JP2816775B2 - Fragrance composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to corn, cooked rice,
Sugar-like, egg-like, chicken-like, pineapple-like, tropical fruit-like, ozone-like, green-like, marine-like flavor characteristics and the following formula (1) having the persistence of these characteristics

Embedded image In the formula, R represents a C _{1 to} C ₃ alkyl group, and relates to a novel persistent fragrance composition containing 1-pyrrolines represented by the following formula as an active ingredient.

[0002]

2. Description of the Related Art 2- is included in the compound of the formula (1).
Alkyl-1-pyrrolines are all known compounds, and many reports on such compounds have been made. As a report on the production method, for example, a method of producing 1-alkanoyl-2-pyrrolidinone from 2-pyrrolidinone and acetic anhydride and treating the product with calcium oxide to synthesize 2-alkyl-1-pyrrolines [ Indian
J. Chem. , Sect. B, 27B (6), 580
1988], and a method of decarboxylating cyclic β-enamine esters with boric acid to synthesize 2-alkyl-1-pyrrolines [Tetrahedron Lett. , 28
(21), 2353-4 1987], and a method of synthesizing 2-alkyl-1-pyrrolines by heating acylpyrrolilone in the presence of magnesium oxide [Bull. Ko
Rean Chem. Soc. , 8 (3), 218 1
987] and a method of synthesizing the compound of the formula (1) by oxidatively cyclizing an aminoalkene in the presence of a palladium catalyst [J. Am. Chem. Soc. , 105 (2
3), 6877-81 1983].

However, the above-mentioned proposal only discloses a method for synthesizing the compound of formula (1), but does not mention the aroma and flavor characteristics of the compound and the use of the compound as a raw material of a compounded flavor. Not. Further, as far as the present inventors have investigated the compound of formula (1), there is no report suggesting that the compound is used as a fragrance.

[0004]

In recent years, with the diversification of foods and beverages, cosmetics, and the like, a conventionally known perfume compound alone cannot meet the demand for perfume, and there is a strong demand for a new type of perfume material that has never existed before. Is coming. In order to solve the above-mentioned demands, the present inventors have focused on a compound containing a nitrogen atom or a sulfur atom that is functionally distinctive, and have intensively studied it. As a result, the compound of the above formula (1) can be easily synthesized from inexpensive raw materials, and the compound of the formula (1)
Compounds have corn-like, cooked rice-like, sugar cane-like, egg-like, chicken-like, pineapple-like, tropical fruit-like, ozone-like, green-like, marine-like flavor and excellent persistence. The present invention has been completed by discovering that the compound of formula (1) of the present invention is extremely useful as a persistent fragrance substance, and that the compound of the formula (1) satisfies the above-mentioned requirements.

Accordingly, an object of the present invention is to provide a persistent corn-like, cooked rice-like, sugar cane-like, egg-like, chicken-like, pineapple-like, tropical fruit-like, ozone-like, green-like, and marine-like flavor. An object of the present invention is to provide a fragrance compound having characteristics. Another object of the present invention is to provide a novel fragrance composition using the compound as a preparation material. Furthermore, the present invention provides a compound of the formula (1) from inexpensive raw materials by a simple operation.
An object of the present invention is to provide a method for synthesizing with high yield and high purity.

[0006]

According to the present invention, the compound of the formula (1) can be synthesized by the above-mentioned conventionally proposed method. For example, 2-pyrrolidinone and trimethylsilyl halide of the following formula (3) can be synthesized. To produce 1- (trimethylsilyl) -2-pyrrolidinone of the formula (2) described below, and reacting the compound of the formula (2) with an alkyl lithium, whereby the compound can be easily synthesized.
2-alkyl-1- represented by the compound of the formula (1) of the present invention
When a method for synthesizing pyrrolines is shown by a reaction formula, for example, it can be represented as follows.

[0007]

Embedded image Reaction formula (A) In the formula, R represents a C ₁ -C ₃ alkyl group, and X represents a halogen atom.

A method for synthesizing the compound of formula (1) of the present invention according to the above reaction formula (A) will be described below. The compound of formula (3) in the above reaction scheme can be easily obtained on the market. In the above reaction scheme, in order to synthesize the compound of the formula (2) from the compound of the formula (3), the compound of the formula (3) is mixed with an organic solvent in an inert atmosphere such as argon in the presence of a base in the presence of trimethylsilyl halide. (Me ₃ SiX)
The reaction can be easily carried out by reacting

The above reaction can be carried out, for example, in a temperature range of about 0 ° C. to about 100 ° C., usually for about 1 hour to about 10 hours. Examples of the type of the base used in this reaction include triethylamine, tributylamine, triethanolamine, pyridine, quinoline, and the like. The amount of the base used is, for example, 1 mol of the compound of the formula (3). About 1 mol to about 10 mol can be mentioned.

The amount of trimethylsilyl halide which is a halide such as chlorine, bromine or iodine used in the above reaction is, for example, about 1 mol to about 10 mol per 1 mol of the compound of the formula (3). It can be preferably exemplified. Further, examples of the organic solvent used in this reaction include, for example, toluene, benzene, hexane, ether, tetrahydrofuran and the like.
May be about 1 to about 20 times the weight of the compound. After completion of the reaction, neutralization, washing, concentration, if necessary, for example, by using a purification means such as distillation according to a conventional method,
The compound of the formula (2) of the present invention can be obtained in high yield and high purity.

In the above reaction formula, in order to synthesize the compound of the formula (1) from the compound of the formula (2), the compound of the formula (2) is treated with an alkyl lithium (RLi) in an organic solvent under an inert atmosphere such as argon. ) Can be easily carried out. The reaction temperature is, for example, about −50 ° C. to about 30 ° C., and the reaction time varies depending on the reaction temperature.
Usually, about 0.5 to about 10 hours can be exemplified. The amount of the alkyl lithium used in this reaction can be, for example, at least equimolar, preferably about 1 mol to about 2 mol, per 1 mol of the compound of the formula (2). Further, as the organic solvent, for example, ether, toluene, hexane, tetrahydrofuran and the like can be exemplified,
The amount of the solvent used is, for example, based on the compound of the formula (2).
It may be about 1 to about 50 times by weight. After completion of the reaction, the compound of the formula (1) of the present invention can be obtained in good yield and good purity by neutralizing, washing, concentrating and, if necessary, using purification means such as distillation. it can.

The compounds of the formula (1) of the present invention which can be obtained as described above are corn-like, cooked rice-like, sugar cane-like, egg-like, chicken-like, pineapple-like, tropical fruit-like, ozone-like. It has green-like and marine-like aroma characteristics, and has extremely excellent persistence, and can be used by being added to various flavor compositions. The amount of the compound of the formula (1) varies depending on the purpose or the type of the fragrance composition, but, for example, is generally about 0.001 to about 3 with respect to the total amount of the fragrance composition.
A range of about 0% by weight can be exemplified.

Thus, according to the present invention, the above formula (1)
A novel fragrance composition imparting aroma and flavor characteristics comprising a compound of the formula (I) as an active ingredient can be provided, and the composition of the present invention contains the compound of the formula (1) as a fragrance and flavor component using the composition. Provided are cosmetics characterized by containing the compound of the formula (1) as an aroma component, and health, hygiene and pharmaceutical products characterized by containing the compound of the formula (1) as an aroma component. be able to.

For example, drinks such as fruit juice drinks, fruit liquors, milk drinks and carbonated drinks; ice creams, sorbets, and ice confections such as popsicles; Japanese and Western confections, jams, chewing gums, and breads Luxury items such as coffee, cocoa, black tea, tea; soups such as Japanese soups and Western soups; flavoring seasonings, various instant drinks or foods, various snack foods, etc., can be imparted with its unique aroma and flavor. Foods and drinks to which an appropriate amount is added can be provided. Also, for example, shampoos, hair creams, pomades, and other hair cosmetic bases; oscilloscopes, lipsticks, other cosmetic bases, cosmetic detergent bases, and the like, which can impart a unique fragrance to the base. It is possible to provide cosmetics with an added amount. 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 Reference Examples and Examples.

[0015]

【Example】

Reference Example 1 Synthesis of 1- (trimethylsilyl) -2-pyrrolidinone [compound of formula (2)]. A reaction flask is charged with 17 g (0.2 mol) of 2-pyrrolinone, 25 g (0.25 mol) of triethylamine and 200 ml of toluene. Under an argon stream, 23.9 g (0.22 mol) of trimethylsilyl chloride was added to 25
The mixture was added dropwise at 40 ° C. and reacted at 40 ° C. with stirring for 4 hours.
After completion of the reaction, the reaction product was cooled to 0 ° C.
Dilute with 200 ml of a mixed solvent of ether = 1: 1. After filtering the diluted solution through celite, the obtained filtrate is concentrated by an evaporator, and the residue is distilled under reduced pressure to obtain 30 g of a compound of the formula (2). Boiling point: 90 ° C / 20mm
Hg. Yield: 95%.

[0016]

Reference Example 2 Synthesis of 2-methyl-1-pyrroline [compound of formula (1)]. Under a stream of argon, 38.2 ml (0.057 mol) of a 1.5 M methyllithium ether solution is charged into a reaction flask, and cooled to -20 ° C. The flask was then charged with 1- (trimethylsilyl) -2-pyrrolidinone 8.17.
g (0.052 mol) in 60 ml of an ether solution are added dropwise. After the dropwise addition, the mixture was reacted with stirring at -20 ° C for 30 minutes and at 25 ° C for 1 hour, and then 2.7 g of ammonium chloride was added.
Of water, and stirred at 25 ° C. for 30 minutes. The ether layer is washed with brine, dried over magnesium sulfate, and distilled under normal pressure to obtain 3.9 g of the compound of the formula (1). Boiling point: 105 ° C. Yield: 90%.

According to the above synthesis method, 1- (trimethylsilyl) -2-pyrrolidine is reacted with the corresponding alkyllithium to give 2-ethyl-1-pyrroline, 2-ethyl-1-pyrroline contained in the compound of the formula (1). Isopropyl-1-pyrroline,
2-Propyl-1-pyrroline was produced.

[0018]

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

A novel blended flavor composition was prepared by mixing 2 g of 2-methyl-1-pyrroline with 98 g of the above composition. About the new prepared perfume composition and the above-mentioned lira-type prepared perfume composition to which the compound has not been added, a specialized panelist 1
Compared by 0 people. As a result, all of the 10 specialized panelists added the compound to the new compounded fragrance composition, which emphasized the green-like fragrance with a nachoral sensation. I said

[0020]

Example 2 According to the method of Example 1, 2-methyl-1
2 included in the compound of formula (1) instead of pyrroline
-Ethyl-1-pyrroline, 2-isopropyl-1-pyrroline and 2-propyl-1-pyrroline were added and their changes in odor were compared and examined. As a result, as in Example 1, all of the ten specialized panelists added the compound of formula (1) of the present invention to the newly prepared perfume composition as compared to the prepared perfume composition to which the compound was not added. Fragrance is emphasized,
The characteristics of natural lyre are captured and it is said that it is much better in terms of sustainability.

[0021]

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

In 97 g of the above composition, 2-methyl-1-pyrroline and 2-ethyl-1- included in the compound of the formula (1).
Pyroline, 2-isopropyl-1-pyrroline and 2-
Propyl-1-pyrroline was added to compare the change in the odor. As a result, all of the 10 specialized panelists added the compound of formula (1) of the present invention to the novel compounded fragrance composition.
The pineapple-like aroma is emphasized as compared with the compounded fragrance composition to which the compound is not added, and the characteristics of natural pineapple are taken into account, and it is considered that the pineapple is remarkably superior in terms of sustainability.

[0023]

According to the present invention, 1 represented by the formula (1)
-It is possible to provide a novel fragrance composition containing a pyrroline as an active ingredient. The compound of formula (1) of the present invention has corn-like, cooked rice-like, sugar cane-like, egg-like, chicken-like, pineapple-like, tropical fruit-like, ozone-like, green-like, and marine-like flavor characteristics. The compound is a food or drink,
It is useful as a compounding material of a fragrance composition used for cosmetics, health, hygiene, pharmaceuticals and the like.

Continued on the front page (58) Fields investigated (Int.Cl. ⁶ , DB name) C11B 9/00 A23L 1/226 A61K 7/46 435 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] [Claim 1] The following formula (1) In the formula, R represents a C _{1 to} C ₃ alkyl group. A fragrance composition comprising 1-pyrrolines represented by the following formula as an active ingredient: