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Esters with musky odor and their use in perfumery |
| RE38659 |
Esters with musky odor and their use in perfumery
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| Patent Drawings: | |
| Inventor: |
Williams |
| Date Issued: |
November 23, 2004 |
| Application: |
10/326,341 |
| Filed: |
December 23, 2002 |
| Inventors: |
Williams; Alvin S. (Nyon, CH)
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| Assignee: |
Firmenich SA (Geneva, CH) |
| Primary Examiner: |
Qazi; Sabiha |
| Assistant Examiner: |
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| Attorney Or Agent: |
Winston & Strawn LLP |
| U.S. Class: |
560/126; 560/198; 560/231; 560/249 |
| Field Of Search: |
514/506; 560/198; 560/126; 560/231; 560/249 |
| International Class: |
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| U.S Patent Documents: |
5166412 |
| Foreign Patent Documents: |
1923223; 0472966 |
| Other References: |
Kawai, Y. et al. Bioorganic Chemistry 27, (1999), pp. 3-19.*.
Givaudan et al. (DN 72:54884, CAPLUS, abstract of DE 1,923,223).*.
H.R. Ansari, Tetrahederon, vol. 29, pp. 1559-1564 (1973).*.
G. Lhommet et al., Synthetic Communications, vol. 26, No. 21, pp. 3897-3901 (1996).*.
Givaudan et al. (DN 72:54884 CAPLUS, abstract of DE 1923223), 1969.*.
H.R. Ansari, "Cyclisation of Optically Active Dihydromyrcenes (2,6-Dimethyl-2, 7-Octadiene)", Tetrahedron, vol. 29, pp. 1559-1564 (1973).*.
G. Lhommet et al., "A General and Versatile Synthesis of 4- and 5-Oxoacids", Synthetic Communications, vol. 26, No. 21, pp. 3897-3901 (1996).. |
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| Abstract: |
The compounds of formula ##STR1##in which the symbols R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent independently from each other a hydrogen atom or a methyl or ethyl group, the symbol X represents an oxygen atom or an alkylene group of formula ##STR2##in which n is an integer from 1 to 3, the symbols R.sup.6 and R.sup.7 represent each a hydrogen atom or a methyl or ethyl group, and R.sup.5 represents an alkyl or alkoxy group from C.sub.1 to C.sub.4, linear or branched, an alkenyl group from C.sub.2 to C.sub.4, linear or branched, or a group of formula ##STR3##in which Y has the same meaning as X and R.sup.8 is a linear or branched alkyl group from C.sub.1 to C.sub.4 or a linear or branched alkenyl group from C.sub.2 to C.sub.4, are novel compounds showing musky odors and which confer musky-velvety, voluminous and very tenacious notes to the products to which they are added. |
| Claim: |
What is claimed is:
1. A compound of formula ##STR11##
in which the symbols R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent independently from each other a hydrogen atom or a methyl or ethyl group, the symbol X represents an oxygen atom or an alkylene group of formula ##STR12##
in which n is an integer from 1 to 3, the symbols R.sup.6 and R.sup.7 represent each a hydrogen atom or a methyl or ethyl group, and R.sup.5 represents an alkyl or alkoxy group from C.sub.1 to C.sub.4, linear or branched, an alkenyl group fromC.sub.2 to C.sub.4, linear or branched, or a group of formula ##STR13##
in which Y has the same meaning as X and R.sup.8 is a linear or branched alkyl group from C.sub.1 to C.sub.4 or a linear or branched alkenyl group from C.sub.2 to C.sub.4.
2. A compound according to claim 1, of formula ##STR14##
wherein X is an oxygen atom or an unsubstituted methylene or ethylene group and R.sup.5 is a group as defined in claim 1 and having from 1 to 3 carbon atoms.
3. A compound selected from the group consisting of 1-[(3,3-dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl propanoate, 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl]methyl butanoate, 1-(3,3-dimethyl-1-cyclohexyl)ethyl 4-oxohexanoate,1-(3,3-dimethyl-1-cyclohexyl)ethyl 5-oxohexanoate, 1-[(3,3-dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl methyl oxalate, 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl]methyl 2-propenoate, and 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl]methyl2-butenoate.
4. 1-[(3,3-Dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl propanoate.
5. A compound according to claim 1, in the form of the stereoisomer of configuration (1S,1'R) or of a mixture containing a preponderant amount of this isomer together with at least one of its other stereoisomers.
6. Perfuming composition or perfumed article containing as a perfuming ingredient a compound according to claim 1.
7. Perfumed article according to claim 6, in the form of a perfume or a cologne, a soap, a bath or shower gel, a shampoo or other hair care product, a cosmetic preparation, a deodorant or antiperspirant, an air freshener, a detergent or fabricsoftener, or an all-purpose cleaner.
8. A method for the preparation of a perfuming composition or of a perfumed product, wherein there is added to said composition or product a compound according to claim 1.
9. A compound of formula .Iadd.(III) .Iaddend. ##STR15##
wherein X is an oxygen atom and R.sup.5 is a group as defined in claim 1 and having from 1 to 3 carbon atoms.
10. The method of claim 8, wherein the compound is added in an amount sufficient to impart an odor of the musky type accompanied by a slight fruity-ambrette connotation. |
| Description: |
TECHNICALFIELD AND PRIOR ART
The present invention relates to the field of perfumery. It relates, more particularly, to esters derived from 1-(3,3-dimethyl-1-cyclohexyl)-1-ethanol which have remarkable odor properties.
We have found that the esters according to the present invention and as defined in the formula (I) below, show useful and prized odor properties and that, as a result, they can be used for the preparation of perfumes, perfuming compositions andperfumed articles. They are employed in order to confer musky type odor effects.
In the field of the synthesis of compounds having musky odors, there has been great activity for the last ten years, resulting from the need to find novel musky odor compounds which can replace certain compounds of widespread use in perfumery andwhich use is becoming more and more restricted due to toxicological and ecological reasons. The esters according to the present invention are products which fulfil the requirements for perfuming compounds, and they are capable of replacing theabove-mentioned known compounds.
The prior art, in particular the application DE-OS 1 923 223, discloses certain esters derived from 1-(3,3-dimethyl-1-cyclohexyl)-ethanol. However, there is no mention of a musky odor from any of the compounds disclosed. The olfactive characterof the known compounds is generally described as being of the floral-woody type.
On the other hand, U.S. Pat. No. 5,166,412 discloses compounds of the type ##STR4##
wherein R is an alkyl group from C.sub.1 to C.sub.3, and which show an odor of the musky type characterized by an intense note of the type ambrette seeds, fruity-pear, reminiscent of the odor of Williams pears.
We have now surprisingly found that the compounds described by formula (I) defined below have musky odors which are quite distinct from those of the compounds of the above formula (II), and which are very much appreciated in perfumery.
DESCRIPTION OF THE INVENTION
The object of the present invention is therefore to provide new compounds which are useful as perfume ingredients, to impart odors of the musky type.
This object is attained by the compounds of formula ##STR5##
in which the symbols R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent independently from each other a hydrogen atom or a methyl or ethyl group, the symbol X represents an oxygen atom or an alkylene group of formula ##STR6##
in which n is an integer from 1 to 3, the symbols R.sup.6 and R.sup.7 represent each a hydrogen atom or a methyl or ethyl group, and R.sup.5 represents an alkyl or alkoxy group from C.sub.1 to C.sub.4, linear or branched, an alkenyl group fromC.sub.2 to C.sub.4, linear or branched, or a group of formula ##STR7##
in which Y has the same meaning as X and R.sup.8 is a linear or branched alkyl group from C.sub.1 to C.sub.4 or a linear or branched alkenyl group from C.sub.2 to C.sub.4.
According to a preferred embodiment of the invention, there will be used compounds of the general formula (III) ##STR8##
in which X is an oxygen atom or an unsubstituted methylene or ethylene group and R.sub.5 is a group as defined in formula (I) and having 1 to 3 carbon atoms.
The esters of the above formulae (I) and (III) are novel compounds.
Another object of the invention is the use of the compounds of the above formulae in perfumery, as well as the perfumes perfuming compositions and perfumed articles containing these compounds.
The compounds of the invention show musky odor notes in which a slight fruity-ambrette connotation is found, which however is clearly less pronounced than in the compounds of the prior art, namely those according to formula (II). The globalolfactive impression of the compounds of the present invention is generally that of musky odor compounds having a sweet and heavy connotation, close to that of the so-called polycyclic musks, quite unlike that of the compounds of formula (II) which showlighter and less tenacious olfactive notes.
The compounds of the invention can be present in the form of 4 stereoisomers in the pure state or as a mixture of the stereoisomers. The invention thus includes all these possible mixtures and all the possible individual isomers. As theolfactive note of each of these isomers can of course be different from that of the others, the odor of every possible isomer mixture can also change as a function of the content of any given diastereomer or enantiomer.
We have moreover been able to establish that within the above-identified preferred compounds of the invention according to formula (III), the best olfactive characteristics were represented in the isomers of the esters of the present inventionderived from the alcohol (+)-(1S, 1'R)-1-(3',3'-dimethyl-1'-cyclohexyl)-1-ethanol, which is used as a starting product for the synthesis of some of the compounds of the invention.
As the most preferred compound of the invention, there is cited in particular 1-[(3,3-dimethyl-1-cyclohexyl) ethoxycarbonyl]methyl propanoate. This compound possesses a classical musky type odor, reminiscent of that of Galaxolide.RTM. (7,8-dihydro-4,6,6,7,8,8-hexamethyl-6H-cyclopenta[9]-2-benzopyrane; trademark of International Flavors and Fragrances, USA), and confers an olfactive impression which is that of a sweet and natural musky odor, with a velvety connotation, and whichprovides much volume. There is also found a light ambrette nuance which is accompanied by an undernote reminiscent of the odor of green fruits. When compared to the odor of the compounds according to the prior art, this compound of the inventiondevelops a musky odor which is distinctly more tenacious and heavier than those of known compounds, which makes it particularly useful for the creation of base notes in perfumes and perfuming compositions of musky odor.
The above-described odor properties are best represented in the isomer of the configuration (1S, 1'R), namely (1S, 1'R)-1-[(3',3'-dimethyl-1'-cyclohexyl) ethoxycarbonyl]methyl propanoate, which renders this compound a choice ingredient of theinvention.
Moreover, the mixtures containing a preponderant amount of this isomer together with its enantiomer or with its other stereoisomers give appreciated odor effects. Accordingly, mixtures containing a preponderant amount of this most preferredisomer of the invention are also a preferred embodiment of the invention.
The compounds of the invention can be used in practically all fields of modern perfumery. There can be cited here applications in fine perfumery, namely for the preparation of perfumes and colognes in which original olfactive effects can beobtained.
The compounds can also be used in functional perfumery. Non-limiting examples for this type application include soaps, bath and shower gels, shampoos and other hair care products, deodorants and an antiperspirants, air fresheners, liquid andsolid detergents for the treatment of textiles, fabric softeners, or all purpose cleaners.
In these applications, the compounds (I) and (III) can be used alone or in admixture with other perfuming ingredients, solvents or adjuvants of current use in perfumery. The nature and the variety of these coingredients do not require a moredetailed description here, which, moreover, would not be exhaustive, and the person skilled in the art will be able to choose the latter through its general knowledge and as a function of the nature of the product to be perfumed and of the desiredolfactive effect. These perfuming ingredients belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitrites, terpene hydrocarbons, sulfur- and nitrogen-containing heterocyclic compounds, as well as essentialoils of natural or synthetic origin. A large number of these ingredients is moreover listed in reference textbooks such as the book of S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, N.J., USA, or its more recent versions, or in other worksof similar nature.
The proportions in which the compounds according to the invention can be incorporated in the various products mentioned beforehand vary within a large range of values. These values depend on the nature of the article or product that one desiresto perfume and the olfactive effect searched for, as well as on the nature of the coingredients in a given composition when the compounds of the invention are used in admixture with perfuming coingredients, solvents or adjuvants of current use in theart.
As an example, there can be cited typical concentrations of the order of 5 to 10%, or even 20%, by weight of these compounds relative to the weight of the perfuming composition in which it is incorporated. Far lower concentrations than thosementioned can be used when the compound (I) or (III) is directly applied for the perfuming of the various consumer products cited beforehand.
The compounds of the invention are generally prepared by esterification of an alcohol of formula (IV) below with the respective acid of formula (V), or an appropriate derivative of it. The reaction is illustrated in the following scheme I, inwhich the symbols R.sup.1 to R.sup.5 and X have the meaning indicated in formula (I). ##STR9##
As an appropriate derivative of the acid (V), there can, for example, be cited the acid halides, like the chloride. Other appropriate derivatives are known to a person skilled in the art. In case one wants to synthesize an optically activecompound of formula (I), there will be used the corresponding optically active alcohol of formula (IV) in the esterification reaction. According to a preferred embodiment of the invention, there will be used 1-(3,3-dimethyl-1-cyclohexyl)-1-ethanol orone of its enantiomers as starting alcohol for the preparation of the preferred compounds of the invention.
Where the acids of formula (V), respectively an appropriate derivative thereof, are not available or do not react as wanted, there can be used an alcohol of formula (VI) below in which X is an oxygen atom and the symbols R.sub.1 to R.sup.4 havethe meaning indicated in formula (I), in an esterification reaction with an acid of formula (VII) in which R.sup.5 has the meaning given in formula (I), or, respectively, with an appropriate derivative of this acid, such as, for example, a halide. ##STR10##
The alcohols of formula (VI) can be obtained by saponification of certain compounds of the invention of formula (I) in which X is an oxygen atom.
In the methods described above for the preparation of the compounds of the invention, the stereochemistry of the alcohols (IV) and (VI) is retained. The stereochemistry of the compounds of the invention is thus that of the alcohols used asstarting products.
The specific reaction conditions will now be described in the following examples in which the abbreviations have the usual meaning in the art and the temperatures are given in degrees Celsius (.degree.C); the NMR spectral data(chemical shift .delta.) are given in ppm relative to TMS as an internal standard. The invention will also be illustrated by examples describing the use of the compounds of the invention in perfumery.
EMBODIMENTS OF THE INVENTION
EXAMPLE 1
Preparation of the Compounds of Formula (I)
a) (1S,1'R)-1-[(3',3'-Dimethyl-1'-cyclohexyl) ethoxycarbonyl]methyl Propanoate
3 g of (1S,1'R)-1-(3',3'-dimethyl-1'-cyclohexyl)-1-ethanol (prepared from (+)-.beta.-citronellene (Fluka) according to the process described by H. R. Ansari, Tetrahedron 29, 1559 (1973), [.alpha.].sup.20.sub.D =+11.6.degree., containing about 17%of other stereoisomers, or bought from DRT, France) and 1.52 g of pyridine were dissolved in 50 ml of diethyl ether. There were then added 2.9 g of 2-chloro-2-oxoethyl propanoate (prepared according to F. K. Thayer, Organic Synthesis Col. Vol. 1(1932), p. 12), dissolved in 20 ml of diethyl ether over 10 minutes. The reaction mixture was then stirred for 30 minutes, after which another portion of 2-chloro-2-oxoethyl propanoate was added. After 1 h reaction time, the reaction was quenched byadding 5 ml of aqueous HCl (1 M), and the mixture was extracted with ether. After flash column chromatography of the extract and concentration of the solution, the thus-obtained crude product was distilled at 120.degree./9.times.10.sup.2 Pa to obtain(1S,1'R)-1-[(3',3'-dimethyl-1'-cyclohexyl) ethoxy-carbonyl]methyl propanoate. The yield was 4.12 g (79.5%)
NMR(.sup.1 H): 4.78(1 H, quintet, J=6.3 Hz); 4.58(2H, s); 2.45(2H, q, J=7.5Hz); 1.7-0.7(9H, m); 1.18(3H, t, J=7.5 Hz); 1.16(3H, d, J=6.3 Hz); 0.89(3H, s) 0.85(3H, s). NMR (.sup.13 C): 173.7(s); 167.6(s); 76.3(d); 60.8(t); 41.1(t); 39.1(t);38.3(d); 33.5(q); 30.5(s); 28.3(t); 27.2(t); 24.6(q); 21.9(t); 17.0(q); 9.0(q). MS: 57(100), 123(77), 69(69), 115(68), 83(57), 138(44), 95(42), 109(40).
When there was used, in the preparation mode described under a), (1R,1'S)-1-(3',3'-dimethyl-1-cyclohexyl)-1-ethanol [<<(-)-cyclademol>>; origin DRT, France; [.alpha.].sup.D.sub.20 =-10.4.degree., containing about 18% of otherstereoisomers], there was obtained (1R,1'S)-1-[(3',3'-dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl propanoate, the analytical data of which (NMR, MS) were identical to those given under a).
b) (1S,1'R)-1-[(3',3'-Dimethyl-1'-cyclohexyl) ethoxycarbonyl]methyl Butanoate
The reaction was carried out as described above under a), using 4.78 g of 2-chloro-2-oxoethyl butanoate (prepared according to the above-cited literature). The yield was 5.22 g (95.8%) of a product having a boiling point of120.degree./6.times.10.sup.2 Pa.
NMR(.sup.1 H): 4.78(1H, quintet, J=6.3 Hz); 4.60(2H, s); 2.40(2H, t, J=7.5 Hz); 1.70(2H, m, J=7.5 Hz); 1.75-0.75(9H, m); 1.18(3H, d, J=6.3 Hz); 0.99(3H, t, J=7.5 Hz); 0.91(3H, s); 0.87(3H, s). NMR(.sup.13 C): 173.0(s); 167.7(s); 76.3(d);60.7(t); 41.1(t); 39.1(t); 38.4(d); 35.7(t); 33.5(q); 30.5(s); 28.3(t); 24.7(q); 21.9(t); 18.4(t); 17.0(q); 13.6(q). MS: 71(100), 123(81), 69(79), 83(68), 43(58), 109(54), 129(52), 95(49).
c) (1S,1'R)-1-(3',3'-Dimethyl-1'-cyclohexyl)ethyl 4-oxohexanoate
1.09 g (8.4 mmole) of 4-oxo-hexanoic acid (prepared according to G. L. Hommet et al., Synth. Commun., 26, 3897 (1996)) were mixed with 1.25 g (8 mmole) of (1S,1'R)-1-(3',3'-dimethyl-1-cyclohexyl)-1-ethanol, and p-toluenesulfonic acid (0.012 g)in 70 ml of toluene. The reaction mixture was heated under reflux over 15 h in a Dean-Stark type separator. The thus-obtained solution was washed with water, saturated NaHCO.sub.3 solution and again with water, before the solvent was removed underreduced pressure. After distillation in a bulb-to-bulb apparatus at 140.degree./5.times.10.sup.2 Pa, there were obtained 0.84 g (39%) of the product.
NMR(.sup.1 H): 4.68(1H, quintet, J=6.3 Hz); 2.71(2H, m); 2.58(2H, m); 2.48(2H, q, J=7.5 Hz); 1.7-0.7(9H, m); 1.14(3H, d, J=6.3 Hz); 1.03(3H, t, J=7.5 Hz); 0.91(3H, s); 0.88(3H, s). NMR(.sup.13 C): 209.4; 172.5; 75.1; 41.3; 39.1; 38.3; 36.7;35.9; 33.5; 30.5; 28.4; 28.3; 24.6; 22.0; 17.1; 7.8. MS: 113(100), 138(31), 123(28), 83(23), 139(22), 69(19), 95(19), 57(17).
d) (1S,1'R)-1-(3',3'-Dimethyl-1-cyclohexyl)ethyl 5-oxohexanoate
To a solution of 2.00 g (12.8 mmole) of (1S,1'R)-1-(3', 3'-dimethyl-1-cyclohexyl)-1-ethanol, 1.66 g (12.8 mmole) of 5-oxo-hexanoic acid and 0.26 g of 4-dimethylaminopyridine in 20 ml of dichloromethane, there were added 2.06 g (14.1 mmole) ofdicyclohexylcarbodiimide. The solution was stirred over 90 min, filtered over Celite.RTM., dried over MgSO.sub.4 and filtered. After evaporation of the solvent, there was obtained a yellow oil (3.0 g) which was distilled in a bulb-to-bulb apparatus at160.degree./1.times.10.sup.3 Pa, to obtain 2.12 g (62%) of the desired product.
NMR(.sup.1 H): 4.69(1 H, quintet, J=6.3 Hz); 2.51(2H, t, J=7.1 Hz); 2.32(2H, t, J=7.1 Hz); 2.14(3H, s); 1.89(2H, quintet, J=7.1 Hz); 1.7-1.0(9H, m); 1.15(3H, d, 6.3 Hz); 0.90(3H, s); 0.87(3H, s). NMR(.sup.13 C): 208.0; 172.8; 74.8; 42.6; 41.4;39.1; 38.3; 33.6; 33.5; 30.5; 29.9 28.4; 24.6; 22.0; 19.1; 17.2. MS: 113(100), 123(31), 85(30), 138(29), 43(22), 69(22), 130(20), 55 (19).
e) (1S,1'R)-[1-(3',3'-Dimethyl-1'-cyclohexyl) ethoxycarbonyl]methyl Methyl Oxalate
i) (1S,1'R)-1-(3',3'-Dimethyl-1'-cyclohexyl)ethyl Hydroxyacetate
This alcohol was prepared by saponification of (1S,1'R)-1-[3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl propanoate. To this end, 50.0 g (185 mmol) of this compound were dissolved in 250 ml of methanol in a 500 ml flask. After cooling ofthe mixture to -780.degree., a solution containing about 5.4 M of sodium methoxide in methanol (34.3 ml, 185 mmol) was added over 30 min, stirring was then continued over 90 min at -50.degree. and the reaction mixture was then neutralized with 100 ml ofaqueous HCl (2 M) at this temperature. The mixture was extracted with diethyl ether and washed to neutrality with a saturated NaHCO.sub.3 solution and then water. After drying and concentration of the organic phase, the crude product was distilled on aVigreux type column at 62.degree./5.times.10.sup.2 Pa to obtain 23.65 g (60%) of the desired product.
NMR(.sup.1 H): 4.81(1H, quintet, J=6.3 Hz); 4.11(2H, m); 2.70(1H, large s); 1.7-0.7(9H, m); 1.20(3H, d, J=6.3 Hz); 0.91(3H, s); 0.88(3H, s). NMR(.sup.13 C): 173.1(s); 76.2(d); 60.7(t); 41.3(t); 39.0(t); 38.3(d); 33.5(q); 30.5(s); 28.1(t);24.6(q); 21.9(t); 17.1(q). MS: 69(100), 123(71), 83(68), 55(67), 41(63), 31(51), 95(49), 45(46).
The compound was then esterified as described below, under ii).
ii) 2 g of the product obtained under i) (9.4 mmol) and mixed with 1.1 g (14 mmol) of pyridine in 25 ml of diethyl ether were esterified by the dropwise addition of 1.7 g (14 mmol) of methyl chlorooxalate over 10 min. The temperature wasmaintained at 30.degree. with an ice bath, and the mixture was stirred over 30 min, then hydrolyzed with 3 ml of aqueous HCl (2 M). The ether phase was washed with a saturated NaHCO.sub.3 solution, then with water. After drying and filtration, thesolution was concentrated and distilled in a bulb-to-bulb apparatus at 140.degree./3.times.10.sup.2 Pa, to obtain 2.59 g (92%) of the product.
NMR(.sup.1 H): 4.80(1H, m); 4.78(2H, s); 3.94(3H, s); 1.7-0.7(9H, m); 1.18(3H, d, J=6.3Hz); 0.91(3H, s); 0.87(3H, s). NMR(.sup.13 C): 165.8(s); 157.4(s); 156.8(s); 77.2(d); 62.5(t); 53.8(q); 41.0(t); 39.0(t); 38.3(d); 33.5(q); 30.5(s); 28.3(t);24.5(q); 21.9(t); 17.0(q). MS: 123(100), 69(49), 138(44), 95(34), 109(33), 139(30), 83(27), 111(27).
f) (1S,1'R)-1-[(3',3'-Dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl 2-propenoate
This compound was prepared from the alcohol (1S,1'R)-1-(3',3'-dimethyl-1-cyclohexyl)ethyl hydroxyacetate, obtained as described under 1)e)i). 1 g (4.67 ml) of this alcohol were added at 0.degree. and over a period of 10 min to a suspensionprepared from 0.21 g (5.14 mmol) of a 60% suspension of NaH in mineral oil and 20 ml of THF. The suspension was stirred at room temperature over 30 min, then 0.47 g (5.14 mmole) of acryloyl chloride were added after the mixture had been cooled to-20.degree.. The mixture was warmed to room temperature and stirred for 5 h at that temperature, before another 0.47 g (5.14 mmol) of acryloyl chloride and 0.21 g of a 60% suspension of NaH in mineral oil were added. Stirring was continued for 2 h,then the reaction was quenched with water and the solution extracted with ether. The organic extract was washed with aqueous HCl (1 M), a saturated NaHCO.sub.3 solution and water and dried over MgSO.sub.4. After evaporation of the solvent, the crudeproduct was distilled in a bulb-to-bulb apparatus at 120.degree./4.times.10.sup.2 Pa, to obtain 1.13 g (90%) of the desired product. NMR(.sup.1 H): 6.52(1H, d, J=17.4 Hz); 6.21(1H, dd, J=10.7, 17.4 Hz); 5.93(1H, 10.3Hz); 4.79(1H, m); 4.68(2H, s);1.8-0.8(9H, m); 1.20(3H, d, 6.4 Hz); 0.90(3H, s); 0.87(3H, s). NMR(.sup.13 C): 167.4(s); 165.4(s); 132.0(t); 127.5(d); 76.4(d); 61.0(t); 41.0(t); 39.0(t); 38.3(d); 33.5(q); 30.5(s); 28.3(t); 24.6(q); 21.9(t); 17.0(q). MS: 123(100), 55(76), 138(68),113(64), 109(63), 69(59), 95(50), 83(46).
g) (1S, 1'R)-1-[(3',3'-Dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl 2-butenoate
This compound was prepared as described above, under f), replacing acryloyl chloride by crotonoyl chloride (0.49 g, 4.67 mmol) which was added at room temperature. After drying and evaporation of the solvent, there were obtained 1.43 g of an oilwhich was chromatographed over silica, followed by a distillation in a bulb-to-bulb apparatus at 120.degree./4.times.10.sup.2 Pa, to provide 0.83 g (71%) of the desired product.
NMR(.sup.1 H): 7.06(1H, m), 5.94(1H, d, J=15.9 Hz); 4.78(1H, quintet, J=6.0 Hz); 4.65(2H, d); 1.91(3H, d, J=6.7 Hz); 1.7-1.0(9H, m); 1.19(3H, d, J=6.3 Hz); 0.90(3H, s); 0.87(3H, s). NMR(.sup.13 C): 167.7; 165.6; 146.3; 121.7; 76.3; 60.8; 41.0;39.1; 38.3; 33.5 30.5; 28.3; 24.6; 21.9; 18.1; 17.0. MS: 69(100), 123(67), 138(56), 127(49), 109(45), 83(42), 95(33), 139 (25).
EXAMPLE 2
Preparation of a Perfuming Composition
A base perfuming composition was prepared from the following ingredients:
Ingredients Parts by weight Amyl acetate 50 (E)-3-Hexenyl acetate 10 .gamma.-Undecalactone 300 Ethyl butyrate 50 Allyl cyclohexylpropanoate 50 10% *.alpha.-Damascone 150 Allyl heptanoate 300 Phenoxyethyl Isobutyrate 1500 4-tert-Butyl-cyclohexyl acetate.sup.1) 500 Hedione .RTM..sup.2) 300 Jasmolactone.sup.3) 40 Hexyl salicylate 1000 Veloutone.sup.4) 50 2-tert-Butyl-1-cyclohexyl acetate 2500 .alpha.-Ionone 150 2,4-Dimethyl-3-cyclohexene-1-carbaldehyde.sup.5) 150 Total 7000 *in dipropylene glycol .sup.1) origin: Firmenich SA. Geneva, Switzerland .sup.2) methyl dihydrojasmonate: origin: Firmenich SA Geneva, Switzerland .sup.3) (E)-8-decen-5-olide; origin: Firmenich SA. Geneva, Switzerland .sup.4)2,5,5-trimethyl-5-pentyl-1-cyclopentanone; origin: Firmenich SA. Geneva, Switzerland .sup.5) origin: Firmenich SA. Geneva, Switzerland
To this base composition of the apple type, there were added 2000 parts by weight of 1-[(3,3-dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl propanoate. There was thus obtained a novel composition in which the fruity aspect was clearly stronger withrespect to the base composition. Furthermore, the composition containing the compound of the invention possessed an appreciated and very natural velvety-musky connotation, the compound having also imparted far more volume to the odor of the basecomposition. The perfumers found furthermore that the diffusion of the composition had become superb, both as regards its top note and its heart note, and in particular as regards the bottom note, thanks to the tenaciousness and the heavy character ofthis musky compound.
The above-described odor effect was particularly pronounced and rich when the isomer of the configuration (1S,1'R) was used.
When the compound of the invention was replaced by (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propanoate (described in application EP 472 966), there was observed a different effect, the resulting composition being lessheavy and velvety, thus underlining less the fruity-apple aspect and showing a diffusion of the bottom note which was less pronounced and voluminous. In a general way, this known composition was lighter, less tenacious and less musky-heavy than thecomposition containing the compound of the invention.
EXAMPLE 3
Preparation of a Perfuming Composition
A base perfuming compositions was prepared from the following ingredients:
Ingredients Parts by weight Hexyl acetate 50 Tetramethylnonyl acetate.sup.1) 1500 TCD acetate.sup.2) 1500 Methyl cinnamate 250 10% *.gamma.-Decalactone 200 .gamma.-Dodecalactone 50 50% *.beta.-Damascone 250 Isopentyrate.sup.3) 100 Myroxyde .RTM..sup.4) 100 Veloutone.sup.5) 700 10% *Bourgeonal .RTM..sup.6) 300 10% *Lilial .RTM..sup.7) 2700 1% *n-Octanal 100 Mayol .RTM..sup.8) 200 Total 8000 *in dipropylene glycol (DIPG) .sup.1) origin: Firmenich SA. Geneva, Switzerland .sup.2) tricyclo(5,2,1,0.sup.2.6)dec-4-yl)methyl acetate; origin: Firmenich SA. Geneva, Switzerland .sup.3) 1,3-dimethyl-3-butenyl isobutyrate origin: Firmenich SA. Geneva, Switzerland .sup.4) isomer mixture of ocimene epoxide; origin: Firmenich SA.Geneva, Switzerland .sup.5) see Example 2 .sup.6) 3-(4-tert-butyl-1-phenyl)propanol; origin: Quest International .sup.7) 3-(4-tert-butyl-1-phenyl)-2-methylpropanol; origin: Givaudan-Roure SA, Vernier, Switzerland .sup.8) 1-hydroxymethyl-4-isopropylcyclohexane; origin: Firmenich SA. Geneva, Switzerland
When there were added to this base composition with a fruity, pear type odor 2000 parts by weight of 1-[(3,3-dimethyl-1-cyclohexyl)ethoxycarbonyl]methylpropanoate, there was obtained a novel composition, the odor of which was considerablymodified with respect to the note of the base composition. The modification was mainly apparent in the fruity-pear connotations, which had aquired a rich and full character and a pronounced and elegant volume, recalling the odor of a ripe pear. Thisvoluminous impression persisted during the slow evaporation of the composition over time, thus prolongating the fruity and elegant tonality of the composition. This fragrance effect was particularly marked and rich when the isomer of(1S,1'R)-configuration was added to the base composition.
EXAMPLE 4
Preparation of a Perfuming Composition for a Powder Detergent
A base perfuming composition for a powder detergent was prepared by mixing the following ingredients:
Ingredients Parts by weight Citronellyl acetate 200 Amylcinnamic aldehyde 1000 Hexylcinnamic aldehyde 2000 10% *Ambrox .RTM. DL.sup.1) 100 Isononyl acetate 200 Verdyl acetate 400 Verdyl propionate 500 10% *Intreleven aldehyde.sup.2) 100 10% *Aldehyde 13--13.sup.3) 200 Coumarin 100 Lilial .RTM..sup.4) 1000 4-tert-Butyl-cyclohexyl acetate.sup.5) 1300 Fleuramone .RTM..sup.6) 200 3-Methyl-5-phenyl-1-pentanol.sup.7) 500 Hexyl salicylate 700 Tetrahydromuguol.sup.8) 400 10%*.alpha.-Damascone 250 Polywood .RTM..sup.9) 150 Iralia .RTM..sup.10) total 300 Vertofix coeur.sup.11) 400 Total 10000 *in DIPG .sup.1) racemic tetramethyl perhydronaphthofurane; origin: Firmenich SA. Geneva, Switzerland .sup.2) isomer mixture ofundecenal; origin: International Flavors & Fragrances, USA .sup.3) tridecanal and 11-methyldodecanal; origin: Firmenich SA. Geneva, Switzerland .sup.4) see Example 3 .sup.5) see Example 2 .sup.6) 2-heptyl-1-cylopentanone; origin: InternationalFlavors & Fragrances, USA .sup.7) origin: Firmenich SA. Geneva, Switzerland .sup.8) isomeric mixture; origin: International Flavor & Fragrances, USA .sup.9) perhydro-5,5,8a-trimethyl-3-naphthyle acetate; origin: Firmenich SA. Geneva, Switzerland .sup.10) mixture of iso-methyl ionones; origin: Firmenich SA. Geneva, Switzerland .sup.11) origin: International Flavors & Fragrances, USA
When there were added to this base perfuming composition intended for a powder detergent 1000 parts by weight of 1-[(3,3-dimethyl-1-cyclohexyl)ethoxycarbonyl]methyl propanoate, there was obtained a novel composition, the olfactive note of whichhad aquired a very remarkable volume and tenaciousness. The typical odor impression conferred by the aldehydes in the base composition was well sustained by the musky-heavy note of the compound of the invention. The perfumers also found that thediffusion of the composition had become stronger, putting an accent on the fruity and rose tonality of the composition.
The above-described fragrance effects are perceptible both from the novel composition and on linen washed with a powder detergent perfumed with that said composition. The musky aspect of the odoriferous note of the composition according to theinvention, which could also be smelled on the thus-treated linen, was similar to the notes typically conferred by polycyclic musky odor compounds of the indane type, i.e. a bewitching, warm, powdery, slightly animal and velvety connotation. The bestolfactive effect was obtained with the preferred compound of the invention, namely the (1S,1'R)-isomer of the above-identified compound. The musky effect observed by our perfumers was olfactively closest to that typically conferred by Galaxolide.RTM.,under similar application conditions.
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