SYNTHESIS AND USE OF 2-ETHYL-5,5-DIMETHYL-CYCLOHEXANOL AS FRAGRANCE AND FLAVOR MATERIAL

Abstract

The present invention relates to the compound 2-ethyl-5,5-dimethyl-cyclohexanol, which can impart, modify and/or enhance one or more odours selected from the group consisting of minty, fresh tobacco leaf, cresol, horse and animalistic, mixtures comprising 2-ethyl-5,5-dimethyl-cyclohexanol, and a new method for producing the same, a fragrance composition comprising 2-ethyl-5,5-dimethyl-cyclohexanol, the use of 2-ethyl-5,5-dimethyl-cyclohexanol as a fragrance, particularly for imparting, modifying and/or enhancing one or more odours selected from the group consisting of minty, fresh tobacco leaf, cresol, horse and animalistic, a perfumed product comprising 2-ethyl-5,5-dimethyl-cyclohexanol, a method for perfuming such a product and a method for modifying an olfactory impression.

Claims

1-12. (canceled)

13. A compound according to formula (I) (2-ethyl-5,5-dimethyl-cyclohexanol) ##STR00010##

14. The compound according to claim 13, wherein the compound is obtainable by a method comprising: i) providing methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (formula II), ##STR00011## ii) converting the methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (formula II) to 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) with a base.

15. The compound according to claim 14, wherein step i) of the method is performed by providing 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethan-1-one (formula III) ##STR00012## and converting the 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethan-1-one (formula III) to the methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (formula II).

16. The compound according to claim 14, wherein the base in step ii) is provided in a solvent.

17. The compound according to claim 14, wherein the base is heated to at least 80° C. before or during addition to the methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (formula II) and/or wherein step ii) of the method is performed at a temperature of least 80° C.

18. A mixture comprising the compound according to claim 14.

19. A method for producing 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) ##STR00013## comprising: i) providing methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino]carbamate (formula II), ##STR00014## ii) converting the methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (formula II) to 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) with a base.

20. The method according to claim 19, wherein step i) is performed by providing 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethan-1-one (formula III) ##STR00015## and converting the 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethan-1-one (formula III) to methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (formula II).

21. The method according to claim 18, wherein the base in step ii) is provided in a solvent.

22. The method according to claim 18, wherein the base is heated to at least 80° C. before or during addition to the methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (formula II) and/or wherein step ii) is performed at a temperature of at least 80° C.

23. A fragrance composition comprising the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) according to claim 13 in an amount sufficient to enhance an odour selected from minty, fresh tobacco leaf, cresol, horse, and animalistic.

24. The fragrance composition according to claim 23, wherein the total amount of the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) in the fragrance composition is 0.0001 to 99.9 wt.-%, based on the total weight of the fragrance composition.

25. A method for imparting, modifying, and/or enhancing one or more odours selected from minty, fresh tobacco leaf, cresol, horse, and animalistic comprising incorporating the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) according to claim 13 into a composition in an amount sufficient to impart, modify, and/or enhance the one or more odours selected from minty, fresh tobacco leaf, cresol, horse, and animalistic.

26. A perfumed product comprising the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) according to claim 13.

27. The perfumed product according to claim 26, wherein the product is selected from washing and cleaning agents, hygiene or care products, perfumed refreshing tissues, acid, alkaline or neutral cleaning agents, textile refreshing agents, ironing aids, liquid washing agents, washing agents in powder form, laundry pre-treatment agents, fabric softeners, laundry soap, laundry tablets, disinfectants, surface disinfectants, air refreshers, aerosols, waxes and polishes, body 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, anti-perspirants, products of decorative cosmetics, candles, lamp oils, joss sticks, insecticides, repellents, and propellants.

28. The perfumed product according to claim 26, wherein the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) in the product is in an amount of 0.00001 to 10 wt.-%, based on the total weight of the product.

29. A method for perfuming a product comprising adding the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) according to claim 14 to the product in a sensorialy effective amount.

30. The method according to claim 29, wherein the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) is added to the product in an amount sufficient to impart, modify, and/or enhance an odour selected from minty, fresh tobacco leaf, cresol, horse and animalistic.

31. A method for modifying one or more olfactory impression(s) of one or more fragrance(s) comprising combining a sensorially effective amount of the 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) according to claim 14 with the one or more fragrance(s).

Description

EXAMPLES

Example 1: Synthesis of Methyl N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl) Ethylidene Amino] Carbamate (Formula II)

[0092] To a solution of 1-(2-hydroxy-4,4-dimethylcyclohexyl)ethan-1-one (5.0 g) in Isopropanol (75 mL), portion wise methyl N-amino carbamate (2.95 g) was added followed by catalytic amount of acetic acid. Reaction mixture was refluxed for 4-5 h. At room temperature, reaction mixture was quenched with cold water, compound extracted in MTBE (50 mL×3), combined organic later washed with water until neutral pH, dried with MgSO.sub.4 and evaporated to get crude followed by Kugelrohr distillation (150° C., 0.9 mbar) gave the title compound 4.3 g, 61%.

[0093] .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.71 (s, 1H), 3.98 (td, J=10.8, 3.9 Hz, 1H), 3.82 (s, 3H), 2.10 (ddd, J=13.3, 9.6, 3.6 Hz, 1H), 1.83 (s, 3H), 1.76 (dddd, J=10.5, 8.5, 5.3, 2.6 Hz, 2H), 1.45-1.40 (m, 1H), 1.38 (qd, J=12.9, 3.1 Hz, 1H), 1.24 (td, J=13.4, 12.1, 3.9 Hz, 1H), 1.20 (t, J=13.2, 12.4 Hz, 1H), 0.97 (s, 3H), 0.94 (s, 3H).

[0094] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 155.15, 154.62, 67.69, 54.63, 52.96, 46.55, 38.46, 32.87, 32.01, 25.25, 25.15, 13.48.

[0095] GC-MS: 242, 209, 168, 143, 111, 83, 69, 55, 41, 29

Example 2: Synthesis of 2-ethyl-5,5 dimethyl-cyclohexanol (Formula I)

[0096] To a solution of KOH (3.89 g) in triethylene glycol (30 mL), at 100° C. methyl-N—[(Z)-1-(2-hydroxy-4,4-dimethyl-cyclohexyl)-ethylidene amino] carbamate (4.3 g) was added and maintained until consumption of starting material. At room temperature, reaction mixture was further diluted with water (30 mL), compound extracted in MTBE (30 mL×3), combined organic later washed with water, dried with MgSO.sub.4 and evaporated to get crude. Crude product was purified by column chromatography (cyclohexane:ethyl acetate 10:1) gave the required product (weight=1.1 g, 39%).

[0097] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 3.40 (ddd, J=11.2, 9.4, 4.4 Hz, 1H), 1.87-1.76 (m, 1H), 1.71-1.64 (m, 2H), 1.35 (dq, J=11.7, 2.5 Hz, 1H), 1.21-1.07 (m, 4H), 1.06-0.98 (m, 1H), 0.94 (s, 3H), 0.92 (t, J=7.6 Hz, 3H), 0.89 (s, 3H).

[0098] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 71.52, 48.72, 46.87, 38.63, 32.98, 32.25, 25.85, 25.08, 24.54, 10.93.

[0099] GC-MS: 141, 123, 85, 69, 41

Application Example 1: Fragrance Composition without 2-Ethyl-5,5-Dimethyl-Cyclohexanol (Formula I)

[0100]

TABLE-US-00001 Ingredient Amount [wt.-%] Agrumex LC 1.00 Amarocit ® 10% in DPG 1.00 Calone 1951 10% in DPG 1.00 Cedar wood oil 1.00 Cedrol Krist 5.00 Citral 10% in DPG 1.00 Citonellol 0.50 Cumarin 1.00 Cyclogalbanate ® 10% ig in DPG 1.50 Dihydromyrcenol 8.00 Farenal ® 10% in DPG 0.50 Galbex 10% in DPG 2.50 Geraniol 8.00 Geranyl nitrile 4.00 Hedion 9.00 Helional 2.00 Heliotropin 0.50 Hexenol cis-3 10% in DPG 1.50 Hexenylsalicylate cis-3 1.00 Beta-Ionon 0.50 Iso E Super 6.50 Isodamascon ® 10% in DPG 1.00 Isogalbanate 2.00 Isoraldein 70 2.00 Lavandinoel Grosso Nat. 1.50 Lilial 2.00 Linalool 2.00 Linalylacetate 4.00 Mandarin oil Brazil. green 5.00 Vanillin 0.50 Veloutone 10% in DPG 2.00 DPG 21.00 Total 100.00

[0101] The olfactory impression of the fragrance composition (i.e. without 2-ethyl-5,5-dimethyl-cyclohexanol (formula I)) is described as flowery, woody, slightly fresh.

[0102] According to the perfumers, the olfactory impression of the fragrance composition becomes more fresh, more minty and with a slight tobacco smell when 5 wt.-% of 2-ethyl-5,5-dimethyl-cyclohexanol (formula I) is added.