ACETATE COMPOUNDS USEFUL AS ODORANTS

Abstract

The present invention refers to acetates possessing woody creamy sandalwood olfactory properties. The invention further refers to fragrance compositions and consumer products comprising them.

Claims

1. A compound of formula (I) in the form of any one of its stereoisomers or a mixture thereof ##STR00002## wherein (I) R.sup.1 and R.sup.2 form together with the carbon atoms to which they are attached cyclopropyl or a double bond, or R.sup.1 and R.sup.2 are hydrogen; and R.sup.3 and R.sup.4 form together with the carbon atom to which they are attached cyclopropyl, and the dotted lines together with the carbon-carbon bond forms a single bond; or R.sup.3 and R.sup.4 are hydrogen, and one of the dotted lines together with the carbon-carbon bond forms a double bond.

2. The compound according to claim 1 wherein R.sup.1 and R.sup.2 and/or R.sup.3 and R.sup.4 form together with the carbon atom to which they are attached cyclopropyl.

3. IM compound according to claim 2 wherein the compound is (1-methyl-2-((1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methyl acetate in the form of any one of its stereoisomers or a mixture thereof.

4. IM compound according to claim 3 wherein the compound is (1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methyl acetate.

5. A fragrance composition comprising: a) at least one compound of formula (I) as defined in claim 9, and b) [1-methyl2-[(1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)methyl]cyclopropyl]methanol in the form of any one of its stereoisomers or a mixture thereof.

6. The fragrance composition according to claim 5, wherein the compound of formula (I) is (1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methyl acetate), and b) is [1-methyl2-[((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)methyl]cyclopropyl]methanol.

7. The fragrance composition according to claim 5 wherein the weight ratio of a) to b) is in the range from 0.05:99.95 to 5:95 (a:b).

8. A consumer product comprising a compound of formula (I) as defined in claim 9, and a consumer product base.

9. A method comprising utilizing a compound of formula (I) as a fragrance ##STR00003## wherein R.sup.1 and R.sup.2 form together with the carbon atoms to which they are attached cyclopropyl or a double bond, or R.sup.1 and R.sup.2 are hydrogen; and R.sup.3 and R.sup.4 form together with the carbon atom to which they are attached cyclopropyl or a double bond, and the dotted lines together with the carbon-carbon bond forms a single bond; or R.sup.3 and R.sup.4 are hydrogen, and one of the dotted lines together with the carbon-carbon bond forms a double bond; the method comprising mixing the compound of formula (I) with a consumer product base, or mixing a fragrance composition comprising the compound of formula (I) with a consumer product base.

10. A method of improving, enhancing or modifying a consumer product base by adding thereto an olfactory acceptable amount of a compound of formula (I) as defined in claim 9.

11. A fragrance composition consisting of: a) at least one compound of formula (I) as defined in claim 9, and b) [1-methyl2-[(1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)methyl]cyclopropyl]methanol in the form of any one of its stereoisomers or a mixture thereof.

12. A fragrance composition comprising: a) at least one compound of formula (I) as defined in claim 2, and b) [1-methyl2-[(1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)methyl]cyclopropyl]methanol in the form of any one of its stereoisomers or a mixture thereof.

13. A fragrance composition consisting of: a) at least one compound of formula (I) as defined in claim 2, and b) [1-methyl2-[(1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)methyl]cyclopropyl]methanol in the form of any one of its stereoisomers or a mixture thereof.

14. The fragrance composition according to claim 6 wherein the weight ratio of a) to b) is in the range from 0.05:99.95 to 5:95 (a:b).

15. A consumer product comprising a fragrance composition as defined in claim 5 and a consumer product base.

16. A consumer product comprising a fragrance composition as defined in claim 6 and a consumer product base.

17. A consumer product comprising a fragrance composition as defined in claim 7 and a consumer product base.

18. A method of improving, enhancing or modifying a consumer product base by adding thereto an olfactory acceptable amount of a fragrance composition as defined in claim 3.

19. A method of improving, enhancing or modifying a consumer product base by adding thereto an olfactory acceptable amount of a fragrance composition as defined in claim 4.

20. A method of improving, enhancing or modifying a consumer product base by adding thereto an olfactory acceptable amount of a fragrance composition as defined in claim 5.

Description

EXAMPLE 1: (1-METHYL-2-(((1S,3R,5R)-1,2,2-TRIMETHYLBICYCLO[3.1.0]HEXAN-3-yl)methyl)cyclopropyl)methyl Acetate

[0030] To a reactor with a reflux condenser was charged under nitrogen 1-methyl-2-[[(1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hex-3-yl]methyl]cyclopropanemethanol) (mixture of diasteriomers; isomer 1: 40.9%; isomer 2: 53.4%; 50 g; purity: 94.3%; 212 mmol), pyridine (20 g; 253 mmol), and toluene (200 g). To the mixture stirred at 0° C., acetyl chloride (18 g; 229 mmol) were added dropwise within 15 minutes. The resultant reaction mixture was allowed to rise up to 20° C. and stirred for additional 2 hours. Water was added. The organic layer was separated, washed (water) and concentrated by rotavapory distillation (60° C.; 10 mbar) to give 58 g of a yellowish oil containing 90% of (1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methylacetate. Further purification by distillation using a 15 cm Vigreux column under 0.08 Torr afforded 48 g (purity: 93.9%; isomer 1: 41.4%; isomer 2: 52.5%; 170 mmol) of (1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methylacetate. More product could be recovered from 8.7 g of rejected (82% pure) fractions. (1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)-cyclopropyl)methylacetate molar yield based on (1-methyl-2-(1,2,2-trimethylbicyclo(3.1.0)-hex-3-ylmethyl)cyclopropyl)methanol represented about 80% without taking into account rejected fractions. The 48 g obtained after the second distillation were further distilled using a Sulzer column (20 cm) leading to 40 g of 98% (isomer 1: 43.2%; isomer 2: 54.8%) of olfactory pure product ((1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)methylacetate).

[0031] Odor description: soft, woody creamy sandalwood character with a soft fruity floral aspect (violet/orris direction).

[0032] Isomer 1 (rel-(1R, 2R)-(1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)methyl acetate): .sup.1H NMR (C.sub.6D.sub.6, 600 MHz): 3.83 (d, J=11.3, 1H), 3.77 (d, J=10.9, 1H), 1.95 (dd, J=12.4, 6.4, 1H), 1.73 (s, 3H), 1.37 (td, J=11.7, 4.1, 1H), 1.22-1.16 (m, 2H), 1.04 (s, 3H), 1.03 (s, 3H), 1.01-0.93 (m, 2H), 0.92 (s, 3H), 0.74 (s, 3H), 0.55-0.47 (m, 3H), 0.08 (dd, J=7.5, 4.5, 1H), −0.13 (br t, J=4.5, 1H). .sup.13C NMR (C.sub.6D.sub.6, 150 MHz): 170.0, 73.2, 45.1, 41.1, 32.4, 31.2, 29.5, 22.8, 22.75, 21.4, 20.3, 19.5, 18.7, 17.4, 17.3, 15.3, 14.0

[0033] Isomer 2 (rel-(1S, 2S)-(1-methyl-2-(((1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)methyl acetate): .sup.1H NMR (C.sub.6D.sub.6, 600 MHz): 3.84 (d, J=11.3, 1H), 3.79 (d, J=10.9, 1H), 1.88 (dd, J=12.1, 6.8, 1H), 1.72 (s, 3H), 1.37 (td, J=11.7, 4.1, 1H), 1.22-1.13 (m, 2H), 1.09-1.06 (m, 1H), 1.04 (s, 3H), 1.04 (s, 3H), 1.00-0.97 (m, 1H), 0.93 (s, 3H), 0.74 (s, 3H), 0.54-0.47 (m, 3H), 0.06 (dd, J=7.9, 4.9, 1H), −0.18 (br t, J=4.5, 1H).

[0034] .sup.13C NMR (C.sub.6D.sub.6, 150 MHz): 170.0, 73.2, 44.8, 41.1, 32.2, 31.3, 28.8, 22.8, 22.6, 21.9, 20.2, 19.6, 19.6, 17.2, 16.8, 15.9, 13.9

EXAMPLE 2: WOODY, ORIENTAL FRAGRANCE ACCORD

[0035]

TABLE-US-00001 parts by weight Compound/Ingredient 1/1000 AMBRINOL (2,5,5-trimethy1- 3 1,2,3,4,4a,5,6,7-octahydronaphthalen- 2-ol) ARMOISE essential oil 2 BOISIRIS (2-ethoxy-9-methylen-2,6,6- 50 trimethylbicyclo[3.3.1]-nonane) CASHMERAN (6,7-DIHYDRO-1,1,2 ,3,3- 15 PENTAMETHYL-4(5H)-INDANONE) CEDARWOOD essential oil 10 BUTANOIC ACID, 1,1-DIMETHYL-2- 4 PHENYLETHYL ESTER ETHYL LINALYL ACETATE (3,7- 10 DIMETHYL-1,6-NONADIEN-3-YL ACETATE) ETHYL MALTOL (3-HYDROXY-2- 1 ETHYL-4H-PYRAN-4-ONE) GALAXOLIDE 80 (1,3,4,6,7,8-HEXAHYDRO-4,6,6,7,8,8- HEXAMETHYLINDENO(5,6- C)PYRAN) GARDENOL (1-PHENYLETHYL 1 ACETATE) HEDIONE (methyl 3-oxo-2- 40 pentylcyclopentaneacetate) IONONE BETA (4-(2,6,6-TRIMETHYL- 10 1-CYCLOHEXEN-1-YL)-3-BUTEN- 2-ONE) ISO E SUPER 430 ISORALDEINE 8 LEMON OIL 6 CIS-3-HEXENYL METHYL 3 CARBONATE LINALOOL 7 MAHONIAL (9-HYDROXY-5,9- 10 DIMETHYLDEC-4-ENAL) NYMPHEAL (3-(4-isobutyl-2- 5 methylphenyl)propanal) PATCHOULI OIL 4 ROSYFOLIA ((1-methyl-2-(5-methylhex- 4 4-en-2-yl)cyclopropyl)methanol) VANILLIN (4-HYDROXY-3- 5 METHOXYBENZALDEHYDE) VETIVER OIL 2 DIPROPYLENE GLYCOL 290 Total: 1000

[0036] The replacement of 4 parts of DPG of the accord above by (1-methyl-2-((1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methyl acetate (i.e. a compound of formula (I)) softens the accord both, on fresh and dry down, and brings in particular a soft creamy orris violet to the dry down note.

[0037] The replacement of 20 parts of DPG of the accord above by a mixture of (1-methyl-2-((1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methyl acetate and (1-methyl-2-((1,2,2-trimethylbicyclo[3.1.0]hexan-3-yl)methyl)cyclopropyl)-methanol (in a ratio of 2:98), alcohol delivers performance and the overall sandalwood character, soften by the combination with the acetate, with a general sandalwood character which appears more natural, closer to the sandalwood essential oil effect and character, with the soft fruity floral orris facet.