PERFUMING INGREDIENTS WITH LILY OF THE VALLEY NOTE

Abstract

The present invention primarily relates to the use of 3-(4-isobutyl-2-methyl-cyclohexyl)pro-panal, 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-meth-ylene-cyclohexen-1-yl)propanal, or 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal as perfuming ingredients. Moreover, the present invention relates to perfume compositions and perfumed products comprising the before mentioned perfuming ingredients. Still more particularly, the invention relates to a method for producing said perfumed products and a method of imparting and/or increasing i) floral and/or ii) green and/or iii) lily of the valley odor characteristics to perfumed products. This invention also relates to 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal, or 3-(4-isobutyl-6-methyl-cyclohexen-yl)propanal and a process for the preparation of said compounds.

Claims

1. A method of imparting a fragrance to a composition comprising adding a compound selected from the group consisting of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal, and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal to the composition.

2. The method according to claim 1, wherein the fragrance has a i) floral and/or ii) green and/or iii) lily of the valley odor characteristic.

3. The method according to claim 2, wherein the fragrance additionally has a sweet or creamy odor characteristic.

4. The method according to claim 1, wherein the compound is 3-(4-isobutyl-2-methyl-cyclohexyl)propanal.

5. The method according to claim 1, wherein the compound is 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal.

6. The method according to claim 1, wherein the compound is 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal.

7. The method according to claim 1, wherein the compound is 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal.

8. A perfume composition comprising a compound selected from the group consisting of 3-(4-isobutyl-2-methylcyclohexyl)propanal, 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal, and 3-(4-isobutyl-6-methylcyclohexen-1-yl)propanal.

9. The perfume composition according to claim 8 comprising one or more additional fragrance ingredients.

10. A perfumed product comprising the perfume composition according to claim 8.

11. The perfumed product according to claim 10, wherein the product is selected from the group consisting of perfume extraits, eau de perfumes, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes, perfumed refreshing tissues, acidic, alkaline and neutral detergents, textile fresheners, ironing aids, liquid detergents, powdery detergents, laundry pretreatment agents, fabric softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants, air improvers, aerosol sprays, waxes and polishes, personal care agents, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants and antiperspirants, products for decorative cosmetic, candles, lamp oils, incense sticks, insecticides, repellents, and fuels.

12. A method for producing the perfumed product according to claim 10 comprising: i) providing a compound selected from the group consisting of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal, and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal, ii) providing one or more further components of the perfumed product to be produced, and iii) contacting or mixing the one or more further components of (ii) with a sensorially effective amount of the compound of (i).

13. A method of imparting and/or increasing a i) floral and/or ii) green and/or iii) lily of the valley odor characteristic to a perfumed product comprising adding a perfume composition according to claim 8 to the product.

14. A process for preparing a compound selected from the group consisting of 3-(4-isobutyl-2-methylcyclohexyl)propanal, 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal, and 3-(4-isobutyl-6-methylcyclohexen-1-yl)propanal comprising at least one, two, three, four, five, or six of the following reaction steps: ##STR00022## ##STR00023## ##STR00024## ##STR00025## wherein R′ is alkyl, and R″ and R′″ are independently alkyl, or may be connected via an alkyl group to form a ring.

15. The process according to claim 14, wherein R′ is ethyl.

16. The process according to claim 14, wherein R″ and R′″ are independently methyl or ethyl, or may be connected ethane-1,2-diyl or propane-1,2-diyl to form a ring.

Description

EXAMPLES

Example 1: Perfume Composition A

[0109]

TABLE-US-00001 Parts by weight perfume perfume compositio composition A1 A2 (according to Components (comparison) the invention) ETHYL ACETOACETATE 4.0 4.0 HEXENOL CIS-3 10% DPG 3.0 3.0 HEXENYL ACETATE CIS-3 10% DPG 3.0 3.0 HEXENYL BENZOATE CIS-3 10% DPG 3.0 3.0 VERTOCITRAL 10% DPG 5.0 5.0 CYCLOGALBANAT ® 10% DPG 3.0 3.0 STYRALYL ACETATE 10% DPG 6.0 6.0 BERGAMOT OIL BERGAPTEN FREE FF 6.0 6.0 MANDARIN OIL DIST. DECOL. 15.0 15.0 METHYL ANTHRANILATE 10% DPG 5.0 5.0 RED BERRY EXTR. 2.0 2.0 DECALACTONE GAMMA 2.0 2.0 ALLYL CAPROATE 10% DPG 5.0 5.0 PRUNELLA TYPE BASE 6.0 6.0 HELIONAL 20.0 20.0 MUGETANOL 10.0 10.0 ETHYL LINALOOL 35.0 35.0 CITRONELLOL 950 10.0 10.0 GERANIOL SUPER 3.0 3.0 ROSAPHEN ® 8.0 8.0 CITRONELLYL ACETATE EXTRA 2.0 2.0 DAMASCONE BETA 10% DPG 6.0 6.0 BENZYL ACETATE 10.0 10.0 HEDION HC/30 30.0 30.0 HEDIONE 140.0 140.0 HEXYL CINNAMIC ALDEHYDE ALPHA 30.0 30.0 LACTOJASMONE 3.0 3.0 BENZYL SALICYLATE 80.0 80.0 HEXENYL SALICYLATE CIS-3 30.0 30.0 METHYL IONONE GAMMA COEUR 3.0 3.0 CLOVE BUD OIL 1.0 1.0 VANILLIN 1.5 1.5 COUMARIN 1.0 1.0 AMBERWOOD ® F 5.0 5.0 CASHMERAN 8.0 8.0 CEDRENE 15.0 15.0 ISO E SUPER NON DISCOLORING 50.0 50.0 BRAHMANOL ® 25.0 25.0 SANDALORE 5.0 5.0 AMBROXIDE 2.0 2.0 AMBRETTOLIDE 5.0 5.0 AURELIONE ® 16.0 16.0 GLOBALIDE ® 24.0 24.0 MACROLIDE ® SUPRA 16.0 16.0 INDOLE FF 10% DPG 5.0 5.0 Compound A to D — 50.0 DIPROPYLENE GLYCOL 332.5 282.5 1,000.0 1,000.0

[0110] By adding 5 wt. % of a compound A, B, C or D or a mixture of compounds A, B, C or D in perfume composition A2 the floral note is intensified relative to perfume oil A1 (without a compound A, B, C, or D). Furthermore, the compound A, B, C, or D endows the composition with perfume oil A2 more power and fullness than the composition with perfume oil A1; on the whole, addition a compound A, B, C or D or a mixture of compounds A, B, C or D results in an odor impression reminiscent of lily of the valley.

Example 2: Perfume Composition B

[0111]

TABLE-US-00002 Parts by weight perfume perfume compositio composition B1 B2 (according to the Components (comparison) invention) NONADIENAL TRANS,CIS-2,6 5% TEC 20% DPG 2.0 2.0 ETHYL ACETOACETATE 3.0 3.0 FARENAL ® 10% DPG 5.0 5.0 VERTOCITRAL 3.0 3.0 CYCLOGALBANAT ® 10% DPG 2.0 2.0 STYRALYL ACETATE 3.0 3.0 MELONAL ® 0.5 0.5 DIHYDRO MYRCENOL 15.0 15.0 LINALYL ACETATE 20.0 20.0 LEMON OIL TERPENES FLAVOR WONF 8.0 8.0 EUCALYPTOL NAT. 10% DPG 0.5 0.5 HEXYL ACETATE 1.5 1.5 ISOAMYL ACETATE 10% DPG 4.0 4.0 PRENYL ACETATE 10% DPG 4.0 4.0 ALDEHYDE C14 SO-CALLED 2.0 2.0 ETHYL METHYL BUTYRATE-2 1.0 1.0 ALLYL CYCLOHEXYL PROPIONATE 2.0 2.0 ALDEHYDE C16 SO-CALLED 1.0 1.0 FRAGOLANE ® 0.5 0.5 MAJANTOL ® 25.0 25.0 LINALOOL 40.0 40.0 DIMETHYL BENZYL CARBINOL 10.0 10.0 TERPINEOL PURE 10.0 10.0 PHENIRAT ® 30.0 30.0 CITRONELLOL 950 15.0 15.0 GERANIOL 60 10.0 10.0 CITRONELLYL ACETATE EXTRA 2.0 2.0 HEDIONE 90.0 90.0 HEXYL CINNAMIC ALDEHYDE ALPHA 35.0 35.0 HEXYL SALICYLATE 160.0 160.0 METHYL OCTIN CARBONATE 10% DPG 2.0 2.0 CALONE 1951 10% DPG 1.0 1.0 GALAXOLIDE 50% IN IPM 20.0 20.0 ANETHOL SUPRA 21.5 CELSIUS 2.0 2.0 AGRUMEX HC 15.0 15.0 ORYCLON SPECIAL 40.0 40.0 Compound A to D — 15.0 DIPROPYLENE GLYCOL 415.0 400.0 1,000.0 1,000.0

[0112] By adding 1.5 wt. % of a compound A, B, C or D or a mixture of compounds A, B, C or D in perfume composition B2 the floral and natural note is intensified relative to perfume oil B1 (without a compound A, B, C, or D). Furthermore, the compound A, B, C, or D endows the composition with perfume oil B2 more power and fullness than the composition with perfume oil A1; on the whole, addition a compound A, B, C or D or a mixture of compounds A, B, C or D results in an odor impression reminiscent of lily of the valley.

Example 3: Perfume Compositions C

[0113]

TABLE-US-00003 Parts by weight perfume perfume compositio composition C1 C2 (according to Components (comparison) the invention) FARENAL ® 3.0 3.0 FLORAZON 0.5 0.5 HEXENYL ACETATE CIS-3 3.0 3.0 VERTOCITRAL 1.0 1.0 DYNASCONE 10% DPG 2.0 2.0 CYCLOGALBANAT ® 2.0 2.0 STYRALYL ACETATE 1.5 1.5 DIHYDRO MYRCENOL 6.0 6.0 OXANTHIA 50% IN TEC 10% DPG 10.0 10.0 LEMON OIL ITAL. 10.0 10.0 ORANGE OIL BRASIL 50.0 50.0 HEXYL ACETATE 2.0 2.0 ISOAMYL ACETATE 0.5 0.5 PRENYL ACETATE 0.5 0.5 ETHYL BUTYRATE 10% DPG 2.0 2.0 ALDEHYDE C14 SO-CALLED 25.0 25.0 DECALACTONE GAMMA 5.0 5.0 ETHYL METHYL BUTYRATE-2 1.0 1.0 ALLYL CAPROATE 1.5 1.5 ALLYL CYCLOHEXYL PROPIONATE 3.0 3.0 ALLYL HEPTOATE 2.5 2.5 MELOZONE 2.0 2.0 CALONE 1951 0.5 0.5 MUGETANOL 10.0 10.0 LINALOOL 25.0 25.0 DIMETHYL BENZYL CARBINYL 6.0 6.0 ACETATE DIMETHYL BENZYL CARBINYL 4.0 4.0 BUTYRAT PHENYLETHYL ACETATE 1.5 1.5 PHENYLETHYL ALCOHOL 15.0 15.0 CITRONELLOL 950 10.0 10.0 GERANIOL SUPER 5.0 5.0 GERANYL ACETATE PURE 15.0 15.0 ISODAMASCON ® 2.0 2.0 BENZYL ACETATE 15.0 15.0 HEDIONE 90.0 90.0 HEXYL CINNAMIC ALDEHYDE ALPHA 35.0 35.0 JASMONE CIS 0.5 0.5 BENZYL SALICYLATE 80.0 80.0 HEXENYL SALICYLATE CIS-3 30.0 30.0 ISORALDEINE 70 35.0 35.0 HERBAFLORAT 15.0 15.0 ISO E SUPER 15.0 15.0 ISOBORNYL CYCLOHEXANOL 30.0 30.0 BRAHMANOL ® 10.0 10.0 AMBROXIDE 1.5 1.5 GLOBALIDE ® 5.0 5.0 GALAXOLIDE 50% IN DPG 120.0 120.0 Compound A to D — 65.0 DIPROPYLENE GLYCOL 290.0 225.0 1,000.0 1,000.0

[0114] By adding 6.5 wt. % of a compound A, B, C or D or a mixture of compounds A, B, C or D in perfume composition C2 the aqueous-fruity character is intensified relative to perfume oil C1 (without a compound A, B, C, or D). Moreover, in the perfume composition C2 with compound A, B, C, or D, the diffusivity is increased relative to the perfume composition C1, without a compound A, B, C or D; on the whole, addition of a compound A, B, C or D results in an odor impression reminiscent of lily of the valley.

Example 4: Synthesis of ethyl-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylate

[0115] 201.4 g (1.54 mol) ethylacetoacetate (CAS Number: 141-97-9) and 53.0 g (0.62 mol) isovaleraldehyde (CAS Number: 590-86-3) were added to a three-necked round bottom flask. 5.2 g piperidine in 35 mL ethanol were added at room temperature to the reaction mixture. The reaction mixture was then stirred for five hours under reflux. Subsequently the reaction mixture was cooled down to room temperature and methyl tert-butyl ether was added. The layers are separated, and the aqueous phases was washed with methyl tert-butyl ether. The organic phases were collected, washed two times with water and dried over sodium sulfate (30 g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by distillation. Ethyl-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylate is obtained as a liquid (138.5 g, 93.8%).

[0116] MS: m/z (%)=238, 165, 154, 126, 121, 109, 98, 79, 57, 41, 29.

[0117] .sup.1H NMR (400 MHz, Chloroform-d) δ 5.97 (d, J=2.6 Hz, 1H), 5.97-5.94 (m, 1H), 4.24 (dtd, J=10.7, 7.3, 3.6 Hz, 2H), 4.20 (dd, J=14.3, 7.2 Hz, 2H), 3.19 (d, J=5.0 Hz, 1H), 3.06 (d, J=6.4 Hz, 1H), 2.66 (dd, J=16.2, 4.6 Hz, 1H), 2.59 (d, J=3.0 Hz, 1H), 2.59-2.48 (m, 1H), 2.43-2.31 (m, 1H), 2.33-2.25 (m, 1H), 2.09 (dd, J=16.5, 8.2 Hz, 1H), 1.98 (d, J=1.3 Hz, 3H), 1.97-1.95 (m, 3H), 1.75 (dp, J=13.5, 6.7 Hz, 1H), 1.69-1.53 (m, 1H), 1.37-1.23 (m, 2H), 1.30 (t, J=7.1 Hz, 3H), 1.28 (t, J=7.2 Hz, 3H), 1.24-1.13 (m, 2H), 0.90 (d, J=6.6 Hz, 3H), 0.90 (d, J=6.6 Hz, 3H), 0.88 (d, J=6.6 Hz, 3H), 0.86 (d, J=6.5 Hz, 3H).

[0118] .sup.13C NMR (101 MHz, CDCl3) δ=199.39, 198.12, 171.86, 170.26, 156.69, 155.72, 128.45, 128.11, 61.31, 61.18, 53.07, 51.01, 42.98, 42.37, 40.37, 39.09, 35.35, 34.79, 24.98, 24.46, 23.38, 23.20, 23.09, 22.61, 22.49, 21.70, 14.31, 14.22.

Example 5: Synthesis of ethyl-3-(3,3-dimethoxypropyl)-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylate

[0119] 5.5 g (49.0 mmol) Potassium tert-butoxide were added to 100 mL tert-butyl alcohol. 0.2 g Tetrabutylammonium iodide (TBAI) and 10.0 g ethyl-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylate (40.8 mmol) were added to the mixture at room temperature. The mixture was stirred at 65° C. for four hours. Subsequently the mixture was let cool down to room temperature and 9.0 g (49.0 mmol) 3-bromo-1,1-dimethoxypropane was added dropwise. Subsequently tert-butoxide was removed under reduced pressure. To the residue methyl tert-butyl ether and water were added. The layers are separated, and the aqueous phases was washed with methyl tert-butyl ether. The organic phases were collected, washed two times with water and dried over sodium sulfate (30 g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by distillation. Ethyl-3-(3,3-Dimethoxypropyl)-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylate is obtained as a liquid (7.5 g, 51.5% %) with a purity of 97%.

[0120] MS: m/z (%)=325, 308, 277, 203, 147, 109, 82, 67, 41.

[0121] .sup.1H NMR (400 MHz, Chloroform-d) δ 4.35 (tt, J=5.7, 1.6 Hz, 2H), 4.26-4.16 (m, 4H), 3.31 (d, J=1.0 Hz, 12H), 3.20 (dd, J=5.5 Hz, 1H), 3.07 (dd, J=11.8, 6.3 Hz, 1H), 2.71-2.60 (m, 1H), 2.49-2.40 (m, 1H), 2.40-2.32 (m, 6H), 2.32 (s, 2H), 2.16-2.07 (m, 2H), 1.97 (s, 3H), 1.94 (d, J=0.8 Hz, 3H), 1.82-1.70 (m, 1H), 1.68-1.56 (m, 5H), 1.31-1.27 (m, 6H), 1.25 (dd, J=7.1, 3.3 Hz, 2H), 1.23-1.10 (m, 2H), 0.95-0.82 (m, 12H).

[0122] .sup.13C NMR (101 MHz, CDCl3) δ 198.32, 197.16, 172.46, 170.86, 150.10, 148.62, 136.72, 136.50, 104.14, 104.12, 61.17, 60.99, 54.49, 52.72, 52.65, 52.59, 42.93, 42.54, 40.71, 39.54, 34.62, 33.88, 31.17, 24.99, 24.37, 23.14, 22.67, 22.51, 21.82, 20.74, 20.69, 20.24, 19.77, 14.33.

Example 6: Synthesis of 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-en-1-one

[0123] 20 g (3.4 mmol) ethyl-3-(3,3-dimethoxypropyl)-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylate was mixed with 24 mL methanol. 4 g (50 mmol) sodium hydroxide and 30 g water were added at room temperature. The mixture was stirred for five seven hours under reflux. Subsequently the methanol was removed under reduced pressure. To the residue methyl tert-butyl was added. The layers are separated, and the aqueous phases was washed with methyl tert-butyl ether. The organic phases were collected, washed two times with water and dried over sodium sulfate (30 g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by distillation. 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-en-1-one is obtained as a liquid (13.2 g, 72.4%) with a purity of 98%.

[0124] MS: m/z (%)=253, 236, 221, 205, 191, 75, 71, 41.

[0125] .sup.1H NMR (400 MHz, Chloroform-d) δ 4.35 (t, J=5.7 Hz, 1H), 3.32 (s, 6H), 2.51-2.44 (m, 1H), 2.32 (dt, J=13.9, 7.2 Hz, 3H), 1.96 (s, 3H), 1.95 (s, 3H), 1.72-1.58 (m, 1H), 1.66-1.58 (m, 2H), 1.20 (t, J=6.7 Hz, 2H), 0.88 (d, J=2.5 Hz, 3H), 0.87 (d, J=2.3 Hz, 3H).

[0126] .sup.13C NMR (101 MHz, CDCl3) δ 198.97, 154.80, 134.65, 104.21, 52.61, 52.56, 45.29, 44.34, 39.79, 31.99, 31.47, 24.62, 22.74, 22.63, 21.16, 20.46.

Example 7: Synthesis of 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-en-1-ol

[0127] 0.38 g (10.0 mmol) lithium aluminium hydride were added to 60 mL THE and cooled down to 5° C. At this temperature 8.04 g (30 mmol) 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methylcyclohex-2-en-1-one were added carefully. The mixture was stirred at room temperature for three hours. Subsequently the mixture was quenched with water. To the residue methyl tert-butyl was added. The layers are separated, and the aqueous phases was washed with methyl tert-butyl ether. The organic phases were collected, washed two times with water and dried over sodium sulfate (30 g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by distillation. 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-en-1-ol is obtained as a liquid (8.0 g, 98.8%) with a purity of 98%.

[0128] MS: m/z (%)=238, 223, 206, 167, 149, 123, 105, 75, 41.

[0129] .sup.1H NMR (600 MHz, Benzene-d6) δ 4.44 (t, J=5.7 Hz, 1H), 4.11 (q, J=6.5 Hz, 1H), 3.20 (s, 3H), 3.19 (s, 3H), 2.51 (ddd, J=14.8, 9.6, 6.3 Hz, 1H), 2.34 (ddd, J=13.5, 9.4, 6.8 Hz, 1H), 1.98-1.88 (m, 3H), 1.78 (q, J=11.1, 10.5 Hz, 1H), 1.60 (d, J=1.7 Hz, 3H), 1.59-1.51 (m, 3H), 1.26 (d, J=6.5 Hz, 1H), 1.09-1.00 (m, 3H), 0.85 (d, J=6.6 Hz, 3H), 0.84 (d, J=6.5 Hz, 3H).

[0130] .sup.13C NMR (151 MHz, C6D6) δ 133.86, 129.07, 104.57, 70.08, 52.28, 51.87, 46.49, 40.94, 39.79, 31.89, 30.48, 24.94, 23.55, 23.16, 22.80, 19.34.

Example 8: Synthesis of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene

[0131] 6.0 g (22.2 mmol) 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-en-1-ol were dissolved in 60 mL toluene and 360 mg 4-dimethylaminopyridine (DMAP) and 18 g (0.18 mol) triethylamine were added at room temperature. The mixture was cooled down to 0 to 5° C. and 4.8 g (44.4 mmol) methanesulfonyl chloride were added dropwise at this temperature. The mixture was stirred for at least 12 hours at room temperature and subsequently for two hours under reflux. Subsequently the mixture was cooled down to 0 to 5° C. and 50 mL water was added to the mixture and the mixture was stirred for 1 hour. The phases were separated and the aqueous phase was extracted with toluene twice. The organic phases were collected, washed with water and dried over sodium sulfate (30 g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 4.8 g of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylenecyclohexene and 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene were obtained as mixture.

[0132] 1-(3,3-Dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene:

[0133] MS: m/z (%)=252, 220, 175, 131, 119, 105, 88, 75, 58, 41.

[0134] .sup.1H NMR (600 MHz, Benzene-d6) δ 5.65-5.60 (m, 1H), 5.13-5.09 (m, 1H), 4.87-4.84 (m, 1H), 4.39 (t, J=5.6 Hz, 1H), 3.17 (s, 3H), 3.16 (s, 3H), 2.46-2.39 (m, 2H), 2.39 (ddd, J=14.9, 3.0, 1.3 Hz, 1H), 2.08 (dt, J=17.7, 4.8 Hz, 1H), 2.00 (ddt, J=13.6, 11.3, 2.0 Hz, 1H), 1.94 (ddt, J=9.6, 6.6, 5.6 Hz, 2H), 1.80-1.72 (m, 1H), 1.65 (ddhept, J=17.8, 9.5, 1.4 Hz, 1H), 1.61-1.53 (m, J=6.7 Hz, 1H), 1.08 (dt, J=14.1, 7.1 Hz, 1H), 1.03 (dt, J=13.5, 7.2 Hz, 1H), 0.83 (d, J=6.8 Hz, 3H), 0.82 (d, J=6.8 Hz, 3H).

[0135] .sup.13C NMR (151 MHz, Benzene-d6) δ 143.66, 136.75, 127.22, 108.32, 104.49, 52.23, 52.65, 45.72, 39.83, 33.39, 32.34, 32.21, 28.26, 25.07, 23.11, 22.81.

[0136] 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene

[0137] .sup.1H NMR (400 MHz, Benzene-d6) δ 5.56 (t, J=4.7 Hz, 1H), 5.52-5.48 (m, 1H), 3.17 (s, 3H), 3.16 (s, 3H), 2.29-2.21 (m, 3H), 2.04-1.97 (m, 1H), 1.87-1.80 (m, 3H), 1.78 (t, J=1.8 Hz, 3H), 1.77-1.68 (m, 1H), 1.60-1.53 (m, 1H), 1.40-1.17 (m, 2H), 0.85 (d, J=6.6 Hz, 3H), 0.84 (d, J=6.5 Hz, 3H).

[0138] .sup.13C NMR (101 MHz, Benzene-d6) δ 137.67, 132.83, 128.98, 121.20, 104.27, 52.25, 52.20, 44.12, 32.44, 31.59, 30.04, 28.18, 25.31, 22.97, 22.84, 19.72.

Example 9: Synthesis of 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal and 3-(4-isobutyl-6-methylenecyclohexen-1-yl)propanal (B+C)

[0139] 1 g of a mixture of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene were mixed with 1.2 g formic acid and stirred for 1.5 hours at room temperature. Subsequently the mixture was added to sodium bicarbonate (NaHCO.sub.3). The organic phases were separated, washed two times with water, dried over sodium sulfate and the solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 0.7 g of 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal and 3-(4-isobutyl-6-methylenecyclohexen-1-yl)propanal were obtained as mixture with a purity of 93%. Both aldehydes can be separated by preparative GC.

[0140] 3-(4-Isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal (B):

[0141] Odor: Floral, Green, Lily of the valley.

[0142] MS: m/z (%)=206, 131, 119, 105, 91, 79, 41.

[0143] .sup.1H NMR (600 MHz, Benzene-d6) δ 9.32 (t, J=1.6 Hz, 1H), 5.46 (p, J=3.6, 1.8 Hz, 1H), 5.33 (t, J=4.7 Hz, 1H), 2.21 (ddddd, J=9.7, 7.6, 5.8, 4.1, 2.1 Hz, 1H), 2.17 (tq, J=7.7, 1.7 Hz, 2H), 2.08-2.02 (m, 1H), 2.01-1.97 (m, 2H), 1.80-1.72 (m, 1H), 1.62 (t, J=1.9 Hz, 3H), 1.64-1.56 (m, J=6.7 Hz, 1H), 1.26 (dt, J=13.3, 7.4 Hz, 1H), 1.12 (dt, J=13.3, 7.4 Hz, 1H), 0.85 (d, J=6.6 Hz, 3H), 0.83 (d, J=6.6 Hz, 3H).

[0144] .sup.13C NMR (151 MHz, Benzene-d6) δ 200.29, 136.39, 132.25, 129.23, 121.40, 43.98, 42.66, 31.41, 29.85, 25.29, 25.15, 22.92, 22.82, 19.56.

[0145] 3-(4-Isobutyl-6-methylene-cyclohexen-1-yl)propanal (C):

[0146] Odor: Floral, Green, Lily of the valley.

[0147] MS: m/z (%)=206, 188, 164, 149, 131, 121, 105, 91, 79, 41.

[0148] .sup.13C NMR (151 MHz, Benzene-d6) δ 200.41, 143.27, 135.44, 127.74, 108.27, 45.59, 42.76, 39.60, 33.21, 32.17, 25.21, 25.05, 23.07, 22.79.

[0149] .sup.1H NMR (600 MHz, Benzene-d6) δ 9.33 (t, J=1.6 Hz, 1H), 5.45-5.40 (m, 1H), 4.85-4.80 (m, 1H), 4.78-4.73 (m, 2H), 2.41-2.33 (m, 1H), 2.35-2.29 (m, 1H), 2.14-2.09 (m, 2H), 2.01 (dt, J=17.9, 5.0 Hz, 1H), 1.92 (ddt, J=13.5, 11.2, 2.0 Hz, 1H), 1.73-1.64 (m, 1H), 1.63-1.55 (m, 1H), 1.60-1.49 (m, J=6.9 Hz, 1H), 1.04 (dt, J=14.1, 7.1 Hz, 1H), 0.99 (dt, J=13.5, 7.2 Hz, 1H), 0.81 (d, J=7.0 Hz, 6H).

Example 10: Synthesis of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal (A)

[0150] 1.1 g (2.15 mmol) of a mixture of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene were mixed with 2 ml cyclohexane. 80 mg of palladium on activated charcoal were added. The mixture was hydrogenated with hydrogen at 100-190° C. for 8 h at a pressure of 20-25 bar. The catalyst was filtered off. 1.0 g 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methylcyclohexane was obtained with a purity of 95%.

[0151] 1 g 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methylcyclohexane were mixed with 1.2 g formic acid and stirred for 1.5 hours at room temperature. Subsequently the mixture was added to sodium bicarbonate (NaHCO.sub.3). The organic phases were separated, washed two times with water, dried over sodium sulfate and the solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 0.7 g of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal (A) were obtained with a purity of 94%.

[0152] Odor: Floral, Green, Lily of the valley, Sweet.

[0153] MS: m/z (%)=210, 192, 166, 151, 135, 109, 95, 81, 67, 55, 41, 29.

[0154] .sup.1H NMR (400 MHz, Benzene-d6) δ 9.38 (t, J=1.7 Hz, 1H), 1.96-1.75 (m, 3H), 1.70-1.58 (m, 2H), 1.52-1.43 (m, 2H), 1.40-1.18 (m, 5H), 1.06-0.97 (m, 3H), 0.89 (d, J=6.6 Hz, 6H), 0.80 (d, J=7.0 Hz, 3H), 0.69-0.56 (m, 1H).

[0155] .sup.13C NMR (101 MHz, C.sub.6D.sub.6) δ 200.94, 47.34, 42.62, 38.36, 36.48, 35.77, 35.71, 29.22, 27.03, 24.95, 23.11, 23.08, 20.10, 17.00.

Example 11: Synthesis of 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methyl-cyclohexene

[0156] 1.1 g (4.36 mmol) of a mixture of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene were mixed with 2 ml cyclohexane. 20 mg of palladium on activated charcoal were added. The mixture was hydrogenated with hydrogen at 50° C. for 5 h at a pressure of 2 bar. The catalyst was filtered off. 1.0 g 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methyl-cyclohexene was obtained with a purity of 95%.

[0157] MS: m/z (%)=222, 207, 190, 133, 107, 93, 79, 75, 67, 55, 41.

[0158] .sup.1H NMR (400 MHz, CDCl3) δ 4.32 (t, J=5.7 Hz, 1H), 3.32 (s, 6H), 2.03 (ddt, J=12.0, 7.2, 3.9 Hz, 2H), 1.99-1.89 (m, 2H), 1.76-1.63 (m, 5H), 1.60 (s, 3H), 1.60-1.47 (m, 2H), 1.17-1.06 (m, 3H), 0.87 (d, J=6.6 Hz, 6H).

[0159] .sup.13C NMR (101 MHz, CDCl3) δ 128.82 (C-4), 126.20 (C-5), 104.25 (C-10), 52.49 (C-12), 52.47 (C-14), 46.27 (C-15), 39.02 (C-6), 31.73 (C-1), 30.80 (C-9), 29.98 (C-2), 29.60 (C8), 28.09 (C-3), 24.88 (C-16), 23.10 (C-17), 22.75 (C-18), 18.96 (C-7).

Example 12: Synthesis of 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal (D)

[0160] 1 g 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methyl-cyclohexene were mixed with 1.2 g formic acid and stirred for 1.5 hours at room temperature. Subsequently the mixture was added to sodium bicarbonate (NaHCO.sub.3). The organic phases were separated, washed two times with water, dried over sodium sulfate and the solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 0.7 g of 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal (D) were obtained with a purity of 93%.

[0161] Odor: Floral, Sweet, Lily of the valley, Creamy.

[0162] MS: m/z (%)=208, 190, 165, 151, 133, 107, 81, 67, 55, 41, 29.

[0163] .sup.1H NMR (600 MHz, Benzene-d6) δ 9.37 (t, J=1.8 Hz, 1H), 2.12 (dd, J=7.4, 2.8 Hz, 2H), 2.00-1.96 (m, 2H), 1.84-1.79 (m, 1H), 1.75-1.70 (m, 1H), 1.65-1.58 (m, 2H), 1.54-1.49 (m, 2H), 1.48 (t, J=1.9 Hz, 3H), 1.41-1.33 (m, 1H), 1.07-1.02 (m, 3H), 0.88 (d, J=2.5 Hz, 3H), 0.87 (d, J=2.6 Hz, 3H).

[0164] .sup.13C NMR (151 MHz, Benzene-d6) δ 200.66, 128.32, 126.84, 46.52, 42.52, 39.22, 31.92, 30.16, 29.60, 25.85, 25.15, 23.26, 22.89, 19.06.