Note: Descriptions are shown in the official language in which they were submitted.
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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
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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:
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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).
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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
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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.
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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.
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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.
