CA1178893A - Aliphatic nitriles - Google Patents

Abstract

- 9 - R.193/100 ABSTRACT

This invention provides perfume compositions containing certain substituted, saturated, aliphatic nitriles of the formula:

CH3(CH2)nRCN

in which R = CHCH3- or -CHCH3CH2- and in which, when R = CHCH3-, n is an integer from 5-9 and when R = CHCH3CH2-, n is an integer from 4-8.

Description

1:178893 - 1 - R.193/100 ALIPHATIC NITRILES

This invention relates to substituted ~aturated aliphatic nitriles, more particularly to alpha- and beta-substituted nitriles which have been found to have value in perfume compositions.
Various substituted aliphatic nitriles have been known for some years, but hitherto their value as perfume components has not been appreciated. Our work has shown that certain of the alpha- and beta-substituted aliphatic nitriles, some of which are novel, have particular merit in perfumery compositions.
Accordingly, the present invention provides a perfume composition comprising perfume components and an organoleptically discernible amount of a nitrile of the formulas CH3~CH2)nRCN

in which R e -CHCH3- or -CHCH3CH2- and in which, when R - -CHCH3-, n i8 an integer from 5-9 and when R ~ -CHCH3CH2-, n is an integer from 4-8.
In addition, this invention provides certain novel substituted nitriles of particular value in perfume formulations, having the formula:
C~3(cH2lncHcH3cH2cN

, :

.

-` 1178893

- 2 - R.193/100 in which n is 6, 7 or 8.
The nitriles useful in perfume compositions provided by this invention have, in addition to their useful odour characteristics, good stability when used in perfume formulations which are to be used or stored in an aggressive environment, such as in soaps, disinfectants, laundry powders and other compositions in which active chemicals are present or which have to withstand the effects of daylight or heat. Preferably the amount of nitrile does not exceed 95% by weight of the perfume composition.
The nitriles useful according to this invention may be prepared by various processes, but a convenient process for the preparation of the alpha-substituted nitriles is as follows:
Procedure A
A solution of the required methyl alkyl ketone (50 m mol) and tosylmethylisocyanide (12 g, 60 m mol) in dry diglyme (120 ml) was added over 15 minutes at 0C under nitrogen to a stirred solution of potassium t-butoxide (freshly prepared from potassium 4.3 g, 0.11 g atom) in dry t-butanol ~100 ml) and diglyme (100 ml). When the addition was complete, the mixture was allowed to warm to room temperature then stirred for 2 hours and left to stand overnight. The resultant solution was poured into water (400 ml) and extracted with light petroleum (3 x 100 ml, bp 40-60C). The combined organic extracts were washed with water (2 x 500 ml), then brine (500 ml) and dried (MgSO4). The solvent was removed under reduced pressure and the residue chromatographed using a column (3 cm diameter, 30 cm height) of silica gel with 5% et~er in light petroleum (bp 40-60C) as solvent. Those fractions containing the product were freed of solvent under reduced pressure and the residue distilled to give the desired 2-methyl substituted nitrile.
A convenient process for the preparation of the beta-nitriles is as follows:

....

117~893

3 R.193/100 Procedure B
The required methyl alkyl ketone (1 mol), cyanoacetic acid (93.5 g, 1.1 mol), ammonium acetate (13 9, 0.17 mol) and toluene (175 ml) were stirred under reflux (pot temperature 140-160C) in a Dean-Stark apparatus until carbon dioxide ceased to be evolved (3-6 hours). The resultant mixture was cooled, washed with saturated aqueous ~odium hydrogen carbonate (2 x 50 ml) and water (50 ml) then the solvent was removed under reduced pressure. The crude mixture of nitriles was then added to one ~uarter of its volume of 50~ aqueous sodium hydroxide to which Tergitol* (3 drops) had been added. The resulting mixture was fitirred under reflux for 1 hour then cooled. The organic layer was removed, washed with water (3 x 50 ml) and distilled. 5% Palladium on carbon (0.1~ by weight relative to the nitrile mixture) was then added followed by ethyl acetate (2 x weight of distillate) and the suspension ~tirred vigorously in an atmosphere of hydrogen until uptake of gas ceased. The catalyst was removed by filtration and the solvent by evaporation under reduced pressure. Fractional distillation of the residue afforded the desired 3-methyl substituted nitrile.
The following table sets out the physical and the organoleptic properties of the nitriles useful in this invention:

Tergitol is a trade name for a surfactant (Union Carbide).

1178~393 R.193/100 Table Carbon Chain Sample Series Length Name 1 ~-methyl 8 2-methyloctanonitrile 2 ~-methyl 9 2-methylnonanonitrile 3 ~-methyl 10 2-methyldecanonitrile

4 ~-methyl 11 2-~ethylundecanonitrile ~-methyl 12 2-methyldodecanonitrile 6 ~-methyl 8 3-methyloctanonitrile 7 B -methyl 9 3-methylnonanonitrile 8 ~B-methyl 10 3-methyldecanonitrile 9 ~-methyl Il 3-methylundecanonitrile ~-methyl 12 3-methyldodecanonitrile Table contd.
SampleStructure Preparation 1 CH3(CH2)5CHCH3CNProcedure A, 76~ yield from 2-octanone 2 CH3(CH2)6CHCH3CNProcedure A, 69% yield from 2-nonanone 3 CH3(CH2)7CHCH3CNProcedure A, 77% yield from 2-decanone 4 CH3(CH2)8CHCH3CNProcedure A, 74% yield from 2-undecanone CH3(CH2)9CHCH3CNProcedure A, 59% yield from 2-dodecanone 6 CH3(CH2)4CHCH3CH2CN Procedure B, 59%
yield from 2-heptanone 7 CH3~CH2)5CHCH3CH2CN Procedure B, 16%
yield from 2-octanone 8 CH3~CH2)6CHCH3CH2CN Procedure B, 49%
yield from 2-nonanone 1~78893

5 _ R.193/lO0 Sample Structure Preparation 9 CH3(CH2)7CHCH3CH2CN Procedure B, 35%
yield from 2-decanone CH3(CH2)8CHCH3CH2CN Procedure B, 26%
yield from 2-undecanone Table contd.
Boiling Point 10 Sample (lit. bp) Odour Description 1 78-80C at 8 m bar Floral jasminic character (85 at 10 mm Hg) with some celery aspects and a hint of coconut/lactone -very diffusive.
2 72-73C at 3 m bar Soft, floral, lactonic, (100 at 10 mm Hg) jasmine/peachy character.
3 85-87C at 3 m bar A fine, light, jasmine/floral tll5 at 10 mm Hg) character with a soft peach guality.
204 84C at 1 m bar Fresh, floral with some lilac (133 at 12 mm Hg) character - tenacious.
125-127C at 7 m bar Soft, floral with a green (146 at 10 mm ~9) jasminic type odour - very persistent.

6 66-68C at 4 m bar An unusual floral type (207-8 at 760 mm Hg) consisting of a distinct fatty jasminic character combined with an agrumen quality.
307 93C at 8 m bar Fresh, jasminic floral type ~95-6 at 2-3 mm Hg) with a slightly green quality.
8 72-74C at 0.7 m bar Soft, citru~ floral -reminiscent of jasmine.

., .

,~

117~893 - 6 - R.193/lO0 Boiling Point Sample (lit. bp) Odour Description 9 99-100C at 3 m bar Light, fresh, green, floral suggesting lilac, with slight citrus undertones.
5 10 95-97C at 0.7 m bar Distinct orange character which is suffused by a light green sea-fresh quality.
The following are two examples of perfume compositions comprising the nitriles of this invention:
Formula 1 Phenylethyl Alcohol 30.5 -Terpineol ~-~aratertiary butyl cyclohexyl acetate high cis (PPL) lS.0 Benzyl Salicylate 14.8 Cinnamic Alcohol 10.0 Sandalone (PPL) 5.0 Galaxolide (IFF) 3.0 Hexyl Cinnamic Aldehyde 10.0 Coumarin 2.0 Rose Base AB 380 (PPL) 2.0 Isoeugenol 0.1 Vetivert Brazilian 0.1 Nitrile No 3 1.5 Formula 1 in the absence of nitrile 3 has a floral, woody bouquet suitable for a toilet soap. The addition of 1.5~ of nitrile 3 enhances the overall freshness, giving a light floral, fruity effect. Using the above formulation but ~ubstituting nitrile 9 in place of nitrile 3, a perfume 30 i6 created having an added fresh lightness with an enhanced floral, fruity and citrus character.
The three novel nitriles provided by this invention are those numbered 8, 9 and 10 in the samples list and their mass spectral data are as follows.

i~78893 _ 7 _ R.193/100 Sample ~ase Peak Ml M2 M3 M4 M5 8 C10 41 43:85 57:84 68:66 S5:50 96:46 9 Cll 41 57:85 43:84 68:56 55:~0 69:43 C12 41 57:92 43:90 ~5:54 68:53 70:48 Perfumes formulated using as an odorous component the nitriles provided by this invention may be employed in the various products, such as soaps, detergents, hairsprays, talcum powders and the like, which are normally augmented by the addition of a perfume.

Claims (2)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A perfume composition comprising perfume components and an organoleptically discernible amount of a nitrile of the formula:

CH3(CH2)nRCN

in which R = CHCH3- or -CHCH3CH2- and in which, when R = CHCH3-, n is an integer from 5-9 and when R = CHCH3CH2-, n is an integer from 4-8.

2. A perfume composition as claimed in claim 1 in which the amount of the nitrile does not exceed 95% by weight of the perfume composition.