JP2794331B2 - 3,7-decadiene-5-olides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a compound represented by the following formula (A) useful as a fragrance substance not described in a conventional literature. The wavy lines indicate cis- or trans-isomers, and relate to 3,7-decadiene-5-olide represented by

More specifically, the present invention is included in the above formula (A) and has a scent such as milk-like, butter-like, fruit-like, peach-like, apricot-like, pineapple-like, floral-like, jasmine-like with a green feeling. Formula (A) -1 Cis-3-cis-7-decadiene-5-olide represented by the formula: and milk-like, butter-like, fruit-like, peach-like, apricot, which are included in the above formula (A) and have a slight greenish sweetness. Formula (A) -2 having aroma such as pineapple-like, floral-like, jasmine-like Cis-3-trans-7-decadiene-5 represented by the formula:
About Orido.

(Prior Art) δ-Lactones (5-olides) are important components of compounded fragrances, for example, cis-7-decene-5-olide (commonly known as jasmine lactone) and 2-decene-5-olide (commonly known). : Masoyalactone) and the like have been widely used. Research on δ-lactones has also been actively conducted, and many reports have been proposed.

Among these proposals, δ-lactones similar in structure to the compound of the formula (A) of the present invention include, for example, 3,7- having maple-like, sugar-like, walnut-like and jasmon-like aroma characteristics. Dimethyl-6-octene-5
-Oride (Japanese Patent Laid-Open No. 63-60982) and 3,7 having a fragrance such as maple, floral, green, etc.
-Dimethyl-2,6-octadiene-5-olide (JP-A-6
No. 3-316719), and 9- which has a butter-like odor.
Decene-5-olide (JP-A-56-22722) is known.

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

Thus, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, can provide a compound of the formula (A) which is excellent in aroma or persistence of the aroma and which is not described in the conventional literature. And a compound of the formula (A) -1 included in the formula (A), which has a persistent green feeling with milk-like, butter-like, fruit-like, peach-like, apricot-like, pineapple-like, floral-like, Aroma such as jasmine, etc., and formula (A)-included in formula (A) above
Compound 2 has a fragrance such as milk-like, butter-like, fruit-like, peach-like, apricot-like, pineapple-like, floral-like, jasmine-like, etc., with a sustained green feeling and slightly sweetness. The present invention has been found to be extremely useful and has been completed.

Therefore, the object of the present invention is to provide a conventional literature useful as a fragrance substance of milk-like, butter-like, fruit-like, peach-like, apricot-like, pineapple-like, floral-like, jasmine-like with a persistent green feeling. The object of the present invention is to provide an undescribed compound of the formula (A).

(Means for Solving the Problems) According to the present invention, a compound of the formula (A) is represented by the formula (B)
In an organic solvent, 2,7-decadiene-5-olides represented by the formula: lithium diisopropylamide (hereinafter, referred to as LDA) and hexamethylphosphoric triamide (hereinafter, HMPA)
) In the presence of isomerization reaction.

The method of synthesizing the compound of the formula (A) obtainable by the present invention can be represented, for example, by the following reaction scheme.

The wavy lines indicate cis- or trans-isomers. 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 starting compound of the formula (B) is cis-2-cis-7-decadiene-5-olide [hereinafter referred to as the compound of (B) -1] and cis-2-trans-7-decadiene-5. -Olide [hereinafter referred to as compound (B) -2]. These compounds are known and can be easily synthesized by the invention of the same applicant as the present invention (JP-A-63-215676). That is, the compound of formula (B) -1 is a commercially available jasmine lactone, and the compound of formula (B) -2 is trans-7-
Decene-5-olide is reacted with chlorotrimethylsilane in the presence of LDA to give 2-trimethylsilyloxy-6-
It can be prepared by producing (cis- or trans-2-pentenyl) -5,6-dihydropyran and then contacting the product with allylmethyl carbonate in a palladium acetate catalyst.

The above-mentioned 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 about 5 hours.

The amount of LDA used in the above reaction is determined, for example, by the formula (B)
May be in the range of about 0.5 mol to about 5 mol per 1 mol of the compound. The amount of HMPA used can be in the range of about 0.1 mol to about 5 mol per 1 mol of the compound of the formula (B).

Examples of the type of the organic solvent used in this reaction include tetrahydrofuran, diethyl ether and the like. The amount of the organic solvent to be used is not particularly limited, but is generally about, for example, about 1 to about 50 times the weight of the compound of the formula (B).

After completion of the reaction, the compound of the formula (A) can be obtained in good yield and good purity by using purification means such as washing, drying and concentration, and further, distillation under reduced pressure and column chromatography in accordance with a conventional method. .

The compound of the formula (A) obtainable as described above has a milky, buttery, fruity, peachy, apricot, pineapple, floral, jasmine-like odor with a green sensation. Furthermore, it has extremely excellent persistence, and can be used by being added to various flavor compositions. The amount of the compound of the formula (A) varies depending on the purpose or the type of the fragrance composition.
A range of about 30% by weight can be exemplified.

Thus, according to the present invention, it is possible to provide a fragrance and flavor imparting composition containing the compound of the formula (A) as an active ingredient, and the compound of the formula (A) is used as the fragrance and flavor component by using the composition. Food or drink characterized by containing, formula (A)
And a health, hygiene and pharmaceutical product characterized by containing the compound of formula (A) as a flavor component.

For example, beverages such as fruit juice beverages, fruit liquors, milk beverages, carbonated beverages; ice creams, sorbets, frozen desserts such as popsicles; Japanese and Western confectionery;
Jams, chewing gums, breads, coffee, cocoa, black tea, tea and other luxury goods; soups such as Japanese soups and Western soups; flavor seasonings, various instant drinks and foods, various snack foods, etc. Foods and drinks to which an appropriate amount capable of imparting the unique flavor can be provided. Also, for example, shampoos, hair creams, pomades, and other hair cosmetic bases;
It is possible to provide cosmetics obtained by adding an appropriate amount capable of imparting a unique fragrance to oscilloscope, lipstick, other cosmetic bases, cosmetic detergent bases, and the like. Furthermore, laundry, disinfecting detergents, room air fresheners and various other health and hygiene materials; health, hygiene and medicines such as flavoring and flavoring agents to facilitate taking of medicines can be provided. .

Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples.

Examples Example 1 Synthesis of cis-3-cis-7-decadiene-5-olide [compound of formula (A) -1].

A 50 ml flask purged with argon gas is charged with 2.0 ml (3.0 mmol) of an n-hexane solution of n-butyllithium and 5 ml of dry tetrahydrofuran. While cooling the flask with dry ice-acetone, a solution of 360 mg (3.6 mmol) of diisopropylamine in 3 ml of dry tetrahydrofuran is added dropwise at -30 ° C to -20 ° C for 5 minutes. After the dropwise addition, the mixture is stirred for 1 hour while further cooling to -20 ° C to -10 ° C to prepare LDA. In this solution, −20 ° C. to −10 ° C., 5
In a minute, a solution of 540 mg (3.0 mmol) of HMPA in 3 ml of dry tetrahydrofuran is added dropwise and stirred at the same temperature for another hour. Next, liquid nitrogen-acetone (-100 ° C to -90 ° C)
While cooling with, a solution of 500 mg (3 mmol) of the compound of formula (B) -1 in 3 ml of dry tetrahydrofuran is added dropwise over 10 minutes. After the dropwise addition, the mixture is further reacted by stirring at the same temperature for 40 minutes.

After completion of the reaction, the reaction product is poured into a saturated aqueous solution of ammonium chloride, and the tetrahydrofuran layer is separated. The tetrahydrofuran layer is washed with aqueous hydrochloric acid, washed with brine, dried over magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 7/1) to give pure formula (A)-
280 mg (yield: 56%) of compound 1 was obtained. The structure is MS, I
It was confirmed by R and NMR.

Boiling point: 114-116 ° C / 3 mmHg Example 2 Synthesis of cis-3-trans-7-decadiene-5-olide [compound of formula (A) -2].

In Example 1, the compound of the formula (B) -1 was replaced with the compound of the formula (B)
Compound of formula (A) -2 was synthesized in the same manner as in Example 1, except that compound of formula (A) -2 was used.

Yield: 54% Boiling point: 113 to 116 ° C./3 mmHg (Reference Example) Reference Example 1 The following components (parts by weight) were mixed as a lira-type compounded flavor composition.

Phenylethyl acetate 10 Cinnamic alcohol 40 Terpineol 130 Cyclamenaldehyde 10 Heliotropin 50 Cinnamyl acetate 10 Carnation 20 Linalool 30 Indole 2 Styrax resinoid 30 Ylang ylang 10 Hydroxysiloneral 290 Benzyl acetate 20 Anisaldehyde 20 Absolute jasmine 20 Phenyl ethyl alcohol 278 Anise alcohol 30 in total 1000 7 g of the compound of the formula (A) -1 was mixed with 93 g of the above composition to prepare a novel lira-like compounded fragrance composition. This new prepared perfume composition and the above-mentioned lira 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 determined that the new compounded fragrance composition containing the compound emphasized the green floral-like fragrance, captured the characteristics of natural lyre, and was significantly superior in terms of sustainability.

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

Reference Example 2 The aroma was compared by 10 expert panelists in the same manner as in Reference Example 1 except that the compound of the formula (A) -1 was changed to the compound of the formula (A) -2. As a result, all of the 10 specialized panelists added the compound to the new compounded fragrance composition, which emphasized the green floral-like scent with slightly added sweetness, and captured the characteristics of natural lyre and also in terms of sustainability. It was markedly superior.

In addition, effects similar to those described above were confirmed for various types of compounded fragrance compositions such as gardenia, osmanthus, and jasmine other than the lira type.

Reference Example 3 The following components (weight) were mixed as a pineapple-like compounded flavor composition.

Ethyl acetate 300 Ethyl acetate 250 Isoamyl acetate 100 Isoamyl valerate 55 Isobutyric acid 70 Isovaleric acid 30 Allyl caproate 35 Ethyl caproate 20 Ethyl caprylate 15 Ethyl caprate 20 Isoamyl alcohol 35 Diethyl malonate 30 Citral 15 Linalool 5 Maltol 20 1000 4 g of the compound of the formula (A) -1 was mixed with 96 g of the above composition to prepare a novel pineapple-like compounded flavoring composition. A panelist specializing in this novel compounded fragrance composition and the pineapple-like compounded fragrance composition not containing the compound.
Compared by 10 people. As a result, all of the 10 expert panelists added the compound to the new compounded fragrance composition, which assumed the characteristics of natural pineapple with a fresh fruit-like aroma emphasized, and that it was significantly superior in terms of sustainability. .

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

Reference Example 4 The effect was compared by 10 expert panelists in the same manner as in Reference Example 3 except that the compound of the formula (A) -1 was changed to the compound of the formula (A) -2. As a result, all of the 10 expert panelists said that the newly prepared perfume composition to which the compound was added was significantly superior in terms of sustainability by capturing the characteristics of a natural pineapple with a fresh fruit-like aroma emphasized. .

In addition, effects similar to those described above were confirmed for various types of compounded fragrance compositions such as peach, strawberry, apricot, milk, and butter other than the pineapple type.

(Effects of the Invention) The present invention is to provide 3,7-decadiene-5-olides represented by the formula (A), which is not described in the conventional literature.

The compound of the formula (A) has a long-lasting green feeling or a slightly greenish sweetness such as milk-like, putter-like, fruit-like, peach-like, apricot-like, pineapple-like, floral-like, jasmine-like, etc. It has an aroma and is useful as a fragrance substance.

Continuation of front page (56) References JP-A-3-59564 (JP, A) JP-A-63-215676 (JP, A) JP-A-63-222164 (JP, A) JP-A-63-57583 (JP, A) JP-A-57-188584 (JP, A) Patent 2639746 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 309/32 C11B 9/00 A61K 7/46 REGISTRY (STN) CA (STN)

Claims (1)

(57) [Claims] 1. The following formula (A) The wavy lines indicate cis- or trans-isomers, 3,7-decadiene-5-olides represented by