JPS5896014A - Flavor composition containing unsaturated fatty acid - Google Patents

Abstract

PURPOSE:A flavor composition suitable for use in cosmetic, food, feed and tobacco that contains a straight-chained 5-alkenoic acid as an active ingredient, thus smelling fatty and intensifying butter, milk or cheese-like smell. CONSTITUTION:The objective flavor composition contains 0.01-10wt% of a compound of the formula (n is integer of 2-5) as an active ingredient. The compound of the formula smells fatty as such, however, the addition to flavor formulations intensifies butter, milk, or cheese-like smell and makes the smell mild and mellow.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fragrance composition characterized by containing a linear 5-alkenoic acid.

The present inventors have discovered that certain unsaturated organic fatty acids have the following general formula (I): CH3(CH2)nCH=CH(CH2)3COOH':; )
It has been found that the linear 5-alkenoic acid represented by is effective as a flavor component. This compound has a pleasantly fatty odor characteristic, whereas linear 5-alkenoic acids having double bonds in other positions do not have such an odor. The compounds are therefore particularly useful for enhancing the aroma properties of dairy products such as butter, milk, cheese and the like. It is known that some fatty acids such as 9-decenoic acid and capric acid exist in natural dairy products. 9-decenoic acid has a green aroma, and capric acid has a hard aroma, but the compound, linear 5-alkenoic acid, has a 9-
It was found that it has a soft, fresh flavor unique to dairy products, which is not found in decenoic acid or capric acid, and that it significantly enhances the natural flavor. The compound, linear 5-alkenoic acid, has two stereoisomers, cis and trans, but both have basically the same aroma as mentioned above, and the cis and trans forms are similar. Compared to , it has a slightly bluer aroma. Many of the linear 5-alkenoic acids that are the compounds are known; for example, 5-nonenoic acid and 5-decenoic acid have C,R,A
cad, Sci, Paris, Ser, C2
64(1), 109 (1967). However, the straight chain 5- represented by general formula (I)
As mentioned above, there have been no reports on the usefulness of alkenoic acids as fragrances, and the present inventors have discovered for the first time that the compound has an irresistible fatty aroma and is extremely useful as a fragrance.

The compound itself has a fatty odor, but
The present inventors have discovered that by adding this to flavored products, etc., the characteristics of butter, milk, and cheese-like aromas can be strengthened, and the aromas become mellower, leading to the completion of the present invention.

The linear 5-alkenoic acid compound can be used in cosmetic flavorings, food flavorings, feed flavorings, and tobacco flavorings. The amount of the compound that can be used to produce an effective fragrance varies somewhat depending on the purpose of use, but the amount that can be used to produce an effective fragrance is 0.
．． It is preferable to use it in a range of 0.01 to 10.0 by weight.

However, it does not necessarily have to be within this range.

The compound, linear 5-alkenoic acid, can be prepared by methods described in the literature, such as (C,R,Acad, Sci, Par
is.

Ser., C264(1), 109 (1967): ],
(J, Med.

Chem, 14.236 (1971)) or easily synthesized by the following method. That is, e MeOOC(CH2)3cH('OMe)2--m--
-→CH3(CH2)ncH=PPh3 MeOOC(CH2)3CHO-1-------C
Ha(CH2)nCH=CH(CH2), +COOMe
---1----→CH3(CH2)nCH=CH(C
H2)3COOH7C (cis form) ~ θ0H CH3(CH2) n CH-CH(CH2)3 CO
OMe -1111---→6t (trans form) CHs(CH2)nCH=CH(CHz)acOOH7
t (trans form) (where n is an integer from 2 to 5) The methyl enol ether 1 of cyclopentanone is electrolytically oxidized to convert it to the trimethoxy form 2, which is further electrolytically oxidized to form the acetal ester 3, which is acidicly hydrolyzed to formyl. Let it be ester 4. Wittig reaction between this product and ylide 5 derived from the phosphonium salt yields cis-5-alkenoic acid methyl ester 6c. By hydrolyzing this, cis-5-alkenoic acid 7C can be obtained. Further, 6c is isomerized using a catalytic amount of para-toluenesulfinic acid to give trans-5-alkenoic acid methyl ester 6t, and further alkaline hydrolysis yields trans-5-alkenoic acid 7t.

Depending on the method of synthesizing the compound, a trans isomer and a cis isomer may be generated as a by-product, resulting in a mixture thereof, but even if such a mixture is used, similar aroma characteristics are exhibited.

Examples will be described in detail below, but the present invention is not limited thereto.

Example 1 Preparation of cis- and trans-5-decenoic acid Commercially available 50% sodium hydride (1,00f) was placed in a reactor, and n-
Wash several times with pentane. Then dry dimethyl sulfoxide (
DMSO) (20 ml) is added, and the mixture is heated and stirred at 75-80° C. until hydrogen generation is complete. DMS of n-amyltriphenylphosphonium bromide (8,58y) after cooling
Add O (10m6) solution. After 10 minutes, formylbutyric acid methyl ester (2,971) was added, and the
Stir for 0 minutes. After the reaction is complete, water is added and extracted with ether, washed twice with saturated brine, dried, and the solvent is distilled off. When this substance is purified by column chromatography, cis-5-
Decenoic acid methyl ester (1,472) is obtained. Cis-5-decenoic acid (1,29f) is obtained by alkaline hydrolysis according to a conventional method.

On the other hand, trans-5-decenoic acid is produced by the following method. That is, cis-5-decenoic acid methyl ester (1,47
S'),! : para-toluenesulfinic anhydride (1,00
! i') was dissolved in anhydrous dioxa 7 (50 mA) and refluxed for 1 hour. After the reaction, the solvent was distilled off, treated in the usual manner, and purified by column chromatography to yield trans-5-decenoic acid methyl ester (t32f). Trans-5-decenoic acid (1,162) is obtained by alkali hydrolysis of this product according to a conventional method.

5-nonenoic acid, 5-undecenoic acid, and 5-dodecenic acid can also be produced in a similar manner.

The 4-formylbutyric acid methyl ester used here is produced by the following method.

Production of 4-formylbutyric acid methyl ester 1-methoxy-
Dissolve 1-cyclopentene (10,00 L?) and sodium methoxide (s, 51y) in methanol (80 ml), and use a diaphragmless electrolytic cell with carbon electrodes (SO=) for both anode and cathode to produce a constant current of 6 A. Perform electrolysis to 3.5 F
/mo 1 energize. After completion of the reaction, methanol is distilled off, ether is added, washed twice with water, dried, and the solvent is distilled off to obtain a crude product of 1.1.2-)rimethoxycyclopebutano (8,83f). This and tetraethylammonium paratoluenesulfonate (3, o7f)
Dissolve it in methanol (80ml) and connect it again to the carbon electrode (
5offl), 6F/mo1 current is applied by constant current electrolysis of filter A using a non-diaphragm electrolytic cell. After the reaction is completed, methanol is distilled off and treated in the same manner to obtain a crude product (947 grams) of 5,5-dimethoxyvaleric acid methyl ester. To this was added a 10% hydrochloric acid aqueous solution, stirred at room temperature for 6 hours, worked up in the usual way, and purified by column chromatography to obtain 4-formylbutyric acid methyl ester (2,q 7 y
) is obtained.

Example 2゜For the basic butter flavor shown in the following formulation, 5-
10 parts of decenoic acid was added. A sensory test was conducted on the butter flavor (additive) obtained in this way and the basic butter flavor.Formulation Parts by weight Ethyl acetate 2 Acetoin
15 diacetyl 7 2-hebutanone 4 2-nonanone 102-undecanone 4butyric acid 4゜2-tridecanone 6caproic acid
18δ-octalactone
3 Cagrilic acid 25δ-decalactone 1゜δ-undecalactone
5 Capric acid 6 δ-dodecalactone 35 total 990 Out of the 10 judges, 9 thought the additive was good, and 1 said there was no change. The reason why it was good was that the additives emphasized the Yoshishi butter-like quality and gave it a natural feel.

Example.

Example 1. 10 parts of 5-dodecenoic acid was added to 990 parts of the basic butter flavor shown in . When a sensory test was conducted on the butter flavor (additive) obtained in this way and the basic butter flavor, 10 judges unanimously agreed that the additive had a slightly green buttery aroma and was good. .

Example 4゜Example 1. 10 parts of 5-undecenoic acid was added to 990 parts of the basic butter flavor shown in . When a sensory test was conducted on the butter flavor (additive) obtained in this way and the basic butter flavor, 10 judges agreed that the additive had a rich and soft buttery aroma and was good. did.

Example 5゜Example 1. 10 parts of 5-nonenoic acid was added to 990 parts of the basic butter flavor shown in . When a sensory test was conducted on the butter flavor (additive) thus obtained and the basic butter flavor, 10 judges agreed that the additive had a soft buttery aroma and was good.

Example 6゜ A tobacco flavoring agent was prepared according to the composition shown below.

Black tea extract 20.0 Coffee extract 300 Rum (500)
450.0 ethyl stearate
10. Oethyl oleate 10.0 Anisole O, Oδ-decalactone 0.1 Maltol
5.0 Veratraldehyde 10.0 St. John's Breed Alcohol Extract 210.0 Fennel Oil 1.095 Thiethyl Alcohol 100.0 Water
140.9990 A blended flavor in which 1.0 part of 5-decenoic acid of the present invention was added to the above formulation and an additive-free blended flavor were injected at 0.01 to 1.0% by weight into commercially available cigarette shreds or filters, and 10 people When expert panelists compared the results, all of them agreed that cigarettes containing the compound of the present invention had a more cigarette-like flavor, and especially had a fine-grained, irritating texture when smoking.
It was rated as good because it suppressed bitterness, astringency, spiciness, etc., and provided a mild and light aromatic taste.

Example Z A tuberose base is prepared according to the following recipe. Add this and 5 parts of 5-decenoic acid to this and formulate: Part by weight linalool 8 linalyl acetate 3 benzyl acetate 15 γ-nonalactone 10 eugenol
4. Methyl anthranilate 20. Hexyl cinnamic aldehyde 12. Benzyl salicylate 8. Musk ketone 5. When sensory tests were conducted on 95 ingredients in total, 10 judges agreed that the additive was a naturally soft and creamy tuberose. It was rated as good because it increased the fragrance tone.

Patent applicant: Soda Fragrance Co., Ltd.

Claims (3)

[Claims] (1) General formula (I) CH3(CH2)nCH=CH(CH2)3cOOH-
A fragrance composition characterized by containing a linear 5-alkenoic acid represented by (I) (wherein n represents an integer from 2 to 5''!). (2) The fragrance composition according to claim 1, wherein the linear 5-alkenoic acid is a trans form and/or a cis form. (3) The flavor composition according to claim 1, wherein the flavor composition is a cosmetic flavor, a food flavor, a feed flavor, or a tobacco flavor.