USE OF 1-ETHYL-4,4-DIMETHYL-CYCLOHEXANE DERIVATIVES AS FRAGRANCES
20210395640 · 2021-12-23
Inventors
Cpc classification
A61Q13/00
HUMAN NECESSITIES
C07C269/00
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to the use of 1-(4,4-dimethylcyclohexyl)ethanone, 1-(4,4-dimethylcyclohex-1-en-1-yl)ethanone, 1-(4,4-dimethylcyclohexyl)ethanol, 1-(4,4-dimethylcyclohexyl)ethyl acetate and 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethanone as a fragrance substance, in particular with a flowery and/or fruity olfactory characteristic. The present invention further relates to fragrance compositions and perfumed products comprising the compounds listed above. The present invention also relates to a method producing perfumed products and a method producing 1-(4,4-dimethylcyclohexyl)ethanol or 1-(4,4-dimethylcyclohexyl)ethyl acetate. Further, the invention relates to the compounds 1-(4,4-dimethylcyclohexyl)ethyl acetate, 1-(4,4-dimethylcyclohexyl)ethanol and 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethanone.
Claims
1. A method for imparting a fragrance to a composition comprising adding a compound selected from the group consisting of 1-(4,4-dimethylcyclohexyl)ethanone, 1-(4,4-dimethylcyclohex-1-en-1-yl)ethanone, 1-(4,4-dimethylcyclohexyl)ethanol, 1-(4,4-dimethylcyclohexyl)ethyl acetate, and 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethanone to the composition.
2. The method according to claim 1, wherein the fragrance has a flowery and/or fruity olfactory characteristic.
3. The method according to claim 1, wherein the compound imparts, enhances, or modifies a flowery and/or fruity olfactory characteristic.
4. The method according to claim 1, wherein the compound is 1-(4,4-dimethylcyclohexyl)ethyl acetate.
5. The method according to claim 1, wherein the compound is 1-(4,4-dimethylcyclohexyl)ethanol.
6. The method according to claim 1, wherein the compound is 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethanone.
7. A fragrance composition comprising a compound selected from 1-(4,4-dimethylcyclohexyl)ethanone, 1-(4,4-dimethylcyclohex-1-en-1-yl)ethanone, 1-(4,4-dimethylcyclohexyl)ethanol, 1-(4,4-dimethylcyclohexyl)ethyl acetate, and 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethanone.
8. The fragrance composition according to claim 7, additionally comprising one or more further fragrance substance(s).
9. The fragrance composition according to claim 7, additionally comprising 1-(3,3-dimethylcyclohexyl)ethyl acetate.
10. The fragrance composition according to claim 9, wherein the molar ratio between the compound and 1-(3,3-dimethylcyclohexyl)ethyl acetate is 1:199 to 1:4.
11. The fragrance composition according to claim 9, wherein the molar ratio between the compound 1 and 1-(3,3-dimethylcyclohexyl)ethyl acetate is 1:199 to 1:9.
12. The fragrance composition according to claim 9, wherein the molar ratio between the compound 1 and 1-(3,3-dimethylcyclohexyl)ethyl acetate is 2:99 to 1:19.
13. The fragrance composition according to claim 9, wherein the molar ratio between the compound 1 and 1-(3,3-dimethylcyclohexyl)ethyl acetate is 1:49 to 1:24.
14. The fragrance composition according to claim 7, wherein the compound is 1-(4,4-dimethylcyclohexyl)ethyl acetate.
15. A perfumed comprising the fragrance composition accord to claim 7.
16. The perfumed product according to claim 15, wherein the product is selected from the group consisting of perfume extracts, eau de parfums, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes, perfumed refreshing tissues, acid, alkaline and neutral detergents, fabric refreshers, ironing aids, liquid detergents, powder detergents, laundry pre-treatment products, fabric softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants, air refreshers, aerosol sprays, waxes and polishes, personal care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products, deodorants and antiperspirants, products of decorative cosmetics, candles, lamp oils, incense sticks, insecticides, repellents, and propellants.
17. A method for producing a perfumed product according to claim 15 comprising: (i) providing a compound selected from 1-(4,4-dimethylcyclohexyl)ethanone, 1-(4,4-dimethylcyclohex-1-en-1-yl)ethanone, 1-(4,4-dimethylcyclohexyl)ethanol, 1-(4,4-dimethylcyclohexyl)ethyl acetate, and 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethanone, 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 with a sensorially effective amount of the compound of (i).
18. A method for producing 1-(4,4-dimethylcyclohexyl)ethanol or 1-(4,4-dimethylcyclohexyl)ethyl acetate comprising the following reaction step: ##STR00025##
Description
EXAMPLE 1: PRODUCTION OF 1-(2-HYDROXY-4,4-DIMETHYL-CYCLOHEXYL)ETHANONE (C)
[0137] To a solution of N,N-diethylgeranylamine (10 g, 0.048 mol) in methanol (50 mL) was added a 31% aqueous hydrogen peroxide solution (15.8 mL) at room temperature. The mixture was stirred for 48 hours and then about 30 mg of MnO.sub.2 was added to decompose the excess oxidant. The reactant mixture was filtered over Celite and post-rinsed with methanol. The filtrate was freed from methanol under reduced pressure. The crude N-oxide (2a) was obtained. To this colorless aqueous solution was added 50% H.sub.2SO.sub.4 aq. (v/v 9.8 mL) was added. The mixture changed color from colorless to pink while stirred at 100° C. for eight hours. After cooling the solution to 0° C., a mixture of NaOH (10 g) and ice (10 g) was added to the solution. After controlled neutralization, the mixture was extracted with MTBE (100 mL×3) and the combined organic phases were washed with water, dried over Na.sub.2SO.sub.4 and freed from the solvent. 7 g of 1-(2-hydroxy-4,4-dimethyl-cyclohexyl)ethanone (C) was obtained. The crude product can be used for the subsequent synthesis (Example 2) without further processing.
[0138] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.01 (ddd, J=11.7, 9.8, 4.4 Hz, 1H), 2.29-2.22 (m, 1H), 2.20 (s, 3H), 1.91-1.83 (m, 1H), 1.71 (ddd, J=12.6, 4.5, 2.1 Hz, 1H), 1.49-1.39 (m, 2H), 1.32-1.01 (m, 2H), 0.97 (s, 3H), 0.92 (s, 3H).
[0139] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 212.87, 67.62, 59.06, 46.33, 38.32, 32.75, 31.88, 29.21, 24.91, 24.36.
[0140] Odor description: flowery, green, minty.
EXAMPLE 2: SYNTHESIS OF 1-(4,4-DIMETHYLCYCLOHEXEN-1-YL)ETHANONE (E)
[0141] To a solution of 1-(2-hydroxy-4,4-dimethyl-cyclohexyl)ethanone (C) (2.9 g, 0.171 mol) in methanol (15 mL), NaOH pellets (340 mg) were slowly added and the mixture was heated at reflux for two hours. Then, the mixture was mixed with 10% aqueous hydrochloric acid solution and extracted with MTBE (30 mL×3). The organic phases were combined, washed with saturated NaHCO.sub.3 solution and subsequently with water and dried over Na.sub.2SO.sub.4. The mixture was freed from solvent and then purified by Kugelrohr distillation (70° C., 0.44 mbar). 1-(4,4-dimethylcyclohexen-1-yl)ethanone (E) was obtained (2.1 g, 81%).
[0142] .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.83 (tt, J=3.9, 1.7 Hz, 1H), 2.29 (s, 3H), 2.26 (tq, J=6.5, 2.3, Hz, 2H), 2.04 (dt, J=4.7, 2.6, Hz, 2H), 1.40 (t, J=6.5 Hz, 2H), 0.92 (s, 6H).
[0143] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 199.20, 140.10, 138.47, 40.06, 34.84, 28.41, 28.12, 28.12, 25.30, 20.83.
[0144] Odor description: fruity, banana-like, caraway.
EXAMPLE 3: SYNTHESIS OF 1-(4,4-DIMETHYLCYCLOHEXYL)ETHANONE (D)
[0145] A mixture of 1-(4,4-dimethylcyclohexen-1-yl)ethanone (E) (11.8 g, 0.77 mol), isopropanol (60 mL) and a catalytic amount of Ru/C 5 wt.-% (0.9 g) was placed in a sealed reactor and hydrogenation was carried out at 130° C. and 5 to 10 bar hydrogen for 6 to 7 hours. The reaction mixture was subsequently filtered off, freed from solvent, and distilled by Kugelrohr distillation (131° C., 0.3 bar). 9.1 g (76%) 1-(4,4-dimethylcyclohexyl)ethanone (D) was obtained.
[0146] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 2.24 (tt, J=11.6, 3.8 Hz, 1H), 2.14 (s, 3H), 1.75-1.66 (m, 2H), 1.58-1.40 (m, 4H), 1.20 (td, J=13.1, 3.9 Hz, 2H), 0.92 (s, 3H), 0.89 (s, 3H).
[0147] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 212.47, 51.41, 38.42, 38.43, 32.40, 29.80, 28.05, 24.44, 24.44, 24.35.
[0148] Odor description: spicy, savory, caraway.
EXAMPLE 4: SYNTHESIS OF 1-(4,4-DIMETHYLCYCLOHEXYL)ETHANOL (B)
[0149] To a cooled solution of 1-(4,4-dimethylcyclohexyl)ethanone (D) (7.0 g, 0.045 mol) in MeOH (13.5 mL) a mixture of NaBH.sub.4 (0.7 g, 0.018 mol) in 1% NaOH solution (2.8 mL) was carefully added and then stirred for four hours at room temperature. Approximately half of the methanol was subsequently removed at the rotary evaporator and 100 mL of cooled water was added. The aqueous mixture was extracted with MTBE (50 mL×3). The combined organic phases were washed with water, dried over Na.sub.2SO.sub.4, and then freed from solvent at 60° C. and 500 to 10 mbar. 6 g of 1-(4,4-dimethylcyclohexyl)ethanol (B) was obtained as crude product. The crude product can be purified by column chromatography (cyclohexane:ethyl acetate 3:1). 5.8 (83%) 1-(4,4-dimethylcyclohexyl)ethanol (B) is obtained.
[0150] .sup.1H NMR (600 MHz, Benzene-d.sub.6) δ 3.31 (h, J=6.09 Hz, 1H), 1.65-1.57 (m, 1H), 1.39-1.30 (m, 3H), 1.16-1.05 (m, 4H), 0.99 (d, J=6.32 Hz, 3H), 0.98 (d, J=6.28 Hz, 1H), 0.90 (s, 3H), 0.84 (s, 3H), 0.69 (d, J=4.84 Hz, 1H, —OH).
[0151] .sup.13C NMR (151 MHz, C.sub.6D.sub.6) δ 71.60, 45.38, 39.38, 39.28, 33.20, 24.97, 24.32, 24.33, 24.25, 20.94.
[0152] Odor description: flowery, blossoming, citrus, soft, plum, body lotion.
EXAMPLE 5: SYNTHESIS OF 1-(4,4-DIMETHYLCYCLOHEXYL)ETHYL ACETATE (A)
[0153] A mixture of 9.6 g (61.4 mmol) 1-(4,4-dimethylcyclohexyl)ethanol (B), cyclohexane (150 mL), and pyridine (7.4 mL) was placed under a nitrogen atmosphere and 6.3 g acetyl chloride was added dropwise at a temperature between 0 and 5° C. After the reaction was complete, 50 mL of water was added and the mixture was stirred for 15 minutes. The organic phase was separated and washed with 25% H.sub.2SO.sub.4 solution (25 mL×2), water (25 mL×2) and saturated NaHCO.sub.3 solution. The organic phase was then dried over sodium sulfate, filtered and then freed from solvent at 60° C. and 500 to 10 mbar. 10.84 g (89%) of 1-(4,4-dimethylcyclohexyl)ethyl acetate (A) was obtained.
[0154] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.75 (p, J=6.4 Hz, 1H), 2.03 (s, 3H), 1.56 (ddd, J=10.5, 7.1, 5.1 Hz, 1H), 1.49 (ddd, J=11.1, 5.7, 1.8 Hz, 1H), 1.45-1.35 (m, 1H), 1.38-1.30 (m, 1H), 1.27-1.19 (m, 2H), 1.18 (d, J=6.4 Hz, 3H), 1.16-1.08 (m, 3H), 0.89 (s, 3H), 0.86 (s, 3H). 13C NMR (101 MHz, CDCl.sub.3) δ 170.84, 74.55, 42.55, 38.81, 38.76, 32.84, 29.98, 24.31, 24.31, 24.15, 21.33, 17.31.
[0155] Odor description: green, herbaflorate, violet, rose, flowery, powdery.
EXAMPLE 6: PERFUME EXAMPLES WITH ADDITION OF 1-(4,4-DIMETHYLCYCLOHEXYL)ETHYL ACETATE (A)
[0156]
TABLE-US-00001 Reference example (not Example according to according to the invention the invention AGRUMEX HC 80 80 ALDEHYDE C14 SOG 50 50 ALDEHYDE C16 SOG. 1 1 AMBROXIDE 4 4 ANISALDEHYDE PURE 16 16 APPLE GREEN AROMABASE 15 15 APRIFLOREN ® 1 1 BERGAMOT OIL 20 20 CITRONELLOL 950 40 40 CITRONELLYL ACETATE 10 10 EXTRA 1-(4,4-dimethylcyclohexyl)ethyl 0 20 acetate (A) DECALACTONE GAMMA 5 5 DIHYDROMYRCENOL 100 100 DIPROPYLENE GLYCOL 58 38 ETHYLVANILLIN 10% DPG 4 4 EUGENOL NAT. 3 3 FRAMBINON ® 10% DPG 6 6 GERANYL ACETATE 60 20 20 GERANYL TIGLATE 5 5 GLOBALIDE ® 25 25 HEDIONE 60 60 HEXENAL TRANS-2 10% DPG 6 6 HEXENYL ACETATE CIS-3 10% 9 9 DPG HEXYL ACETATE 50 50 HEXYLSALICYLATE 15 15 INDOFLOR ® CRYST. 10% DPG 2 2 ISO E SUPER 20 20 ISORALDEINE 70 15 15 JASMIN 61 TYPE BASE 20 20 LINALOOL 80 80 LINALYL ACETATE 150 150 PHENIRAT ® 50 50 ROSE DE MAI-BASE 30 30 ROSE OXIDE L 5 5 SANDRANOL ® 15 15 VERTOCITRAL 10 10 1000 1000
[0157] Addition of 2% of 1-(4,4-dimethylcyclohexyl)ethyl acetate gives the perfume blend a more flowery, natural and softer fragrance.
EXAMPLE 7: COMBINATION OF 1-(4,4-DIMETHYLCYCLOHEXYL)ETHYL ACETATE WITH 1-(3,3-DIMETHYLCYCLOHEXYLLETHYL ACETATE
[0158] Four mixtures of 1-(4,4-dimethylcyclohexyl)ethyl acetate with 1-(3,3-dimethylcyclohexyl)ethyl acetate were prepared according to the table below and the odor of each mixture was determined.
TABLE-US-00002 Proportion of 1-(3,3-dimethyl- Dosage of 1-(4,4- cyclohexyl)ethyl dimethylcyclo- No.: acetate hexyl)ethyl acetate Odor 1 100 parts by without addition fruity-apple-pear-like, weight sweet, flowery-woody 2 100 parts by with 1 wt.-% the mixture becomes weight addition more flowery, softer and more natural 3 100 parts by with 2 wt.-% the mixture gets a slight weight addition musk-ambergris odor 4 100 parts by with 4 wt.-% the effects become weight addition distinctly stronger than for the 2% addition 5 100 parts by with 8 wt.-% the mixture becomes weight addition more spicy
[0159] Addition of 1-(4,4-dimethylcyclohexyl)ethyl acetate to 1-(3,3-dimethylcyclohexyl)ethyl acetate significantly improved the fragrance profile. The addition of 2-4 wt.-% of 1-(4,4-dimethylcyclohexyl)ethyl acetate was found to be of particular interest.
EXAMPLE 8: ALCOHOLS FROM THE DIHYDROMYRCENOL PROCESS
[0160] In the table below, products of the dihydromyrcenol process are represented. The structures, the proportions determined by GC and the odor description of the respective compound are given in the table:
TABLE-US-00003 Structure % Odor 1
EXAMPLE 9: ACTATES FROM THE DIHYDROMYRCENOL PROCESS
[0161] The compounds of the alcohol mixture from Example 8 were converted into the respective ethyl acetate analogously to the synthesis procedure from Example 5. In the table below, products of the acetylation are shown. The structures, the proportions determined by GC and the odor description of the respective compound are given in the table:
TABLE-US-00004 Structure % Odor 1