ALICYCLIC MUSK FRAGRANCE COMPOUNDS

Abstract

The present invention primarily relates to the use of a compound according to the general formula (I) wherein i) m is 1, n is 1, o is 0 or 1, Y is Hydrogen, or ii) m is 2, n is 0, o is 1, Y is methyl, and wherein X is O or methylene, R and R1 are each methyl or form together with the carbon atom attached to a carbonyl group, and R2 is methyl, ethyl, propyl, butyl, butan-2-one-4-yl, tetrahydrofuran-2-yl, or tetrahydrofuran-3-yl, 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 musk odor characteristics to perfumed products. This invention also relates to a process for the preparation of said compounds according to the general formula (I).

Claims

1-4. (canceled)

5. A compound according to the general formula (I) ##STR00018## wherein i) m is 1, n is 1, o is 0 or 1, Y is hydrogen, or ii) m is 2, n is 0, o is 1, Y is methyl, and wherein X is O or methylene, R and R1 are each methyl or form together with the carbon atom attached to a carbonyl group, and R2 is methyl, ethyl, propyl, butyl, butan-2-one-4-yl, tetrahydrofuran-2-yl, or tetrahydrofuran-3-yl.

6. A compound according to claim 5 selected from the group consisting of 1-(3,3-dimethylcyclohexyl)ethyl 4-oxopentanoate, 2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl tetrahydrofuran-2-carboxylate, 1-(3,3-dimethylcyclohexyl)ethyl 4-oxoheptanoate, 1-(3,3-dimethylcyclohexyl)ethyl 4-oxooctanoate, 1-(3,3-dimethylcyclohexyl)ethyl 3-oxohexanoate, 1-(3,3-dimethylcyclohexyl)ethyl 3-oxoheptanoate, 2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-oxoethyl 4-oxopentanoate, 2,6,6-trimethylcycloheptyl 4-oxopentanoate, and 2-oxo-2-((2,6,6-trimethylcycloheptyl)oxy)ethyl 4-oxopentanoate.

7. A perfume composition comprising a compound according to claim 5.

8. A perfume composition according to claim 7 comprising one or more additional fragrance ingredients.

9. A perfumed product comprising a compound as according to claim 5.

10. A perfumed product according to claim 9, 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.

11. A method for producing a perfumed product comprising: i) providing a compound according to claim 5, ii) providing one or several further components of the perfumed product to be produced, and iii) contacting or mixing the further components with a sensorially effective amount of the compound.

12. A method of imparting and/or increasing musk odor characteristics to a perfumed product comprising adding a compound according to claim 5 to the product and imparting and/or increasing a musk odor characteristic.

13. A method for perfuming a product comprising adding a sensorially effective amount of a compound according to claim 5 to the product.

14. The method of claim 13, wherein the compound is selected from the group consisting of 1-(3,3-dimethylcyclohexyl)ethyl 4-oxopentanoate, 2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl tetrahydrofuran-2-carboxylate, 1-(3,3-dimethylcyclohexyl)ethyl 4-oxoheptanoate, 1-(3,3-dimethylcyclohexyl)ethyl 4-oxooctanoate, 1-(3,3-dimethylcyclohexyl)ethyl 3-oxohexanoate, 1-(3,3-dimethylcyclohexyl)ethyl 3-oxoheptanoate, 2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-oxoethyl 4-oxopentanoate, 2,6,6-trimethylcycloheptyl 4-oxopentanoate, and 2-oxo-2-((2,6,6-trimethylcycloheptyl)oxy)ethyl 4-oxopentanoate.

15. The method of claim 13, wherein the method imparts a musk odor to the product.

16. The method of claim 13, wherein the method imparts a fruity odor to the product.

17. The method of claim 13, wherein the method imparts both a musk odor and a fruity odor to the product.

18. The method of claim 13, 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.

Description

EXAMPLES

Compound 1

1-(3,3-dimethylcyclohexyl)ethyl 4-oxopentanoate

[0135] A mixture of Cyclodumol (10.0 g, 64.1 mmol), Levulinic acid (8.9 g, 76.9 mmol) in toluene (50 mL) was added catalytic amount of pTs (0.52 g). This mixture was refluxed for about 5 h, after the reaction completion, at room temperature this reaction mixture was washed with water (2×30 ml) and the organic layer was concentrated on a rotary evaporator which gave crude material (17.5 g). Crude material was purified by Kügelrohr distillation (KRD)/bulb to bulb distillation, 160° C., 1.8 mbar to provide 1-(3,3-Dimethylcyclohexyl)ethyl 4-oxopentanoate (14.6 g, 90%), as mixture of isomers. By PGC individual isomers were also identified and confirmed by NMR.

[0136] .sup.1H NMR (600 MHz, Benzene-d.sub.6) δ 4.86 (p, J=6.3 Hz, 1H), 2.42-2.37 (m, 2H), 2.18 (td, J=6.1, 1.2 Hz, 2H), 1.62 (s, 3H), 1.56 (dddd, J=16.1, 6.7, 5.2, 3.4 Hz, 2H), 1.51-1.43 (m, 2H), 1.32 (tt, J=13.3, 3.6 Hz, 1H), 1.29-1.23 (m, 1H), 1.11 (d, J=6.4 Hz, 3H), 0.98 (td, J=13.3, 4.2 Hz, 1H), 0.91 (s, 3H), 0.87 (d, J=12.7 Hz, 1H), 0.84 (s, 3H), 0.77 (qd, J=12.9, 3.9 Hz, 1H).

[0137] .sup.13C NMR (151 MHz, Benzene-d.sub.6) δ 204.63, 172.08, 74.86, 41.48, 39.34, 38.66, 37.72, 33.71, 30.60, 29.17, 28.64, 28.44, 24.68, 22.30, 17.27.

(2,6,6-trimethylcycloheptyl) 4-oxopentanoate (Compound 8)

Trans-isomer

[0138] .sup.1H NMR (600 MHz, Benzene-d.sub.6) δ 4.78 (ddd, J=9.9, 1.5 Hz, 1H), 2.39 (qdd, J=17.0, 7.1, 5.7 Hz, 2H), 2.25-2.13 (m, 2H), 1.70 (dd, J=14.4, 9.8 Hz, 2H), 1.62 (s, 3H), 1.61 (d, J=14.4 Hz, 1H), 1.59-1.54 (m, 1H), 1.34-1.27 (m, 2H), 1.21-1.13 (m, 1H), 1.12 (s, 3H), 1.11-1.06 (m, 1H), 0.98 (d, J=6.5 Hz, 3H), 0.96-0.90 (m, 1H), 0.83 (s, 3H).

[0139] .sup.13C NMR (151 MHz, Benzene-d.sub.6) δ 204.65, 171.67, 76.32, 47.82, 42.60, 40.65, 37.72, 36.58, 31.63, 31.44, 30.19, 29.17, 28.50, 21.94, 20.06.

Cis-isomer

[0140] .sup.1H NMR (600 MHz, Benzene-d.sub.6) δ 5.18 (ddd, J=9.9, 3.6, 1.5 Hz, 1H), 2.45-2.31 (m, 2H), 2.17 (tddd, J=18.2, 15.3, 7.3, 5.5 Hz, 2H), 1.98-1.91 (m, 1H), 1.86 (dd, J=14.5, 9.9 Hz, 1H), 1.62 (s, 3H), 1.44-1.38 (m, 1H), 1.37-1.25 (m, 4H), 1.25-1.16 (m, 2H), 1.00 (s, 3H), 0.97 (d, J=6.9 Hz, 3H), 0.87 (s, 3H).

[0141] .sup.13C NMR (151 MHz, Benzene-d.sub.6) δ 204.70, 171.71, 74.40, 42.90, 41.90, 37.67, 36.35, 34.42, 32.31, 31.88, 30.27, 29.19, 28.48, 20.55, 15.98.

Compound 2

[2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methyl-propyl] tetrahydrofuran-2-carboxylate

[0142] To a mixture of tetrahydrofuran-2-carboxylic acid (5.5 g, 47.4 mmol), 2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methyl-propan-1-ol (Lit: EP1262474A1) (11.4 g, 2 50 mmol) in DCM (50 mL) was added 4-DMAP (0.9 g, 7.4 mmol) and by portion wise 1,3 Dicyclohexylcarbodiimide (DCC) (10.0 g, 49.0 mmol). This reaction mixture was stirred at room temperature overnight. This reaction mixture was filtered, washed with DCM (50 mL) and the filtrate was concentrated on a rotary evaporator to get crude product (16.9 g), which was purified by KRD, 115° C., 0.7 mbar (14.1 g, 87%).

[0143] .sup.1H NMR (400 MHz, Chloroform-d) δ 4.50 (dd, J=8.4, 5.1 Hz, 1H), 4.07-3.98 (m, 3H), 3.98-3.89 (m, 1H), 3.42-3.33 (m, 1H), 2.26 (dtd, J=12.0, 8.3, 6.3 Hz, 1H), 2.11-2.00 (m, 1H), 2.00-1.87 (m, 2H), 1.66 (dddd, J=12.1, 5.2, 3.4, 1.7 Hz, 1H), 1.59-1.52 (m, 1H), 1.47-1.41 (m, 2H), 1.41-1.36 (m, 1H), 1.36-1.28 (m, 1H), 1.18 (s, 6H), 1.08-1.02 (m, 4H), 0.90 (s, 3H), 0.88 (s, 1H), 0.86 (d, J=2.5 Hz, 3H), 0.83-0.75 (m, 1H).

[0144] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 173.29, 73.71, 71.78, 70.70, 69.34, 42.16, 40.38, 39.40, 33.71, 30.66, 30.26, 28.30, 25.24, 24.67, 23.97, 23.71, 22.30, 19.69.

Compound 3

Dimethyl 2-butanoylbutanedioate (step 1)

[0145] A solution of Methyl-2-Chloracetat (6.2 g, 56.7 mmol) und Methyl-3-Oxohexanoate (24.5 g, 170 mmol) in THE (125 mL) was taken in a three-necked round bottom flask, equipped with a reflux condenser. To this reaction mixture, portionwise, was added potassium tert-butoxide (6.4 g, 56.7 mmol) (Exothermic: T<38° C.) and after the addition, it was refluxed for 7 h. After the completion of the reaction, reaction mixture temperature was reduced to room temperature and quenched with cold water. Compound was extracted using MTBE (200 mL×2) and the organic phase was washed with water (100 mL×3), dried over sodium sulphate and the solvent was removed by evaporation (60° C., 500-10 mbar) to yield the crude product Dimethyl 2-butanoylbutanedioate (11.5 g, 94%).

[0146] .sup.1H NMR (400 MHz, Chloroform-d) δ 3.99 (dd, J=8.3, 6.3 Hz, 1H), 3.75 (s, 3H), 3.68 (s, 3H), 3.04-2.79 (m, 2H), 2.75-2.57 (m, 2H), 1.64 (sextet, J=7.4 Hz, 2H), 0.92 (t, J=7.4 Hz, 3H).

[0147] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 203.82, 171.84, 168.97, 53.81, 52.72, 52.04, 44.64, 32.16, 16.87, 13.49.

Methyl 4-oxoheptanoate (Step 2)

[0148] A solution of Dimethyl 2-butanoylbutanedioate (8.4 g, 38.8 mmol) in water (20 mL) and methanol (2.2 mL) mixture, was taken in a three-necked round bottom flask, equipped with a reflux condenser. By dropwise, added NaOH solution 32% solution in water (12.1 g, 97.7 mmol) and refluxed for ˜15 min and brought it to room temperature. To this reaction mixture was added H.sub.2SO.sub.4 (11.1 g, 108.6 mmol) and refluxed for ˜15-30 min. After the completion of the reaction, at room temperature reaction mixture was further diluted with water (50 mL) and compound was extracted with MTBE (100 mL×2). Combined organic layer was washed with sat. NaHCO.sub.3 solution, water (until neutral), dried over sodium sulphate and the solvent was removed by evaporation (60° C., 500-10 mbar) to yield the crude product methyl 4-oxoheptanoate (6.4 g) Lit: Tetrahedron, 2008, 64 (51), 11713-11717).

[0149] .sup.1H NMR (400 MHz, Chloroform-d) δ 3.68 (s, 3H), 2.74-2.69 (m, 2H), 2.61-2.56 (m, 2H), 2.43 (t, J=7.4 Hz, 2H), 1.63 (sextet, J=7.4 Hz, 2H), 0.92 (t, J=7.4 Hz, 3H).

[0150] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 209.01, 173.33, 51.77, 44.69, 37.05, 27.71, 17.29, 13.71.

1-(3,3-dimethylcyclohexyl)ethyl 4-oxoheptanoate (Step 3)

[0151] To a mixture of Zirkon-n-propylat (0.42 g) in Cyclodumol (4.7 g, 30.37 mmol), methyl 4-Oxoheptanoate (3.20 g, 20.25 mmol) was added. It was heated to 130-150° C., atm.press—450 mbar for ˜8 h to get the crude product (6.3 g). Crude was purified by bulb-to bulb distillation (T=180° C., p=0.80 mbar) gave 1-(3,3-dimethylcyclohexyl)ethyl 4-oxoheptanoate (2.88 g, 51%, GC purity 94,4%).

[0152] .sup.1H NMR (400 MHz, Chloroform-d) δ 4.72-4.64 (m, 1H), 2.70 (t, J=6.3 Hz, 2H), 2.56 (t, 2H), 2.43 (t, J=7.3 Hz, 2H), 1.67-1.54 (m, 5H), 1.46-1.30 (m, 3H), 1.15 (d, J=6.4 Hz, 3H), 1.07 (dd, J=13.0, 4.1 Hz, 1H), 0.92 (t, 3H), 0.91 (s, 3H), 0.87 (s, 3H), 0.89-0.78 (m, 2H).

[0153] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 209.06, 172.48, 75.10, 44.74, 41.26, 39.11, 38.30, 37.16, 33.52, 30.52, 28.32, 28.30, 24.59, 21.96, 17.29, 17.06, 13.74.

Compound 4

1-(3,3-dimethylcyclohexyl)ethyl 4-oxooctanoate

O1-ethyl 04-methyl 2-pentanoylbutanedioate (step 1)

[0154] A solution of Methyl-2-Chloracetat (4.6 g, 42.4 mmol) und Methyl-3-Oxoheptanoate (18.4 g, 116.5 mmol) in THE (100 mL) was taken in a three-necked round bottom flask, equipped with a reflux condenser. To this reaction mixture, portion wise, was added potassium tert-butoxide (4.13 g, 36.8 mmol) (Exothermic: T<37° C.) and after the addition, it was refluxed for 8-10 h. After the completion of the reaction, reaction mixture temperature was reduced to room temperature and quenched with cold water. Compound was extracted using MTBE (200 mL×2) and the organic phase was washed with water (100 mL×3), dried over sodium sulphate and the solvent was removed by evaporation (60° C., 500-10 mbar) to yield the crude product, which was further purified by bulb-to bulb distillation (T=90° C., p=0.88 mbar), afforded Dimethyl 2-pentanoylbutanedioate (7.4 g, 76%).

[0155] .sup.1H NMR (600 MHz, Chloroform-d) δ 4.00 (dd, J=8.3, 6.2 Hz, 1H), 3.75 (s, 3H), 2.98 (dd, J=17.6, 8.3 Hz, 1H), 2.84 (dd, J=17.6, 6.3 Hz, 1H), 2.71 (dt, J=17.6, 7.5 Hz, 1H), 2.62 (dt, J=17.6, 7.3 Hz, 1H), 1.59 (mc, 2H), 1.37-1.28 (m, 2H), 0.91 (td, J=7.4, 1.2 Hz, 6H).

[0156] .sup.13C NMR (151 MHz, CDCl3) δ 203.97, 171.87, 169.00, 53.81, 52.74, 52.06, 42.50, 32.18, 25.47, 22.10, 13.82,

Methyl 4-oxooctanoate (Step 2)

[0157] A solution of Dimethyl 2-pentanoylbutanedioate (7.3 g, 31.7 mmol) in water (15 mL) and methanol (1.5 mL) mixture, was taken in a three-necked round bottom flask, equipped with a reflux condenser. By dropwise, added 32% NaOH solution in water (7.3 g, 58.02 mmol) and refluxed for ˜30 min and brought it to room temperature. To this reaction mixture was added H.sub.2SO.sub.4 (6.6 g, 64.98 mmol) and refluxed for ˜30 min. After the completion of the reaction, at room temperature reaction mixture was further diluted with water (50 mL) and compound was extracted with MTBE (100 mL×2). Combined organic layer was washed with sat. NaHCO.sub.3 solution, water (until neutral), dried over sodium sulphate and the solvent was removed by evaporation (60° C., 500-10 mbar) to yield the crude product methyl 4-oxooctanoate (4.0 g, 73%, GC Purity 93%).

[0158] .sup.1H NMR (600 MHz, Chloroform-d) δ 3.68 (s, 3H), 2.72 (td, J=6.6, 4.7 Hz, 2H), 2.59 (t, J=6.6 Hz, 2H), 2.45 (m, 2H), 1.58 (p, J=7.5 Hz, 2H), 1.32 (m, 2H), 0.91 (t, J=7.3 Hz, 3H).

[0159] .sup.13C NMR (151 MHz, CDCl3) δ 209.32, 173.43, 51.81, 42.53, 37.02, 27.75, 25.92, 22.32, 13.83.

1-(3,3-dimethylcyclohexyl)ethyl 4-oxooctanoate (Step 3)

[0160] To a mixture of Zirkon-n-propylat (0.48 g, 1.0 mmol) in Cyclodumol (4.8 g, 30.8 mmol), methyl 4-Oxooctanoate (4.0 g, 23.3 mmol) was added. It was heated to 140-160° C., atm.press—380 mbar for ˜8 h to get the crude product, which was purified by bulb-to bulb distillation (T=200° C., p=1.5-0.55 mbar) gave 1-(3,3-dimethylcyclohexyl)ethyl 4-oxooctanoate (5.2 g, 76%, GC purity 95%).

[0161] .sup.1H NMR (400 MHz, Chloroform-d) δ 4.68 (t, 1H), 2.71 (t, 2H), 2.59-2.54 (m, 2H), 2.45 (t, 2H), 1.69-1.53 (m, 5H), 1.45-1.26 (m, 5H), 1.15 (d, J=6.4 Hz, 3H), 1.10-1.02 (m, 1H), 0.94-0.88 (m, 6H), 0.88 (d, J=2.5 Hz, 3H), 0.87-0.82 (m, 2H).

[0162] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 209.22, 172.50, 42.57, 41.26, 39.11, 38.30, 37.13, 33.52, 33.52, 30.52, 28.32, 28.32, 25.93, 24.59, 22.34, 21.96, 17.06, 13.85.

Compound 5

1-(3,3-dimethylcyclohexyl)ethyl 3-oxopentanoate

[0163] To a mixture of Zirkon-n-propylat (0.50 g) in Cyclodumol (5.9 g, 37.8 mmol), methyl 3-Oxopentanoate (5.0 g, 38.4 mmol) was added. It was heated to 140-160° C., atm.press—450 mbar for ˜8 h to get the crude product, which was purified by bulb-to bulb distillation (T=190° C., p=1.1 mbar) gave 1-(3,3-dimethylcyclohexyl)ethyl 3-oxopentanoate (8.3 g, 85%, GC purity 96%).

[0164] .sup.1H NMR (400 MHz, Chloroform-d) δ 4.78-4.71 (m, 1H), 3.42 (d, J=2.6 Hz, 2H), 2.57 (qd, J=7.2, 2.5 Hz, 2H), 1.70-1.54 (m, 3H), 1.51-1.31 (m, 3H), 1.19 (d, J=6.4 Hz, 3H), 1.12-0.99 (m, 4H), 0.95-0.79 (m, 8H).

[0165] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 203.40, 166.97, 76.17, 49.35, 41.23, 39.05, 38.23, 36.30, 33.49, 30.51, 28.29, 24.57, 21.91, 17.02, 7.57.

Compound 6

1-(3,3-dimethylcyclohexyl)ethyl 3-oxoheptanoate

[0166] A mixture of Cyclodumol (20.2 g, 129.5 mmol), Methyl-3-oxoheptanoate (13.0 g, 82.3 mmol) and catalytic amount of Zr-n-propylate (˜2 g) was heated/distilled at 150° C. with 500 mbar. It was continued until no distillate comes from the reaction mixture. Crude mixture was purified by bulb to bulb distillation (T=190° C., p=1.0-0.5 mbar) to afford 1-(3,3-dimethylcyclohexyl)ethyl 3-oxoheptanoate (32.2 g, 88%).

[0167] .sup.1H NMR (600 MHz, Chloroform-d) δ 4.74 (pd, J=6.4, 2.6 Hz, 1H), 3.41 (d, J=2.6 Hz, 2H), 2.56-2.52 (m, 2H), 1.67-1.60 (m, 2H), 1.61-1.55 (m, 3H), 1.44-1.38 (m, 2H), 1.38-1.28 (m, 3H), 1.19 (d, J=6.4 Hz, 3H), 1.07 (dd, J=13.4, 4.1 Hz, 1H), 0.93-0.88 (m, 6H), 0.85 (s, 3H), 0.85-0.81 (m, 2H).

[0168] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 203.03, 166.96, 76.15, 49.65, 42.78, 41.23, 39.06, 38.23, 33.49, 3.51, 28.30, 25.56, 24.57, 22.19, 21.91, 17.02, 13.83.

Compound 7

1-(3,3-dimethylcyclohexyl)ethyl 2-chloroacetate (Step 1)

[0169] To a solution of Cyclodumol (63 g, 0.402 mol), Toluene (200 mL) and Pyridine (38 g, 0.482 mol) at 30° C., a predissolved solution of Chloroacetyl chloride (50 g, 0.442 mol) in toluene (100 mL) was added dropwise (exothermic reaction). After the addition, the reaction temperature was maintained for another 2-3 h. The, reaction mixture was cooled 10-15° C. and quenched with ice cold water (100 mL) (slow addition). Organic phase was separated, organic layer washed with water (100 mL×2), 5% soda solution (100 mL×2) and evaporated (60° C./150-20 mbar) to get the crude (99 g). Crude was purified using 5 cm Vigreux distillation (Flask temp=94-120° C., Head temp=80-87° C.) to afford the title compound 1-(3,3-dimethylcyclohexyl)ethyl 2-chloroacetate (85 g, 91%). (Lit: EP1262474A1).

[0170] .sup.1H NMR (400 MHz, Chloroform-d) δ 4.83-4.75 (m, 1H), 4.08-3.99 (m, 2H), 1.81-1.53 (m, 2H), 1.53-1.31 (m, 3H), 1.21 (dd, J=6.4, 1.1 Hz, 3H), 1.11-0.99 (m, 2H), 0.91 (s, 3H), 0.88 (s, 3H), 0.87-0.81 (m, 2H).

[0171] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 166.96, 77.29, 41.25, 41.18, 39.02, 38.27, 33.47, 30.52, 28.24, 24.57, 21.88, 16.96.

[2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-oxo-ethyl] 4-oxopentanoate (Step 2)

[0172] To a mixture of 1-(3,3-dimethylcyclohexyl)ethyl 2-chloroacetate (14.0 g, 60.3 mmol) and NMP (80 mL) was slowly added Luvilic acid (11.1 g, 95.7 mmol), slight exothermic was observed. Between 25-45° C., calcium carbonate (19.9 g, 14.4 mmol) was added portionwise. The reaction mixture was maintained at 55° C. After the reaction is completed after 5 h, reaction mixture was quenched by slowly added water (200 ml) (observed exothermic). Compound was extracted with MTBE (50 ml×3). Combined organic layer was washed with 5% NaCl solution (50 ml×2), dired over Na.sub.2SO.sub.4 and evaporated organic layer. To the crude, once again water (200 mL) water to remove the salt and extracted with Tolune (50 ml×3). Toluene was evaporated which gave 16 g of crude product, which upon purification by column chromatography (Cyclohexane: Ethylacetate, 95:5) gave the title compound (14.7 g, 78%).

[0173] .sup.1H NMR (600 MHz, Chloroform-d) δ 4.78 (p, J=6:3 Hz, 1H), 4.67 (td, J=9.9, 1.4 Hz, 1H), 4.60 (s, 3H), 4.56 (d, J=15.8 Hz, 1H), 2.80 (td, J=7.0, 1.6 Hz, 4H), 2.73-2.67 (m, 4H), 2.20 (s, 3H), 2.19 (s, 3H), 1.86-1.75 (m, 2H), 1.72 (dd, J=14.2, 10.0 Hz, 1H), 1.67-1.61 (m, 2H), 1.61-1.56 (m, 1H), 1.54-1.49 (m, 1H), 1.47 (ddd, J=13.3, 10.8, 1.4 Hz, 2H), 1.44-1.39 (m, 1H), 1.39-1.32 (m, 3H), 1.25-1.20 (m, 1H), 1.18 (d, J=6.4 Hz, 3H), 1.17-1.10 (m, 1H), 1.08-1.03 (m, 1H), 1.03 (s, 3H), 0.91 (s, 3H), 0.89 (s, 3H), 0.89 (d, J=6.3 Hz, 3H), 0.87 (s, 3H), 0.86-0.80 (m, 2H).

[0174] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 206.31, 206.28, 172.16, 172.16, 167.45, 167.07, 77.97, 76.39, 61.05, 61.02, 47.16, 42.38, 41.13, 40.14, 39.04, 38.25, 37.86, 37.86, 36.18, 33.48, 31.46, 31.35, 30.51, 29.87, 29.86, 29.83 28.23, 27.63, 27.61, 24.56, 21.88, 21.61, 19.75, 17.00.