JP2001152177A - Aroma composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aroma composition the smell of which rises in a good state and which has a strong musk-like aroma, powderiness, and animal-type excellent aroma characteristics having a strong diffusibility. SOLUTION: This composition contains at least two macrocyclic lactones represented by formula (1) (n) is an integer of 8-11).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fragrance composition containing a macrocyclic lactone which is important as a musk-like fragrance substance particularly in the perfumery industry.

[0002]

2. Description of the Related Art In general formula (1), The macrocyclic lactone represented by the formula (where n represents an integer of 8 to 11) has a musk-like odor and plays an important role in the perfumery industry. In recent years, due to its high biodegradability, it has also attracted attention as an environmentally friendly musk fragrance that can be substituted for the polycyclic musk compound that has been mainly used so far. However, these compounds have the disadvantage of being inferior to polycyclic musk fragrances in that they are generally more expensive than polycyclic aromatic compounds.

[0003] As macrocyclic lactones, cyclopentadecanolide and cyclohexadecanolide have been mainly known (Steffen Arctander; Perfume and Flav).
or Chemicals, Motoichi Indo; synthetic fragrance). However,
The descriptions are only for the respective odor characteristics. In addition, both have a refined and elegant musk-like aroma, but have a drawback of being vegetable and lacking animal-like strength such as civet and amber.

[0004] Cyclotetradecanolide and cyclotridecanolide were also known to have musk-like aromas. Fragrance No.93,19-27 (1
970)), its value as a musk-like fragrance has been overlooked.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an animal-based fragrance composition which has a good odor, has a strong musk-like odor, and has excellent odor characteristics of a highly diffusible animal.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a mixture of homologues of macrocyclic lactone has surprising properties in terms of aroma. That is, in the present invention, the general formula (1) (Wherein, n represents an integer of 8 to 11). A mixture of cycloalkanolides represented by the formula (1) has a better odor and a strong musk-like aroma than that used alone, and has a powdery taste. It has been found that it has an excellent aroma characteristic of an animal system having strong diffusibility.

The mixture of macrocyclic lactones is represented by the general formula (2): HOOC (CH ₂ ) _n COOH (where n = 8 to 11)
It is obtained by the method of International Publication No. WO 97/06156 using a mixture of dicarboxylic acids represented by the following formula:
Further, the mixture of dicarboxylic acids used in the present production method is widely distributed as a rust inhibitor and is easily available.
In addition, since it is inexpensive, it is also excellent as an industrial raw material, and the macrocyclic lactone mixture obtained therefrom can also be kept at a lower cost than before, so that it also has the advantage of being able to eliminate the inferior points of the above-mentioned polycyclic musk.

That is, the mixture of dicarboxylic acids is esterified as it is to obtain a compound of the general formula (3) (Wherein, R is an alkyl group having 1 to 6 carbon atoms, n = 8 to 11)
A mixture of diesters of dicarboxylic acids represented by This is subjected to a condensation reaction with γ-butyrolactone and a base such as an alkali metal alcoholate to give a compound of the general formula (4) (Wherein, R is an alkyl group having 1 to 6 carbon atoms, n = 8 to 11)
2 (ω-alkoxycarbonylalkanoyl) -4-butanolide represented by the following formula: This is hydrolyzed and decarboxylated to obtain a compound represented by the general formula (5) (Where n represents an integer of 8 to 11), ω-
This gives hydroxy- (ω-3) -ketoalkanoic acid. This is reduced by Wollf-Kishner or Clemmensen to obtain the general formula (6) (Wherein n represents an integer of 8 to 11). This is advanced dilution method, polymerization-depolymerization,
The formula (1) is obtained by a technique such as intramolecular transesterification. (Wherein, n represents an integer of 8 to 11), thereby obtaining a macrocyclic lactone as a mixture.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The mixed composition of a dicarboxylic acid represented by the general formula (2) HOOC (CH ₂ ) _n COOH (where n is an integer of 8 to 11) used as a raw material in the present invention is as follows: n = 8 is 1 to 15
wt%, n = 9 is 1-70 wt%, n = 10 is 10-80 wt%
%, N = 11 is 0 to 10% by weight, preferably n = 8
Is 1 to 7 wt%, n = 9 is 5 to 50 wt%, and n = 10 is 30
６０60 wt%.

The mixture of macrocyclic lactones obtained in the present invention substantially conforms to the mixture composition of the dicarboxylic acids used as the raw materials. (Wherein n represents an integer of 8 to 11), the mixed composition of the macrocyclic lactone represented by n = 8 is 1 to 15 wt%, and n = 9
Is 1 to 70 wt%, n = 10 is 10 to 80 wt%, n = 11
Is 0 to 10% by weight, and preferably, n = 8 is 1 to 7% by weight.
%, N = 9 is 5 to 50 wt%, n = 10 is 30 to 60 wt%
It is. The present invention will now be described by way of examples, which should not be construed as limiting in any way.

[0011]

Example 1 Preparation of a mixture of macrocyclic lactones 39.7% by weight of dodecandioic acid, 38.63 of undecandioic acid
Mixture of dicarboxylic acid 1 wt% and 5.4 wt% decandioic acid 1
To 00 g, 550 g of anhydrous methanol and 12.5 g of concentrated sulfuric acid
And heated to distill. After cooling, the mixture was neutralized with sodium carbonate, and methanol was distilled off under reduced pressure. The concentrated residue was dissolved in ethyl acetate, washed with water and dehydrated with magnesium sulfate, and the solvent was recovered to obtain 110.4 g of an ester compound.

[0012] 9.0 g of γ-butyrolactone was added to this,
Mix 5.7 g of sodium methoxide at room temperature,
The mixture was heated and stirred for 2 hours while removing the methanol produced in the above. After cooling, the mixture was poured into diluted sulfuric acid and extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate. The concentrated residue obtained by distilling off the solvent was distilled under reduced pressure (oil bath temperature to 180 ° C).
/〜26.7 Pa) to remove excess ester. 94.2 g of a fraction and 31.8 g of a distillation residue were obtained.

490 g of a 6.5% aqueous sodium hydroxide solution and 240 g of methanol were added to the distillation residue, and the mixture was heated and distilled for 6 hours to effect hydrolysis and decarboxylation. After cooling, the mixture was poured into diluted sulfuric acid and extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate. The solvent was distilled off, and a crystalline product was obtained.
9 g were obtained. 14.6 g of sodium hydroxide,
120 ml of diethylene glycol and 9.5 ml of 85% hydrazine hydrate were mixed and stirred at 110 ° C. for 30 minutes while removing water. 195-200 while removing water
The mixture was heated and stirred for 8 hours. After cooling and acidifying with dilute sulfuric acid, the mixture was extracted with ethyl acetate. The organic layer was washed with water, dehydrated with magnesium sulfate, and then the solvent was distilled off.
2.5 g were obtained.

This was mixed with tetraethylene glycol, and heated and stirred at 105 ° C. while removing water. Tetrabutoxytitanium was added, and the inside of the system was heated to 250 ° C. while depressurizing to carry out a depolymerization reaction. The effluent was extracted with toluene, and the organic layer was washed with water and dried over magnesium sulfate. The solvent was distilled off to obtain 10.9 g of crystals. This was distilled under reduced pressure to obtain 9.8 g of a main fraction. This was analyzed by gas chromatography to find that 13-cyclotridecanolid 6.5% and 14-cyclotetradecanolid 46.2.
%, 47.4% of 15-cyclopentadecanolide. As a result of sensory evaluation of the aroma characteristics of this mixture,
It was found to have an elegant musk-like and animal-like aroma with a slightly floral, woody, fragrant, powdery taste.

Claims (3)

[Claims] 1. At least two or more general formulas (1) (Wherein, n represents an integer of 8 to 11). 2. General formula (1) When producing a macrocyclic lactone represented by the formula (where n represents an integer of 8 to 11), two or more types of HOOC (CH ₂ ) _n COOH (where n = 8 to 11) 11
The aromatic composition according to claim 1, wherein a dicarboxylic acid represented by the following formula is used as a raw material. 3. The fragrance composition according to claim 1, wherein the compound has the general formula (1): (In the formula, n = 8 to 11 represents an integer.) The weight ratio of the macrocyclic lactone represented by n = 8 is 1 to 15 wt% and n = 9 is 1
~ 70wt%, n = 10 is 10 ~ 80wt%, n = 11 is 0
A fragrance composition characterized by being 10 wt% to 10 wt%.