JPH0491087A - 3,7-decadien-5-olide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (the wavy line is cis or trans isomer). EXAMPLE:cis-3-cis-7-Decadien-5-olide. USE:A perfumery substance. Useful for drinks, fancy foods, soups, foods, base for hair cosmetics such as shampoos, base for cosmetics such as face powder, washing detergent, etc. PREPARATION:The objective compound can be produced by isomerizing cis-2- cis-7-decadien-5-olide or cis-2-trans-7-decadien-5-olide of formula II in the presence of lithium diisopropylamine and hexamethylphosphoric acid triamide preferably at-120 to 0 deg.C for 0.5-5hrs.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a cis-3-cis-7-zocadien-5-olide represented by the following formula (A) which is useful as a fragrance substance that has not been described in conventional literature. and milk-like, butter-like, fruit-like, peach-like, apricot-like, pineapple-like, 70-ral-like, which are included in the above formula (A) and have a green feeling with a slight sweetness.
It relates to a 3-transdecadiene-5-olide represented by the following formula (A)-2 having a jasmine-like aroma, etc. The wavy line indicates a cis- or trans-isomer.

(Prior art) δ-lactones (5-olides) are important components of mixed fragrances, such as cis-7-decene-5-olide (common name: jasmine lactone), 2-decene-5-olide (common name:
Masoyalactone) etc. have been commonly used. Further, research on δ-lactones is being actively conducted, and many reports have been proposed.

Among these proposals, δ-lactones having a structure similar to the compound of formula (A) of the present invention include, for example, 3,7-dimethyl-lactones having maple-like, shugo-like, walnut-like, and jasmon-like aroma characteristics. 6-octene-5
3,7-dimethyl-2,6-octadiene-5-olide (Japanese Unexamined Patent Publication No. 63-316719), which has maple-like, 70-ral-like, and green-like aromas. 9-decene-5-olide having a butter-like aroma (JP-A-56-2)
No. 2722) and the like are known.

(Problems to be Solved by the Invention) However, the above-mentioned conventionally proposed δ-lactones are not necessarily satisfactory in terms of fragrance or fragrance sustainability, and there are problems to be solved.

Therefore, the present inventors conducted intensive research to solve the above problems, and found that it is possible to provide a compound of the formula (A) that has excellent fragrance or fragrance persistence and has not been described in conventional literature. , and the formula (A) included in the above formula (A)
-1 compound has a milk-like, butter-like, fruit-like, peach-like, apricot-like, pineapple-like, 70-ral-like, jasmine-like aroma with a persistent green feeling, and furthermore, the compound of formula (A) Compounds of formula (A)-2 include milk-like, butter-like, fruit-like, peach-like, apricot-like, pineapple-like, floral-like, jasmine-like, etc. with a persistent green feeling and a slight sweetness. They discovered that it has an aromatic aroma and is extremely useful as a fragrance substance, and completed the present invention.

It is therefore an object of the present invention to provide a conventional flavor material useful as a milky, buttery, fruity, peach-like, apricot-like, pineapple-like, 70-ral-like, jasmine-like flavoring substance with a persistent green feel. The object of the present invention is to provide a compound of the formula (A) that has not been described in the literature.

(Means for Solving the Problems) According to the present invention, the compound of formula (A) is obtained by converting 2,7-zocadien-5-olide represented by formula (B) below into lithium diisopropylamide ( (hereinafter referred to as LDA) and hexamethylphosphoric acid triamide (hereinafter referred to as H
It can be easily synthesized by carrying out an isomerization reaction in the presence of MPA (referred to as MPA).

The method for synthesizing the compound of formula (A) that can be obtained in the present invention can be expressed, for example, as shown below using a reaction formula.

(Blank below) (B) (A) The wavy line indicates the /su or trans isomer. The method for synthesizing the compound of formula (A) of the present invention will be described in detail below according to the above reaction formula.

The compound of formula (B) which is the starting material is cis-2-7
-decadiene-5-olide [hereinafter referred to as compound (B)-1] and cis-2-trans-fuzocadien~5-olide [hereinafter referred to as compound (B)2] There is. These compounds are known and can be easily synthesized by the invention (Japanese Patent Application Laid-Open No. 63-215676) of the same applicant as the present invention. That is, the formula CB)-1
The compound of formula (B)-2 is a commercially available jasmine lactone, and the compound of formula (B)-2 is a trans-7
-Decene-5-olide is reacted with chlorotrimethylsilane in the presence of LDA to produce 2-trimethylsilyloxy-
6-(cis- or trans-2-pentenyl)-5,
It can be prepared by forming 6-cyhydropyran and then contacting the product with allylmethyl carbonate in a palladium acetate catalyst.

The above isomerization reaction is preferably carried out at a low temperature, for example, in a temperature range of about -120°C to about 0°C for about 0°5 hours to
The reaction can be carried out for about 5 hours.

The amount of LDA used in the above reaction is, for example, formula (B)
The amount may range from about 0.5 mol to about 5 mol per mol of the compound. In addition, the amount of HMPA used can be calculated using the formula (
A range of about 0.1 mol to about 5 mol can be adopted per 1 mol of the compound B).

Examples of the types of organic solvents used in this reaction include:
Examples include tetrahydrofuran and diethyl ether. The amount of these organic solvents to be used is not particularly limited, but generally ranges from about 1 to about 50 times the weight of the compound of formula (B).

After the reaction is completed, the compound of formula (A) can be obtained in good yield and purity by washing, drying, concentrating, and further purifying means such as vacuum distillation and column chromatography according to conventional methods. .

The compound of formula (A) that can be obtained as described above has milk-like, butter-like, fruit-like,
It has peach-like, apricot-like, pineapple-like, 70-ral-like, and jasmine-like aromas, and it also has extremely long-lasting properties, so it can be used by adding it to various fragrance compositions. . The amount of the compound of formula (A) to be added varies depending on the purpose or the type of perfume composition, but for example, it is about 0.001 to 100% of the total amount of the perfume composition.
A range of about 30% by weight can be exemplified.

Thus, according to the present invention, it is possible to provide an aroma and flavor imparting composition containing the compound of the formula (A) as an active ingredient, and to use the composition, the compound of formula (A) can be used as an aroma and flavor component. Food and drink products characterized by containing the compound of formula (A) as an aroma component; aroma products characterized by containing the compound of formula (A) as an aroma component; Health, hygiene, medicine, etc. can be provided.

For example, beverages such as fruit juice drinks, fruit alcoholic drinks, milk drinks, carbonated drinks; ice creams, sharpettes,
Frozen desserts such as popsicles; Japanese and Western sweets, jams, chewing gums, breads, coffee, cocoa,
Appropriate amounts are added to black tea and tea-like luxury goods: soups such as Japanese-style soups and Western-style soups, flavor seasonings, various instant beverages and foods, and various snack foods to impart their unique aroma and flavor. Food and beverages can be provided. In addition, it is suitable for imparting a unique fragrance to, for example, shampoos, hair creams, pomades, and other hair cosmetic bases; We can provide cosmetics with added amounts. In addition, we can provide laundry detergents, disinfectant detergents, room air fresheners, and various other health and hygiene materials; health, hygiene, and pharmaceutical products such as flavorings and flavoring agents to make it easier to take medicines. .

The present invention will be described in more detail below with reference to Examples and Reference Examples.

(Example) Example 1 A solution of n-butyllithium in n-hexane was placed in a 50 ml flask purged with argon gas. Charge Omfl (3.0 mmol) and 75 ml of dry tetrahydrochloride. While cooling the flask with dry ice-acetone, a solution of 360 mg (3.6 mmol) of diisopropylamine in 3 mQ of dry tetrahydrofuran was added to 30 mQ of dry tetrahydrofuran.
'(1!~-20'0°C. Dropped over 5 minutes. After dropping, stir for 1 hour while cooling to -20'0~-10°C to prepare LDA. In this solution, add LDA at -20°C ~-1O℃
A solution of 540 mg (3.0 mmol) of HMPA in 3 ml of dry tetrahydrofuran was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 1 hour. Next, liquid nitrogen-acetone (
While cooling at ~100°C ~ -90°C), formula (B)-1
A solution of 500 mg (3 mmol) of the compound in 3 mQ dry tetrahydrofuran is added dropwise over 10 minutes. After the dropwise addition, the mixture was further stirred at the same temperature for 40 minutes to react.

After the reaction is completed, the reactant is poured into a saturated aqueous ammonium chloride solution, and the tetrahydrofuran layer is separated. This tetrahydro-7 run layer is washed with hydrochloric acid, brine, dried over magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silicage gel chromatography (n-hexane/ethyl acetate = 7/l) to obtain pure formula (A)-
280 mg (yield: 56%) of compound No. 1 was obtained. The structure was confirmed by MS, TR, and NMR.

Least point: 114-116°073 mmHg Example 2 In Example 1, the compound of formula (B)-1 was replaced with the compound of formula (B)-
In the same manner as in Example 1 except that the compound of formula (2) was used, formula (
A)-2 compound was synthesized.

Yield: 54% Boiling point: 1I3-116°C/3 mm Hg (Reference example) Reference example 1 The following components (parts by weight) were mixed as a Lira type blended fragrance composition.

Phenylethyl acetate IO cinnamic alcohol 40 terpineol
130 N clamen aldehyde
lO heli otropine
50 cinnamyl acetate lO carnation 20 linalool 30 indole
2 Steel lux resinoid
30 ylang ylang
IO Hydroxycitronellal 290 Benzyl Acetate 20 Anisaldehyde 20 Absolute Diasmine 20 Phenylethyl Alcohol
278 Anise Alcohol 30
Total: 1000 A novel straw-like blended fragrance composition was prepared by mixing 7 g of the compound of formula (A)-1 with 93 g of the above composition. This novel blended fragrance composition and the above-mentioned Lila blended fragrance composition to which the compound was not added were compared by a panel of 10 experts. As a result, all 10 expert panelists agreed that the new blended fragrance composition containing the compound had an accentuated green floral aroma, captured the characteristics of natural lyra, and was significantly superior in terms of sustainability. .

In addition, when the compound of formula (A)-1 was added to various types of perfume compositions other than the lira type, such as gardenia, osmanthus, and jasmine, the same results as above were obtained.

Reference Example 2 The aroma was compared by ten expert panelists in the same manner as Reference Example 1 except that the compound of formula (A)-1 was replaced with the compound of formula (A)-2. As a result, all 10 expert panelists found that the newly formulated fragrance composition to which the compound was added had a green floral-like aroma with a slight sweetness, and that it captured the characteristics of natural Lira and had a long-term sustainability point. But I think it's much better.

Furthermore, the same effects as described above were confirmed for various types of blended fragrance compositions other than the Lila type, such as gardenia, osmanthus, and jasmine.

Reference Example 3 A pineapple-like blended fragrance composition was prepared and each of the following ingredients (
weight) were mixed.

Ethyl acetate 300 Ethyl butyrate 250 The above composition 96g
A novel pineapple-like blended fragrance composition was prepared by mixing 4 g of the compound of formula (A)-1 with the following. This novel blended fragrance composition and the above-mentioned pineapple-like blended fragrance composition to which the compound was not added were compared by a panel of experts. As a result, exclusive! A new blended fragrance composition in which all Fupiler IO people added the isoamyl acetate, isoamyl valerate, isobutyric acid, isovaleric acid, allyl caproate, ethyl caproate, ethyl caprylate, ethyl caprate, isoamyl alcohol, diethyl malone, toral, linalool, maltol compound. It captures the characteristics of natural pineapple, which emphasizes the fresh, fruity aroma, and is said to be extremely long-lasting.

In addition, when the compound of formula (A)-1 was added to various types of mixed flavor compositions such as peach, strawberry, apricot, milk, and butter other than pineapple type,
Results similar to those above were obtained.

Reference Example 4 The aroma was compared by 10 expert panelists in the same manner as Reference Example 3 except that the compound of formula (A)-1 was replaced with the compound of formula (A)-2. As a result, all 10 expert panelists agreed that the new fragrance composition to which the compound was added had the characteristics of natural pine oak with an emphasis on the fresh, fruity aroma, and was significantly superior in terms of sustainability. .

Furthermore, the same effects as described above were confirmed for various types of blended flavor compositions other than the pineapple type, such as peach, strawberry, apricot, milk, and butter.

(Effects of the Invention) The present invention provides a 3,7-zocadien-5-olide represented by the formula (A) that has not been described in conventional literature.

The compound of formula (A) has a persistent green feeling or a milk-like, butter-like, green feeling with a slight sweetness.
It has fruit-like, peach-like, apricot-like, pineapple-like, floral, and jasmine-like aromas, and is useful as a fragrance substance.

Patent applicant: Hasegawa Fragrance Co., Ltd.

Claims (1)

[Claims] 1. The following formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) Wavy lines indicate cis- or trans-isomers, 3,7-decadiene-5-olide represented by