*].69(100)[C5H9*]. Odor description Musky, pleasant, powdery, strong. 30067 PCT 10.11.3003 CG Example 3: Propionic acid 2'-[1"-(5"'.5"'-dimethvlcvclohex-1"'-envl)ethoxv1-2'-methyl-propvl ester Phosphorus pentoxide (33.1 g, 233 mmol) was added to a solution of 1-ethynyl-3,3-dimethylcyclohexanol (152 g, 1.00 mol) in MePh (800 ml). The slurry was heated to reflux, and stirred at this temp, for 90 min. The reaction mixture was allowed to cool to room temp., and then poured into ice/water {1:1, 500 ml). The product was extracted with Et20 (2x 500 ml), and the combined organic extracts were washed with water (500 ml) and brine (100 ml), dried (Na2S04) and concentrated under reduced pressure. Silica-gel FC (pentane/ EtsO, 9:1, R, = 0.70) provided 13.8 g (9 %) of 1-(5',5'-dimethylcyclohex-1'-enyl)ethanone. A solution of 1-(5',5'-dimethylcyclohex-1'-enyl)ethanone (13.1 g, 85.8 mmol) in EtO (50 ml) was added dropwise with stirring within 50 min. to a suspension of LAH (895 mg, 23.6 mmol) in Et20 (150 ml). The reaction mixture was refluxed for 1 h prior to quenching at 0 °C by careful addition of water (50 ml) followed by 5 N aq. HCI (50 ml). The organic layer was separated and the aqueous one extracted with Et20. The combined ethereal solutions were washed with water and brine, dried (Na2S04), and concentrated in a rotary evaporator. Silica-gel FC (pentane/EtjO, 9:1, Rf = 0.14) of the resulting residue (14.7 g) gave 11.2 g (85 %) of 1-(5',5'-dimethylcyclohex-1'-enyl)ethanol. At 0 °C under N2, a 1 M solution of MeAICl2 (33.6 ml, 33.6 mmol) in hexane was added dropwise during 1 h to a stirred solution of 1-(5',5'-d(methyl-cyclohex-1'-enyl)ethanol (10.4 g, 67.2 mmol) and isobutylene oxide (5.82 g, 80.7 mmol) in cyclohexane (67 mi). The cooling bath was removed, the reaction mixture stirred at room temp, for 23 h, and then poured into ice/water(1:1,200ml). The slurry was brought into solution by addition of cone. aq. H3PO4, and the product was extracted with Et20 (2x 100 ml). The combined organic extracts were washed with water (100 ml) and brine (25 ml), dried (Na2S04). and concentrated in a rotary evaporator. The crude material (12.4 g) was purified by silica-ge) FC (pentane/EtzO, 9:1, R, = 0.17) to provide 3.31 g (22 %) of 2-[1'-(5",5"-dimethylcyclohex-1 "-enyl)ethoxy]-2-methy!propan-1-ol. Following the same procedure according to Example 1, Steglich esterification of 2-[1'-(5",5"-dimethylcyclohex-1"-enyl)ethoxy]-2-methylpropan-1-ol (1.29g, 5.70 mmol) with 30067 PCT 19.11.2003 CS propionic acid (420 mg, 5.70 mmol), and purification by silica-gel FC {pentane/EtjO, 9:1, Rf = 0.56) furnished 420 mg (26%) of propionic acid 2'-[1"-(5"'.5"'-dimethylcyciohex-1 "'-enyl)etlioxyl-2'-methylpropyi ester. (R(ATR): v= 1169 /1068 cm"'(s, vC-0), 1741 cm"'(s, vO=CO), 1365 cm"'(m, 5CH3). - 'H NMR {CDCI3): S = 0.89 / 0.91 (2s, 6H, 5'"-Me2), 1.14 (d, J = 6.5 Hz, 3H, 2"-H3), 1.16 (t, J = 7.5 Hz, 3H, S-Ha), 1.17 /1.18 (2s, 6H, 2'-Me2), 1.29 (t, J = 6.5 Hz, 2H, 4'"-H2), 1.69 (dd, ^= 17.0, 2.0 Hz, 1H, 6"'-HB), 1.83 (dd, ^= 17.0, 2.0 Hz, 1H, 6'"-Ha), 2.01 (mc, 2H, 3"'-H2), 2.36 (q, J = 7,5 Hz, 2H, 2-H2), 3.92 (d, J= 11.0 Hz, 1H, I'-Hb), 4.00 (d, J= 11.0 Hz, 1H, 1'-Ha), 4.02(q, J = 6.5Hz, 1"-H), 5.54 (s, IN, 2"'-H). -'=^0 NMR circus): 5 = 8.98 (q, C-3), 22.4 (q, C-2"), 22.7 (t, C-3'"), 23.4 (t, C-6'"), 23.4 123.6 (2q, 2'-Me2), 27.5 (t,C-2), 27.9 / 28.0 (2q, 5"'-IVIe2), 28.6 (s, C-5'"), 35.2 (t, C-4'"), 37.5 (t, C-6"'), 69.8 (t, C-1'), 71.9 (d, C-l"), 74.2 (s, C-2'), 119.1 (d, C-2'"), 140.4 (s, C-1'"), 174.1 (S, C-1). - MS (70 eV); mlz= 153 (16) IC,oH,70*], 147 (2) rCrHjsOa'], 137 (59) [C,oH,/], 129 (30) [C7Hi302*], 121 (37) [C9H13I. 107 (29) [CaHn*], 95 (29) [C7H11*], 93 (39) [C7H9*], 79 (48) [CflH7l, 57 (100) [C4H9']. Odor description: Muslty, powdery, fruity. Example 4: Cvciopropanecarboxvlic acid 2'-ri"-(5"'.5"'-dimethvlcvclohex-1"'-envi)-ethoxy]-2'-methvlpropvl ester Following the same procedure according to Example 1, Steglich esterification of 2-[1'-(5",5"-dimethytcyciohex-1 "-ennui)ethoxy]-2-methylpropan-1 -ol (1.29 g, 5.70 mmol) with cyciopropanecarboxyiic acid (490 mg, 5.70 mmol), and purification by silica-gel FC (pentane/Et20, 9:1, R^ - 0.58) furnished 590 mg (35%) of cyciopropanecarboxyiic acid 2'-[1"-{5"',5"'-dimethylcyclohex-r"-enyl)ethoxyI-2'-methylpropyl ester. tR(ATR):v= 1163/1067 cm"'(s, vC-O), 1730 cm"^ (s, vO=CO). 1382/1400/ 1382 cm"' (m, SCHa). - 'H NMR (CDCI3): 6 = 0.85 (dt. J = 8.0, 4.5 Hz, 2H. 3-,4-Hb), 0.89 / 0.91 (s, 6H, 5"'-Me2), 1.01 (dt, J= 8.0, 4.5, 2H, 3-,4-Ha), 1.14 (d, J = 6.5 Hz, 3H, 2"-H3), 1.17/1.18 (2s, 6H, 2'-Me2), 1 29 (dd, J = 6.5, 2.5 Hz, 1H, 4-Ht,), 1.30 (dd, J = 6.5, 2.5 Hz, 1H, 4-H,}, 1.64 (tt, J = a.O, 4.5 Hz, 1H, 2-H), 1.70 (dd, J= 17.0, 2.0 Hz, 1H. 6"'-H,), 1.84 (dd, J = 17.0, 2.0 Hz, 1H, 6"'-Ha), 2.01 (mc, 2H, r'-Hz), 3.91 (d, J = 11,0 Hz, 1H, 3QQ67-PeT 19.11.20(B-CS 1 '-Hb), 3.98 {d, J = 11.0 Hz, 1H 1 '-H,), 4.02 (q, J = 6.5 Hz, 1H, 1 "-H). 5.54 (s. 1H, 2'"-H>. - '^C NMR (CDCk): 5 = 8.14 (2t. C-3,-4), 12.8 (d, C-2}, 22.4 (q, C-2"), 22.7 (t, C-3'"), 23.5 / 23.6 (2q, 2'-Me2), 27.9 / 28.0 (2q, S^-Mes), 28.6 (s, C-5'"). 35.2 (t, C-4'"), 37.5 (t, C-6'"), 69.8 (t, C-1'}, 71.9 (d, C-1"), 74.3 {s, C-2'), 119.1 (d, C-2'"), 140.3 (s, C-1'"), 174.5 (S, C-1). - MS (70 eV); miz = 294 (1) [M*], 159 (2) [CeHisOal, 153 (25) [C10H17OI, 141 (27) [CaH.aO^I, 137 (54) [C,oH,7l, 121 (27) [CgH.al. 107 (22) [CaH,/], 95 (25) [CyHn*], 93 (26) [C7H9*]. 81 (19) [CeH/], 79 (30) [CeU/], 69 (100) [CsHgl. Odor description: Musky, fresh, floral, slightly metallic. Example 5: Propionic acid 1"-f5"'.5"'-dlmethvlcvclohex-1"'-envl)ethoxvcarbonvlmethvl ester W,W-Dicyclohexylcarbodiimide (DOC. 2.58 g, 12.5 mmol) was added at 0 °C under N2 to a solution of 1-(5.5-dimethylcyclohex-1-enyl)ethanol, chloroacatic acid (1.07 g, 11.3 mmol) and 4-(dimethylamlne)pyridine (DMAP, 140 mg, 1.13 mmol) in CHjCIa (15 ml). The cooling bath was removed and the reaction mixture was stirred for 1 h at room temp., prior to vacuum filtration of the precipitates. The filtrate was concentrated under reduced pressure, the resulting residue purified by silica-gel FC (pentane/Et20,19:1, R, = 0.65) to furnish 2.17 g (83 %) of chloroacetlcacid 1'-(5",5"-dimethylcyclohex-1"-enyl)ethyl ester. A mixture of chloroacetic acid 1 '-(5",5"-dimethylcyclohex-1 "-enyl)ethyl ester (1.00 g, 4.33 mmol). propionic acid (320 mg, 4.33 mmol), KjCOa (1.20 g, 8,67 mmol) and NaBr (450 mg, 4.33 mmol) in Et2C0/dioxane (4:1,10 ml) was refluxed for 1 day prior to pouring into water (50 ml). The product was extracted with Et20 (2x 50 ml), and the combined extracts were washed with water (50 ml) and brine (25 ml). After drying with Na2SO* and evaporation of the solvent under reduced pressure, silica-gel FC (pentane/Et20, 9:1, Rf = 0,41) afforded 370 mg (32%) of propionic acid 1 "-(5"',5"'-dimethylcyclohex-1 "'-enyl)ethoxycarbonyl methyl ester. IR (ATR): V = 1161 cm"^ (s, vC-0), 1747 cm"^ (s. vO=CO). - 'H NMR (CDCI3): S = 0,89 / 0.91 (2s, 6H. 5"'-Me2), 1,19 (t, J = 7.5 Hz, 3H. 3-H. 3-H3), 1.31 (d. J = 6,5 Hz. 3H, 2"-H3), 1,34 (mc, 2H, 4"'-H2), 1.69 (d. J= 16.5 Hz, 1H, 6"'-Hb). 1.78 (d, J= 16.5 Hz, 1H, 6'"-Ha), 2.05 (mc. 2H, 3'"-H2), 2.45 (q, J = 7.5 Hz, 2H, 2-H2), 4.56 (d. J = 16.0 Hz. 1H, 30067 PCT 19.11,2003 CS 2'-Hb), 4.61 (d, J = 16.0 Hz, 1H, 2'-Ha), 5.32 (q, J = 6.5 Hz, 1H, 1"-H), 5.67 (s, 1H, 2'"-H). - '^C NMR (CDOa): 5 = 8,81 (q, C-3), 18.5 (q, C-2"), 22.7 (t, C-3"'), 27,0 (t, C-2), 27.5 /28,3 (2q, 5"'-Me2), 28.6 (s, C-5'"), 34.7 (t, C-4'"), 37.5 (t, C-6-), 60.6 (t. C-2'), 75.5 (d, C-l"), 123.1 (d, C-2'"), 135,2 (s, C-1'"), 167.1 {s, C-1'), 173.5 {s. C-1). - MS (70 eV); m/z= 154 (3) [COH.BO*], 136 (58) [doHie'], 121 (86) [C9H13I, 107 (75) [CaHn'], 93 (100) [C7H9*]. 79 (100) [CeHyl. 41 (36) [C3H5I. Odor description: Musky, green. Example 6: Cyclopropanecarboxylic acid 1"-f5"'.5"'-dimethvlcvclohex-1"'-envl)ethoxv-carbonvlmethvi ester A mixture of chioroacetic acid 1'-(5",5"-dimethylcyclohex-1"-enyl)ethyl ester (I.OOg, 4.33 mmol), cyclopropanecarboxylic acid (370 mg, 4.33 mmol), KzCOs (1.20 g, 8,67 mmol and NaBr (450 mg, 4,33 mmol) in EtjCO/dioxane (4:1, 10 ml) was refluxed for 1 day prior to pouring into water (50 mi). Tlie product was extracted with Et20 (2x 50 mi), and tine combined extracts were washed with water (50 ml) and brine (25 mi). After drying with Na2S04 and evaporation of the solvent under reduced pressure, siiica-gei FC (pentane/EtiO, 9:1, Rf = 0.30) afforded 870 mg (72%) of cyciopropanecarboxyiic acid 1 "-(5"',5"'-dimethylcyciohex-1 "'-enyi)ethoxycarbonyimethyl ester. iR (ATR): V = 1156 cm"^ (s, vC-0), 1736 cm"' (s, vO=CO), - 'H NMR (CDCI3): 5 = 0.89 / 0.91 (2s, 6H, 5"'-Me2), 0.93 (m^, 2H, 3-,4-Hb), 1,07 (m^, 2H, 3-,4-Ha), 1,30 (d, J = 6.5 Hz, 3H, 2"-H3), 1,33 (m^, 2H, 4"'-H2). 1.68-1,80 (m, 3H, 2-H, 6"'-H2), 2.05 (mc, 2H, 3"'-H2), 4,56(d, J= 16.0 Hz, IN, 2'-Hb), 4,61 (d, J= 16.0 Hz, 1H, 2'-Ha), 5.30 (q, J = 6.5 Hz, 1H, 1"-H), 5.67 (S, 1H, 2"'-H). - '^C NMR (CDCI3): 6 = 8.67/8.65 (t, C-3,-4), 12,4 (d, C,-2), 18.5 (q, C-2"), 22.7 (t, C-3'"), 27,5 /28.3 (2q, 5"'-Me2), 28,5 (s, C-5"'), 34,7 (t, C-4'"), 37,5 (t, C-6"'), 60.6 (t, C-2'), 75.5 (d, C-l"), 123.0 (d, C-2'"), 135.2 (s, C-1'"), 167.1 (s, C-1'). 174.0 (s, C-1), - MS {70 eV); mlz= 153 (2) [C,oH,70*], 136 (61) [CioHie1, 121 (84) [C9H13I, 107 (71) [CeHnl, 93 (98) [C7H9I. 79 (100) [CeH/], 69 (34) [C5H9I. Odor description: Musky, green, floral, Example 7: Floral-musky, powdery perfume formulation for shower lei 30067 PCT 19.11.2003 CS The propanoic acid 2'-[1"-(3"',3"'-climethyicyclohex-1"'-enyl)ethoxy]-2'-methylpropyl ester forms a very powerful and pleasant musk accord together with the polycyclic and macrocode musk odorants, to which it adds freshness, fruitiness and a powdery aspect. This accord conveys smoothness, and richness to the fragrance and imparts a caressing, comfortable feeling to the perfumed product. In combination with the elemi and lemon oils it as well enhances fresh and clean aspects of the perfume and makes it ideally suited for application in shower gels. We claim, wherein R is C1 to C4 alkyl; or R is vinyl or a linear, branched or cyclic C3 to O alkenyl; X is carbonyl or a divalent radical -(CMe2)-; V is oxygen or a divalent radical -(CH2)- ; the bond between C-b and C-c is a single bond and the bond between C-a and C-b together with the dotted line represents a double bond; or the bond between C-b and C-c together with the dotted line represents a double bond and the bond between C-a and C-b is a single bond . 2. The compound as claimed in claim l wherein the bond between C-b and C-c together with 'the dotted line represents a double bond and the bond between C-a and C-b is a single bond. 3. The compound as claimed in claim 1 wherein the bond between C-b and C-c Is a single bond and the bond between C-a and C-b together with the dotted line represents a double bond. 4. The compound as claimed in claim 1 selected from the group consisting of propanoic acid 2'- [1 "-(3"',3"'-dimethytcyclohex-l "'-enyl)ethoxy]-2'-methylpropy( ester, cyclopropanecarboxylrc acid 2'-[l "-(3'" ,3"'-dimethylcyclohex-l '" -enyl)ethoxy]-2' methylpropyl ester, propionic acid 2'_[1 "-(5"',5"'-dimel:hyicyclohex-l '"■enyl)ethoxy]-2'methylpropyl ester, cydopropanecarboxylic acid 2'-[l "-(5'",5"'-dimethylcyclohex-l "'enyl)ethoxy]-2' -methyl propyl ester, propionic acid l"-(5"' ,5'" -dimethylcyclohex-1 '"- enyl)ethoxycarbonylmethyl methyl ester, and cydopropanecarboxylic acid l"-(5"', 5"'-dimethylcyclohex-r"-eny0ethoxycarbonylemethyl ester. 5. A fragrance comprising a compound as ciaimed in claims 1 to 4 6. A fragrance composition comprising a compound as claimed in claim 1 to 4. 7. A fragrance application comprising a compound as claimed in any of the claims 1 to 4, or a mixture thereof. 8. The fragrance application as claimed in claim 7 wherein the fragrance application is a perfume, household product, laundry product, body care product or cosmetic product. •4

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