JP3143189B2 - Fragrance composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an 8-, 8-, 8-, 4-, 4-, 4-, 4-, or 4- (4-)-(4)-(4)-(4)-(4)-(4)-(4)-(4)-(8)-(8)-(8)-(8)-(8)
The present invention relates to a methyl-7-nonenal derivative and a novel fragrance composition containing the same as an active ingredient.

More specifically, the present invention provides the following formula (1)

Embedded image In the formula, R is as defined above, and is represented by 8-methyl-7-
The present invention relates to a nonenal derivative and a fragrance composition containing the compound as an active ingredient.

[0003]

2. Description of the Related Art 8-methyl-7, which is a starting material of the present invention, is used.
-Nonenal is disclosed, for example, in EP 4238
No. 74 and JP-A-3-167148 and the like, the general formula R ¹ -CH ₂ -CH (R ² )-(CH ₂ ) n-CH = C (C
H ₃ ) _{2 wherein} ^one of R ¹ and R ² represents a formyl group and the other represents a hydrogen atom, and n is an integer from 2 to 8; It is a known compound that is inexpensive and easily available on the market. The patent specification discloses 8-methyl-7.
-It is described that nonenal has a fragrance property and is useful for producing a fragrance composition, but there is no specific description of what fragrance properties it has.

[0004]

SUMMARY OF THE INVENTION The present inventors have found that the odor characteristics of compounds having an aromatic property are completely different due to slight differences in substituents or structures, and the properties possessed by the compounds, such as volatility, retention, Noting that unexpected results were obtained in terms of persistence and stability, various derivatives of the above-mentioned 8-methyl-7-nonenal were examined.

[0005]

Means for Solving the Problems] As a result, in addition to inexpensively available in market as commercial products, easily synthesized by Ri lower alcohol can 8-methyl-7-nonenal known methods of that from inexpensive raw materials The corresponding acetal can be easily synthesized by an acetalization reaction with a compound or a diol, and 8-methyl-7-nonenol can be obtained by reducing the formyl group by a known method. Focusing on the fact that these ester derivatives can be synthesized, these acetals, alcohols and ester derivatives were synthesized, and their odor characteristics were examined.

As a result, the compound represented by the formula (1) has fresh green-based flower-like, fruit-like, and grass-like aroma characteristics, and is extremely useful as a perfume compound, and is stable and persistent. Thus, the present invention was completed.

Accordingly, an object of the present invention is to provide an 8-methyl-7-nonenal derivative represented by the formula (1) and a fragrance composition containing the same.

[0008] 8-methyl-7- used in the present invention
Nonenal can be obtained, for example, by converting 2-methyl-2,7-octadiene, which is commercially available at a low price, into hydrogen and carbon monoxide in an autoclave in the presence of a rhodium-based catalyst such as rhodium carbon and triphenyl phosphite. It can be easily synthesized by reacting the mixed gas of 1 with 5 to 10 atm and hydroformylating.

Further, the compound of the present invention can be easily produced, for example, by the following method. (A): 8-methyl-7 represented by the formula (2) according to the following formula
The formyl group of -nonenal is reduced by a conventional method to obtain the compound of the present invention 8-methyl-7-nonenol (1a), which is then esterified to give the ester of 8-methyl-7-nonenol of the present invention ( 1b) can be obtained.

[0010]

Embedded image In the formula, R ¹ is the same as described above.

In the above reaction, the reduction reaction of the compound of the formula (2) to the compound of the formula (1a) is carried out by reducing the compound of the formula (2) in an organic solvent, for example, a reducing agent such as lithium aluminum hydride or lithium borohydride. It can be easily obtained by contacting with. The amount of the reducing agent to be used can be appropriately selected. For example, the compound 1 of the formula (2)
About 0.5 to about 2 moles per mole can be exemplified. The reaction can be performed, for example, in a range of about -10 to about 30C, more preferably about 0 to about 5C.

Specific examples of the organic solvent used in the above reaction include, for example, methanol, ethanol, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, dioxane and the like. These organic solvents can be used alone or in combination of two or more.
The amount of the organic solvent used is not particularly limited, but may be about 3 to about 50 times the weight of the compound of the formula (2).

After the completion of the above reaction, the reaction mixture is cooled with ice water or the like, the reducing agent is decomposed with a small amount of an aqueous alkali solution such as sodium hydroxide or potassium hydroxide, and the solid is filtered off and concentrated. 8-methyl-7-nonenol of (1a) can be obtained with high purity and high yield. If desired, it can be purified by such means as distillation under reduced pressure or column chromatography.

Further, the alcohol of the formula (1-a) is converted to the formula (1)
The esterification reaction to -b) can be carried out by utilizing any conventionally known esterification reaction between the compound of formula (1-a) and a lower fatty acid. Examples of lower fatty acids include C ₁ -C ₄ carboxylic acids such as acetic acid, propionic acid, butyric acid, and acetoacetic acid.

(B): According to the following formula, 8-methyl-7-nonenal (2) is acetalized using, for example, a lower alcohol or diol compound having about C _{1 to} C ₃ to thereby obtain the compound of formula (1-c). A compound can be obtained.

[0016]

Embedded image (Wherein, R ² has the same meaning as described above, and A represents a lower alkylene group which may have 1 to 3 lower alkyl substituents)

In the above reaction, the acetalization reaction is 8
The reaction can be carried out by reacting -methyl-7-nonenal with lower alcohols or diols in the presence of an acid catalyst.

Here, the lower alcohol includes C ₁ -C ₄ monohydric lower alcohols such as methanol, ethanol, n- or iso-propyl alcohol, n-, iso- or sec-butyl alcohol;
Ethylene glycol, propylene glycol, 1,2
-, 1,3, can be exemplified C ₂ -C ₄ diols, such as such as 1,4- or 2,3-butylene glycol.

In place of the above alcohols or diols, tri-C ₁ -C ₄ alkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate and the like can also be used.

The amounts of these alcohols, diols and alkyl orthoformates used are represented by the formula (2)
For example, the range of about 1 to about 10 mol can be mentioned based on 1 mol of 8-methyl-7-nonenal.

As the above-mentioned acid catalyst, generally, an inorganic or organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or p-toluenesulfonic acid, oxalic acid can be used. These acid catalysts include, for example, alcohols and diols. From about 0.1 to about 1% by weight, based on the weight of such, is often utilized.

This reaction can be carried out in the presence or absence of a solvent. At this time, the alcohol used as a reaction component can also serve as a solvent. If desired, the reaction can be carried out while azeotropically distilling off water produced using, for example, benzene or toluene as a solvent, or in a water-miscible organic solvent such as dioxane, tetrahydrofuran or the like. .

The reaction is preferably carried out at room temperature or under heating, for example, at about 10 ° C. to the boiling point of the solvent used, for about 1 to about 50 hours.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples.

[0025]

Example 1 8-methyl-7-nonenol [compound of formula (1-a)]
Synthesis was dissolved in 95% ethanol 500ml sodium borohydride NaBH ₄ 18 g (0.48 mol), the solution was cooled to 0 ℃ with stirring, 8-methyl-7-nonenal 150g of (0.97 mol) It was dropped. 1 at 0 ° C
After the reaction, water was added little by little to decompose sodium borohydride. The solid is filtered, the filtrate is washed and then concentrated,
The residue was distilled under reduced pressure to obtain 132 g of 8-methyl-7-nonenol (1-a) having a bp of 95 to 96 ° C / 4 torr; a refractive index of 1.4546 (20 ° C). Yield: 87%. This compound had a flowery aroma reminiscent of rose, lily of the valley and cyclamen.

[0026]

Example 2 8-methyl-7-nonenyl-acetoacetate [formula (1)
Synthesis of compound of -b) A 100 ml flask was charged with 20 g (128 mmol) of 8-methyl-7-nonenol (1-a) and 20 g (154 mmol; 1.2 equivalents) of ethyl acetoacetate,
After reacting at 110 ° C. for 1.5 hours, 50 ml of benzene was added, and benzene and ethanol generated by the reaction were distilled out of the system at normal pressure. The reaction was terminated when the distillation of the solvent stopped, and after cooling, the crude product was distilled under reduced pressure.
１４149 ° C./4 torr; 17 g of 8-methyl-7-nonenyl-acetoacetate having a refractive index of 1.4564 (20 ° C.)
(54% yield). This compound had hyacinth, rose, and lily of the valley odor characteristics.

Example 3 Synthesis of 8-methyl-7-nonenal diethyl acetal [compound of formula (1-c)] A 1-liter 4-diameter flask was equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. , ethyl ol preparative formic acid 231
g and 12 g of p-toluenesulfonic acid as a catalyst were added, and 185 g of 8-methyl-7-nonenal was added dropwise over about 20 minutes while stirring under ice cooling. After stirring for 1 hour under the same conditions, the mixture was neutralized with an aqueous sodium carbonate solution, washed with water, and ethanol was recovered under reduced pressure. Then, distillation under reduced pressure was performed at about 4 mmHg, and the boiling point was 109 to 110 ° C./4 torr;
249 g (91% yield) of a (20 ° C.) fraction was obtained. This compound had herbal, tomato-like and hyacinth-like odor characteristics.

[0028]

Examples 4 to 12 In the same manner as in Examples 1 to 3, ester derivatives of 8-methyl-7-nonenal and acetal derivatives of 8-methyl-7-nonenal were synthesized. Table 1 shows their physical properties, and Table 2 shows their aroma characteristics.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

Example 13 The following components (parts by weight) were mixed as a blended flavor composition of the lira type.

3 g of 8-methyl-7-nonenyl acetate was mixed with 97 g of the above composition to prepare a new compounded fragrance composition. This new prepared perfume composition and the above-mentioned lira-type prepared perfume composition to which the compound was not added were compared by 10 expert panelists. As a result, all of the 10 expert panelists added the compound to the new compounded fragrance composition, which emphasized the citrus-like aroma with a fresh, fresh green sensation. Excellent.

[0033]

Example 14 The following components (weight) were mixed as a pineapple-like compounded flavor composition.

A novel pineapple-like perfume composition was prepared by mixing 96 g of the above composition with 4 g of 8-methyl-7-nonenyl-isobutyrate. This new compounded perfume composition and the pineapple-like compounded perfume composition to which the compound was not added were compared by 10 expert panelists. As a result, the new compounded fragrance composition to which all the 10 expert panelers added the compound was found to have the characteristics of natural pineapple with a fresh green citrus-like fragrance emphasized, and was also excellent in sustainability. did.

[0035]

According to the present invention, 8-methyl-7-nonenol represented by the above formula (1), lower fatty acid esters of 8-methyl-7-nonenol, and acetal of 8-methyl-7-nonenal A novel fragrance composition containing a derivative as an active ingredient can be provided. These compounds included in the formula (1) of the present invention have flavor characteristics such as fresh green, mugue-like, citrus-like, melon-like, cucumber-like, and tomato-like. It is useful as a compounding material of a fragrance composition used for cosmetics, health, hygiene, pharmaceuticals and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI A61K 7/46 385 A61K 7/46 385 (58) Fields investigated (Int.Cl. ⁷ , DB name) C11B 9/00 A61K 7 / 46 315 A61K 7/46 365 A61K 7/46 385 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] [Claim 1] The following formula (1) In the formula, R represents a group —CH ₂ OH or —CH ₂ OCOR ¹ (wherein R ¹ represents a C1-C3 lower alkyl group) or a group (Wherein R ² represents the same C1-C3 lower alkyl group) or a group (Wherein R ³ represents hydrogen or a methyl group). A perfume composition comprising, as an active ingredient, an 8-methyl-7-nonenal derivative represented by the following formula: