ESTERS AS FRAGRANCE COMPOUNDS

Abstract

The present invention relates to novel esters of formula (I) as defined below and their use as fragrance or malodour reducing agents. Moreover, the present invention relates to fragrance compositions comprising a compound or a mixture of compounds of formula (I) and one or more further fragrance substance(s). The invention also provides a method for perfuming a product with a compound or a mixture of compounds of formula (I) as defined below and the perfumed product as well as a method for perfuming hair, skin, textile fibers, surfaces and/or ambient air with a compound or a mixture of compounds of formula (I) as defined below.

Claims

1. A compound or mixture of compounds of formula (I) ##STR00009## wherein R represents (CO)CH.sub.2—COOEt, (CO)CH.sub.2—O—CO-Et, C(CH.sub.3).sub.2—CH.sub.2—O—COOEt or COEt.

2. The compound or mixture of compounds of claim 1, wherein the compound or the mixture of compounds are selected from: ##STR00010##

3-6. (canceled)

7. A method for perfuming or reducing malodor of a product comprising: providing the compound or the mixture of compounds of claim 1; and (ii) adding the compound or the mixture of the compounds to the product.

8. The method of claim 7, wherein: compound (1) is added to the product and imparts or enhances a strawberry and/or anise note, compound (2) is added to the product and imparts or enhances a woody and/or powdery and/or musky note, compound (3) is added to the product and imparts or enhances a fruity and/or musky note, compound (4) is added to the product and imparts or enhances a pear and/or woody, and/or musky note, compound (5) is added to the product and imparts or enhances a fruity and/or musky and/or woody note, and/or compound (6) is added to the product and imparts or enhances a fruity and/or sweet note.

9. A perfumed product comprising the compound or the mixture of the compounds of claim 1.

10. The perfumed product of claim 9, selected from detergents and cleaning agents, hygiene or care products textile fresheners, ironing aids, liquid detergents, powder detergents, laundry pre-treatments, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, body 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, antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides, repellents and fuels.

11. The perfumed product of claim 9, wherein the compound or the mixture of compounds is in a total amount of from 0.01 to 10 wt. %, with respect to the total weight of the product.

12. A method for perfuming hair, skin, textiles, surfaces, or ambient air and/or reducing malodor of the hair, skin textiles, surfaces, or ambient air comprising (i) providing the compound or the mixture of compounds of claim 1; and (ii) applying or introducing a sensorially effective amount of the compound or the mixture of compounds to the hair, skin, textiles, surfaces, or ambient air and imparting or enhancing one or more olfactory notes selected from fruity, musky, woody, powdery, sweet, pear, strawberry, and anise to the hair, skin, textiles, surfaces, or ambient air.

13. The method of claim 12, wherein: compound (1) is applied or introduced and imparts or enhances a strawberry and/or anise note, compound (2) is applied or introduced and imparts or enhances a woody and/or powdery and/or musky note, compound (3) is applied or introduced and imparts or enhances a fruity and/or musky note, compound (4) is applied or introduced and imparts or enhances a pear and/or woody and/or musky note, compound (5) is applied or introduced and imparts or enhances a fruity and/or musky and/or woody note, and/or compound (6) is applied or introduced and imparts or enhances a fruity and/or sweet note.

14. The compound of the mixture of compounds of claim 1 comprising the compound of formula (1): ##STR00011##

15. The compound or the mixture of compounds of claim 1 comprising the compound of formula (2): ##STR00012##

16. The compound or the mixture of compounds of claim 1 comprising the compound of formula (3): ##STR00013##

17. The compound or the mixture of compounds of claim 1 comprising the compound of formula (4): ##STR00014##

18. The compound or the mixture of compounds of claim 1 comprising the compound of formula (5): ##STR00015##

19. The compound or the mixture of compounds of claim 1 comprising the compound of formula (6): ##STR00016##

20. The perfumed product of claim 9, wherein the compound or the mixture of compounds is in a total amount of from 0.1 to 5 wt.-%, with respect to the total weight of the product.

21. The perfumed product of claim 9, wherein the compound or the mixture of compounds is in a total amount of 0.25 to 3 wt.-%, with respect to the total weight of the product.

Description

EXAMPLE 1: PREPARATION OF PROPANEDIOATE DERIVATIVES

General Experimental Procedure:

[0043] A mixture of alcohol (1.00 eq), Diethylmalonate (2.1 eq) and Sodium ethoxide (0.01 eq) was heated to 160° C. Ethanol was distilled/collected by reactive distillation. After completion of the reaction, at room temperature, water (2 vol) was added to reaction mixture, compound was extracted with MTBE (10 vol×2), combined organic layer washed with sat. NaCl (10 vol×2), dried with MgSO.sub.4 and solvents were removed using rotary evaporator to get the crude compound. Crude compound was purified by Kugelrohr distillation T=180° C.; p=0.80 mbar) followed by column chromatography (2.5-5% EtOAc in Cyclohexane).

O3-[1-(4,4-dimethylcyclohexyl)ethyl] O1-ethyl Propanedioate was Obtained in 75% Yield, >95% Purity, Starting from 1-(4,4-dimethylcyclohexyl)ethanol

[0044] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.82 (p, J=6.4 Hz, 1H), 4.20 (qd, J=7.1, 2.2 Hz, 2H), 3.35 (s, 2H), 1.63-1.54 (m, 1H), 1.52-1.45 (m, 1H), 1.39 (dtt, J=10.2, 7.0, 2.9 Hz, 3H), 1.28 (t, J=7.2 Hz, 3H), 1.21 (d, J=6.4 Hz, 3H), 1.20-1.11 (m, 4H), 0.89 (s, 3H), 0.86 (s, 3H).

[0045] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 166.74, 166.29, 76.05, 61.45, 42.44, 42.07, 38.75, 38.69, 32.81, 29.96, 24.27, 24.13, 24.11, 17.18, 14.07.

[0046] MS: 255, 226, 208, 193, 155, 138, 115, 109, 95, 82

[0047] Odor: strawberry, anise

O3-[1-(4,4-dimethylcyclohexen-1-yl)ethyl] O1-ethyl Propanedioate was Obtained in 65% Yield, >96% Purity, Starting from 1-(4,4-dimethylcyclohexen-1-yl)ethanol

[0048] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.68-5.61 (m, 1H), 5.32 (q, J=6.6 Hz, 1H), 4.24-4.15 (m, 2H), 3.37-3.32 (m, 2H), 2.12-1.91 (m, 2H), 1.84-1.78 (m, 2H), 1.37 (t, J=6.4 Hz, 2H), 1.33 (d, J=6.6 Hz, 3H), 1.28 (t, J=7.1 Hz, 3H), 0.90 (s, 3H), 0.88 (s, 3H).

[0049] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 166.69, 165.95, 135.19, 123.38, 75.40, 61.44, 42.04, 38.83, 35.17, 28.58, 28.43, 27.76, 21.72, 18.76, 14.08.

[0050] MS: 268, 250, 235, 194, 177, 154, 136, 121, 93, 79, 55.

[0051] Odor: woody, powdery, musky

EXAMPLE 2: PREPARATION OF PROPANOATE DERIVATIVES

General Experimental Procedure:

[0052] (a) Chloroacetate derivative: To a mixture of alcohol (1.00 eq), toluene (3 vol) and pyridine (1.2 eq), below 30° C. chloroacetyl chloride (1.1 eq) was added, reaction maintained at 30° C. until completion of the reaction (2-3 h). reaction mixture was quenched at <15° C., with cold water (5 vol), organic phase was separated, washed with water (5 vol×2), sat. NaCl solution (10 vol×2), dried with Na.sub.2SO.sub.4 and solvents were removed using rotary evaporator to get the crude compound. Purification by bulb to bulb (Kugelrohr) distillation (˜T=141° C., p=0.81 mbar). [0053] (b) ethoxy-2-oxo-ethyl-propanoate derivative: To a solution of chloroacetate derivative (1.0 eq) in THF (15 vol), below 40° C. slowly added propionic acid (1.5 eq) followed by portionwise addition of K2003 (2.5 eq). Reaction maintained at reflux temperature until completion of the reaction. Reaction mixture quenched with water (20 mL) and compound extracted with MTBE (10 vol×2), organic layer washed with water (5 vol×2), dried with MgSO.sub.4, filtered and the solvents were removed using rotary evaporator to get the crude compound. Crude was purified by bulb to bulb (Kugelrohr) distillation (˜T=190° C.; p=0.85 mbar) followed by column chromatography (1:20.fwdarw.1:10, EtOAc in Cyclohexane).

1-(4,4-dimethylcyclohexyl)ethyl 2-chloroacetate was Obtained in 85% Yield, >95% Purity, Starting from 1-(4,4-dimethylcyclohexyl)ethanol

[0054] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.85 (dq, J=6.4 Hz, 1H), 4.06 (d, J=14.6 Hz, 1H), 4.02 (d, J=14.7 Hz, 1H), 1.62-1.54 (m, 1H), 1.53-1.45 (m, 1H), 1.45-1.34 (m, 3H), 1.23 (d, J=6.4 Hz, 3H), 1.25-1.10 (m, 4H), 0.90 (s, 3H), 0.86 (s, 3H).

[0055] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 167.00, 77.03, 42.46, 41.23, 38.71, 38.65, 32.80, 29.96, 24.28, 24.10, 24.08, 17.19.

[0056] MS: 183, 165, 155, 138, 123, 95, 81, 69.

[2-[1-(4,4-dimethylcyclohexyl)ethoxy]-2-oxo-ethyl] Propanoate was Obtained in 70% Yield, >98% Purity, Starting from 1-(4,4-dimethylcyclohexyl)ethyl 2-chloroacetate

[0057] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.85 (dq, J=6.4 Hz, 1H), 4.59 (s, 2H), 2.45 (q, J=7.6 Hz, 2H), 1.58 (m, 1H), 1.47 (dtd, J=10.9, 3.6, 1.8 Hz, 1H), 1.43-1.31 (m, 3H), 1.21 (d, J=6.4 Hz, 3H), 1.19 (t, J=7.5 Hz, 3H), 1.19-1.11 (m, 4H), 0.89 (s, 3H), 0.86 (s, 3H).

[0058] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 173.80, 167.67, 76.05, 60.80, 42.51, 38.73, 38.69, 32.81, 29.96, 27.19, 24.26, 24.19, 24.11, 17.21, 8.98.

[0059] MS: 255, 211, 183, 154, 138, 123, 109, 95, 83

[0060] Odor: fruity, musky

1-(4,4-dimethylcyclohexen-1-yl)ethyl 2-chloroacetate was Obtained in 90% Yield, Starting from 1-(4,4-dimethylcyclohexen-1-yl)ethanol

[0061] .sup.1H NMR (600 MHz, CDCl.sub.3) δ 5.67 (tdt, J=3.7, 2.4, 1.5 Hz, 1H), 5.38-5.32 (m, 1H), 4.04 (s, 2H), 2.08-1.95 (m, 2H), 1.82 (tdt, J=18.2, 14.8, 3.1 Hz, 2H), 1.38 (ddd, J=7.4, 6.2, 1.6 Hz, 2H), 1.35 (d, J=6.6 Hz, 3H), 0.90 (s, 3H), 0.88 (s, 3H).

[0062] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 166.63, 134.96, 123.93, 76.40, 41.25, 38.81, 35.12, 28.58, 28.52, 27.65, 21.65, 18.78.

[0063] MS: 230, 215, 193, 181, 161, 136, 121, 107, 93, 79, 67, 55, 41, 29

[2-[1-(4,4-dimethylcyclohexen-1-yl)ethoxy]-2-oxo-ethyl] Propanoate was Obtained in 60% Yield, >98% Purity, Starting from 1-(4,4-dimethylcyclohexen-1-yl)ethyl 2-chloroacetate

[0064] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.64 (qd, J=3.8, 3.0, 1.3 Hz, 1H), 5.34 (q, J=6.5 Hz, 1H), 4.62 (d, J=15.9 Hz, 1H), 4.57 (d, J=15.9 Hz, 1H), 2.44 (q, J=7.6 Hz, 2H), 2.09-1.90 (m, 2H), 1.88-1.73 (m, 2H), 1.37 (t, J=6.4 Hz, 2H), 1.33 (d, J=6.5 Hz, 3H), 1.18 (t, J=7.6 Hz, 3H), 0.89 (s, 3H), 0.88 (s, 3H).

[0065] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 173.77, 167.33, 135.08, 123.67, 75.49, 60.79, 38.81, 35.14, 28.58, 28.48, 27.70, 27.18, 21.67, 18.82, 8.98.

[0066] MS: 268, 250, 194, 154, 136, 121, 93

[0067] Odor: pear, woody, musky

2-[1-(4,4-dimethylcyclohexyl)ethoxy]-2-methyl-propyl] Propanoate

[0068] 2-[1-(4,4-dimethylcyclohexyl)ethoxy]-2-methyl-propyl] propanoate was prepared according to EP1262474.

a) 2-[1-(4,4-dimethylcyclohexyl)ethoxy]-2-methyl-propan-1-ol: According to EP1262474

[0069] .sup.1H NMR (600 MHz, CDCl.sub.3) δ 3.49-3.43 (m, 1H), 3.41-3.35 (m, 2H), 2.19 (t, J=6.3 Hz, 1H, —OH), 1.61-1.57 (m, 1H), 1.53-1.48 (m, 1H), 1.44-1.41 (m, 1H), 1.41-1.40 (m, 1H), 1.24-1.12 (m, 11H), 1.10 (d, J=6.2 Hz, 3H), 0.90 (s, 3H), 0.87 (s, 3H).

[0070] .sup.13C NMR (151 MHz, CDCl.sub.3) δ 75.13, 71.19, 71.03, 44.97, 39.30, 39.23, 33.03, 30.14, 25.08, 24.19, 24.16, 23.07, 22.76, 19.87.

[0071] MS: 228, 197, 139, 117, 97, 83, 73, 59.

b) [2-[1-(4,4-dimethylcyclohexyl)ethoxy]-2-methyl-propyl] Propanoate

[0072] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 3.95 (s, 2H), 3.44 (p, J=5.8 Hz, 1H), 2.36 (q, J=7.6 Hz, 2H), 1.63-1.59 (m, 1H), 1.52-1.47 (m, 1H), 1.41-1.35 (m, 2H), 1.19 (s, 3H), 1.19 (s, 3H), 1.18 (s, 2H), 1.16 (t, J=7.6 Hz, 3H), 1.16-1.08 (m, 3H), 1.08 (d, J=6.2 Hz, 3H), 0.88 (s, 3H), 0.85 (s, 3H).

[0073] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 174.35, 73.78, 71.55, 70.40, 44.94, 39.32, 39.29, 33.04, 30.11, 27.69, 25.11, 24.28, 24.16, 24.12, 23.80, 20.01, 9.17.

[0074] MS: 269, 245, 197, 129, 97, 83, 69, 57

[0075] Odor: fruity, musky, woody

1-(4,4-dimethylcyclohexyl)ethyl Propanoate

[0076] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.80 (p, J=6.4 Hz, 1H), 2.34 (q, J=7.4 Hz, 2H), 1.65-1.58 (m, 1H), 1.56-1.49 (m, 1H), 1.42 (ddd, J=10.2, 4.0, 1.9 Hz, 2H), 1.42-1.33 (m, 1H), 1.30-1.14 (m, 4H), 1.20 (d, J=6.4 Hz, 3H), 1.17 (t, J=7.6 Hz, 3H), 0.92 (s, 3H), 0.89 (s, 3H).

[0077] .sup.13C NMR (101 MHz, CDCl.sub.3) δ 174.18, 74.25, 42.60, 38.82, 38.77, 32.85, 29.99, 28.00, 24.39, 24.20, 24.14, 17.37, 9.31.

[0078] MS: 168, 138, 123, 109, 69, 57, 41, 29

[0079] Odor: fruity, sweet

EXAMPLE 3; SENSORY ANALYSIS OF THE MALODOR COUNTERACTING EFFECT

[0080] The compounds of formula (I) were found to provide a malodour counteracting effect. Of all the compounds tested, compound (1) showed the best malodour counteracting effect, i.e. highly significant more perfume and lower malodour intensity.

[0081] Kitchen Malodor Vs formula 1 (3.7:4.0); Sweat Malodor Vs Formula 1 (2.6:3.6); smoke malodour Vs Formula 1 (2.9:4.6). The numbers in parentheses represent the compared intensity.

[0082] Magnitude Scale: (0-10; no odor-strongest); 1-5 μl sample and 5-10 μl standard malodor solutions were used for analysis.