JP2005281628A - Fragrance composition or flavor composition - Google Patents

Abstract

（式中、Ｒ^１及びＲ^２は、互いに同一または異なるメチル基又はエチル基である。）
で表される３級メルカプトエーテルの１種又は２種以上を含有することを特徴とするフレグランス組成物及び香料成分として、下記の一般式（２）：
【化２】

（式中、Ｒ^３は、エチル基であり；Ｒ^４は、メチル基又はエチル基である。）
で表される３級メルカプトエーテルの１種又は２種以上を含有することを特徴とするフレーバー組成物。
【選択図】 なし

PROBLEM TO BE SOLVED: To provide a fragrance composition or a flavor composition having high palatability, excellent in aroma, richness, depth and the like and can be effectively used for aroma and flavoring to various products.
As a fragrance component, the following general formula (1):
[Chemical 1]

(In the formula, R ¹ and R ² are the same or different methyl or ethyl groups.)
As a fragrance composition and a fragrance component characterized by containing one or more of the tertiary mercapto ethers represented by the following general formula (2):
[Chemical 2]

(In the formula, R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group.)
The flavor composition characterized by including the 1 type (s) or 2 or more types of the tertiary mercapto ether represented by these.
[Selection figure] None

Description

  The present invention relates to a novel tertiary mercapto ether, a process for producing the same, a fragrance composition or flavor composition containing the tertiary mercapto ether, and a fragrance or flavoring using the tertiary mercapto ether or fragrance composition or flavor composition. Related to the product.

  In recent years, with the diversification of various foods and beverages, cosmetics, and health and hygiene materials, there has been an increasing new demand for fragrance compositions or flavor compositions used for aroma or flavoring. The fragrance or flavor component is particularly required to have impact, to have a unique aroma and flavor with high palatability, and to be excellent in blendability with other fragrances used in combination. Therefore, the development of a fragrance or flavor material having these requirements has become a very important issue in the perfume industry.

  Some sulfur-containing compounds have a low threshold, a characteristic strong odor, and many are known as fruit-like or other key aroma components having aroma or flavor. For example, among the chained β-mercaptoethers, 4-methoxy-2-methyl-2-butanethiol is a component of the 1958 Food Additive Improvement Method of the Expert Panel of the Flavor and Extract Manufacturers Association (FEMA). It is known as a flavor component determined as GRAS in the examination of a flavor component for evaluation of a GRAS (usually recognized as safe) state (Non-patent Document 1). In addition, with regard to 4-methoxy-2-methyl-2-butanethiol, it is possible to obtain a soft and plump green scent of freshly added green tea by using a very small amount as an additive for tea beverage. It has been reported (see Patent Document 1).

However, the above-described conventional sulfur-containing compounds used as flavoring components are not monotonous in terms of aroma and flavor quality and strength, and are still not sufficient in terms of texture, richness, etc. In the diversified flavoring products, it was not able to respond sufficiently to the deep texture, richness and other demands.
On the other hand, there has been no report on the application of β-mercaptoethers to fragrance applications.

Food Technology-June 1993, 103-104, 106, 108, 112, 114, 116-117 Japanese Patent No. 3026436 “J. Org. Chem.”, 1961, Vol. 26, p 1768-1772 Arctander S. , “Perfume and Flavor Chemicals”, published by the author, Montclair, N .; J. et al. (U.S.A.) 1969

  An object of the present invention is a fragrance composition that can satisfy the demands of diversifying fragrance products, has high palatability, is excellent in fragrance, richness, depth, etc., and is useful for aroma or flavoring. It is to provide a flavor composition and a product scented or flavored using it.

  As a result of intensive studies to meet the above-mentioned demands, the present inventors have found that tertiary mercapto ether having a specific structure or a fragrance or flavor composition containing the same is useful for aroma or flavoring of various products. Of these, the present invention was completed by finding that it is particularly useful for aroma or flavoring of tea-based foods and beverages such as tea beverages.

That is, the present invention
(1) As a fragrance component, the following general formula (1):

（式中、Ｒ^１及びＲ^２は、互いに同一または異なるメチル基又はエチル基である。）
で表される３級メルカプトエーテルの１種又は２種以上を含有することを特徴とするフレグランス組成物；

(In the formula, R ¹ and R ² are the same or different methyl or ethyl groups.)
A fragrance composition comprising one or more of the tertiary mercaptoethers represented by:

(2) The tertiary mercapto ether represented by the general formula (1) is 4-methoxy-2-methyl-2-butanethiol, 4-ethoxy-2-methyl-2-butanethiol, 5-methoxy-3- The fragrance composition according to item 1, which is one or more selected from methyl-3-pentanethiol and 5-ethoxy-3-methyl-3-pentanethiol;

(3) One or more of the tertiary mercapto ethers represented by the general formula (1) is used at a concentration of 1 * 10 ^{−6 to} 5 * 10 ⁻³ mass% with respect to the fragrance composition. The fragrance composition according to item 1 or 2, characterized in that:

(4) Fragrance products, basic cosmetics, finished cosmetics, hair cosmetics, tanning cosmetics, medicinal cosmetics, hair care products, which are given fragrance by the fragrance composition according to any one of items 1 to 3. Products with aromas selected from soaps, body cleaners, bath preparations, detergents, softeners, detergents, kitchen detergents, bleaches, aerosols, deodorants / fragrances or miscellaneous goods;

(5) As a fragrance ingredient, the following general formula (2):

（式中、Ｒ^３は、エチル基であり；Ｒ^４は、メチル基又はエチル基である。）
で表される３級メルカプトエーテルの１種又は２種以上を含有することを特徴とするフレーバー組成物；

(In the formula, R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group.)
A flavor composition comprising one or more of the tertiary mercaptoethers represented by:

(6) The tertiary mercapto ether represented by the general formula (2) is selected from 5-methoxy-3-methyl-3-pentanethiol and 5-ethoxy-3-methyl-3-pentanethiol, or 6. The flavor composition according to item 5, which is two or more types;

(7) One or more of the tertiary mercapto ethers represented by the general formula (2) is used at a concentration of 1 * 10 ⁻⁷ to 1 * 10 ⁻¹ mass% with respect to the flavor composition. Item 5. The flavor composition according to Item 5 or 6, wherein

(8) A flavored product selected from foods and drinks, oral compositions or pharmaceuticals, which is flavored by the flavor composition according to any one of Items 5 to 8;

(9) The following general formula (2):

（式中、Ｒ^３は、エチル基であり；Ｒ^４は、メチル基又はエチル基である。）
で表される３級メルカプトエーテル；

(In the formula, R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group.)
A tertiary mercapto ether represented by:

(10) The following general formula (3):

（式中、Ｒ^３は、エチル基であり；Ｒ^５は、炭素数１〜４のアルキル基である。）
で表わされるα，β−共役エステルに、触媒の存在下で下記の一般式（４）：
Ｒ^６ＳＨ （４）
（式中、Ｒ^６は、置換基を有していてもよいベンジル基である。）
で表わされるチオール類を反応させ、下記一般式（５）：

(In the formula, R ³ is an ethyl group; R ⁵ is an alkyl group having 1 to 4 carbon atoms.)
In the presence of a catalyst, an α, β-conjugated ester represented by the following general formula (4):
R ⁶ SH (4)
(In the formula, R ⁶ is a benzyl group which may have a substituent.)
And the following general formula (5):

（式中、Ｒ^３、Ｒ^５及びＲ^６は、前記と同義である。）
で表わされる３級スルフィドエステルへ変換後、エステル基の還元に続き水酸基をエーテル化し、下記一般式（６）：

(In the formula, R ³ , R ⁵ and R ⁶ are as defined above.)
After conversion to a tertiary sulfide ester represented by the following formula, reduction of the ester group followed by etherification of the hydroxyl group yields the following general formula (6):

（式中、Ｒ^３及びＲ^６は前記と同義であり；Ｒ^４は、メチル基又はエチル基である。）
で表わされる３級スルフィドエーテルとし、次いで脱保護することを特徴とする下記一般式（２）：

(In the formula, R ³ and R ⁶ are as defined above; R ⁴ is a methyl group or an ethyl group.)
The following general formula (2), characterized in that it is a tertiary sulfide ether represented by

（式中、Ｒ^３及びＲ^４は前記と同義である。）
で表わされる３級メルカプトエーテルの製造方法；

(In the formula, R ³ and R ⁴ are as defined above.)
A process for producing a tertiary mercaptoether represented by:

(11) The following general formula (5):

（式中、Ｒ^３は、エチル基であり；Ｒ^５は、炭素数１〜４のアルキル基であり；Ｒ^６は、置換基を有していてもよいベンジル基である。）
で表わされる３級スルフィドエステル；

(In the formula, R ³ is an ethyl group; R ⁵ is an alkyl group having 1 to 4 carbon atoms; and R ⁶ is a benzyl group which may have a substituent.)
A tertiary sulfide ester represented by:

(12) The following general formula (6):

（式中、Ｒ^３は、エチル基であり；Ｒ^４は、メチル基又はエチル基である。；Ｒ^６は、置換基を有していてもよいベンジル基である。）
で表わされる３級スルフィドエーテル；

(Wherein R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group; R ⁶ is an optionally substituted benzyl group.)
A tertiary sulfide ether represented by:

(13) The following general formula (7):

（式中、Ｒ^３は、エチル基であり；Ｒ^６は、置換基を有していてもよいベンジル基である。）
で表わされる３級スルフィドアルコール；
である。

(In the formula, R ³ is an ethyl group; R ⁶ is a benzyl group which may have a substituent.)
A tertiary sulfide alcohol represented by:
It is.

The tertiary mercapto ether of the present invention represented by the above formula (1) or formula (2) has a unique and unique palatability, ie, meaty, green-like, grapefruit-like, catty-like, floral-like. It has a strong fragrance and is excellent in fragrance sustainability and stability, can maintain its unique fragrance and flavor over a long period of time, and is excellent in harmony with other fragrances.
Therefore, the tertiary mercapto ether of the present invention represented by the above formula (1) or formula (2) is used alone or mixed with other components to form a fragrance composition or a flavor composition. It can be used effectively for product fragrance or flavoring.
When the fragrance composition or flavor composition composition containing the tertiary mercapto ether of the present invention represented by the above formula (1) or formula (2) and the fragrance composition or flavor composition containing the same is used, it is extremely small amount. Can be used to give the product a deep texture, richness, freshness, naturalness, and freshness.

  The tertiary mercapto ether of the present invention represented by the above formula (1) or formula (2) and the fragrance composition or flavor composition of the present invention containing the same can be utilized in various ways utilizing the above-described excellent characteristics. It can be used effectively for fragrance or flavoring of various products such as products such as foods and drinks, cosmetics, daily and miscellaneous goods, oral products, and pharmaceuticals.

The present invention is described in detail below.
The tertiary mercapto ether of the present invention has the following formula (1):

（式中、Ｒ^１及びＲ^２は、互いに同一または異なるメチル基又はエチル基である。）
又は、下記の一般式（２）：

(In the formula, R ¹ and R ² are the same or different methyl or ethyl groups.)
Or the following general formula (2):

（式中、Ｒ^３は、エチル基であり；Ｒ^４は、メチル基又はエチル基である。）
で表される。

(In the formula, R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group.)
It is represented by

In the tertiary mercapto ether of the present invention represented by the general formula (1), R ¹ and R ² are a methyl group or an ethyl group.

Specifically, as the tertiary mercapto ether of the present invention represented by the above general formula (1) [hereinafter sometimes referred to as “tertiary mercapto ether (1)”], 4-methoxy-2- Mention may be made of methyl-2-butanethiol, 4-ethoxy-2-methyl-2-butanethiol, 5-methoxy-3-methyl-3-pentanethiol, 5-ethoxy-3-methyl-3-pentanethiol. . These tertiary mercapto ethers (1) are colorless to light lemon-colored oils.
Among the above-described tertiary mercaptoethers (1) of the present invention, 5-methoxy-3-methyl-3-pentanethiol is more effective as an aroma / flavoring component in terms of aroma and strength.

In the tertiary mercapto ether of the present invention represented by the above general formula (2), R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group.

Specifically, as the tertiary mercapto ether of the present invention represented by the above general formula (2) [hereinafter sometimes referred to as “tertiary mercapto ether (2)”], 5-methoxy-3- Mention may be made of methyl-3-pentanethiol and 5-ethoxy-3-methyl-3-pentanethiol. These tertiary mercapto ethers (2) are colorless to light lemon-colored oils.
Among the above-described tertiary mercaptoethers (2) of the present invention, 5-methoxy-3-methyl-3-pentanethiol is more effective as an aroma / flavoring component in terms of aroma and strength.
Moreover, the tertiary mercapto ether of the present invention represented by the above general formula (2) is a novel compound which has never been obtained.

  The production method of the tertiary mercapto ether (2) of the present invention is not particularly limited and may be produced by any method, but can be easily and efficiently produced by the method of the present invention described below. .

[Production Method of Tertiary Mercapto Ether (2)]
As shown in the following reaction formula, α, β-conjugated ester represented by the general formula (3) [hereinafter sometimes referred to as “α, β-conjugated ester (3)”] in the presence of a base, After conversion to the tertiary sulfide ester (5) by adding the thiols of the general formula (4), the hydroxyl group is etherified to the tertiary sulfide ether (6) following the reduction of the ester group, followed by deprotection to give a tertiary Mercapto ether (2) is produced.

（式中、Ｒ^３は、エチル基であり；Ｒ^４は、メチル基又はエチル基であり；Ｒ^５は、炭素数１〜４のアルキル基であり；Ｒ^６は、置換基を有していてもよいベンジル基である。）

(Wherein R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group; R ⁵ is an alkyl group having 1 to 4 carbon atoms; and R ⁶ has a substituent. It may be a benzyl group.)

In the above method for producing the tertiary sulfide ester (5) by adding the thiols (4) to the α, β-conjugated ester (3), the base may be a secondary amine, a tertiary amine or Pyridines and the like.
When the base is a secondary amine, specifically, diethylamine, di-n-propylamine, diisopropylamine, methylisopropylamine, ethylisopropylamine, di-n-butylamine, diisobutylamine, disec-butylamine, ditert- Examples include butylamine, N-methylaniline, N-ethylaniline, pyrrolidine, piperidine, morpholine, piperazine, imidazole, and dibenzylamine.
When the base is a tertiary amine, specifically, trimethylamine, triethylamine, tripropylamine, triisopropylamine, diisopropylmethylamine, diisopropylethylamine, tri-n-butylamine, tribenzylamine, N-methylpiperidine, N- Ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, , 4-diazabicyclo [2.2.2] octane, N, N, N, N-tetramethylethylenediamine, N, N, N, N-tetramethyl1,3-propanediamine, dimethylaniline, diethylaniline, etc. be able to.
When the base is a pyridine, specifically, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, N, N-dimethylaminopyridine, quinoline, isoquinoline and the like can be mentioned.
Preferably, diethylamine, di-n-propylamine, diisopropylamine, methylisopropylamine, ethylisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, piperazine, etc. are versatile, and the selectivity and yield of the reaction. It is more preferable because of its high rate.
These may be used alone or in admixture of two or more.
The base used in the present invention can be a commercially available product, or can be used after purification.

The amount of the base used is 1.0 to 2.0 molar equivalents, preferably 1.1 to 1.5 molar equivalents per 1 mol of the α, β-conjugated ester (3). It is preferable from the point of progress.
In the thiol compound represented by the general formula (4), R ⁶ is a benzyl group which may have a substituent.
Specific examples of R ⁶ include benzyl group, p-methylphenylmethyl group, p-ethylphenylmethyl group, p-methoxyphenylmethyl group, 3,5-dimethylphenylmethyl group, 3,5-dimethoxyphenylmethyl. Group, p-fluorophenylmethyl group, p-chlorophenylmethyl group, 2,6-dichlorophenylmethyl group, α-phenylethyl group, o-nitrophenylmethyl group, p-nitrophenylmethyl group, p-cyanophenylmethyl group, Examples thereof include a diphenylmethyl group, a triphenylmethyl group, a naphthylmethyl group, a naphthyldiphenylmethyl group, and a p-methoxyphenyldiphenylmethyl group.
Specific examples of preferable R ⁶ include benzyl group, p-methylphenylmethyl group, p-ethylphenylmethyl group, p-methoxyphenylmethyl group, 3,5-dimethylphenylmethyl group, 3,5-dimethoxyphenylmethyl group. , P-fluorophenylmethyl group, p-chlorophenylmethyl group, α-phenylethyl group and the like are preferably exemplified. More preferably, a benzyl group is illustrated.
Specific examples of the thiols (4) include benzylthiol, p-methylphenylmethylthiol, p-ethylphenylmethylthiol, p-methoxyphenylmethylthiol, 3,5-dimethylphenylmethylthiol, 3,5-dimethoxy. Examples include phenylmethylthiol, p-fluorophenylmethylthiol, p-chlorophenylmethylthiol, and α-phenylethylthiol.
Preferably, benzylthiol and p-methylphenylmethylthiol are exemplified.
Moreover, in said reaction, it is 1.0-2.0 molar equivalent with respect to the usage-amount of the thiols of General formula (4), (alpha), (beta) -conjugated ester (3), Preferably 1.1- It is preferable that the molar equivalent is 1.5 because the tertiary mercapto ether (2), which is the target product, can be produced with good yield and is economical.

The reaction of α, β-conjugated ester (3) and thiols (4) may be carried out directly, but α, β-conjugated ester (3) is converted into an organic solvent (for example, methylene chloride, toluene, xylene, hexane, heptane). , Ethyl acetate, tetrahydrofuran, etc.) and may be reacted.
As the reaction temperature, generally, a temperature of 80 to 170 ° C., particularly 100 to 150 ° C. is preferably employed. Moreover, although reaction time changes with reaction conditions, such as a reaction substrate and temperature, reaction is completed in several minutes to 30 hours.
The mixture containing the tertiary sulfide ester (5) produced by the reaction is cooled to stop the reaction, and then washed with water to purify the crude product obtained by an appropriate method (for example, column chromatography, distillation). Can give a tertiary sulfide ester (5).
The tertiary sulfide ester (5) thus obtained is a novel compound that has not been known so far.

In the above method for producing tertiary sulfide ether (6) by etherification of the hydroxyl group following reduction of the ester group of tertiary sulfide ester (5), the reducing agent includes lithium aluminum hydride, sodium aluminum hydride, At least one selected from lithium borohydride, sodium borohydride, RED-AL and DAIBAL-H is preferably used. In particular, lithium aluminum hydride is preferable because it can produce the target tertiary mercaptoalcohol (7) with good yield and is economical.
The amount of the reducing agent used is 1.5 to 4.0 molar equivalents, preferably 1.8 to 2.5 molar equivalents per mole of the tertiary sulfide ester (5), so that the reaction proceeds smoothly. From the point of view, it is preferable.

The reduction reaction of the ester group of the tertiary sulfide ester (5) is performed in an organic solvent. Examples of the organic solvent used include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and dioxolane.
The amount of solvent is determined by the solubility and economics of the reaction substrate. Usually, 1.0 to 50 parts by volume, preferably 2.0 to 10 parts by volume, are used with respect to 1 part by mass of the tertiary sulfide ester (5).
As the reaction temperature, generally, a temperature of −30 to 50 ° C., particularly 0 to 25 ° C. is preferably employed. Moreover, although reaction time changes with reaction conditions, such as a reaction substrate and temperature, reaction is completed in several minutes to 30 hours.
The reaction mixture is quenched with an acid such as dilute hydrochloric acid or dilute sulfuric acid in the mixed solution containing the tertiary sulfide ester (5) produced by the reaction, and then washed with water to give a crude product obtained by an appropriate method (for example, column chromatography). The tertiary sulfide alcohol (7) can be obtained by purification by chromatography, distillation).
The tertiary sulfide alcohol (5) thus obtained is a novel compound that has not been known so far.

A tertiary sulfide ether (6) is produced by etherifying the hydroxyl group of the obtained tertiary sulfide alcohol (7).
The etherification of the hydroxyl group proceeds by the presence of a base and a phase transfer catalyst, and reaction with methyl halide or ethyl halide.
Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; lithium methoxide, lithium ethoxide, lithium propoxide, lithium t-butoxide, sodium methoxide, sodium ethoxide, sodium propoxy And at least one selected from alkali metal alkoxides such as sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium t-butoxide and the like. In particular, sodium hydroxide and potassium hydroxide are preferable because tertiary mercapto ether (6), which is the target product, can be produced in good yield and is economical.
The amount of the base used is 1.0 to 5.0 molar equivalents, preferably 2.0 to 4.0 molar equivalents per mole of the tertiary sulfide alcohol (7), so that the reaction proceeds smoothly. It is preferable from the point.

Phase transfer catalysts include quaternary ammonium salts or quaternary phosphonium salts, specifically Et ₄ NCl, Et ₄ NBr, Et ₄ NI, Bu ₄ NCl, Bu ₄ NBr, Bu ₄ NI, (Benzyl ) Et ₃ NCl, (Benzyl) Et ₃ NBr, (Benzyl) Et ₃ NI, (Benzyl) Pr ₃ NCl, (Benzyl) Pr ₃ NBr, (Benzyl) Pr ₃ NI, (C ₈ H ₁₇ ) Me ₃ NCl, _{(C 8 H 17) Me 3} NBr, (C 8 H 17) Me 3 NI, (C 16 H 33) Me 3 NCl, (C 16 H 33) Me 3 NBr, (C 16 H 33) Me 3 NI, MePh ₃ PCl, MePh ₃ PBr, MePh ₃ PI, EtPh ₃ PCl, EtPh ₃ PBr, EtPh ₃ PI, BuPh ₃ PCl, BuPh ₃ PBr, BuPh ₃ PI, (C ₈ H ₁₇ ) Ph ₃ PCl, (C ₈ H ₁₇ ) Ph ₃ PBr, (C ₈ H ₁₇ ) Ph ₃ PI, (C ₁₆ H ₃₃ ) Ph ₃ PCl, (C ₁₆ H ₃₃ ) Ph ₃ PBr, (C ₁₆ H ₃₃ ) Ph ₃ PI, (C ₁₆ H ₃₃ ) Bu ₃ PCl, (C ₁₆ H ₃₃ ) Bu ₃ PBr, (C ₁₆ H ₃₃ ) Bu ₃ PI, etc. are used.
The amount of the phase transfer catalyst used is preferably 0.1 to 1.0 molar equivalent per 1 mole of the tertiary sulfide alcohol (7) from the viewpoint of smooth progress of the reaction.

As methyl halide or ethyl halide, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, and the like are used.
The amount of methyl halide or ethyl halide used is 1.0 to 2.0 moles, preferably 1.05 to 1.5 mole equivalents per mole of tertiary sulfide alcohol (7). It is preferable from the viewpoint of smooth progress.

The etherification reaction of the hydroxyl group of the tertiary sulfide alcohol (7) is carried out in a solvent. Examples of the solvent to be used include water; alcohol solvents such as methanol, ethanol, propanol, and isopropanol.
The amount of solvent is determined by the solubility and economics of the reaction substrate. Usually, 0.02 to 20 parts by volume, preferably 1.0 to 5 parts by volume, are used with respect to 1 part by mass of the tertiary sulfide ester (5).
As the reaction temperature, generally, a temperature of 50 to 150 ° C., particularly 70 to 120 ° C. is preferably employed. Moreover, although reaction time changes with reaction conditions, such as a reaction substrate and temperature, reaction is completed in several minutes to 30 hours.

Water is added to the mixture containing the tertiary sulfide ether (6) produced by the reaction to stop the reaction, and then washed with water to purify the crude product obtained by an appropriate method (for example, column chromatography, distillation). By doing so, tertiary sulfide ether (6) can be obtained.
The tertiary sulfide ether (6) thus obtained is a novel compound that has not been known so far.

  The deprotection method of the benzylic protecting group of the tertiary sulfide ether (6) is not particularly limited as long as the reaction proceeds. Specifically, (1) a method by hydrogenation with a heterogeneous hydrogenation catalyst, (2) Birch reduction with alkali metal is employed.

As the heterogeneous hydrogenation catalyst used in the method (1) of hydrogenation with a heterogeneous hydrogenation catalyst, a heterogeneous hydrogenation catalyst that is often used is generally used.
Examples of heterogeneous hydrogenation catalysts include Raney nickel, platinum oxide, platinum black, palladium hydroxide, palladium black, rhodium black, palladium carbon, iridium carbon, rhodium carbon, ruthenium carbon, osnium carbon, palladium alumina, palladium silica. And palladium silica alumina. Preferably, Raney nickel, platinum black, palladium hydroxide, palladium black, palladium carbon, palladium alumina, palladium silica, palladium silica alumina, and the like are used. Among them, Raney nickel, palladium black, palladium carbon and the like are more preferably used because of high reaction selectivity and yield and high versatility.

This hydrogenation reaction can be carried out in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene, benzene, and chlorobenzene, aliphatic esters such as ethyl acetate, propyl acetate, and butyl acetate, ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran, dichloromethane, dichloroethane, and the like. And halogen hydrocarbons such as methanol, alcohols such as methanol, ethanol and isopropanol. These may be used singly or as a mixed solution of two or more. The solvent is preferably an alcohol, and among them, methanol, ethanol, isopropanol, toluene and the like can be mentioned. Among these, methanol, ethanol, isopropanol and the like are more preferably used because of their versatility and high reaction selectivity and yield.
Moreover, the usage-amount of these solvents is about 0.1-10 times volume with respect to tertiary sulfide ether (6), Preferably it is the range of about 0.5-3 times volume.

The amount of the heterogeneous hydrogenation catalyst used in the present invention is about 0.02 to 20% by mass, preferably about 0.1 to 5% by mass, based on 1 mass of the tertiary sulfide ether (6). Is done.
The hydrogen pressure is in the range of about 0.05 to 10 MPa, preferably about 0.1 to 3 MPa.
The reaction temperature is in the range of about 20 to 100 ° C., preferably about 30 to 60 ° C., and the reaction is performed for about 1 to 50 hours, preferably 1 to 10 hours while maintaining the above temperature. Can be performed smoothly.
After completion of the reaction, the heterogeneous hydrogenation catalyst is removed by filtration from the reaction solution obtained by the above reaction, and then the solvent is distilled off under reduced pressure. By subjecting the obtained residue to distillation under reduced pressure, tertiary mercaptoate (2), which is the target compound of the present invention, can be produced with high purity and high yield.

As the alkali metal used for the birch reduction with the alkali metal (2) above, metallic lithium, metallic sodium, metallic potassium, etc. are used.
The amount of alkali metal used is 1.5 to 4.0 moles, preferably 2.0 to 3.0 mole equivalents per mole of the tertiary sulfide ether (6). It is preferable from the point.

Birch reduction of the tertiary sulfide ether (6) is performed in a solvent. Examples of the solvent used include ether solvents such as ethyl ether, tetrahydrofuran, diisopropyl ether, and tert-butyl methyl ether in addition to liquid ammonia.
The amount of solvent is determined by the solubility and economics of the reaction substrate. Usually, 1.0 to 50 parts by volume, preferably 3.0 to 10 parts by volume, are used with respect to 1 part by mass of the tertiary sulfide ether (6).
As the reaction temperature, generally, a temperature of −100 to −20 ° C., particularly −80 to −30 ° C. is preferably employed. Moreover, although reaction time changes with reaction conditions, such as a reaction substrate and temperature, reaction is completed in several minutes to 30 hours.

Ammonium chloride is added to the mixed solution containing tertiary mercapto ether (2) produced by the reaction to stop the reaction, and then washed with water to obtain a crude product obtained by an appropriate method (for example, column chromatography, distillation). The tertiary mercapto ether (2) can be obtained by purification with
The tertiary sulfide ether (2) thus obtained is a novel compound that has not been known so far.

  The α, β-conjugated ketone (3) used for the production of the tertiary mercaptoether (2) is a known compound and can be produced by a known production method, for example, a series of reactions shown in the following reaction formula ( (Refer nonpatent literature 2).

（式中、Ｒ^３は、エチル基であり；Ｒ^５は、炭素数１〜４のアルキル基である。）

(In the formula, R ³ is an ethyl group; R ⁵ is an alkyl group having 1 to 4 carbon atoms.)

The tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention has a unique strong aroma such as meaty-like, green-like, grapefruit-like, catty-like, floral-like, and fragrance persistence. It has excellent properties and stability, and can maintain its unique aroma and flavor over a long period of time. Therefore, the tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention may be used directly as it is for fragrance or flavoring of a product, or mixed with other ingredients to produce a fragrance composition or A flavor composition may be prepared and used for flavoring or flavouring of various products using the fragrance composition or flavor composition, so the present invention provides a tertiary mercaptoketone (1) or tertiary mercapto ether (2 The fragrance composition or flavor composition prepared by using the above) is included in the scope of the present invention.
The tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention is directly used as it is, or an aromatic / flavoring composition containing the tertiary mercaptoketone (1) or tertiary mercapto ether (2) is used. When fragrance and flavoring of various products are performed, the fragrance or flavoring effect is maintained over a long period of time by using a small amount, and a desired fragrance persistence, a fragrance or flavored product having a high residual fragrance property is prepared. be able to.
On the other hand, in the tertiary mercapto ether represented by the general formula (1) or the general formula (2), the total number of carbon atoms of R ¹ and R ² or R ³ and R ⁴ is 5 or more, and the present invention Compounds that fall outside this range have low odor intensity and do not have sufficient aroma or flavoring effects.

The fragrance composition or flavor composition prepared using the tertiary mercapto ether (1) or the tertiary mercapto ether (2) is used as a fragrance or flavoring component as the tertiary mercapto ether (1) or tertiary mercapto ether (2 ), Or other perfume ingredients commonly used with tertiary mercaptoketone (1) or tertiary mercapto ether (2).
Examples of other perfume ingredients that the fragrance composition or flavor composition may contain with the tertiary mercapto ether (1) or tertiary mercapto ether (2) include various synthetic perfumes, natural essential oils, synthetic essential oils, citrus oils, animal nature A fragrance | flavor etc. can be mentioned, For example, the wide kind of fragrance | flavor component as described in the nonpatent literature 3 can be used. Among them, representative examples include, for example, α-pinene, limonene, cis-3-hexenol, phenylethyl alcohol, styryl acetate, eugenol, rose oxide, linalool, benzaldehyde, muscone, and musk T (Takasago International Corporation). ), Tesalon (Takasago International Corporation) and the like.

More specifically, the tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention is used in synthetic essential oils such as bergamot oil, galvanum oil, lemon oil, geranium oil, lavender oil, and mandarin oil. When blended into a natural essential oil, it is possible to add mildness, richness, and freshness to the aroma and flavor inherent in natural essential oils, thereby enhancing the durability of synthetic essential oils with high palatability and improved diffusibility and retention. A base fragrance / flavor composition can be obtained.
The tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention includes, for example, citrus essential oils such as orange, lime, and grapefruit; lavender oil, vetiver oil, cedarwood oil, citronellyl oil, geranium oil, Since it can be well harmonized with natural essential oils such as lavandin oil, sandalwood oil, etc. and the characteristics of these essential oils can be emphasized, tertiary mercapto ether (1) or tertiary mercapto ether ( By adding 2), it is possible to obtain a fragrance composition or flavor composition that is mellow and rich, rich in naturalness, and further improved in diffusibility and retention, and excellent in sustainability.

  Furthermore, for example, strawberry-like, lemon-like, orange-like, grapefruit-like, apple-like, pineapple-like, banana-like, melon-like, green tea-like prepared from various synthetic fragrances, natural fragrances, natural essential oils, citrus essential oils, animal fragrances, etc. A tertiary mercapto ether (1) or tertiary mercapto ether (2) is added to a fragrance composition or flavor composition having a fragrance or flavor such as oolong tea, salmon, sardine, sardine, shrimp, crab, etc. When blended, it is mild, rich, natural, marine-like, modern green-like, Fatty-like, Fatty-green-like aroma, as well as freshness, high taste aroma, diffusion and retention In addition, an aroma / flavor composition with improved durability can be obtained.

The content of the tertiary mercapto ether (1) or tertiary mercapto ether (2) in the fragrance composition or flavor composition containing the tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention is the same. It can be adjusted according to the kind of fragrance and other ingredients to be prepared in accordance with the purpose of use of the fragrance composition or flavor composition. For example, in a fragrance composition for cosmetics, the content of tertiary mercapto ether (1) is generally 1 * 10 ^{−6 to} 5 * 10 ⁻³ %, particularly 5 *, based on the total mass of the fragrance composition. It is preferable that it is 10 ^<-6 > ^-1 * 10 ^<-3 > mass%.
Moreover, in the flavor composition for foods and drinks, the content of the tertiary mercapto ether (2) is generally 1 * 10 ⁻⁷ to 1 * 10 ⁻¹ mass% with respect to the total mass of the flavor composition. Is preferably 1 * 10 ⁻⁶ to 1 * 10 ⁻² mass%, more preferably 1 * 10 ⁻⁵ to 1 * 10 ⁻³ mass%. In particular, in a flavor composition used for tea-based foods and beverages such as green tea beverages, oolong tea beverages, and tea-based confectioneries, the inclusion of tertiary mercapto ether (2) is generally included with respect to the total mass of the flavor composition. The amount is preferably 1 * 10 ⁻⁶ to 1 * 10 ⁻² mass%, more preferably 1 * 10 ⁻⁵ to 1 * 10 ⁻³ mass%.

  The fragrance composition or flavor composition of the present invention containing the tertiary mercapto ether (1) or tertiary mercapto ether (2) may optionally be replaced with other commonly used fragrance compositions or flavor compositions. You may contain the 1 type (s) or 2 or more types of a fragrance | flavor reservation agent. In this case, as other flavor retention agents, for example, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercoline, medium chain fatty acid triglyceride, medium chain fatty acid diglyceride, etc. 1 type or 2 types or more can be contained.

  The tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention is the tertiary mercapto ether (1) or tertiary mercapto ether (2) alone or tertiary mercapto ether (1) as described above. ) Or tertiary mercapto ether (2) and can be used for aroma or flavoring of various products. Aroma or flavoring by the fragrance composition or flavor composition containing the tertiary mercapto ether (1) or tertiary mercapto ether (2) itself or tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention Examples of products that can be used include foods and drinks, cosmetics, daily and miscellaneous goods, pharmaceuticals, oral products and the like.

Moreover, as a specific example of the food / beverage products which can be flavored by the tertiary mercapto ether (2) of the present invention and the flavor composition containing the same, it is not limited at all. , Milk beverages, carbonated beverages, soft drinks, beverages such as drinks; ice creams, sorbets, frozen confections such as ice candy; desserts such as jelly and pudding; cakes, cookies, chocolate, chewing gum, etc. Western confectionery; Japanese confectionery such as buns, sheep crab and willow; jams; candies; breads; Tea, rooibos tea, gymnema tea, guava tea, coffee, tea drinks such as cocoa or beverages; Japanese-style soup, Wind soup, such as soup of Chinese soup; flavor seasonings; variety of instant beverages or foods; and various snack foods; and oral products can be mentioned.
Among these, the tertiary mercapto ether (2) and the flavor composition containing the same of the present invention are suitable for flavoring tea beverages using tea such as green tea and oolong tea, and tea-use foods. When flavoring a tea-use food, especially a green tea drink or oolong tea drink, using a tertiary mercapto ether (2) or a flavor composition containing the same, the aroma of the tea is improved, and the richness and profound feeling As a thick cocoon that is round and has a ripening sensation, it is possible to express the natural radiance of teas.

  In addition, as cosmetics or daily and miscellaneous goods that can be perfumed with the tertiary mercapto ether (1) of the present invention and a fragrance composition containing the same, for example, fragrance products, basic cosmetics, finished cosmetics, hair Cosmetics, tanning cosmetics, medicinal cosmetics, hair care products, soap, body cleaners, bath preparations, detergents, softeners, cleaning agents, kitchen detergents, bleaching agents, aerosols, deodorants and fragrances, repellents, etc. Goods can be listed.

More specifically,
-Perfume, eau de parfum, eau de toilette, eau de cologne, etc. as fragrance products;
・ As basic cosmetics, facial cream, burnishing cream, cleansing cream, cold cream, massage cream, milky lotion, lotion, beauty liquid, pack, makeup remover, etc .;
・ For finished cosmetics, foundation, powder powder, solid powder, talcum powder, lipstick, lip balm, blusher, eyeliner, mascara, eye shadow, eyebrow, eye pack, nail enamel, enamel rim bar, etc .;
-As hair cosmetics, pomade, brilantine, set lotion, hair stech, hair solid, hair oil, hair treatment, hair cream, hair nick, hair liquid, hair spray, bandlin, hair nourishing agent, hair dye, etc .;
Can be mentioned.

-As tanning cosmetics, suntan products, sunscreen products, etc .;
-Examples of medicinal cosmetics include antiperspirants, after shaving lotions and gels, permanent wave agents, medicated soaps, medicated shampoos, medicated skin cosmetics, etc .;
-Hair care products include shampoo, rinse, rinse-in shampoo, conditioner, treatment, hair pack, etc .;
-As soap, cosmetic soap, bath soap, perfume soap, transparent soap, synthetic soap, etc .;
・ Body soap, body shampoo, hand soap, etc.
-As bath preparations, bath salts (bath salts, bath tablets, bath liquids, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jelly, bath cubes, etc .;
-Detergents include heavy laundry detergents, light laundry detergents, liquid detergents, laundry soaps, compact detergents, powdered soaps, and the like.

-Softeners such as softeners and furniture cares;
・ Cleaners, house cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mold removers, drainpipe cleaners, etc .;
・ As kitchen detergents, kitchen soap, kitchen soap, dishwashing detergent, etc .;
・ As bleaching agents, oxidized bleaches (chlorine bleaches, oxygen bleaches, etc.), reduced bleaches (sulfur bleaches, etc.), optical bleaches, etc .;
・ As aerosols, spray type, powder spray, etc .;
・ As deodorant and fragrance, solid type, gel type, liquid type, etc .;
・ For miscellaneous goods, tissue paper, toilet paper, etc .;
Can be mentioned.
-As the composition for oral cavity, for example, toothpaste, oral cleansing agent, mouthwash, troche, chewing gum and the like;
・ For pharmaceuticals, skin preparations such as haps and ointments, and oral preparations;
Can be mentioned.

When the tertiary mercapto ether (1) or tertiary mercapto ether (2) of the present invention and the fragrance composition or flavor composition aroma containing the same are used for aroma or flavoring of various products as described above, Tertiary mercapto ether (1) or 3 depending on the type of product to be scented or flavored and the final form of the product (eg liquid, solid, powder, gel, mist, aerosol, etc.) Grade mercaptoether (2) or a fragrance composition or flavor composition containing it may be added or applied directly to the product; tertiary mercaptoether (1) or tertiary mercaptoether (2) or Fragrance compositions or flavor compositions containing, for example, alcohols, propylene glycol It may be dissolved in polyhydric alcohols such as glycerin and added or applied in liquid form; natural gums such as gum arabic and tragacanth, surfactants (eg glycerin fatty acid esters, sucrose fatty acid esters, etc.) Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc.) may be added or added in solubilized or dispersed form solubilized or emulsified and dispersed; Arabic It may be added or applied in the form of a powder formed using an excipient such as natural gums such as gums, gelatin, dextrin, etc .; Also good.
In addition, the tertiary mercapto ether (1) or tertiary mercapto ether (2) or a fragrance composition or flavor composition containing the same is stabilized and sustained-released by inclusion in an inclusion agent such as cyclodextrin. May be used.

The amount or amount of tertiary mercapto ether (1) or tertiary mercapto ether (2) added to the product when aroma or flavoring is applied depends on the type and form of the product, the aroma and flavoring effect required for the product, It can be adjusted according to the action and the like. In general, the addition amount or application amount of tertiary mercapto ether (1) or tertiary mercapto ether (2) is about 1 * 10 ^-10 to 1 * 10 ^-1 % by mass relative to the mass of the product. Preferably, it is 1 * 10 ⁻⁹ to 1 * 10 ⁻² mass%. In particular, when added to tea beverages such as green tea beverages and oolong tea beverages, the amount of tertiary mercaptoether (I) added is 1 * 10 ^-9 to 1 * 10 ^-1 % by mass relative to the mass of the tea beverage. Preferably, it is 1 * 10 ⁻⁸ to 1 * 10 ⁻² mass%.

Hereinafter, the present invention will be specifically described with reference to examples and the like, but the present invention is not limited to the following examples. The measurement equipment and measurement conditions used in the following examples are shown below.
(1) Gas chromatograph (measurement of conversion rate);
Equipment: “HP-5890A” manufactured by Hewlett-Packard Company
Column: “HP-5” (30 m * 0.32 mm * 0.25) manufactured by Hewlett-Packard Company
μm)
Carrier gas: helium Measurement temperature: 100-220 ° C. (temperature increase rate: 10 ° C./min)
(2) Infrared absorption spectrum (IR);
Equipment: “AVATER 360FT-IR” manufactured by Nicorey
Measurement method: film method (3) proton nuclear magnetic resonance spectrum ( ¹ H-NMR);
Equipment: “DRX-500” (500 MHz) manufactured by Bruker
Internal standard: tetramethylsilane (4) mass spectrum (MS);
Instrument: “M-80B mass spectrometer” manufactured by Hitachi, Ltd. (ionization voltage: 20 eV)

<< Synthesis Example 1 >> [Production of methyl 3-methyl-2-pentenoate]
To a 3000 ml reaction flask equipped with a thermometer and reflux condenser under a nitrogen stream, 60% -sodium hydride (24.4 g: 610 mmol) and tetrahydrofuran (1000 ml) were charged, and trimethylphosphonoacetate (100 g: 549 mmol) was added. Tetrahydrofuran (500 ml) solution was added dropwise at room temperature. Subsequently, a solution of methyl ethyl ketone (39.6 g: 549 mmol) in tetrahydrane (50 ml) was added dropwise at room temperature, and the reaction was allowed to react for 3 hours while heating at 60 ° C. Under ice-cooling, 10% aqueous hydrochloric acid (35 ml) was added to neutralize the mixture, followed by Celite filtration. The filtrate was evaporated under reduced pressure. The concentrate was dissolved in hexane (500 ml), washed three times with water, and then concentrated under reduced pressure to obtain 65 g of methyl 3-methyl-2-pentenoate.

<< Example 1 >> [Production of 5-methoxy-3-methyl-3-pentanethiol]
(1) Synthesis of methyl 3-benzylmercapto-3-methylpentanoate Methyl 3-methyl-2-pentenoate (11.4 g) obtained in Synthesis Example 1 was added to a 100-ml reaction flask equipped with a thermometer and a reflux condenser. : 92.1 mmol), benzylthiol (15.4 g: 119.7 mmol) and piperidine (10.2 g: 119.7 mmol) were added, and the mixture was heated to reflux at an oil bath temperature of 130 ° C. The disappearance of methyl 3-methyl 2-pentenoate as a raw material was observed by gas chromatography 5 hours after the start of reflux. The reaction solution was poured into 150 ml of dilute hydrochloric acid, extracted with hexane, washed twice with water and then with saturated brine, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure to obtain the desired methyl 3-benzylmercapto-3-methylpentanoate (boiling point 136 ° C .: 58.4 Pa), 19.2 g (yield 82 .6%) was obtained as a colorless transparent oil.

(2) Synthesis of 3-benzylmercapto-3-methylpentanol In a 300 ml reaction flask equipped with a thermometer, methyl 3-benzylmercapto-3-methylpentanoate (18.0 g: 71.3 mmol), 100 ml of anhydrous tetrahydrofuran And cooled in an ice cold bath. To this, lithium aluminum hydride (2.71 g: 142.6 mmol) was added in four portions so as not to raise the temperature, and stirring was continued at room temperature after the addition. One hour after the addition, disappearance of the raw material was confirmed by thin layer chromatography. The reaction solution was poured into 150 ml of dilute hydrochloric acid, extracted with hexane, washed successively with aqueous sodium carbonate solution, aqueous ammonium chloride solution and saturated brine, and dried over anhydrous sodium sulfate. After filtration, the solvent is distilled off under reduced pressure, and purification is performed by distillation under reduced pressure to obtain the desired 3-benzylmercapto-3-methylpentanol (boiling point 122-138 ° C .: 53.2-50.8 Pa), 14. 7 g (yield 91.9%) was obtained as a colorless transparent oily substance.

(3) Synthesis of 3-benzylmercapto-3-methylpentylmethyl ether 3-benzylmercapto-3-methylpentanol (13.2 g: 58.8 mmol) was added to a 100-ml reaction flask equipped with a thermometer and a mechanical stirrer. Sodium hydroxide (7.1 g: 176.5 mmol), water (2.0 g: 111 mmol), and tetrabutylammonium bromide 190 mg were added and suspended by heating and stirring at an oil bath temperature of 90 ° C. Methyl (10.9 g: 76.5 mmol) was added dropwise over 30 minutes, and disappearance of the raw material was observed by gas chromatography 2 hours after the addition. After stopping the reaction, the reaction solution was poured into 150 ml of water, extracted with 50 ml of hexane, washed successively with aqueous ammonium chloride solution and saturated brine, and dried over anhydrous sodium sulfate.
After filtration, the solvent was distilled off under reduced pressure and the residue was purified by distillation under reduced pressure to obtain the desired 3-benzylmercapto-3-methylpentylmethyl ether (boiling point 102 to 111 ° C .: 33.3 Pa), 12.2 g Ratio 87.0%) was obtained as a colorless transparent oil.

(4) Synthesis of 5-methoxy-3-methyl-3-pentanethiol A 200-ml reaction flask equipped with a thermometer and a conical tube condenser was cooled in a dry ice bath, and 60 ml of liquid ammonia was added. Metal sodium (1.8 g: 78.4 mmol) is added here and stirred. Sodium dissolves and shows a deep blue color. 3-Benzyl mercapto-3-methylbutyl methyl ether (8.5 g: 35.7 mmol) was added dropwise thereto over 1 hour while maintaining the temperature at −50 ° C. or lower. The disappearance of the raw material was observed by gas chromatograph 90 minutes after the dropping. After the reaction was stopped, the temperature was naturally increased and ammonia was distilled off. Then, 20 ml of pentane and 50 ml of saturated aqueous ammonium chloride solution were added to separate the organic phase. The organic layer was washed again with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate.
After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure to obtain the desired 5-methoxy-3-methyl-3-pentanethiol (boiling point 78-80 ° C .: 3.3 MPa), 3.46 g ( (Yield 65.8%) was obtained as a colorless transparent oily substance.

¹ H-NMR (500 MHz, CDCl ₃ -d, δ) ppm: 0.98 (t, J = 8.4 Hz, 3H), 1.33 (s, 3H), 1.60 (s, 1H), 1 .60-1.67 (m, 2H), 1.80-1.95 (m, 2H), 3.34 (s, 3H), 3.55 (t, J = 7.4 Hz, 2H).
MS (m / e): 148, 114, 85, 83, 55, 45, 41, 29, 27.
IR (KBr) cm ⁻¹ : 2974, 2931, 2879, 2360, 2340, 1458, 1379, 1204, 1149, 1127, 1005, 980.

<< Example 2 >> [Production of 5-ethoxy-3-methyl-3-pentanethiol]
In Example 1 (3), instead of methyl iodide, ethyl bromide was used, and the others were carried out in the same manner as in Example 1 to obtain 5-ethoxy-3-methyl-3-pentanethiol.

<< Synthesis Example 2 >> [Production of 4-ethoxy-2-methyl-2-butanethiol]
(1) Synthesis of 3-benzylmercapto-3-methylbutanoic acid 3-methyl-2-butenoic acid (25.0 g: 250 mmol), benzylthiol (29. 3 g: 250 mmol) was dissolved in 50 ml of piperidine, and heated to reflux at an oil bath temperature of 130 ° C. The disappearance of 3-methyl 2-butenoic acid as a raw material was observed by gas chromatography 5 hours after the start of reflux. The reaction solution was poured into 300 ml of diluted hydrochloric acid, extracted with hexane, washed twice with water and then with saturated brine, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off with a rotary evaporator under reduced pressure to obtain 3-benzylmercapto-3-methylbutanoic acid.

(2) Synthesis of 3-benzylmercapto-3-methylbutanol 3-benzylmercapto-3-methylbutanoic acid (56.0 g: 250 mmol) and anhydrous tetrahydrofuran (200 ml) were placed in a 300 ml reaction flask equipped with a thermometer. Cooled in an ice cold bath. To this, lithium aluminum hydride (10.63 g: 280 mmol) was added in 7 portions so as not to raise the temperature, and stirring was continued at room temperature after the addition. One hour after the addition, disappearance of the raw material was confirmed by thin layer chromatography. The reaction solution was poured into 350 ml of diluted hydrochloric acid, extracted with hexane, washed successively with aqueous sodium carbonate solution, aqueous ammonium chloride solution and saturated brine, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure and the residue was purified by distillation under reduced pressure. 2%) was obtained as a colorless transparent oil.

(3) Synthesis of 3-benzylmercapto-3-methyl-1-butylmethyl ether 3-benzylmercapto-3-methyl-1-butanol (19.0 g: 1) was added to a 100-ml reaction flask equipped with a thermometer and a mechanical stirrer. 90.3 mmol), sodium hydroxide (10.8 g: 271 mmol), water 6.0 g (333 mmol), and tetrabutylammonium bromide (100 mg) were added, and the mixture was suspended by heating and stirring at an oil bath temperature of 90 ° C. Ethyl bromide (14.1 g: 130 mmol) was added dropwise thereto over 90 minutes, and disappearance of the raw materials was observed by gas chromatography 4 hours after the addition. After stopping the reaction, the reaction solution was poured into 150 ml of water, extracted with 50 ml of hexane, washed successively with aqueous ammonium chloride solution and saturated brine, and dried over anhydrous sodium sulfate.
After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure. 93.5%) was obtained as a colorless transparent oil.

(4) Synthesis of 4-ethoxy-2-methyl-2-butanethiol A 300-ml reaction flask equipped with a thermometer and a conical tube condenser was cooled in a dry ice bath, and 100 ml of liquid ammonia was added. Metal sodium (4.03 g: 175.3 mmol) is added and stirred. Sodium dissolves and shows a deep blue color. 3-Benzyl mercapto-3-methylbutyl methyl ether (19.0 g: 79.7 mmol) was added dropwise thereto over 1 hour while maintaining the temperature at −50 ° C. or lower. The disappearance of the raw material was observed by gas chromatograph 90 minutes after the dropping. After the reaction was stopped, the temperature was naturally increased and ammonia was distilled off. Then, 30 ml of pentane and 70 ml of a saturated aqueous ammonium chloride solution were added to separate the organic phase. The organic layer was washed again with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate.
After filtration, the solvent was distilled off under reduced pressure and the residue was purified by distillation under reduced pressure to obtain the desired 4-ethoxy-2-methyl-2-butanethiol (boiling point 70 ° C .: 3.0 MPa), 7.38 g (yield) 62.4%) was obtained as a colorless transparent oil.

¹ H-NMR (500 MHz, CDCl ₃ -d, δ) ppm: 1.20 (t, J = 7.0 Hz, 3H), 1.42 (s, 6H), 1.79 (s, 1H), 1 .89 (t, J = 7.0 Hz, 2H), 3.49 (q, J = 7.0 Hz, 2H), 3.61 (t, J = 7.0 Hz, 2H).
MS (m / e): 148, 114, 99, 71, 59, 41, 31, 29, 27.
IR (KBr) cm < ^-1 >: 2972, 2929, 2867, 2361, 2340, 1458, 1377, 1206, 1126, 1105.

<< Synthesis Example 3 >> [Production of 4-methoxy-2-methyl-2-butanethiol]
4-Methoxy-2-methyl-2-butanethiol was obtained in the same manner as in Example 1 except that methyl iodide was used instead of ethyl bromide in Synthesis Example 2 (3).

<< Synthesis Example 4 >> [Production of 5-n-butoxy-3-methyl-3-pentanethiol]
5-n-butoxy-3-methyl-3-pentanethiol was obtained in the same manner as in Example 1 except that n-butyl iodide was used in place of methyl iodide in (3) of Example 1. It was.

<< Evaluation Test Example 1 >> [Evaluation of aroma quality]
5-methoxy-3-methyl-3-pentanethiol prepared in Example 1, 5-ethoxy-3-methyl-3-pentanethiol prepared in Example 2, 4-ethoxy-2 prepared in Synthesis Example 2 7-methyl-2-butanethiol, 4-methoxy-2-methyl-2-butanethiol produced in Synthesis Example 3 and 5-n-butoxy-3-methyl-3-pentanethiol produced in Synthesis Example 4 As a result of fragrance evaluation by a human panel, it was as shown in Table 1 below.

As seen in the results of Table 1 above, the tertiary mercapto ethers (2) of the present invention of Examples 1 and 2 [in the above formula (2), R ³ is an ethyl group; R ⁴ is methyl Each of the tertiary mercapto ethers which are a group or an ethyl group] had a peculiar and strong aroma with a taste and / or a caty feeling and high palatability.
In contrast, 5-n-butoxy-3-methyl-3-pentanethiol of Synthesis Example 4 [in the above formula (2), R ³ is an ethyl group, R ⁴ is an n-propyl group, and the tertiary of the present invention] 3rd-class mercaptoether, which is out of the range of mercaptoether (2), has a weak meaty feeling, but has a vegetable-like scent (specifically, Aono-style scent), and its fragrance has low palatability. It was.
Further, conventionally known 4-ethoxy-2-methyl-2-butanethiol and 4-methoxy-2-methyl-2-butanethiol have a meaty and catered feeling, but have a cooking feeling and a feeling of overheating, The aroma was inferior to the product of the present invention in palatability.

<< Example 5 >> [Production of green tea beverage added with 5-methoxy-3-methyl-3-pentanethiol]
Pour 300 ml of hot water at a temperature of 90 ° C. into 10 g of green tea leaves, leave it for about 1 minute, and filter the tea leaves to 100 parts by weight of the green tea extract obtained in Example 1, 5-methoxy-3-methyl. A green tea beverage containing 5-methoxy-3-methyl-3-pentanethiol at a concentration of 0.001 ppb was prepared by adding a 1 ppb ethanol solution of -3-pentanethiol in an amount of 0.1 parts by mass. The green tea beverage thus obtained was evaluated by eight professional panelists according to the evaluation criteria (five-step evaluation) shown in Table 2 below, and the average value was taken. As shown in Table 3 below Met.

Example 6 [Production of Green Tea Beverage with Addition of 5-Ethoxy-3-Methyl-3-Pentanethiol]
In place of 5-methoxy-3-methyl-3-pentanethiol, the same process as in Example 5 was carried out except that 5-ethoxy-3-methyl-3-pentanethiol prepared in Example 2 was used. A green tea beverage containing 5-ethoxy-3-methyl-3-pentanethiol at a concentration of 0.001 ppb was produced. The green tea beverage thus obtained was evaluated by eight professional panelists according to the evaluation criteria shown in Table 2 below, and the average value thereof was as shown in Table 3 below.

<< Comparative Example 1 >> [Production of 5-n-butoxy-3-methyl-3-pentanethiol-added green tea beverage]
The same steps as in Example 5 except that 5-n-butoxy-3-methyl-3-pentanethiol prepared in Synthesis Example 4 was used instead of 5-ethoxy-3-methyl-3-pentanethiol. The green tea beverage containing 5-n-butoxy-3-methyl-3-pentanethiol at a concentration of 0.001 ppb was produced. The green tea beverage thus obtained was evaluated by eight professional panelists according to the evaluation criteria shown in Table 2 below, and the average value thereof was as shown in Table 3 below.

<< Comparative Examples 2-3 >> [Production of 4-ethoxy-2-methyl-2-butanethiol and 4-methoxy-2-methyl-2-butanethiol-added green tea beverage]
Instead of 5-ethoxy-3-methyl-3-pentanethiol, 4-ethoxy-2-methyl-2-butanethiol produced in Synthesis Example 2 above and 4-methoxy-2-methyl produced in Synthesis Example 3 The same process as in Example 5 was performed except that 2-butanethiol was used, and 4-ethoxy-2-methyl-2-butanethiol and 4-methoxy-2-methyl-2-butanethiol were added in 0.001 ppb. A green tea beverage containing a concentration of The green tea beverage thus obtained was evaluated by eight professional panelists according to the evaluation criteria shown in Table 2 below, and the average value thereof was as shown in Table 3 below.

<< Comparative Example 4 >> [Production of Mercapto Ether-Free Green Tea Beverage]
8 green tea drinks (green tea extract) obtained by pouring 300 ml of hot water at a temperature of 90 ° C. into 10 g of green tea leaves, letting them stand for about 1 minute, and then filtering the tea leaves, according to the evaluation criteria shown in Table 2 below. When evaluated by a panelist and averaged, the results were as shown in Table 3 below.
[Evaluation criteria for green tea beverages]

As seen in Table 3 above, the green tea beverages of Examples 5 to 6 to which the tertiary mercapto ether (2) of the present invention was added were all green tea beverages of Comparative Example 4 to which no mercapto ether was added (control example). Compared to, the bitterness and astringency peculiar to green tea is reduced, and there is a deep, green tea-specific meaty feeling accompanied by a ripening feeling, and it has the dignified flavor of fresh green tea . Among them, the green tea beverage of Example 5 to which 5-methoxy-3-methyl-3-pentanethiol is added is particularly excellent in flavor as green tea.
On the other hand, the green tea beverage of Comparative Example 1 to which 5-n-butoxy-3-methyl-3-pentanethiol was added had a sense of ripening, depth, and green tea specific to the green tea beverage of Examples 5-6. It is inferior in terms of feeling and catty feeling, and the original green aroma of green tea is considerably impaired as compared with the green tea beverage of Comparative Example 4 (control example) without addition of mercapto ether.
Moreover, the green tea drinks of Comparative Example 2 and Comparative Example 3 to which 4-ethoxy-2-methyl-2-butanethiol and 4-methoxy-2-methyl-2-butanethiol were added were Comparative Examples 4 to which no mercapto ether was added. Compared to the green tea beverage (control example) of the present invention, it is somewhat improved in terms of maturity, depth, green tea peculiar green tea feel and catty feeling, but compared with the green tea beverages of Examples 5-6, its flavor improving effect Is inferior.

<< Example 7 >> [Manufacturing of flavor composition for green tea beverage and addition of 5-methoxy-3-methyl-3-pentanethiol and green tea beverage]
(1) Pour 30 liters of hot water at a temperature of 90 ° C. into 1 kg of green tea leaves, leave it for about 1 minute, filter the tea leaves, concentrate to 100 times the concentration, and concentrate for green tea beverages Was prepared.
(2) 0.002 mass of 10 ppb ethanol solution of 5-methoxy-3-methyl-3-pentanethiol obtained in Example 1 with respect to 100 mass parts of the concentrated liquid for green tea obtained in (1) above. A flavor composition for green tea beverages containing 5-methoxy-3-methyl-3-pentanethiol at a ratio of 0.0002 ppb (2 * 10 ⁻⁴ ppb) was added.
(3) With respect to 100 parts by mass of the green tea extract obtained by pouring 300 ml of hot water at a temperature of 90 ° C. into 10 g of green tea leaves, leaving the flavor composition obtained in (2) above for about 1 minute, and filtering the tea leaves. The green tea beverage to which 5-methoxy-3-methyl-3-pentanethiol was added at a ratio of 1 part by mass [concentration of 5-methoxy-3-methyl-3-pentanethiol: about 0.000002 ppb ( 2 * 10 ⁻⁶ ppb)]. About the green tea drink obtained by this, when the sensory test was conducted according to the evaluation criteria described in Table 2 by 8 expert panelists, the average value of the 8 panelists was 4.7 points. The bitterness and astringency were reduced, and there was a deep, green tea-specific feel of meat tea with a sense of maturity, and the dull flavor of fresh green tea was added. Moreover, even after 24 hours, the good fragrance was maintained without being lost.

<< Example 8 >> [Production of flavor composition for green tea beverage and addition of 5-methoxy-3-methyl-3-pentanethiol and green tea beverage]
(1) The components shown in Table 4 below are mixed in the proportions shown in Table 4 to produce a flavor composition for green tea beverages containing 5-methoxy-3-methyl-3-pentanethiol at a concentration of 0.1 ppb. did.
(2) Pour 300 ml of hot water at a temperature of 90 ° C. into 10 g of green tea leaves, leave it for about 1 minute, and filter the tea leaves to 100 parts by weight of the green tea extract. A green tea beverage containing 5-methoxy-3-methyl-3-pentanethiol at a concentration of 0.001 ppb was added in an amount of 0.1 parts by weight.
(3) About the green tea drink obtained by said (2), when the sensory test was conducted according to the evaluation criteria described in said Table 2 by 8 expert panelists, as shown in Table 4 below, The average value of the panelists is 4.7 points, the bitterness and astringency unique to green tea is reduced, and there is a deep, green tea-specific taste of green tea with a sense of maturity. A sense of flavor was imparted.

<< Comparative Example 5 >> [Manufacturing of flavor composition for green tea beverage and green tea beverage without addition of 5-methoxy-3-methyl-3-pentanethiol]
(1) The components shown in Table 4 below were mixed at the ratio shown in Table 4 to produce a flavor composition for green tea beverages that did not contain 5-methoxy-3-methyl-3-pentanethiol.
(2) Pour 300 ml of hot water at a temperature of 90 ° C. into 10 g of green tea leaves, leave it for about 1 minute, and then filter the tea leaves to 100 parts by weight of the green tea extract to add the flavor composition obtained in (1) above. A green tea beverage not containing 5-methoxy-3-methyl-3-pentanethiol was added in an amount of 0.1 parts by mass.
(3) About the green tea drink obtained by said (2), when the sensory test was performed according to the evaluation criteria described in said Table 2 by eight expert panelists, as shown in Table 4 below, The average value of the panelists was 1.2 points, and the depth and richness were insufficient as compared with the green tea beverage of Example 8.

<< Example 9 >> [Production of oolong tea beverage to which 5-methoxy-3-methyl-3-pentanethiol is added]
Pour 300 ml of hot water at a temperature of 100 ° C. into 10 g of oolong tea leaves, leave it for about 3 minutes, and filter the tea leaves to 100 parts by weight of the oolong tea extract obtained in Example 1 to obtain 5-methoxy-3-methyl. A 10 ppb ethanol solution of -3-pentanethiol was added in an amount of 0.002 parts by mass to obtain a oolong tea beverage containing 5-methoxy-3-methyl-3-pentanethiol at a ratio of 0.0002 ppb. The obtained oolong tea beverage was evaluated by eight professional panelists according to the evaluation criteria (five-step evaluation) shown in Table 5 below, and the average value was taken. As shown in Table 6 below Met.

<< Example 10 >> [Production of oolong tea beverage with addition of 5-ethoxy-3-methyl-3-pentanethiol]
In place of 5-methoxy-3-methyl-3-pentanethiol, the same process as in Example 9 was carried out except that 5-ethoxy-3-methyl-3-pentanethiol produced in Example 2 was used. A oolong tea beverage containing 5-ethoxy-3-methyl-3-pentanethiol at a concentration of 0.001 ppb was produced.
The obtained oolong tea beverage was evaluated by eight professional panelists according to the evaluation criteria shown in Table 5 below, and the average value was taken. The results were as shown in Table 6 below.

<< Comparative Example 6 >> [Production of oolong tea beverage added with 5-n-butoxy-3-methyl-3-pentanethiol]
The same steps as in Example 10 except that 5-n-butoxy-3-methyl-3-pentanethiol prepared in Synthesis Example 4 was used instead of 5-methoxy-3-methyl-3-pentanethiol. The oolong tea beverage containing 5-n-butoxy-3-methyl-3-pentanethiol at a concentration of 0.001 ppb was produced. The obtained oolong tea beverage was evaluated by eight professional panelists according to the evaluation criteria shown in Table 5 below, and the average value was taken. The results were as shown in Table 6 below.

<< Comparative Examples 7-8 >> [Production of Oolong Tea Beverage with 4-ethoxy-2-methyl-2-butanethiol and 4-methoxy-2-methyl-2-butanethiol]
Instead of 5-methoxy-3-methyl-3-pentanethiol, 4-ethoxy-2-methyl-2-butanethiol produced in Synthesis Example 2 above and 4-methoxy-2-methyl produced in Synthesis Example 3 The same process as in Example 10 was performed except that 2-butanethiol was used, and 4-ethoxy-2-methyl-2-butanethiol and 4-methoxy-2-methyl-2-butanethiol were 0.001 ppb. A oolong tea beverage containing a concentration of The obtained oolong tea beverage was evaluated by eight professional panelists according to the evaluation criteria shown in Table 5 below, and the average value was taken, as shown in Table 6 below.

<< Comparative Example 9 >> [Production of Oolong Tea Beverage without Mercapto Ether Addition]
Pour 300 ml of hot water at a temperature of 90 ° C. into 10 g of oolong tea leaves, leave it for about 1 minute, filter the tea leaves, and then obtain 8 professionals according to the evaluation criteria shown in Table 5 below. When evaluated by a panelist and averaged, the results were as shown in Table 6 below.
[Evaluation criteria for oolong tea beverage]

As seen in Table 6 above, the oolong tea beverages of Examples 9 to 10 to which the tertiary mercapto ether (2) of the present invention was added were all oolong tea beverages of Comparative Example 9 without the addition of mercapto ether (control example). Compared to, there is a sense of maturity, depth, a sense of mellow tea and a sense of catty, and a flavor of oolong tea. Among them, the oolong tea beverage of Example 10 to which 5-ethoxy-3-methyl-3-pentanethiol is added is particularly excellent in the aging feeling, the depth, and the mellow tea-feeling and catty feeling peculiar to oolong tea.
On the other hand, the oolong tea beverage of Comparative Example 6 to which 5-n-butoxy-3-methyl-3-pentanethiol was added had a sense of maturity, depth, and oolong tea-specific meaty as compared to the oolong tea beverages of Examples 9-19. The original fragrance of oolong tea is considerably impaired as compared with the oolong tea beverage of Comparative Example 9 (control example) to which no mercapto ether is added.
Moreover, the oolong tea beverages of Comparative Examples 7 to 8 to which 4-ethoxy-2-methyl-2-butanethiol and 4-methoxy-2-methyl-2-butanethiol were added were the oolong tea of Comparative Example 9 to which no mercapto ether was added. Compared to the beverage (control example), it is improved in terms of aging, depth, meaty feeling and catty feeling peculiar to oolong tea, but it has a slightly strong cooking feeling, accompanied by a feeling of overheating, and improved flavor to oolong tea drinks has no effect.

Example 11 [Production of Flavor Composition for Oolong Tea Beverage Added with 4-Methoxy-2-methyl-2-butanethiol and Oolong Tea Beverage]
(1) Pour 30 liters of hot water at a temperature of 100 ° C. into 1 kg of oolong tea leaves, leave it for about 3 minutes, filter the tea leaves, concentrate the oolong tea extract to a concentration 100 times, and concentrate for oolong tea beverages Was prepared.
(2) To 100 parts by mass of the concentrate obtained in (1) above, 0.002 parts by mass of 10 ppb ethanol solution of 4-methoxy-2-methyl-2-butanethiol obtained in Example 1 A flavor composition for oolong tea beverages containing 4-methoxy-2-methyl-2-butanethiol at a concentration of 0.0002 ppb was added.
(3) The flavor composition 1 obtained in (2) above was added to 100 parts by weight of oolong tea extract obtained by pouring 300 ml of hot water at a temperature of 100 ° C. into 10 g of oolong tea leaves, leaving it for about 3 minutes and filtering the tea leaves. A oolong tea beverage containing 4-methoxy-2-methyl-2-butanethiol at a concentration of about 0.000002 ppb (2 * 10 ⁻⁶ ppb) was prepared by adding parts by mass. About the oolong tea drink obtained by this, when the sensory test was conducted according to the evaluation criteria described in the above Table 5 by eight professional panelists, the average value of the eight panelists was 4.5 points, and the aging feeling was Accompanied by a deep oolong tea leaf-like aroma. Moreover, even after 24 hours, the good fragrance was maintained without being lost.

<< Example 12 >> [Production of flavor composition for oolong tea beverage and oolong tea beverage added with 4-methoxy-2-methyl-2-butanethiol]
(1) A flavor composition for oolong tea beverage containing the components shown in Table 7 below in a proportion shown in Table 7 and containing 4-methoxy-2-methyl-2-butanethiol at a concentration of 0.1 ppb. Prepared.
(2) Pour 300 ml of hot water at a temperature of 100 ° C. into 10 g of oolong tea leaves, leave it for about 3 minutes, filter the tea leaves, and add 100 parts by weight of the oolong tea extract obtained in (1) above. A oolong tea beverage containing 4-methoxy-2-methyl-2-butanethiol at a concentration of 0.001 ppb was added in an amount of 0.1 parts by weight.
(3) The oolong tea drink obtained in (2) above was subjected to a sensory test in accordance with the evaluation criteria described in Table 5 above by eight professional panelists. As shown in Table 7 below, The average value of the panelists was 4.6 points, and the richness unique to oolong tea was given.

<< Comparative Example 10 >> [Manufacture of flavor composition for oolong tea beverage without addition of 4-methoxy-2-methyl-2-butanethiol and oolong tea beverage]
(1) The components shown in Table 7 below were mixed at the ratio shown in Table 7 to produce a flavor composition for oolong tea beverages that did not contain 4-methoxy-2-methyl-2-butanethiol.
(2) Pour 300 ml of hot water at a temperature of 100 ° C. into 10 g of oolong tea leaves, leave it for about 3 minutes, filter the tea leaves, and add 100 parts by weight of the oolong tea extract obtained in (1) above. In addition to 0.1 parts by mass, a oolong tea beverage containing no 4-methoxy-2-methyl-2-butanethiol was produced.
(3) The oolong tea drink obtained in (2) above was subjected to a sensory test in accordance with the evaluation criteria described in Table 5 above by eight professional panelists. As shown in Table 7 below, The average value of the panelists was 1.2 points, and the depth and richness were insufficient as compared with the oolong tea beverage of Example 16.

<< Example 13 >> [Production of matcha pudding added with 5-methoxy-3-methyl-3-pentanethiol]
(1) Formulations for matcha pudding shown in Table 8 below were prepared.

(2) Among the blends for matcha pudding shown in Table 8 above, sugar, skim milk powder, matcha, gelling agent and emulsifier are previously powder-mixed, and the mixture is whipped cream (40% vegetable fat content) ) In addition to the mixture of whole-fat sweetened condensed milk and water, dissolve with heating and stirring at 80 ° C. for 10 minutes, then mix the remaining ingredients, then correct the total amount to 100 parts by mass with water and homogenize at 14700 kPa After filling the container, it was cooled and solidified to produce matcha pudding. The matcha pudding thus obtained was a matcha pudding having a sensation of ripening and having a flavor and image of a deep tea leaf.

<< Example 14 and Comparative Example 11 >> [Production of Grapefruit Flavor Composition]
(1) A grapefruit flavor containing a trace amount of 5-methoxy-3-methyl-3-pentanethiol produced in Example 2 was prepared according to the formulation shown in Table 9 below (Example 14).
(2) As shown in Table 9 below, an additive-free grapefruit flavor was produced by adopting the same formulation as Example 14 except that 5-methoxy-3-methyl-3-pentanethiol was not added ( Comparative Example 11).

(3) When the sensory comparative evaluation by seven expert panelists was performed about the grapefruit flavor of Example 14 obtained in (1) above and the grapefruit flavor of Comparative Example 11, all the panelists were found to be 5-methoxy-3- In the grapefruit flavor of Example 18 to which methyl-3-pentanethiol was added, it was evaluated that natural and deep freshness was imparted that was not found in Comparative Example 11.

<Example 15> [Production of fragrance composition for shampoo containing 5-methoxy-3-methyl-3-pentanethiol and shampoo]
(1) A shampoo flavor composition shown in Table 10 below was prepared, and the components shown in the formulation examples were sufficiently stirred and mixed at room temperature using a stirrer to give 5-methoxy-3-methyl-3- A perfume composition for shampoo added with pentanethiol was produced.

<< Prescription Example 1 >>
Ingredient Example 15
Benzyl salicylate 55
L-citronellol 10
Ethyl acetoacetate 5
Galaxolide 50BB ^* (made by IFF) 390
Geraniol 10
Hedion (Fulmenich) 120
Helioboke (manufactured by Takasago International Corporation) 8
Cis-3-hexen-1-ol 10% DPG ^** solution 10
Acetic acid cis-3-hexenyl 10% DPG solution 5
Hexylcinnamic aldehyde 50
β-Yonon 17
Cobanol (Takasago International Corporation) 40
Lemon oil 40
Linaroll 45
Linalyl acetate 45
Nerolidol 55
Phenylethyl alcohol 30
Phenyl ethyl cinnamate 5
Santarex T (manufactured by Takasago International Corporation) 35
Tripral 10% DPG solution (manufactured by IFF) 5
Maltol 1% DPG solution 15
5-methoxy-3-methyl-3-pentanethiol
10 ppm DPG solution 5
Total 1000
* Benzyl benzoate ** Dipropylene glycol

(2) Using the shampoo perfume composition produced in (1) above, a shampoo was produced by the following shampoo formulation. Specifically, all the components constituting the shampoo formulation shown in Table 11 were mixed and stirred at 80 ° C. until uniform, then cooled to 35 ° C. and then cooled to room temperature to produce a shampoo. .

[Shampoo composition] (wt%)
Sodium lauryl sulfate 40.00
N-coconut oil fatty acid acyl-N-
Carboxymethoxyethyl-
N-carboxymethyl
Ethylenediamine disodium 10.00
Palm oil fatty acid diethanolamide (2) 2.00
Butylene glycol 2.00
Citric acid 0.35
Sodium chloride 0.10
Methylparaben 0.20
Propylparaben 0.10
Edetate tetrasodium 0.10
Fragrance composition of Example 15 0.50
Purified water balance
Total 100.00

(3) The shampoo fragrance composition obtained in the above (1) and the shampoo obtained in the above (2) were both excellent in fragrance diffusibility and had a fresh and natural feeling.

<< Comparative Example 12 >> [Production of fragrance composition for shampoo without addition of 5-methoxy-3-methyl-3-pentanethiol and shampoo]
(1) In the shampoo perfume composition formulation shown in Table 10 above, instead of 5-methoxy-3-methyl-3-pentanethiol 10 ppm DPG (dipropylene glycol) solution, the same amount of dipropylene glycol (DPG) ) Was used in the same manner as in Example 15 (1) to produce a shampoo fragrance composition without addition of 5-methoxy-3-methyl-3-pentanethiol.
(2) In the shampoo formulation used in (2) of Example 15, 5 obtained in (1) above instead of the shampoo flavoring composition to which 5-methoxy-3-methyl-3-pentanethiol was added 5-methoxy-3-methyl-3-pentanethiol added in the same manner as in (2) of Example 15 except that a shampoo fragrance composition free of -methoxy-3-methyl-3-pentanethiol was used. The shampoo was manufactured.
(3) The shampoo fragrance composition obtained in (1) above and the shampoo obtained in (2) above all have insufficient scent diffusibility, and are fresh and natural. It was inferior to that of Example 15.

Example 16 [Production of Fragrance Composition for Body Shampoo Added with 5-Ethoxy-3-methyl-3-pentanethiol and Body Shampoo]
(1) A shampoo composition for body shampoo shown in the following Formulation Example 2 was prepared, and these components were sufficiently stirred and mixed at room temperature using a stirrer to give 5-ethoxy-3-methyl-3-pentane. A fragrance composition for body shampoo added with thiol was produced.

<< Prescription Example 2 >>
Ingredient Example 16
Lemon oil 100
Lime oil 180
Geranil nitrile 10
Aldehyde C-8 10% DPG solution 25
Aldehyde C-10 10% DPG solution 35
Ethyl decanoate 12
Tripar (made by IFF) 3
Isocyclocitral 10% DPG solution (IFF) 25
Styraryl acetate 20
α-Terpineol 30
Linalool 70
Linalyl acetate 50
Geraniol 60
Geranyl acetate 5
Lilianar (Gibodan) 80
Hexylcinnamic aldehyde 120
Mylacaldehyde (made by IFF) 15
Cis-3-hexenyl salicylate 15
β-Yonon 25
Heliotropin 5
Tonalid (manufactured by PFW) 30
Dipropylene glycol balanced 5-ethoxy-3-methyl-3-pentanethiol
10 ppm DPG solution 5
Total 1000

(2) A body shampoo was produced by blending the body shampoo shown below using the shampoo composition for body shampoo produced in (1) above. Specifically, all the components constituting the body shampoo formulation shown below were mixed and heated and stirred until uniform at 40 ° C., and then cooled to room temperature to produce a body shampoo.

[Body shampoo composition] (wt%)
Dibutylhydroxytoluene 0.05
Methylparaben 0.10
Propylparaben 0.10
Edetate tetrasodium 0.10
Potassium chloride 0.20
Glycerin 5.00
Coconut oil fatty acid diethanolamide (2) 3.00
Sodium polyoxyethylene lauryl ether acetate (3EO) (30%) 10.00
Palm oil fatty acid amidopropyl betaine solution (34%) 25.00
Potassium myristate (40%) 25.00
Fragrance composition of Example 16 0.50
Purified water balance
Total 100.00

(3) The fragrance composition for body shampoo obtained in the above (1) and the body shampoo obtained in the above (2) all had a refreshed citrus feeling.

<< Comparative Example 13 >> [Production of perfume composition for body shampoo without addition of 5-ethoxy-3-methyl-3-pentanethiol and body shampoo]
(1) In the shampoo composition for body shampoo shown in Formulation Example 2 above, instead of using 5-ethoxy-3-methyl-3-pentanethiol 10 ppm DPG solution, the same amount of dipropylene glycol is used. The same process as in Example 23 (1) was carried out to produce a shampoo body shampoo fragrance composition free of 5-ethoxy-3-methyl-3-pentanethiol.
(2) In the body shampoo formulation adopted in Example 16, (2), instead of the fragrance composition for body shampoo added with 5-ethoxy-3-methyl-3-pentanethiol, the product obtained in (1) above was obtained. 5-Ethoxy-3-methyl-3-pentanethiol In the same manner as (2) of Example 16 except that a shampoo for body shampoo containing no 5-ethoxy-3-methyl-3-pentanethiol was used. An additive-free body shampoo was produced.
(3) The flavor composition for body shampoo obtained in (1) above and the body shampoo obtained in (2) above are both inferior to those of Example 16 in refreshing and citrus feeling. It was.

<< Example 17 >> [Production of perfume composition for perfume and cosmetic cream added with 4-methoxy-2-methyl-2-butanethiol]
(1) A perfume composition for a perfume shown in the following Formulation Example 3 is prepared, and the components shown in the Formulation Example 3 are sufficiently stirred and mixed at room temperature using a stirrer to give 4-methoxy-2-methyl. A perfume composition for perfume containing 2-butanethiol was produced.

<< Prescription Example 3 >>
Ingredient Example 17
α-Pinene 8
Aldehyde C-16 1
Allyl amyl glycolate 1
Ambret lid (made by IFF) 8
Bergamot 15
Carbitol 100
Cardamom oil 3
L-citronellol 30
β-Damascon 2
Dimethyloctanol 10% DPG solution 4
Dipropylene glycol 29
Dynascon 10% DPG solution 5
Ethyl acetate 10% DPG solution 4
Ethyl acetoacetate 15
Galvanum oil 10% DPG solution 10
Headion (Filmenich) 195
Helioboke (manufactured by Takasago International Corporation) 10
Cis-3-hexen-1-ol 2
Cis-3-hexen-1-ol 10% DPG solution 3
β-Yonon 10
Jasmine Absolute 3
Lime oil 10% DPG solution 5
Linalyl acetate 40
8-Mercaptomenton 10% DPG solution 8
Musk T (manufactured by Takasago International Corporation) 200
Nerolidol 46
Phenylethyl alcohol 17
β-Pinene 117
Rubofix (Filmenich) 12
Rose Absolute 3
Rose oil 10% DPG solution 5
L-rose oxide 10% DPG solution 15
Santarex T (manufactured by Takasago International Corporation) 40
Triplar (made by IFF) 14
Belton (made by Firmenich) 12
Maltol 5
4-Methoxy-2-methyl-2-butanethiol
10 ppm DPG solution 5
Total 1000

(2) Using the perfume fragrance composition produced in (1) above, a cosmetic cream was produced by the cosmetic cream formulation shown below. Specifically, all the components constituting the cosmetic cream formulation shown below were mixed and heated and stirred until uniform at 40 ° C., and then cooled to room temperature to produce a cosmetic cream.

[Cosmetic cream] (wt%)
Stearyl alcohol 6.0
Stearic acid 2.0
Hydrogenated lanolin 4.0
Squalane 9.0
Octyldecanol 10.0
Glycerin 6.0
Polyethylene glycol 1500 4.0
Polyoxyethylene (25) cetyl ether 3.0
Glucerin monostearate 2.0
Methyl paraben Appropriate amount Ethyl paraben Appropriate amount Fragrance composition of Example 17 0.1
Purified water balance
Total 100.0

(3) Both the fragrance composition for perfume obtained in (1) above and the cosmetic cream obtained in (2) above are very excellent in scent diffusibility and have a natural feeling. It was.

<< Comparative example 14 >> [Production of perfume composition for perfume and cosmetic cream without addition of 4-methoxy-2-methyl-2-butanethiol]
(1) In the fragrance composition for perfume shown in the above Formulation Example 3, in place of 4-methoxy-2-methyl-2-butanethiol 10 ppm DPG solution, the same amount of dipropylene glycol was used. The same process as in Example 17 (1) was carried out to produce a perfume composition with no 4-methoxy-2-methyl-2-butanethiol added.
(2) In the cosmetic cream formulation employed in (2) of Example 17, 4 obtained in (1) above instead of the perfume fragrance composition added with 54-methoxy-2-methyl-2-butanethiol 54-methoxy-2-methyl-2-butanethiol-free addition in the same manner as in (2) of Example 17 except that a fragrance composition for perfume without addition of -methoxy-2-methyl-2-butanethiol was used. A cosmetic cream was manufactured.
(3) Neither the fragrance composition for perfume obtained in the above (1) nor the cosmetic cream obtained in the above (2) has sufficient fragrance diffusibility, and even in a natural feeling, Example 17 It was inferior to the one.

The tertiary mercapto ether (1) and tertiary mercapto ether (2) of the present invention and the fragrance composition or flavor composition containing the same have high palatability and are excellent in terms of fragrance, richness and depth. It can be effectively used for aroma and flavoring of various products such as foods and drinks, cosmetics, daily and miscellaneous goods, oral products, and pharmaceuticals.

Claims (13)

As a fragrance ingredient, the following general formula (1):

(In the formula, R ¹ and R ² are the same or different methyl or ethyl groups.)
The fragrance composition characterized by containing the 1 type (s) or 2 or more types of the tertiary mercapto ether represented by these. The tertiary mercapto ether represented by the general formula (1) is 4-methoxy-2-methyl-2-butanethiol, 4-ethoxy-2-methyl-2-butanethiol, 5-methoxy-3-methyl-3. The fragrance composition according to claim 1, which is one or more selected from -pentanethiol and 5-ethoxy-3-methyl-3-pentanethiol. One or more of the tertiary mercapto ethers represented by the general formula (1) are used at a concentration of 1 × 10 ^{−6 to} 5 × 10 ⁻³ mass% with respect to the fragrance composition. The fragrance composition according to claim 1 or 2, characterized by the following. Fragrance products, basic cosmetics, finished cosmetics, hair cosmetics, tanning cosmetics, medicinal cosmetics, hair care products, soaps, body washing agents, which are given fragrance by the fragrance composition according to any one of claims 1 to 3. Products with aromas selected from bathing agents, detergents, softeners, cleaning agents, kitchen detergents, bleaches, aerosols, deodorants, fragrances or miscellaneous goods. As a fragrance ingredient, the following general formula (2):

(In the formula, R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group.)
The flavor composition characterized by including the 1 type (s) or 2 or more types of the tertiary mercapto ether represented by these. The tertiary mercapto ether represented by the general formula (2) is one or more selected from 5-methoxy-3-methyl-3-pentanethiol and 5-ethoxy-3-methyl-3-pentanethiol. The flavor composition according to claim 5. One type or two or more types of tertiary mercapto ether represented by the general formula (2) are used at a concentration of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mass% with respect to the flavor composition. The flavor composition according to claim 5 or 6, characterized by the above. A flavored product selected from foods and drinks, oral compositions or pharmaceuticals, which is flavored by the flavor composition according to any one of claims 5 to 8. The following general formula (2):

(In the formula, R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group.)
A tertiary mercapto ether represented by: The following general formula (3):

(In the formula, R ³ is an ethyl group; R ⁵ is an alkyl group having 1 to 4 carbon atoms.)
In the presence of a catalyst, an α, β-conjugated ester represented by the following general formula (4):
R ⁶ SH (4)
(In the formula, R ⁶ is a benzyl group which may have a substituent.)
And the following general formula (5):

(In the formula, R ³ , R ⁵ and R ⁶ are as defined above.)
After conversion to a tertiary sulfide ester represented by the following formula, reduction of the ester group followed by etherification of the hydroxyl group yields the following general formula (6):

(In the formula, R ³ and R ⁶ are as defined above; R ⁴ is a methyl group or an ethyl group.)
The following general formula (2), characterized in that it is a tertiary sulfide ether represented by

(In the formula, R ³ and R ⁴ are as defined above.)
The manufacturing method of the tertiary mercapto ether represented by these. The following general formula (5):

(In the formula, R ³ is an ethyl group; R ⁵ is an alkyl group having 1 to 4 carbon atoms; and R ⁶ is a benzyl group which may have a substituent.)
A tertiary sulfide ester represented by: The following general formula (6):

(Wherein R ³ is an ethyl group; R ⁴ is a methyl group or an ethyl group; R ⁶ is an optionally substituted benzyl group.)
A tertiary sulfide ether represented by: The following general formula (7):

(In the formula, R ³ is an ethyl group; R ⁶ is a benzyl group which may have a substituent.)
A tertiary sulfide alcohol represented by: