MUGUET TYPE FRAGRANCE COMPOUNDS

Abstract

The present invention primarily relates to compounds of formula (I) as defined herein and to compositions comprising one, two, three or more compounds of formula (I) as defined herein, or consisting of two, three or more compounds of formula (I) as defined herein. The invention further relates to methods for producing compounds of formula (I) (or (Ia) or (Ib)), to the use of compounds of formula (I) as fragrance substances and the use of compositions comprising a compound of formula (I) or consisting of compounds of formula (I) as fragrance substance mixtures. It further relates to fragrance substance compositions comprising or consisting of compounds or compositions as defined herein and one or more additional fragrance substances, to perfumed products comprising compounds or compositions or fragrance substance compositions as defined herein, to methods for producing perfumed products as defined herein and to methods for perfuming hair, skin, textile fibres, surfaces and/or ambient air.

Claims

1-15. (canceled)

16. A compound of formula (I) ##STR00016## wherein R.sub.1 represents H, methyl, isopropyl, or ═CH.sub.2, R.sub.2 represents H, R.sub.3 represents H, isopropyl, or isobutyl, R.sub.4 represents H or ═CH.sub.2, and dashed lines represent a possible double bond, provided the compound comprises one or two double bonds along the dashed lines.

17. The compound of claim 16 selected from 3-(5-isopropyl-2-methylene-cyclohexyl)-propanal, 3-(5-isopropyl-3-methyl-cyclohexen-1-yl)propanal, 3-(3-isopropyl-5-methyl-cyclohexen-1-yl)propanal, 3-(5-isobutyl-3-methyl-cyclohexen-1-yl)propanal, 3-(3-isobutyl-5-methyl-cyclohexen-1-yl)propanal, 3-(3-isobutyl-5-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(5-isobutyl-3-methyl-cyclohexa-1,3-dien-1-yl)propanal, 3-(5-isobutyl-3-methylenecyclohex-1-en-1-yl)propanal, 3-(5-isopropyl-3-methyl-cyclohexa-1,3-dien-1-yl)propanal, 3-(3-isopropyl-5-methyl-cyclohexa-1,5-dien-1-yl)propanal, and 3-(5-isopropyl-3-methylene-cyclohexen-1-yl)propanal.

18. A composition comprising one or more of the compounds of claim 16.

19. A fragrance substance composition comprising one or more of the compounds of claim 16 and one or more additional fragrance substances.

20. A perfumed product comprising a sensorially effective amount of one or more compounds of claim 16.

21. The perfumed product of claim 20, wherein the one or more compounds are in an amount to provide the product with one or more olfactory notes selected from a green note, a fatty note, an ozonic note, a cyclamen-like note, a dusty note, a citrus note, a mandarin note, an aldehydic note, a citral note, a fresh note, a lily of the valley note, a bourgeonal note, a floral note, a cucumber note, a fruity note, or a melon note.

22. The perfumed product of claim 21, wherein the one or more compounds provide the product with a lily of the valley note.

23. A method for producing a perfumed product comprising: providing one or more compounds of claim 16; (ii) providing one or more further components of the perfumed product; and (iii) contacting or mixing the further components of (ii) with a sensorially effective amount of the one or more compounds of (i).

24. A method for perfuming hair, skin, textile fibers, surfaces, ambient air, or a combination thereof comprising: (a) providing one or more compounds of claim 16, a composition comprising the one or more compounds, or a perfumed product comprising the one or more compounds; and (b) imparting the one or more compounds, the composition, or the perfumed product to the hair, skin, textile fibers, surfaces, ambient air, or a combination thereof in a sensorially effective amount.

25. The method of claim 24, wherein the method imparts one or more selected from a green note, a fatty note, an ozonic note, a cyclamen-like note, a dusty note, a citrus note, a mandarin note, an aldehydic note, a citral note, a fresh note, a lily of the valley note, a bourgeonal note, a floral note, a cucumber note, a fruity note, or a melon note.

26. The method of claim 24, wherein the method imparts a lily of the valley note.

27. A method for producing the compound of claim 16 comprising one or more of the following reaction steps: ##STR00017## wherein dashed lines represent a possible double bond, provided the compound of formula (IV) comprises one or two double bonds along the dashed lines.

28. The method of claim 27, wherein the compound of formula (Ia) is selected from 3-(5-isopropyl-3-methyl-cyclohexen-1-yl)propanal, 3-(3-isopropyl-5-methyl-cyclohexen-1-yl)propanal, 3-(5-isobutyl-3-methyl-cyclohexen-1-yl)propanal, 3-(3-isobutyl-5-methyl-cyclohexen-1-yl)propanal, 3-(3-isobutyl-5-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(5-isobutyl-3-methyl-cyclohexa-1,3-dien-1-yl)propanal, 3-(5-isobutyl-3-methylenecyclohex-1-en-1-yl)propanal, 3-(5-isopropyl-3-methyl-cyclohexa-1,3-dien-1-yl)propanal, 3-(3-isopropyl-5-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(5-isopropyl-3-methylene-cyclohexen-1-yl)propanal, or 3-(4-isopropylcyclohexen-1-yl)propanal.

29. A method for producing a compound of formula (I) ##STR00018## wherein R.sub.1 represents isopropyl, R.sub.2 represents H, R.sub.3 represents H, R.sub.4 represents ═CH.sub.2, and dashed lines represent a possible double bond, provided the compound comprises one or two double bonds along the dashed lines, and wherein the compound is designated as a compound of formula (Ib), the method comprising one or more of the following reaction steps: ##STR00019##

30. The method of claim 29, wherein the compound of formula (I) or (Ib) is 3-(5-isopropyl-2-methylene-cyclohexyl)propanal.

Description

EXAMPLES

[0136] General Procedure 1: Grignard Addition

[0137] Under N.sub.2 atmosphere, a solution of 2-(2-bromoethyl)-1,3-dioxolane (1.15 eq) in THF (0.5 vol w.r.t alkyl bromide) was slowly added to a suspension of Mg turnings (1.25 eq) in THF (5 vol w.r.t alkyl bromide). Mg was activated with a spatula of iodine. Grignard formation was maintained at a temperature of 37-40° C. for an hour, then a solution of ketone of formula (II) (1.0 eq) in THF (1 vol w.r.t to ketone) was then slowly added and reaction maintained at a temperature of 40° C. for 4 h. After completion of the reaction, the reaction mixture was quenched with ice cold saturated NH.sub.4Cl solution, compound extracted with MTBE (methyl-tert-butyl ether), washed with saturated NaHCO.sub.3 and brine, and dried over Na.sub.2SO.sub.4, filtered and the solvents were removed in vacuo to yield the crude alcohol (compound of formula (III)).

[0138] General Procedure 2: Alcohol Elimination

[0139] To a solution of alcohol (compound of formula (III); 1.0 eq) in pyridine (2 vol w.r.t alcohol) at 0° C., POCl.sub.3 (1.5 eq) was slowly added dropwise. After the addition, the suspension was stirred at 0° C. for 30 mins, then allowed to warm to room temperature and stirred at 50° C. until completion of the reaction. The reaction mixture was quenched with ice-water, extracted with ethyl acetate, 5% H.sub.2SO.sub.4, washed with saturated NaHCO.sub.3 and brine, and dried over Na.sub.2SO.sub.4, filtered and the solvents were removed in vacuo to yield the compound of formula (IV).

[0140] General Procedure 3: Acetal Deprotection

[0141] The compound of formula (IV) (1.35 g; 1.0 eq) was dissolved in acetone (17 mL) and water (6 mL) and concentrated HCl (0.2 mL) was added, then the mixture was heated under reflux until completion of the reaction. At room temperature, the compound was extracted with MTBE, the organic layer was washed with saturated NaHCO.sub.3 and brine, and dried over Na.sub.2SO.sub.4, filtered and the solvents removed in vacuo to yield the crude aldehyde (compound of formula (Ia)) as mixture of isomers.

Example 1

1-[2-(1,3-Dioxolan-2-yl)ethyl]-3-isopropyl-5-methyl-cyclohexanol

[0142] Following the general procedure 1, 2.0 g of 3-isopropyl-5-methy-cyclohexanone gave 2.3 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-3-isopropyl-5-methyl-cyclohexanol (70% yield).

[0143] 1H NMR (400 MHz, C.sub.6D.sub.6) δ 4.86 (t, J=4.6 Hz; 1H), 3.57-3.52 (m, 2H), 3.40-3.35 (m, 2H), 1.96-1.88 (m, 2H), 1.82-1.70 (m, 1H), 1.63-1.56 (m, 4H), 1.56-1.47 (m, 2H), 1.42-1.30 (m, 1H), 0.86 (d, J=6.8 Hz, 3H), 0.86 (d, J=6.9 Hz, 3H), 0.85 (d, J=6.5 Hz, 3H), 0.78 (t, J=12.7 Hz, 1H), 0.65 (t, J=12.6 Hz, 1H), 0.43 (q, J=12.5 Hz, 1H).

[0144] .sup.13C NMR (101 MHz, C.sub.6D.sub.6) δ 105.30, 71.18, 64.89, 64.89, 46.11, 40.85, 38.83, 38.80, 38.36, 32.86, 28.22, 27.96, 22.84, 20.07, 19.76.

[0145] GC-MS: 237, 213, 195, 171, 155, 137, 102, 73, 58, 41, 29.

2-[2-(5-Isopropyl-3-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane and 2-[2-(3-isopropyl-5-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane

[0146] Following general procedure 2, 2.9 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-3-isopropyl-5-methyl-cyclohexanol gave 2.9 g of a crude isomeric mixture of 2-[2-(5-isopropyl-3-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane and 2-[2-(3-isopropyl-5-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane (77% yield), which was carried forward to next step without further purification.

3-(5-Isopropyl-3-methyl-cyclohexen-1-yl)propanal and 3-(3-isopropyl-5-methyl-cyclohexen-1-yl)propanal

[0147] Following general procedure 3, 2.5 g of an isomeric mixture of 2-[2-(5-isopropyl-3-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane and 2-[2-(3-isopropyl-5-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane gave 1.3 g of aldehyde as mixture of isomers (compounds of formula (I) or (Ia)) after column chromatography (3-5% EtOAc in cyclohexane, 66% yield).

[0148] 1H NMR (600 MHz, C.sub.6D.sub.6) δ 9.37-9.34 (m, 2H), 5.20 (tt, J=2.3, 1.2 Hz, 1H), 5.14-5.10 (m, 1H), 2.07 (dtq, J=6.8, 4.9, 1.9 Hz, 1H), 2.04-1.93 (m, 9H), 1.68-1.60 (m, 3H), 1.55-1.45 (m, 4H), 1.41-1.31 (m, 2H), 1.31-1.24 (m, 1H), 0.93 (d, J=7.0 Hz, 3H), 0.90 (d, J=6.5 Hz, 3H), 0.88 (d, J=6.9 Hz, 3H), 0.87-0.84 (m, 9H), 0.76 (q, J=12.0 Hz, 1H), 0.66 (q, J=12.2, 10.8 Hz, 1H).

[0149] .sup.13C NMR (151 MHz, C.sub.6D.sub.6) δ 200.59, 200.53, 136.42, 135.47, 128.32, 125.48, 43.07, 41.98, 40.98, 35.92, 34.37, 32.78, 32.54, 32.44, 32.07, 30.23, 29.96, 29.72, 22.58, 22.40, 19.92, 19.70, 19.64, 19.13.

[0150] GC-MS: 194, 176, 150, 133, 121, 107, 91, 55, 41, 29.

[0151] Odour: Green, fatty, ozonic, calamus, cyclamen-like, dusty.

Example 2

1-[2-(1,3-dioxolan-2-yl)ethyl]-5-isopropyl-3-methyl-cyclohex-2-en-1-ol

[0152] Following general procedure 1, 2.0 g of 5-isopropyl-3-methyl-cyclohex-2-en-1-one gave 3.0 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-5-isopropyl-3-methyl-cyclohex-2-en-1-ol (63% yield).

[0153] 1H NMR (600 MHz, C.sub.6D.sub.6) δ 5.38 (dq, J=2.7, 1.4 Hz; 1H), 4.89 (t, J=4.7 Hz, 1H), 3.55-3.52 (m, 2H), 3.37-3.33 (m, 2H), 2.15-2.00 (m, 2H), 1.91-1.84 (m, 2H), 1.84-1.76 (m, 1H), 1.64 (dd, J=17.0, 5.3 Hz, 1H), 1.53 (s, 3H), 1.51-1.42 (m, 1H), 1.37-1.34 (m, 1H), 1.34-1.26 (m, J=6.6 Hz, 1H), 1.13 (t, J=12.7 Hz, 1H), 0.80 (d, J=6.7 Hz, 3H), 0.78 (d, J=6.7 Hz, 3H).

[0154] .sup.13C NMR (151 MHz, C.sub.6D.sub.6) δ 134.35, 129.33, 105.29, 72.03, 64.86, 64.83, 40.91, 39.25, 35.81, 34.29, 32.54, 28.69, 23.49, 19.92, 19.53.

[0155] GC-MS: 253, 236, 211, 193, 153, 131, 105, 73, 55, 43, 29.

2-[2-(3-isopropyl-5-methyl-cyclohexa-1,5-dien-1-yl)ethyl]-1,3-dioxolane

[0156] Following general procedure 2, 3.0 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-5-isopropyl-3-methyl-cyclohex-2-en-1-ol gave 2.5 g of an isomeric mixture of 2-[2-(3-isopropyl-5-methyl-cyclohexa-1,5-dien-1-yl)ethyl]-1,3-dioxolane and its isomers.

[0157] GC-MS: 236, 207, 193, 174, 159, 131, 99, 73, 55, 29.

[0158] 3-(5-Isopropyl-3-methyl-cyclohexa-1,3-dien-1-yl)propanal, 3-(3-isopropyl-5-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(5-isopropyl-3-methylene-cyclohexen-1-yl)propanal and its isomers

[0159] Following general procedure 3, 2.1 g of 2-[2-(3-isopropyl-5-methyl-cyclohexa-1,5-dien-1-yl)ethyl]-1,3-dioxolane and its isomers gave an isomeric mixture of aldehydes 3-(5-Isopropyl-3-methyl-cyclohexa-1,3-dien-1-yl)propanal, 3-(3-isopropyl-5-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(5-isopropyl-3-methylene-cyclohexen-1-yl)propanal and its isomers (compounds of formula (I) or (Ia), 1.68 g, 25% yield). The crude product was purified and characterized by preparative liquid chromatography.

[0160] GC-MS: 192, 163, 121, 107, 93, 79, 41, 29.

[0161] Odour: Lily of the valley, aldehydic.

Example 3

1-[2-(1,3-Dioxolan-2-yl)ethyl]-3-isobutyl-5-methyl-cyclohexanol

[0162] Following general procedure 1, 2.0 g of 3-isobutyl-5-methy-cyclohexanone gave 2.6 g of crude product. After column chromatography (10-50% ethyl acetate in petroleum ether) 1.9 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-3-isobutyl-5-methyl-cyclohexanol were obtained.

[0163] .sup.1H NMR (600 MHz, DMSO-d.sub.6) δ 4.73 (t, J=4.9 Hz; 1H), 3.87-3.84 (m, 2H), 3.76-3.72 (m, 2H), 1.77-1.68 (m, 2H), 1.66-1.52 (m, 5H), 1.51-1.46 (m, 2H), 1.38-1.35 (m, 2H), 1.02-0.92 (m, 2H), 0.83 (dd, J=6.6, 3.1 Hz, 5H), 0.81 (d, J=6.6 Hz, 4H), 0.73 (t, J=12.6 Hz, 1H), 0.67 (t, J=12.5 Hz, 1H), 0.38 (q, J=12.1 Hz, 1H).

[0164] .sup.13C NMR (151 MHz, DMSO-d.sub.6) δ 104.72, 70.28, 64.62, 64.62, 46.96, 45.87, 43.90, 42.15, 38.70, 29.90, 27.97, 27.37, 24.75, 23.35, 23.23, 22.98.

[0165] GC-MS: 270, 251, 213, 195, 169, 151, 133, 102, 73, 58, 73, 58, 43, 29.

2-[2-(5-Isobutyl-3-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane and 2-[2-(3-isobutyl-5-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane

[0166] Following general procedure 2, 1.9 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-3-isobutyl-5-methyl-cyclohexanol gave 1.7 g of crude product. After column chromatography (10% ethyl acetate in cyclohexane) 1.4 g of an isomeric mixture of the products 2-[2-(5-isobutyl-3-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane and 2-[2-(3-isobutyl-5-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane were obtained (77% yield).

[0167] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) δ 5.42-5.37 (m; 1H), 5.34 (tt, J=2.6, 1.2 Hz, 1H), 4.90 (t, J=4.7 Hz, 2H), 3.58-3.53 (m, 4H), 3.41-3.37 (m, 4H), 2.26 (t, J=8.2 Hz, 4H), 2.21-2.12 (m, 2H), 2.00-1.92 (m, 4H), 1.94-1.88 (m, 1H), 1.89-1.82 (m, 1H), 1.75-1.58 (m, 6H), 1.60-1.45 (m, 2H), 1.20-1.07 (m, 2H), 1.07 (t, J=7.0 Hz, 2H), 0.96 (d, J=7.0 Hz, 3H), 0.90 (d, J=6.8 Hz, 3H), 0.87 (d, J=6.7 Hz, 6H), 0.86 (d, J=6.6 Hz, 6H), 0.68 (q, J=12.2, 10.7 Hz, 1H), 0.68 (q, J=12.2, 10.7 Hz, 1H).

[0168] .sup.13C NMR (101 MHz, C.sub.6D.sub.6) δ 136.60, 136.42, 127.87, 126.49, 104.70, 104. 55, 64.89, 64.89, 64.89, 64.89, 47.10, 46.91, 39.62, 39.31, 37.93, 36.03, 34.56, 33.04, 33.01, 32.52, 32.40, 32.37, 31.84, 29.77, 25.10, 25.01, 23.39, 23.31, 22.85, 22.62, 22.60, 22.48.

[0169] GC-MS: 252, 224, 209, 190, 164, 133, 107, 99, 86, 73, 55, 41, 29.

3-(5-Isobutyl-3-methyl-cyclohexen-1-yl)propanal and 3-(3-isobutyl-5-methyl-cyclohexen-1-yl)propanal

[0170] Following general procedure 3, 1.4 g of 2-[2-(5-isobutyl-3-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane and 2-[2-(3-isobutyl-5-methyl-cyclohexen-1-yl)ethyl]-1,3-dioxolane gave, after column chromatography (3-5% ethyl acetate in cyclohexane), 1.03 g of isomeric mixture of aldehydes 3-(3-isobutyl-5-methyl-cyclohexen-1-yl)propanal and 3-(5-isobutyl-3-methyl-cyclohexen-1-yl)propanal (compounds of formula (I) or (Ia)).

[0171] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) δ 9.37-9.35 (m, 2H), 5.21-5.16 (m, 1H), 5.16-5.10 (m, 1H), 2.20-2.07 (m, 2H), 2.05-1.92 (m, 8H), 1.75-1.69 (m, 1H), 1.71-1.59 (m, 5H), 1.59-1.47 (m, 2H), 1.42-1.29 (m, 2H), 1.15 (dt, J=13.7, 7.7, 6.9 Hz, 1H), 1.10-1.04 (m, 1H), 1.06 (t, J=7.0 Hz, 2H), 0.93 (d, J=7.0 Hz, 3H), 0.91-0.86 (m, 15H), 0.62 (q, J=12.4, 10.7 Hz, 2H).

[0172] .sup.13C NMR (101 MHz, C.sub.6D.sub.6) δ 200.55, 200.51, 135.45, 135.27, 128.33, 127.05, 47.02, 46.79, 42.00, 41.97, 39.38, 39.07, 37.78, 35.93, 34.48, 32.25, 31.73, 30.09, 29.95, 29.62, 25.11, 25.05, 23.39, 23.25, 22.87, 22.55, 22.52, 22.35.

[0173] GC-MS: 208, 190, 164, 149, 133, 121, 107, 95, 79, 67, 55, 41, 29.

[0174] Odour: Citrus, mandarin, aldehydic, citral, pleasantly fresh.

Example 4

1-[2-(1,3-dioxolan-2-yl)ethyl]-5-isobutyl-3-methyl-cyclohex-2-en-1-ol

[0175] Following general procedure 1, 2.0 g of 5-isobutyl-3-methyl-cyclohex-2-en-1-one, after column chromatography (10-50% ethyl acetate in cyclohexane), gave 2.9 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-5-isobutyl-3-methyl-cyclohex-2-en-1-ol.

[0176] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.33 (d, J=1.4 Hz, 1H), 4.90 (t, J=4.6 Hz, 1H), 4.06-3.93 (m, 2H), 3.93-3.80 (m, 2H), 2.05-1.68 (m, 8H), 1.66 (d, J=1.4 Hz, 3H), 1.64-1.43 (m, 2H), 1.29-1.18 (m, 1H), 1.15 (t, J=7.1 Hz, 2H), 0.88 (dd, J=6.6 Hz, 6H).

[0177] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 135.51, 127.70, 104.79, 71.89, 64.92, 64.92, 46.17, 43.65, 37.49, 35.47, 30.37, 27.93, 24.77, 23.41, 22.97, 22.69.

[0178] GC-MS: 250, 221, 207, 188, 162, 131, 99, 73, 55.

2-[2-(3-isobutyl-5-methyl-cyclohexa-1,5-dien-1-yl)ethyl]-1,3-dioxolane, 2-[2-(5-isobutyl-3-methyl-cyclohexa-1,3-dien-1-yl)ethyl]-1,3-dioxolane, 2-[(2Z)-2-(5-isobutyl-3-methyl-cyclohex-2-en-1-ylidene)ethyl]-1,3-dioxolane, 2-[(2E)-2-(5-isobutyl-3-methyl-cyclohex-2-en-1-ylidene)ethyl]-1,3-dioxolane and 2-[2-(5-isobutyl-3-methylene-cyclohexen-1-yl)ethyl]-1,3-dioxolane

[0179] Following general procedure 2, 2.9 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-5-isobutyl-3-methyl-cyclohex-2-en-1-ol gave 1.96 g of an isomeric mixture of 2-[2-(3-isobutyl-5-methyl-cyclohexa-1,5-dien-1-yl)ethyl]-1,3-dioxolane and its isomers.

[0180] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 6.31 (s, 1H), 6.08 (s, 1H), 5.98 (s, 1H), 5.61 (s, 1H), 5.62 (s, 1H), 5.53 (t, J=7.5 Hz, 1H), 5.42 (t, J=7.5 Hz, 1H), 5.37 (m, 1H), 5.33 (dt, J=3.5 Hz, 1.6 Hz, 1H), 4.95 (t, J=4.9 Hz, 1H), 4.93 (t, J=4.8 Hz, 1H), 4.88 (t, J=4.8 Hz, 1H), 4.85 (t, J=4.8 Hz, 1H), 4.84-4.80 (m, 2H), 4.78 (t, J=4.8 Hz, 1H), 3.56-3.49 (m, 10H), 3.47-3.32 (m, 10H), 2.36 (t, J=7.7 Hz, 2H), 2.34 (mc, 3H), 2.31 (mc, 2H), 2.26 (t, J=7.8 Hz, 2H), 2.09 (dd, J=16.6 Hz, 7.5 Hz, 1H), 2.02 (dd, J=16.9 Hz, 8.3 Hz, 1H), 1.95 (mc, 4H), 1.91 (mc, 6H), 1.75 (mc, 4H),1.71 (t, J=1.8 Hz, 3H), 1.68 (mc, 5H), 1.59 (mc, 7H), 1.32 (mc, 4H), 1.14 (mc, 2H), 1.04 (mc, 6H), 0.87-0.72 (m, 42H).

[0181] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 144.1, 141.2, 138.6, 138.3, 137.9, 136.9, 135.5, 135.5, 135.1, 131.6, 127.3, 125.3, 123.9, 123.1, 122.8, 122.3, 120.8, 118.5, 116.8, 109.3, 104.8, 104.7, 104.6, 104.5, 104.4, 64.9, 64.9, 64.9, 64.9, 64.8, 64.8, 64.8, 64.8, 64.8, 64.8, 46.0, 45.9, 45.6, 44.7, 44.4, 39.2, 38.3, 37.7, 37.6, 35.9, 35.6, 34.4, 33.9, 33.7, 33.4, 32.8, 32.6, 35.5, 32.4, 32.3, 32.1, 32.02, 32.02, 32.02, 32.02, 31.9, 31.8, 31.7, 30.6, 25.4, 25.3, 25.2, 25.2, 24.5, 24.2, 23.8, 23.5, 23.2, 23.1, 23.0, 22.9, 22.9, 22.9, 22.8, 21.7.

3-(5-isobutyl-3-methyl-cyclohexa-1,3-dien-1-yl)propanal, 3-(3-isobutyl-5-methyl-cyclohexa-1,5-dien-1-yl)propanal; 3-(5-isobutyl-3-methylenecyclohex-1-en-1-yl)propanal and 3-(5-isobutyl-3-methyl-cyclohex-2-en-1-ylidene)propanal (1:1:1:1 mixture)

[0182] Following general procedure 3, 1.9 g of the mixture of acetals gave 0.58 g of a crude mixture of aldehydes (compounds of formula (I) or (Ia)). Using preparative liquid chromatography and sniff gas chromatography, the compounds of formula (I) or (Ia) were isolated and characterized.

[0183] GC-MS: 206, 177, 121, 93, 79, 55, 41.

[0184] Odour: Aldehyde, watery, cucumber, green

Example 5

1-[2-(1,3-dioxolan-2-yl)ethyl]-4-isopropyl-cyclohexanol

[0185] Following general procedure 1, 2.0 g of 4-isopropylcyclohexanone gave 2.9 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-4-isopropyl-cyclohexanol (53% yield).

2-[2-(4-isopropylcyclohexen-1-yl)ethyl]-1,3-dioxolane

[0186] Following general procedure 2, 2.8 g of 1-[2-(1,3-dioxolan-2-yl)ethyl]-4-isopropyl-cyclohexanol gave 1.98 g of 2-[2-(4-isopropylcyclohexen-1-yl)ethyl]-1,3-dioxolane.

[0187] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.42 (mc, 1H), 4.86 (t, J=4.86 Hz, 1H), 3.97 (mc, 2H), 3.85 (mc, 2H), 2.06 (mc, 2H), 1.97 (mc, 2H), 1.75 (mc, 5H), 1.44 (mc, 1H), 1.21 (mc, 2H), 0.89 (d, J=6.6 Hz, 3H), 0.87 (d, J=6.7 Hz, 3H).

[0188] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 136.75, 120.90, 104.46, 64.87, 64.85, 40.16, 32.29, 32.18, 31.83, 29.14, 28.93, 26.47, 19.99, 19.68.

[0189] GC-MS: 224, 209, 195, 179, 162, 147, 133, 119, 99, 86, 73, 55, 41, 29.

3-(4-isopropylcyclohexen-1-yl)propanal

[0190] Following general procedure 3, 1.7 g of 2-[2-(4-isopropylcyclohexen-1-yl)ethyl]-1,3-dioxolane gave 1.3 g of 3-(4-isopropylcyclohexen-1-yl)propanal (compound of formula (Ia)).

[0191] GC-MS: 180, 162, 136, 119, 93, 79, 67, 55, 41, 29.

[0192] .sup.1H NMR (400 MHz, CDCl.sub.3): δ=0.87 (d, J=6.8 Hz, 3H), 0.88 (d, J=0.88 Hz, 3H), 1.16-1.28 (m, 2H), 1.42-1.50 (m, 1H), 1.66-1.80 (m, 2H), 1.94-2.06 (m, 3H), 2.28 (t, J=7.5 Hz, 2H), 2.49-2.54 (m, 2H), 5.39-5.43 (m, 1H), 9.75 (t, J=1.9 Hz, 1H).

[0193] .sup.13C NMR (100 MHz, CDCl.sub.3): δ 19.6, 19.9, 26.3, 28.8, 29.2, 29.7, 32.2, 40.0, 41.9, 121.8, 135.5, 202.8.

[0194] Odour: Strong, Lily of the valley, aldehydic.

Example 6

Synthesis of 3-(5-isopropyl-2-methylene-cyclohexyl)propanal a) 2-[2-(1,3-Dioxolan-2-yl)ethyl]-4-isopropyl-cyclohexanone

[0195] To a suspension of NaH (2.7 g, 2.0 eq) in N,N-diethylformamide (25 mL), 4-isopropylcyclohexanone (5.0 g, 1.0 eq) was added at a temperature between 0-5° C. and maintained at this temperature for about 45 min. Below 10° C., 2-(2-bromoethyl)-1,3-dioxolane (7.8 g; 1.2 eq) was added dropwise. After addition, the reaction mixture was maintained at room temperature until completion of the reaction (˜3-4 h). The reaction was quenched with ice-water, the mixture washed with 10% H.sub.2SO.sub.4, water and then the compound was extracted using MTBE. The organic phase was washed with saturated NaHCO.sub.3, washed with water until the pH of the aqueous layer was neutral and then dried over Na.sub.2SO.sub.4, filtered and the solvents were removed in vacuo to yield the crude product (7.73 g). Purification of the crude product by Kugelrohr distillation (T=150° C., p=0.1 mbar) gave the title compound of formula (VI) (6.2 g, 72%).

[0196] .sup.1H NMR (600 MHz, C.sub.6D.sub.6) δ 4.86 (td, J=4.8, 0.9 Hz, 1H), 3.59-3.56 (m, 2H), 3.40 (dt, J=5.5, 1.8 Hz, 2H), 2.26-2.22 (m, 1H), 2.21-2.12 (m, 1H), 2.01-1.95 (m, 1H), 1.94-1.89 (m, 1H), 1.89-1.83 (m, 1H), 1.83-1.77 (m, 1H), 1.77-1.71 (m, 1H), 1.46-1.39 (m, 1H), 1.38-1.27 (m, 2H), 1.24-1.18 (m, 1H), 1.17-1.11 (m, 1H), 0.85-0.83 (m, 1H), 0.70 (d, J=6.8 Hz, 3H), 0.68 (d, J=6.8 Hz, 3H).

[0197] .sup.13C NMR (151 MHz, C.sub.6D.sub.6) δ 210.43, 105.13, 64.85, 64.85, 49.31, 43.07, 41.57, 37.29, 32.15, 32.10, 30.41, 24.46, 20.02, 19.74.

[0198] GC-MS: 240, 222, 197, 178, 135, 99, 73, 55, 45, 29.

[0199] b) 2-[2-(5-Isopropyl-2-methylene-cyclohexyl)ethyl]-1,3-dioxolane

[0200] Under N.sub.2 atmosphere, potassium tert-butoxide (1.07 g, 1.25 eq) was added to a suspension of methyl(triphenyl)phosphonium bromide (2.97 g, 1.0 eq) in THF (20 mL) at a temperature between 0-5° C. and the mixture was maintained at room temperature for 30 min. To this mixture, a solution of 2-[2-(1,3-dioxolan-2-yl)ethyl]-4-isopropyl-cyclohexanone (2.0 g, 1.0 eq) in THF (10 mL) was added dropwise and refluxed until completion of the reaction (˜3 h). The reaction was quenched with ice water, and the compound was extracted using MTBE. The organic phase was washed with water until the pH of the aqueous layer was neutral and then dried over Na.sub.2SO.sub.4, filtered and the solvents were removed in vacuo to yield the crude product (4.78 g, contaminated with Wittig salt). Purification of the crude product by Kugelrohr distillation (T=155° C., p=0.3 mbar) gave the title compound of formula (VII) (1.2 g, 60%).

[0201] .sup.1H NMR (600 MHz, C.sub.6D.sub.6) δ 4.88-4.85 (m, 1H), 4.81 (dq, J=7.6, 1.7 Hz, 2H), 3.58-3.55 (m, 2H), 3.41-3.38 (m, 2H), 2.32 (ddd, J=12.8, 4.0, 2.7 Hz, 1H), 1.95-1.87 (m, 4H), 1.87-1.81 (m, 1H), 1.80-1.76 (m, 1H), 1.68-1.63 (m, 1H), 1.58-1.51 (m, 1H), 1.32-1.28 (m, 1H), 1.17-1.10 (m, 1H), 1.05-0.97 (m, 1H), 0.81 (d, J=5.8 Hz, 3H), 0.79 (d, J=5.7 Hz, 3H), 0.74 (q, J=12.1 Hz, 1H).

[0202] .sup.13C NMR (151 MHz, C.sub.6D.sub.6) δ 152.94, 105.18, 104.69, 64.89, 64.88, 44.35, 42.58, 38.39, 37.33, 32.85, 32.29, 31.99, 27.19, 20.11, 19.80.

[0203] GC-MS: 238, 209, 195, 176, 150, 133, 99, 73, 57, 45, 29.

[0204] c) 3-(5-Isopropyl-2-methylene-cyclohexyl)propanal

[0205] The reaction product of step b) above was deprotected to the product 3-(5-isopropyl-2-methylene-cyclohexyl)propanal (compound of formula (I) or (Ib)) following a procedure analogous to general procedure 3 (acetal deprotection) in 60% yield.

[0206] GC-MS: 194, 176, 161, 133, 91, 79, 67, 55, 41.

[0207] Odour: Lily of the valley, aldehydic, floral.