ALICYCLIC ALIPHATIC 1,3-DICARBONYL DERIVATIVES USEFUL AS FRAGRANCES

Abstract

Disclosed are alicyclic aliphatic 1,3-dicarbonyl derivatives of formula (I) possessing musk odor characteristics.

Claims

1. A compound of formula (I) ##STR00008## wherein R.sub.1 and R.sub.3 are independently selected from hydrogen, methyl and ethyl; R.sub.2 is hydrogen, methyl, ethyl, or methylene; R.sub.4 is H, or C.sub.1-C.sub.4 alkyl; R.sub.5 is H, or methyl; R.sub.6 is selected from hydrogen and methyl; X is selected from the group consisting of the bivalent residues >CH2, >O, >CHMe, >CMe.sub.2; and the bond between C-2 and R.sub.2 is a single bond, and the bond between C-2 and C-3 together with the dotted line represents a double bond; or the bond between C-2 and C-3 is a single bond, and the bond between C-2 and R.sub.2 together with the dotted line represents a double bond; or the bond between C-2 and R.sub.2 is a single bond, and the bond between C-2 and C-3 is a single bond.

2. The compound according to claim 1 wherein the compound of formula (I) is selected from a compound of formula (Ia) ##STR00009## wherein R.sub.1 is selected from hydrogen, methyl and ethyl; R.sub.6 is selected from hydrogen, methyl and ethyl; and R is a hydrocarbon residue comprising 1-6 carbon atoms, optionally comprising one oxygen atom.

3. The compound according to claim 2 wherein the compound is selected from 3,5-dimethylhex-3-en-2-yl 3-oxohexanoate; 3,5-dimethylhex-3-en-2-yl 2-methyl-3-oxohexanoate; (E)-3-methylhex-3-en-2-yl 3-oxohexanoate; (E)-3,5-dimethylhex-3-en-2-yl 4-methyl-3-oxohexanoate; and 3,5-dimethylhex-3-en-2-yl ethyl malonate.

4. A fragranced article comprising as odorant a compound of formula (I) as defined in claim 1, and a consumer product base.

5. A fragranced article according to claim 4 wherein the article is a consumer product base selected from fine fragrance, household products, laundry products, body care products, cosmetic products and air care products.

6. A method of utilizing a compound of formula (I) as defined in claim 1 as a fragrance comprising adding said compound to a consumer product base.

7. 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 1.

8. A fragranced article comprising as odorant a compound of formula (Ia) as defined in claim 2, and a consumer product base.

9. A fragranced article according to claim 8, wherein the article is a consumer product base selected from fine fragrance, household products, laundry products, body care products, cosmetic products and air care products.

10. A method of utilizing a compound of formula (Ia) as defined in claim 2 as a fragrance comprising adding said compound to a consumer product base.

11. A method of improving, enhancing or modifying a consumer product base by adding thereto an olfactory acceptable amount of a compound of formula (Ia) as defined in claim 2.

Description

EXAMPLE 1: 3,5-DIMETHYLHEX-3-EN-2-YL 3-OXOHEXANOATE

[0091] 3,5-Dimethylhex-3-en-2-ol (12.7 g, 99.05 mmol), ethyl 3-oxohexanoate (15.66 g, 99.05 mmol) and cesium fluoride (1.32 g, 9.9 mmol) were mixed in anhydrous Toluene (130 mL). The resulting reaction mixture was stirred at 110 C. for 52 h under nitrogen atmosphere. The reaction mixture was then diluted with water (100 mL) and extracted in Ethyl acetate (EtOAc) (2300 mL), washed with brine, dried over anhydrous sodium sulphate (Na.sub.2SO.sub.4) and concentrated under reduced pressure to obtain the crude. The crude product was purified by column chromatography on silica gel eluting with a gradient of ethyl acetate in heptane to give 3,5-dimethylhex-3-en-2-yl 3-oxohexanoate (8.8 g, 37% yield) as a colorless liquid.

[0092] .sup.1H NMR (400 MHz, CDCl3, 298 K, mixture of E and Z isomers) (ppm)=5.35-4.92 (m, 2H), 3.45-3.35 (m, 2H), 2.76-2.42 (m, 2H), 1.71-1.54 (m, 5H), 1.37-1.27 (m, 3H), 1.00-0.88 (m, 9H).

[0093] .sup.13C NMR (101 MHz, CDCl3, 298 K, mixture of E and Z isomers) b (ppm)=202.8, 166.5, 136.6, 135.5, 131.3, 76.7, 70.2, 49.7, 49.5, 44.8, 44.8, 26.8, 26.7, 23.1, 22.7, 19.0, 18.9, 17.5, 16.9, 13.5, 11.8.

[0094] MS (El, 70 eV): 240 (1, [M].sup.+*), 197 (2), 128 (16), 113 (91), 110 (76), 95 (88), 71 (100), 43 (52).

[0095] Odour description (10% solution in DPG on paper blotter, 4 h): musky, powdery, fatty, slightly green, pear skin.

EXAMPLE 2: (S,E)-3,5-DIMETHYLHEX-3-EN-2-YL 3-OXOHEXANOATE

[0096] Was prepared in the same way as Example 1, using (S,E)-3,5-dimethylhex-3-en-2-ol (3.00 g, 23.4 mmol), ethyl 3-oxohexanoate (3.70 g, 23.4 mmol) and CsF (355 mg, 2.34 mmol) in Toluene (25 mL) to give (S,E)-3,5-dimethylhex-3-en-2-yl 3-oxohexanoate (1.70 g, 30% yield) as a colorless liquid.

[0097] .sup.1H NMR (400 MHz, CDCl3, 298 K) b (ppm)=5.33-5.24 (m, 2H), 3.40 (s, 2H), 2.51 (t, J=7.2 Hz, 2H), 1.67-1.59 (m, 5H), 1.31 (d, J=6.5 Hz, 3H), 0.97-0.89 (m, 9H).

[0098] .sup.13C NMR (101 MHz, CDCl3, 298 K) b (ppm)=202.9, 166.5, 135.6, 131.3, 76.8, 49.7, 44.8, 26.8, 22.7, 18.9, 16.9, 13.6, 11.8.

[0099] Optical rotation: [].sub.D.sup.24=29.497 deg*mL*g.sup.1*dm.sup.1 (c 1.83, EtOH); [].sub.405.sup.24=74.915 deg*mL*g.sup.1*dm.sup.1 (c 1.83, EtOH).

[0100] Odour description (10% solution in DPG on paper blotter, 4 h): musky, powdery, radiant, fatty, green, fruity, pear skin.

EXAMPLE 3: 3,5-DIMETHYLHEX-3-EN-2-YL 2-METHYL-3-OXOHEXANOATE

[0101] NaH (0.16 g, 60 wt-% in mineral oil, 3.9 mmol) was mixed with THF (tetrahydrofuran) (3 mL). A solution of 3,5-dimethylhex-3-en-2-yl 3-oxohexanoate (0.85 g, 3.5 mmol) in THF (5 mL) was added dropwise and the resulting reaction mixture was stirred for 20 min at ambient temperature. A solution of iodomethane (0.55 g, 0.24 mL, 3.9 mmol) in THF (2 mL) was added. The reaction mixture was stirred at ambient temperature for 90 min then poured into iced 1M HCl solution (100 mL) and extracted with MTBE (methyl tert-butyl ether) (2100 mL), washed with water (2100 mL) and brine (100 mL), dried over MgSO.sub.4, filtered and concentrated. The crude product was purified by column chromatography on silica gel eluting with a gradient of MTBE in heptane to give 3,5-dimethylhex-3-en-2-yl 2-methyl-3-oxohexanoate (0.9 g, 97% purity, 57% yield) as a colorless liquid.

[0102] .sup.1H NMR (400 MHz, CDCl3, 298 K, mixture of stereoisomers) b (ppm)=5.89-5.47 (m, 0.5H), 5.35-5.22 (m, 1H), 5.13-4.81 (m, 1H), 3.57-3.40 (m, 1H), 2.74-2.40 (m, 3H), 1.71-1.56 (m, 6H), 1.37-1.28 (m, 5H), 1.01-0.87 (m, 9H). .sup.13C NMR (101 MHz, CDCl3, 298 K mixture of stereoisomers) b (ppm)=205.7, 169.8, 135.7, 135.5, 77.2, 76.6, 76.6, 53.2, 53.1, 43.2, 43.1, 26.7, 26.7, 23.4, 22.7, 18.9, 18.8, 17.4, 17.0, 17.0, 13.6, 13.6, 12.7, 11.8.

[0103] MS (El, 70 eV): 155 (3), 145 (5), 127 (77), 110 (57), 95 (53), 71 (100), 43 (51).

[0104] Odour description (10% solution in DPG on paper blotter, 4 h): musky, animalic, warm.

EXAMPLE 4: (E)-3-METHYLHEX-3-EN-2-YL 3-OXOHEXANOATE

[0105] A mixture of (E)-3-methylhex-3-en-2-ol (3.40 g, 29.8 mmol), ethyl 3-oxohexanoate (4.71 g, 29.8 mmol) and CsF (452 mg, 2.98 mmol) in Toluene (30 mL) was heated up to 110 C. The orange reaction mixture was stirred over night at 110 C. The flask was then equipped with a small distillation head and short Vigreux column and the reaction mixture was heated while distilling a mixture of EtOH and toluene for 2 h. During the distillation, additional Toluene (15 mL) was introduced into the mixture to prevent it from drying. The reaction mixture was then poured into water (50 mL) and was extracted with MTBE (250 mL), washed with water (50 mL) and brine (50 mL), dried over MgSO.sub.4, filtered and concentrated. The crude product was purified by column chromatography on silica gel eluting with a gradient of MTBE in heptane to give (E)-3-methylhex-3-en-2-yl 3-oxohexanoate (3.03 g, 45% yield) as a pale yellow liquid.

[0106] .sup.1H NMR (400 MHz, CDCl3, 298 K) b (ppm)=5.47 (tt, J=1.1, 7.1 Hz, 1H), 5.33 (q, J=6.4 Hz, 1H), 3.42 (s, 2H), 2.53 (t, J=7.2 Hz, 2H), 2.04 (quin, J=7.5 Hz, 2H), 1.69-1.58 (m, 6H), 1.33 (d, J=6.6 Hz, 3H), 0.97 (t, J=7.6 Hz, 3H), 0.94 (t, J=7.3 Hz, 3H).

[0107] .sup.13C NMR (101 MHz, CDCl3, 298 K) b (ppm)=202.9, 166.5, 133.0, 129.9, 76.7, 49.7, 44.8, 20.8, 18.9, 16.9, 13.8, 13.6, 11.7.

[0108] MS (El, 70 eV): 226 (1, [M].sup.+*), 141 (2), 131 (8), 113 (67), 96 (100), 81 (92), 71 (76), 43 (73).

[0109] Odour description (10% solution in DPG on paper blotter, 4 h): warm, musky, fatty.

EXAMPLE 5: (E)-3,5-DIMETHYLHEX-3-EN-2-YL 4-METHYL-3-OXOHEXANOATE

[0110] Example 5a: 2,2-dimethyl-5-(2-methylbutanoyl)-1,3-dioxane-4,6-dione: A solution of 2,2-dimethyl-1,3-dioxane-4,6-dione (1.90 g, 13.2 mmol) and pyridine (2.09 g, 2.13 mL, 26.4 mmol) in CH.sub.2Cl.sub.2 (25 mL) was treated with a solution of 2-methylbutanoyl chloride (1.75 g, 14.5 mmol) in CH.sub.2Cl.sub.2 (10 mL) at 5 C. After the addition the cooling bath was removed and the reaction mixture was stirred for 3 h at ambient temperature. The reaction mixture was poured into iced 1M HCl-solution and extracted with CH.sub.2Cl.sub.2 (100 mL), washed with water (100 mL) and brine (100 mL), dried over MgSO.sub.4, filtered and evaporated to give 2,2-dimethyl-5-(2-methylbutanoyl)-1,3-dioxane-4,6-dione (1.35 g, 68% purity, 30% yield) as a yellow liquid which was used in the next step without further purification.

[0111] Example 5b: (E)-3,5-dimethylhex-3-en-2-yl 4-methyl-3-oxohexanoate: A solution of 2,2-dimethyl-5-(2-methylbutanoyl)-1,3-dioxane-4,6-dione (1.35 g, 68 wt-%, 4.01 mmol) and (E)-3,5-dimethylhex-3-en-2-ol (1.54 g, 12.0 mmol) in Toluene (13 mL) was heated up to reflux for 4 h. The reaction mixture was then diluted with water (100 mL) and extracted in Ethyl acetate (EtOAc) (2300 mL), washed with brine, dried over anhydrous sodium sulphate (Na.sub.2SO.sub.4) and concentrated under reduced pressure to obtain the crude. The crude product was purified by column chromatography on silica gel eluting with a gradient of ethyl acetate in heptane to give (E)-3,5-dimethylhex-3-en-2-yl 4-methyl-3-oxohexanoate (0.47 g, 85% purity, 39% yield) as a colorless liquid.

[0112] .sup.1H NMR (400 MHz, CDCl3, 298 K, mixture of diastereomers) b (ppm)=5.33-5.22 (m, 2H), 3.45 (s, 2H), 2.64-2.43 (m, 2H), 1.79-1.56 (m, 4H), 1.48-1.35 (m, 1H), 1.31 (d, J=6.5 Hz, 3H), 1.10 (dd, J=1.3, 6.8 Hz, 3H), 0.99-0.87 (m, 9H).

[0113] .sup.13C NMR (101 MHz, CDCl3, 298 K, mixture of diastereomers) b (ppm)=206.5, 166.6, 135.5, 131.4, 77.4, 48.1, 48.0, 48.0, 26.8, 25.6, 25.6, 22.7, 22.7, 18.9, 15.4, 11.8, 11.4.

[0114] MS (El, 70 eV): 145 (8), 127 (90), 110 (89), 95 (90), 85 (100), 57 (88).

[0115] Odour description (10% solution in DPG on paper blotter, 4 h): fruity, warm, musky.

EXAMPLE 6: 3,5-DIMETHYLHEX-3-EN-2-YL ETHYL MALONATE

[0116] A mixture of diethyl malonate (14 g, 85 mmol) and 3,5-dimethylhex-3-en-2-ol (7.3 g, 57 mmol) was heated to 180 C. while distilling off ethanol. After 30 min, the reaction mixture was cooled down to ambient temperature and subjected directly to column chromatography on silica gel eluting with a gradient of ethyl acetate in heptane to give 3,5-dimethylhex-3-en-2-yl ethyl malonate (5.79 g, 42% yield) as a colorless liquid.

[0117] .sup.1H NMR (400 MHz, CDCl3, 300 K, mixture of E and Z isomers) b (ppm)=5.88-4.78 (m, 1H), 4.23-4.13 (m, 2H), 3.37-3.29 (m, 2H), 2.73-2.41 (m, 1H), 1.68-1.56 (m, 3H), 1.33-1.21 (m, 6H), 0.97-0.87 (m, 6H).

[0118] .sup.13C NMR (101 MHz, CDCl3, 296 K, mixture of E and Z isomers) b (ppm)=167.0, 167.0, 166.2, 166.1, 136.9, 135.8, 131.7, 131.1, 77.2, 70.8, 61.8, 61.8, 42.4, 42.3, 27.1, 27.1, 23.7, 23.5, 23.0, 19.3, 19.2, 17.8, 14.4, 14.4, 12.1.

[0119] Odour description (10% solution in DPG on paper blotter, 4 h): weak, fruity, green, musky.

EXAMPLE 7: GREEN, NATURAL PEACH/NECTARINE FRAGRANCE COMPOSITION FOR, E.G, BODY DEODORANT

TABLE-US-00001 parts by Ingredient weight Benzaldehyde 0.1 CASSYRANE (2-tert-butyl-5-methyl-2-propyl-2,5- 0.1 dihydrofuran) Beta damascone (1-(2,6,6-trimethyl-1-cyclohexen-1-yl)- 1 2-buten-1-one (e + z)) Gamma Decalactone (decan-4-olide) 20 Hexenol-3-cis (3-hexen-1-ol (z)-) 2 Linalool (3,7-dimethyl-1,6-octadien-3-ol) 20 Manzanate (ethyl 2-methylpentanoate) 1 Triethyl citrate (TEC) 55.8 100.0

[0120] By the replacement of 1 part TEC with 1part 3,5-dimethylhex-3-en-2-yl 3-oxohexanoate, the accord fragrance accord above is rounded off (softer and muskier), better blended, and the green note is even more natural, like the crunchy green peach peel.