JPH023440B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to substituted saturated fatty acid nitriles, and more particularly to α-
and regarding β-substituted nitriles. Various substituted aliphatic nitriles have been known for some time, but until now their value as perfume ingredients has not been recognized. Certain α- and β-substituted aliphatic nitriles, some of which are new, have been found to have particular value in perfume compositions. Therefore, the present invention provides a fragrance component and a formula CH ₃ (CH ₂ ) _o RCN (wherein R=-CHCH ₃ - or -CHCH ₃ CH ₂ -, and when R=-CHCH ₃ -, n is 5 to and n is an integer from ₄ to ₈ ). Furthermore, the present invention provides several novel substituted nitriles of particular value for perfume compositions having the formula CH ₃ (CH ₂ ) _o CHCH ₃ CH ₂ CN, where n is 6, 7 or 8. . Nitriles useful in the perfume compositions provided by the present invention, in addition to their useful odor properties, must contain soaps, disinfectants, detergent powders and active chemicals or resist the action of sunlight or heat. It has excellent stability when used in perfume formulations that are used or stored in harsh environments, such as in other compositions. Nitriles useful according to the invention can be made by various methods. However, an advantageous method of preparation for α-substituted nitriles is as follows: Method A A solution of the required methyl alkyl ketone (50 mmol) and tosylmethyl isocyanide (12 g, 60 mmol) in anhydrous diglyme (120 ml) is heated with nitrogen. 0 below
Potassium t-butoxide (4.3 g freshly made from Potassium, 0.11 g atom) for 15 min at °C.
was added to a stirred solution of dry t-butanol (100 ml) and diglyme (100 ml). Once the addition was complete, the mixture was allowed to warm to room temperature and was stirred for 2 hours and left overnight. The resulting solution was poured into water (400ml) and extracted with petroleum ether (3 x 100ml, bp 40-60°C).
The combined organic extracts were washed with water (2 x 500ml) then brine (500ml) and dried ( _MgSO4 ). The solvent was removed under reduced pressure and the residue was chromatographed using a silica gel column (3 cm diameter, 30 cm height) with 5% ether in petroleum ether (bp 40-60°C) as solvent. These fractions containing the product were freed of solvent under reduced pressure and the desired 2-methyl substituted nitrile was obtained from the distillation residue. An advantageous method for preparing β-nitriles is as follows: Method B The required methyl alkyl ketone (1 mol), cyanoacetic acid (93.5 g, 1.1 mol), ammonium acetate (13 g, 0.17 mol) and toluene (175 ml) of
Under reflux (pot temperature 140-160°C) in a Dean-Stark apparatus until the end of carbon dioxide evolution (3-6 hours).
Stirred. The resulting mixture was cooled, washed with saturated sodium bicarbonate solution (2 x 50 ml) and water (50 ml),
The solvent was then removed under reduced pressure. The crude mixture of nitrile was then added to 4/1 of its volume in 50% aqueous caustic soda solution, and Tergitol (trade name for surfactant,
Union Carbide (3 drops) was added. The resulting mixture was stirred under reflux for 1 hour and then cooled. The organic phase was removed, washed with water (3 x 50ml) and distilled. 5% palladium on carbon (0.1% by weight relative to the nitrile mixture) is then added followed by ethyl acetate (2 x distillate weight) and the suspension is stirred vigorously under hydrogen atmosphere until the end of gas uptake. did. The catalyst was removed by filtration and the solvent was distilled off under reduced pressure. Fractional distillation of the residue yielded the desired 3-methyl substituted nitrile. The following table shows the physical and organoleptic properties of the nitriles useful in this invention.

【table】

【table】 %

[Table] Sweet Orange Characteristics The following are two examples of fragrance compositions containing the nitriles of the present invention: Formulation 1 Phenylethyl Alcohol 30.5 α-Terpineol 6.0 Paratertiary Cyclohexyl Acetate High Cis (PPL) 15.0 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 Vetiver Brazilian 0.1 Nitrile 3 1.5 Formula 1 excluding nitrile number 3 is cosmetic soap It has a flower style and wood bouquet suitable for. The addition of 1.5% Nitrile 3 gives a light floral, fruit effect and improves overall freshness. Using the above formulation, but using nitrile 9 instead of nitrile 3, flower-like,
A fresh, light fragrance with enhanced fruit and sweet fruit notes is created. The three new nitriles provided by the present invention are numbered 8, 9 and 10 in the sample list. Their mass spectral data are as follows:

[Table] Using the nitrile provided by the present invention as an odor component, the perfume formulated can be added to various products that are normally enhanced by the addition of perfume, such as soaps, detergents, hair sprays, cosmetic powders, etc. Can be done.

Claims (1)

[Claims] 1. Fragrance ingredients and formula CH ₃ (CH ₂ ) _o RCN (wherein R=CHCH ₃ - or -CHCH ₃ CH ₂ -, and when R=CHCH ₃ -, n is 5 to 9) and where R= _{CHCH3CH2 ,} n is an integer from 4 to 8). 2. The perfume composition according to claim 1, wherein the amount of nitrile does not exceed 95% by weight of the perfume composition. 3. A perfume composition according to claim 1, wherein the nitrile is a substituted nitrile having the formula CH ₃ (CH ₂ ) _o CHCH ₃ CH ₂ CN, where n is 6, 7 or 8.