JPH0614846B2 - Flavoring agent with milky aroma - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel flavoring agent having a milky aroma.

(Prior Art) As a compound having a milk-like odor, some amyl lactic acid thioesters (JP-A-50-94172), thiazole derivatives (JP-A-55-151577) and the like are known. The present inventors have diligently studied in order to develop an aroma component having structural characteristics different from those of the conventionally known aroma components and having a milky aroma which is easy to produce, and as a result, the specific 5 and / or It was found that the 6-alkenoic acid ester has a milky aroma.

As unsaturated fatty acid esters already known as fragrance materials, methyl 2-nonenate, methyl 3-decenoate,
There are alkenoic acid esters having unsaturation at the 2-, 3-, or 4-position such as methyl 4-dodecenoate, but no compound having a milk-like aroma is known.

(Explanation of the invention) That is, the present invention is represented by the general formula (I) (In the formula, n represents an integer of 1 to 4, R represents an alkyl group having 4 carbon atoms, and a dotted line represents that one of them has a double bond.) And / or 6- It has been found that the alkenoic acid ester has a milk-like odor and can be added to food flavors, cosmetic flavors, feed flavors, tobacco flavors and the like to enhance its individuality and improve the quality. In particular, it was found that addition to dairy flavor enhances its natural tone remarkably, and it became clear that it is extremely effective as a wide range of blending materials.

Even with 5 and / or 6-alkenoic acid esters, the scent is different due to the difference in the alcohol portion. For example, methyl ester has a fresh greenish aroma, ethyl ester has a greenish aroma with a mild sweetness, and isopropyl ester has a fruity greenish aroma. In addition, isoamyl ester has a sweet, fruity aroma. On the other hand, it was found that n-butyl ester, isobutyl ester and sec-butyl ester have milk and buttery aroma. That is, 5
It was found that the 6-alkenoic acid ester and / or 6-alkenoic acid ester are useful as a flavoring material, but it was revealed that only the alkyl group having 4 carbon atoms in the alcohol portion had a milky or buttery aroma. All of these compounds are new compounds.

Specific examples of the compound name of the compound of the present invention include 5 and / or 6-nonenoic acid, 5 and / or 6-decenoic acid, 5 and / or 6-as the carboxylic acid moiety.
Undecenoic acid and also 5- and / or 6-dodecenoic acid are mentioned. Examples of the alcohol portion include n-butyl ester, isobutyl ester and sec-butyl ester. The compound may have a cis-form or a trans-form as the double bond, but any of them may be used, or a mixture in an arbitrary ratio may be used.

The amount of the compound that can be used to produce an effective aroma varies depending on the intended purpose, but is 0.01 to 10 per fragrance.
It is preferably used in the range of weight%. However, it does not have to be within this range.

The compound of the present invention can be prepared according to a known method. For example, the method described in Bull. Soc. Chim. France, 1964 (4), 723 utilizes the so-called Ramberg-Bcklund reaction. When cyclopentanone is used as a starting material, 5-alkenoic acid is used as a starting material and cyclohexanone is used as a starting material. Then, 6-alkenoic acid is obtained. The compound of the present invention can be derived by esterifying these by a conventional method.

Also, the method described in Pharmaceutical Journal, 75, 606 (1955), dehydrobrominates methyl 6-bromodecanoate to obtain a mixture of 5 and 6-methyl decenoate. The compound of the present invention can be derived by transesterifying this product.

The 5 and / or 6-alkenoic acid ester thus obtained can be used as a perfume additive either alone or as a mixture of both.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Reference example 1. Method for producing 5-nonenoic acid a. Synthesis of 2-butylthiocyclopentanone To anhydrous ethanol (600 ml) sodium metal (13.8
g) and butyl mercaptan (64.8 g) added 2
-A solution of chlorocyclopentanone (71.1g) in absolute ethanol (600ml) was added dropwise and left overnight at low temperature. Next, ethanol was recovered under reduced pressure, dissolved in ether, neutralized with an aqueous acetic acid solution, the solvent was distilled off, and this was distilled to obtain 90 g of 2-butylthiocyclopentanone.

B. Synthesis of 2-butylsulfonylcyclopentanone 2-Butylthiopentanone (88 g) is reacted with a 30% excess of an ether solution of monoperphthalic acid at 0 ° C. After the reaction, the excess monoperphthalic acid was treated with sodium sulfite, washed, and the solvent was distilled off. This was distilled to obtain 78 g of 2-butylsulfonylcyclopentanone.

C. Synthesis of 5-bromo-5-butylsulfonylpentanoic acid To 2-butylsulfonylcyclopentanone (10.2 g) 6
A benzene solution of sodium hydride (0.055 mol) is added dropwise at 0 ° C. Bromine (8.8g) at 0 ℃ when hydrogen generation stops
Is added dropwise and the mixture is stirred at 0 ° C. for 30 minutes. Then 2N potassium hydroxide (120 ml) is treated at 0 ° C. for 30 minutes. 12% of water layer
After neutralizing with HCl, extracting with ether, washing, distilling off the solvent and recombining with ethyl acetate and cyclohexane, 5-bromo-5
8.6 g of butylsulfonylpentanoic acid were obtained.

D. Synthesis of 5-nonenoic acid 5-bromo-5-butylsulfonylpentanoic acid (6 g)
2N potassium hydroxide (60 ml) was added to the mixture and the mixture was added at 100 ° C for 2
React on time. Then, the mixture was cooled to 0 ° C., neutralized with 12% HCl, extracted with ether, washed, and the solvent was distilled off. This was distilled to obtain 2 g of 5-nonenoic acid.

Reference example 2. In the following Reference Example 1 using 2-chlorocyclohexanone instead of 2-chlorocyclopentane used in Reference Example 1.
6-decenoic acid was obtained in the same manner as in.

Reference example 3. Method for producing methyl 5- and 6-decenoate a. Synthesis of ethyl 6-oxodecenoate Active zinc-copper catalyst (11.5 g), butyl acetate (4 g), toluene (5 g), butyl iodide (15 g), iodine (3
The mixture of (mg) was heated at 110 to 120 ° C. for 2 hours, and ethyl adipate chloride (15.7 g) was added dropwise at 0 ° C. to carry out the reaction. After the completion of the reaction, ice water was added, the mixture was decomposed with dilute sulfuric acid water, the oil layer was extracted with ether, washed with sodium bicarbonate water, washed with water and dried, and the solvent was distilled off to obtain 8.1 g of ethyl 6-oxodecanoate.

B. Synthesis of 6-oxodecanoic acid 4 g of ethyl 6-oxodecanoate was saponified according to a conventional method and recombined with ethanol and petroleum ether to obtain 2.7 g of 6-oxodecanoic acid.

C. Synthesis of 6-hydroxydecanoic acid 6-oxodecanoic acid (1.86 g), platinum oxide (0.5 g),
198.2 ml of hydrogen are taken up in a mixture of glacial acetic acid (30 ml) in 35 hours. After that, glacial acetic acid was distilled off and the residue was reconstituted with ethanol and water to obtain 1.7 g of 6-hydroxydecanoic acid.

D. Synthesis of methyl 6-bromodecanoate Methyl 6-hydroxydecanoate (2.3 g) obtained by methyl esterification of 6-hydroxydecanoic acid by a conventional method and hydrogen bromide water (28 ml) were stirred at 105 to 110 ° C for 6 hours in a closed tube. After that, it was extracted with ether, transferred to water of heavy soda, treated with diazomethane, washed and dried, and then the solvent was distilled off and distilled to obtain 0.95 g of methyl 6-prodecanoate.

E. Synthesis of methyl 5- and 6-decenoate Methyl 6-bromodecanoate (1.2 g) and quinoline (1.2 g)
g) are mixed and reacted at 240 ° C. for 5 minutes. After completion of the reaction, the reaction mixture was extracted with ether, washed with diluted hydrochloric acid, washed with water, dried, distilled off the solvent and distilled to obtain 310 mg of a mixture of 5 and 6-methyl decenoate.

Example 1. Method for producing isobutyl 5-nonenoate 5-nonenoic acid (10 g) and isobutyl alcohol (9.5
Concentrated sulfuric acid (0.2 g) was added to a solution of g) in toluene (40 ml) and azeotropic dehydration was carried out for 3 hours. After the completion of the reaction, the product was washed with water, washed with sodium bicarbonate water and brine, dried over anhydrous magnesium sulfate, the solvent was distilled off, and this was distilled to obtain 12.9 g of isobutyl 5-nonenoate.

Example 2. 6-decenoic acid (10 g) and n-butyl alcohol (8.7
Then, the same operation as in Example 1 was carried out using g) to obtain 12.6 g of n-butyl 6-decenoate.

Example 3. Process for producing n-butyl 5 and 6-decenoate Methyl 5 and 6-decenoate (methyl 5-decenoate: 6-
Methyl decenoate = 50: 50, 1 g) was added to n-butyl alcohol (40 ml) of potassium cyanide (0.26 g), and the mixture was stirred at room temperature for 19 hours. After completion, the solvent was distilled off, and the residue was extracted with ether, washed with water, washed with a saturated saline solution, dried over anhydrous magnesium sulfate, distilled off the solvent, and further distilled to give n-butyl 5- and 6-decenoate (5-decene). Butyl acid:
1.1 g of 6-butyl decenoate = 50: 50) was obtained.

Example 4. 5 for the basic milk flavor shown in the formula below
And 10 parts of n-butyl 6-decenoate (1/1) were added. A sensory test was conducted on the milk flavor (additive) thus obtained and the basic milk flavor, and 10 judges agreed that the additive was good.
And the reason was that the additive had a more natural feel by emphasizing the mild sweetness of milk.

Basic milk flavor formulation (parts by weight) Dimethyl sulphide 0.1 Octanol 0.2 2-Undecanone 0.2 2-Nonanonone 0.3 Ethylcycloten 0.4 Ethyl levulinate 0.8 Ethylmaltol 1.0 Butyric acid 2.0 Caproic acid 2.0 Caprylic acid 3.0 Vanillin 3.0 Acetoin 5.0 Butyl butyryl lactate 5.0 Capric acid 6.0 δ-decalactone 18.0 δ-undecalactone 20.0 δ- dodecalactone 23.0 Propylene glycol 900.0 Total 990 Example 5. 10 parts of isobutyl 5- and 6-dodecenoate (1/1) were added to 990 parts of the base milk flavor shown in Example 4. A sensory test was conducted on the milk flavor (additive) and the basic milk flavor thus obtained, and 9 out of 10 judges judged that the additive had a slightly sweet milk-like aroma. One said it wouldn't change.

Example 6. To 990 parts of the base milk flavor shown in Example 4 was added 10 parts of isobutyl 5-nonenoate. A sensory test was conducted on the milk flavor (additive) thus obtained and the basic milk flavor, and 10 judges agreed that the additive had a slightly bluish milk-like aroma and was good. .

Example 7. 10 parts of n-butyl 6-decenoate were added to 990 parts of the basic milk flavor shown in Example 4. A sensory test was conducted on the milk flavor (additive) thus obtained and the basic milk flavor, and 10 judges agreed that the additive had a rich, soft milk-like aroma. did.

Example 8. Prepare the scent of a modern bouquet according to the following recipe. This and 5 and 6-decenoic acid formulation (parts by weight) Indoleene 2.0 Hedeion 10.0 Isodiasmon 0.5 Diasmine Absolute 4.0 Pentaritud (Soda) 15.0 Lemon oil CP 23.0 Bergamotte oil 10.0 Benzyl acetate 5.0 Benzylbenzoate 10.0 Citral 2.0 Oakmos Absolute oil 2.0 Sandalwood Bédiver Bourbon 8.0 Essence Armorise 5.0 Cumin Oil 0.5 Total 98.0 A sensory test was conducted on 2 parts of n-butyl (1/1), and a 10-member jury agreed with the results that the added product enhances the fruity and floral feeling. It is good because it gives a mellow mellowness and makes the whole fragrance unique and attractive.

Example 9. A fragrance for cigarette was prepared according to the composition shown below.

Ingredients Weight part Black tea extract 20.0 Coffee extract 30.0 Rum (50 °) 450.0 Ethyl stearate 10.0 Ethyl oreate 10.0 Anisole 3.0 δ-decalactone 0.1 Maltol 5.0 Veratralaldehyde 10.0 St. John's Bullet 210.0 Alcohol extract Fuennel oil 1.0 95% Ethyl alcohol 100.0 Water 140.9 Total 999.0 0.01 to 1.0% by weight of the blended flavor added with 1.0 part of n-butyl 6- decenoate to the above formulation and no blended flavor added to a commercially available tobacco cut or filter were used for 10 persons. Tobacco to which the compound of the present invention was added in agreement with all of the specialist panelists compared with each other promoted the flavor and taste like a cigarette, and the smoke became finer particularly when smoking, irritation, habit (dullness, bitterness,
Astringency, spiciness, etc.) were suppressed and mild and light aroma was obtained, which was considered good.

Claims (4)

[Claims] 1. A general formula (I) (In the formula, n represents an integer of 1 to 4, and R represents 4 carbon atoms.
Represents an alkyl group. The dotted line indicates that either one has a double bond. ) A flavoring agent having a milk-like aroma consisting of an alkenoic acid ester represented by 2. The alkenoic acid ester is 5 and / or 6-.
The fragrance additive according to claim 1, which is n-butyl decenoate. 3. The fragrance additive according to claim 1, wherein the fragrance additive is a dairy product flavor additive. 4. The fragrance additive according to claim 1, wherein the fragrance additive is a food fragrance, a cosmetic fragrance, a feed fragrance, or a tobacco fragrance fragrance additive.