JP3271785B2 - Fragrance composition containing 8-hydroxy-8-methylnonanal - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fragrance composition containing 8-hydroxy-8-methylnonanal, which is useful as a fragrance compound, as an active ingredient. More specifically, the present invention provides the following formula (1)

[0002]

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[0003] The present invention relates to a perfume composition having unique aroma characteristics, which is obtained by blending 8-hydroxy-8-methylnonanal having aroma characteristics such as fresh green and lily of the valley excellent in persistence expressed by

[0004]

2. Description of the Related Art 8-methyl-7-nonenal, which is a starting material of the compound of the formula (1), is disclosed, for example, in EP-A-423874 and JP-A-3-167148.
And the general formula R1-CH2-CH (R2)-(CH
2) one of the compounds included in n-CH = C (CH3) 2, wherein one of R1 and R2 represents a formyl group and the other represents a hydrogen atom, and n is an integer of 2 to 8; And is a known compound that is inexpensive and readily available on the market. Although the above-mentioned patent specification states that 8-methyl-7-nonenal has an aromatic property and is useful alone or for producing an aromatic composition, it does not mention specific aromatic characteristics. .

[0005]

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.

[0006]

As a result, the unsaturated bond of 8-methyl-7-nonenal, which can be obtained as a commercial product at low cost on the market and can be easily synthesized from inexpensive raw materials, can be obtained by a known method. Which is obtained by introducing a hydroxyl group by a hydration reaction of
Hydroxy-8-methylnonanal is a green flower,
The present invention has been found to have a fruit-like and flower-like fragrance, especially lily of the valley, and to be extremely useful as a fragrance, and to be excellent in stability and persistence.

Accordingly, an object of the present invention is to provide a fragrance composition containing 8-hydroxy-8-methylnonanal represented by the formula (1) as an active ingredient. Hereinafter, embodiments of the present invention will be described in detail.

The 8-hydroxy-8-methylnonanal of the present invention can be prepared by directly hydrating 8-methyl-7-nonenal or by a conventional method such as dimethylamine, diethylamine, piperidine, pyrrolidine or morpholine. The enamine obtained by refluxing in benzene with amines and removing generated water can easily lead to 8-hydroxy-8-methylnonanal by hydrating a double bond in the presence of a strong acid. Can be.

Particularly preferably, 8-methyl-7-nonenal represented by the following formula (3) is reacted with diethanolamine to form a tetrahydrooxazole derivative represented by the following formula (2), and the compound of the formula (2) Is easily reacted with a hydration reaction of a double bond in the presence of a strong acid to easily form 8 of the formula (1).
-Hydroxy-8-methylnonanal. This can be represented by a reaction formula, for example, as follows.

[0010]

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In the above reaction, the reaction of the compound of the formula (3) into the compound of the formula (2) is carried out, for example, by stirring 1 mol of the aldehyde of the formula (3) with about 1 to about 2 mol of diethanolamine while stirring at room temperature. The mixture is added little by little over a period of about 1 minute to about 1 hour, and the mixture is stirred and reacted at the same temperature for about 30 minutes to about 5 hours.

After completion of the reaction, the product is extracted by adding a solvent such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, dioxane or the like while salting out with salt or the like, followed by washing with a saturated saline solution or the like. By recovering the solvent, a crude product of the formula (2) can be obtained. This crude product may be used as it is in the next hydration reaction, but if desired, the compound of formula (2) can be obtained in high purity and high yield by purifying it by distillation, column chromatography or the like.

Next, the compound of the formula (2) is hydrated to give the compound of the formula (1)
In the reaction for synthesizing the compound of the formula, for example, the compound of the formula (2) is added dropwise over about 30 minutes to about 1 hour while cooling an aqueous solution of an inorganic acid such as sulfuric acid to about 5 to about 15 ° C. with ice water or the like. After stirring at about 0 to about 5 ° C. for about 1 to about 2 hours, solvent extraction and washing are carried out by a conventional method, and a crude product can be obtained by drying with a dehydrating agent such as sulfuric anhydride. The compound of formula (1) can be easily obtained by using, for example, chromatography.

The amount of the inorganic acid used in the above reaction is, for example, about 0.1 to about 1 to 1 part by weight of the compound of the formula (2).
A range of about 0 parts by weight is often employed.

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

[0016]

EXAMPLES Production Example 1 A 500 ml flask was charged with 50 g (324 mmol) of the aldehyde of the formula (3) and 41 g of diethanolamine [389 mmol (1.2 mmol) was stirred at room temperature.
Equivalent)] at 27-48 ° C / 30 min. After stirring at about 27 ° C. for 3 hours, 100 ml of diethyl ether and 100 ml of saturated saline were added for extraction. The ether layer was separated, washed with 100 ml of saturated saline, and dried over anhydrous magnesium sulfate. After filtration, the ether was recovered and concentrated to obtain 73.75 g of a crude product. This crude product was rectified using a 10 cm packed column, and the bp was 155 ° C./2 t.
57 g of the orr compound of formula (2) were obtained. Yield 72%. N
The purity by MR and GC-MS was 90%.

Preparation Example 2 A 500 ml flask was charged with 87 g of a 50% aqueous sulfuric acid solution, and cooled to about 10 to 15 ° C. with ice water, while 35 g of the formyl group-protected alkene of the formula (2) obtained in Preparation Example 1 was obtained.
(145 mmol) was added dropwise over about 40 minutes. After the dropwise addition, the mixture was stirred at about 5 ° C. for 1.5 hours, and then continued to be cooled.
At ２５25 ° C., 150 g of a 25% aqueous sodium hydroxide solution was added dropwise in about 30 minutes. After neutralization, 200 ml of ether was added for extraction, and the ether layer was washed twice with 200 ml of saturated saline and dried over anhydrous magnesium sulfate. After filtration, ether was recovered to obtain 28.65 g of a crude product of the compound of the formula (1).
Distilled under reduced pressure, bp 107-108 ° C / 3 torr; nD
18 g of the target compound of 1.4487 (72% yield)
I got

Example 1 The following components (parts by weight) were mixed as a lira-type blended fragrance composition.

In 97 g of the above composition, 8 obtained in Production Example 2 was added.
-Hydroxy-8-methyl-nonanal was mixed in an amount of 3 g to prepare a new prepared perfume 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.

Example 2 The following components (by weight) were mixed as a pineapple-like compounded flavoring composition.

In 96 g of the above composition, 8 obtained in Production Example 2 was added.
-Hydroxy-8-methyl-nonanal (4 g) was mixed to prepare a novel pineapple-like perfume composition. 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.

[0022]

According to the present invention, a novel fragrance composition containing 8-hydroxy-8-methylnonanal represented by the formula (1) as an active ingredient can be provided. The compound of the formula (1) of the present invention has a flavor property such as fresh green or lily of the valley, and the compound is used as a fragrance composition for use in foods and drinks, cosmetics, health, hygiene, pharmaceuticals and the like. It is extremely useful as a compounding material.

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Claims (1)

(57) [Claims] [Claim 1] The following formula (1) A fragrance composition comprising, as an active ingredient, 8-hydroxy-8-methylnonanal represented by the following formula: