JP5645389B2 - Persistent aromatizing agent - Google Patents

Description

  The present invention relates to a persistent fragrance imparting agent that can be used to improve the fragrance persistence of food and drink. Specifically, the present invention relates to a long-lasting fragrance imparting agent that can retain a good-quality fragrance that is expressed in the oral cavity at the time of eating and drinking by containing a specific long-lasting fragrance imparting agent.

  Foods and drinks have a unique aroma and flavor with high palatability, good initial aroma and flavor to be felt at the moment they are put in the mouth, or moderate long-term sustainability of so-called reverberation. It is required to control the expression of the flavor so as to conform to the characteristics of various products centering on having (hereinafter referred to as “sustainability”). Therefore, it has become an extremely important issue in the food and beverage industry to develop a fragrance imparting agent that meets these requirements.

  Control of the expression of fragrances and flavors (hereinafter collectively referred to as “fragrance”) emitted by fragrance imparting agents added to edible products such as confectionery, medicines, beverages or foodstuffs, and oral products Various methods have been proposed in the past. For example, by coating the surface of the core substance containing a fragrance component with a hydrophilic polymer to form a matrix (see Patent Document 1), or by including a fragrance in a cyclodextrin (see Patent Document 2), A method for imparting or improving the persistence of flavor to confectionery such as chewing gum is disclosed.

  In addition, regarding the development of the first fragrance, an immediate release powder fragrance obtained by mixing a fragrance, an emulsifier, a sugar alcohol, etc. for the purpose of swift expression when food is put into the oral cavity (patent Reference 3) is disclosed. Furthermore, the fragrance | flavor for foods (refer patent document 4) which intends the expression of the first fragrance | flavor at the same time it maintains the fragrance persistence is disclosed. However, it is difficult to say that fragrances with the physical and chemical means as described above can control either the initial development or appropriate sustainability, and the development of fragrance according to the characteristics of the product. It is extremely difficult to control the current situation. In particular, it has not been realized to retain aroma for an appropriate period of time and to impart a high-quality and long-lasting aroma called a reverberation to a food or drink product.

  On the other hand, as a fragrance precursor composition, a substituent having a furan group or a thiophene group in a molecule is bonded to an SH group such as cysteine or glutathione, and the fragrance is expressed reductively in order to express aroma such as coffee. It has been proposed to be effective (Patent Document 5). However, the compound still has room for improvement as a method for expressing its aroma.

Japanese Patent Laid-Open No. 4-228035 Japanese Patent Laid-Open No. 3-155553 JP-A-11-140482 JP-A-8-173080 Re-published WO00 / 63328

  An object of the present invention is to solve the conventional problems and improve the persistence of a good-quality fragrance in the oral cavity, a persistent fragrance imparting agent in the oral cavity of food and drink, and further the fragrance-imparting agent. The object is to provide a blended fragrance composition, food and drink, oral product, especially a tea beverage.

As a result of diligent research to achieve the above object, the inventors of the present invention are organic compounds represented by the following general formula (1), wherein R ₁ —SH is glutathione or cysteine, and R ₂ is 4 -A compound which is a methyl-2-pentanone-4-yl group, 1-hexanol-3-yl group or 1-hexanal-3-yl group gradually generates a fragrance mainly by an enzymatic reaction in the oral cavity. In order to improve the sustainability of natural and high-quality fragrances by combining the above, a new fact that it is possible to provide a persistent fragrance imparting agent in the oral cavity of food and drinks, etc. is found, and the present invention is completed. It came.
R ₁ —S—R ₂ (1)

That is, the present invention is an organic compound represented by the general formula (1), wherein R ₁ —SH is glutathione or cysteine, and R ₂ is a 4-methyl-2-pentanone-4-yl group, -A persistent fragrance imparting agent characterized by being a hexanol-3-yl group or a 1-hexanal-3-yl group. Furthermore, this invention is a manufacturing method of the fragrance | flavor composition containing the said persistent fragrance | flavor imparting agent, food / beverage products, oral products, tea drinks, and tea drinks.

  When the persistent fragrance imparting agent of the present invention is used for food and drink, etc., it is possible to improve the sustainability of a good quality fragrance and provide the consumer with the above-mentioned product that feels so-called lingering.

Hereinafter, the present invention will be described in detail according to embodiments. The persistent fragrance imparting agent of the present invention is an organic compound represented by the general formula (1), wherein R ₁ —SH is glutathione or cysteine, and R ₂ is 4-methyl-2-pentanone-4- Yl group, 1-hexanol-3-yl group or 1-hexanal-3-yl group, and the specific compound is preferably S- (4-methyl-2-pentanone-4-yl) glutathione or S- ( 4-methyl-2-pentanone-4-yl) cysteine, and particularly preferably S- (4-methyl-2-pentanone-4-yl) glutathione.

These have a characteristic of releasing an aromatic component having a thiol in the oral cavity, and the release characteristic varies depending on the type of R ₁ SH and R ₂ H, that is, a combination of cysteine or glutathione and a volatile aromatic component. Therefore, by adjusting the combination of the types of R ₁ SH and R ₂ H, it is possible to control the persistence of the fragrance in the oral cavity. Although the volatile component of R ₂ H used in the present invention is partially expressed as an aroma component in the form of R ₂ SH depending on the condition in the oral cavity, these R ₂ SH enhances the aroma of various foods and drinks in a very small amount. It has an effect, and particularly shows an extremely useful effect for enhancing the aroma of a palatable beverage such as tea beverage or coffee (see, for example, Japanese Patent No. 3026437).

  Some of the persistent fragrance imparting agents of the present invention are described in conventional literature as components contained in certain plants and animals, and may produce thiol compounds by metabolism in animals or fermentation in wine production. (See Non-Patent Document 1). Furthermore, the possibility that a thiol compound is generated from a compound (substrate) in which cysteine and a volatile compound are bonded is described. However, on the other hand, the above-mentioned conventional literature also describes that the relationship between the substrate that generates the thiol compound and the enzyme has specificity, and compounds other than the substrate to which cysteine and the volatile compound are bound are Of course, it did not suggest that the release characteristics differ depending on the combination of volatile compounds and cysteine or glutathione.

Among the long-lasting fragrance imparting agents of the present invention, the improvement of the long-lasting is particularly effective when R ₁ SH is glutathione. However, in order to control the long-lasting fragrance, the present invention has two types. It is also useful to use the above simultaneously.

  The long-lasting fragrance imparting agent of the present invention can be obtained from natural products by means such as extraction, column chromatography, liquid chromatography, or by synthetic means described in the literature (see Non-Patent Document 2 and Non-Patent Document 3). Can be obtained.

Flavor and Fragrance J., 23, 369-381, 2008 J. Agric. Food Chem., 57, 991-995, 2009 FEMS Microbiology Letters, 240, 125-129, 2004

  The persistent fragrance imparting agent of the present invention can be appropriately added at the processing stage of food and drink, etc., and the amount added varies depending on the composition of the persistent fragrance imparting agent and the type of food and drink, but generally food and drink. 0.0001 ppb to 10000 ppm, preferably 0.001 ppb to 1000 ppm, more preferably 0.01 ppb to 100 ppm, particularly preferably 0.1 ppb to 10 ppm, and most preferably 1 ppb to 5 ppm.

  The persistent fragrance imparting agent of the present invention can be used for various foods and drinks without any particular limitation. For example, fruits or processed products thereof, vegetables or processed products thereof, seafood or processed products thereof, paste products, cooked foods, prepared vegetables, snacks, delicacies, processed foods, nutritional foods, tea drinks and coffee drinks Taste drinks, fruit juice drinks, carbonated drinks, soft drinks, functional drinks, alcoholic drinks, ice cream, confectionery such as sherbet, desserts such as jelly, pudding, sheep cane, cookies, cakes, chocolate, chewing gum, buns, etc. , Breads such as confectionery bread and bread, jams, ramunes, tablets and tablet confectionery. In addition, soup stock of Japanese cuisine, such as bonito, seafood, kelp, shiitake, chicken, vegetables, etc., or soup stock of Western cuisine, eg, beef, chicken, pork, seafood, vegetables And soup and Chinese seasonings such as beef, chicken, pork, seafood, vegetables and the like. Moreover, a persistent fragrance | flavor imparting agent can also mix | blend a flavor component or a pigment | dye suitably, and can also enhance a flavor and a color tone. There is no restriction | limiting in particular in the flavor component or pigment | dye used for preparation, A well-known flavor component or pigment | dye is suitably mix | blended and used according to the objective. Further, the long-lasting fragrance imparting agent of the present invention is not limited to food and drink applications, and can be used for all products used in the oral cavity. For example, toothpaste, toothpaste, powder toothpaste, liquid toothpaste. Oral products such as toothpastes such as mouthwashes, mouthwashes such as mouthwashes, and mouth fresheners such as troches.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description of the examples.

Example 1
Synthesis of S- (4-methyl-2-pentanon-4-yl) glutathione Glutathione (1.0 g; 3.3 mmol), 4-methyl-3-penten-2-one (0.33 g; 3.4 mmol), 8 mL of distilled water was added to pyridine (0.52 g; 6.6 mmol) and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).

(Example 2)
Synthesis of S- (4-methyl-2-pentanon-4-yl) cysteine Cysteine (0.44 g; 3.6 mmol), 4-methyl-3-penten-2-one (0.35 g; 3.6 mmol), 8 mL of distilled water was added to pyridine (0.54 g; 6.7 mmol) and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution obtained by filtering the solid with absorbent cotton, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).

Example 3
Synthesis of S- (1-hexanol-3-yl) glutathione Glutathione (1.0 g; 3.3 mmol), (E) -2-hexenal (0.33 g; 3.4 mmol), pyridine (0.52 g; 6. 6 mmol) was added with 8 mL of distilled water and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. Crystals (100 mg; 0.33 mmol) separated by filtration with a Kiriyama funnel were dissolved in ethanol, sodium borohydride (30 mg; 0.7 mmol) was added, and the mixture was stirred at room temperature. After 4 hours, about 20 mL of diluted hydrochloric acid was added to the reaction solution, and the mixture was further stirred. After 2 hours, the obtained reaction solution was dried at 50 ° C. under reduced pressure (10 mmHg), a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. After complete dissolution, it was recrystallized at room temperature and then in a refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).

Example 4
Synthesis of S- (1-hexanol-3-yl) cysteine Cysteine (0.44 g; 3.6 mmol), (E) -2-hexenal (0.35 g; 3.6 mmol), pyridine (0.54 g; 6. 7 mmol) was added with 8 mL of distilled water and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution obtained by filtering the solid with absorbent cotton, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. Crystals (40 mg; 0.33 mmol) separated by filtration with a Kiriyama funnel were dissolved in ethanol, sodium borohydride (30 mg; 0.7 mmol) was added, and the mixture was stirred at room temperature. After 4 hours, about 20 mL of diluted hydrochloric acid was added to the reaction solution, and the mixture was further stirred. After 2 hours, the obtained reaction solution was dried at 50 ° C. under reduced pressure (10 mmHg), a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. After complete dissolution, it was recrystallized at room temperature and then in a refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).

(Example 5)
Synthesis of S- (hexanal-3-yl) glutathione Glutathione (1.0 g; 3.3 mmol), (E) -2-hexenal (0.33 g; 3.4 mmol), pyridine (0.52 g; 6.6 mmol) 8 mL of distilled water was added thereto and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).

(Example 6)
Synthesis of S- (hexanal-3-yl) cysteine Cysteine (0.44 g; 3.6 mmol), (E) -2-hexenal (0.35 g; 3.6 mmol), pyridine (0.54 g; 6.7 mmol) 8 mL of distilled water was added thereto and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution obtained by filtering the solid with absorbent cotton, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).

(Example 7)
0.1 parts by mass of 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione is added to 100 parts by mass of green tea extract, and S- (4-methyl-2-pentanone-4-yl) is added. ) The green tea beverage of the present invention containing 20 ppb (5 nmol) of glutathione was obtained. When this was drunk, the firm green aroma inherent to green tea in the oral cavity became stronger over time.

(Example 8)
0.1 parts by mass of a 1000 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of black tea extract, and S- (4-methyl-2-pentanone-4-yl) was added. ) A tea beverage of the present invention containing 1 ppm of glutathione was obtained. When this was drunk, the green aroma of the original black tea in the mouth increased with time.

Example 9
0.1 parts by mass of a 1000 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of the coffee extract, and S- (4-methyl-2-pentanone-4-yl) was added. ) A coffee beverage of the present invention containing 1 ppm glutathione was obtained. When this was drunk, the roasted odor unique to coffee in the oral cavity increased with time.

(Example 10)
0.1 mass part of 1000 ppm aqueous solution of S- (1-hexanol-3-yl) glutathione is added to 100 mass parts of black tea extract, and the present invention contains 1 ppm of S- (1-hexanol-3-yl) glutathione. Got a tea drink. When this was drunk, the original fermented feeling of black tea in the oral cavity increased with time.

(Example 11)
The tea beverage of the present invention containing 1 ppm of S- (hexanal-3-yl) glutathione by adding 0.1 parts by mass of a 1000 ppm aqueous solution of S- (hexanal-3-yl) glutathione to 100 parts by mass of black tea extract. Obtained. When this product was drunk, the original fermented feeling and green scent of black tea in the oral cavity became stronger over time.

(Example 12)
0.05 parts by mass of a 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione is added to 100 parts by mass of the green tea extract, and further S- (4-methyl-2-pentanone-4 -Il) 0.047 parts by mass of a 10 ppm aqueous solution of cysteine was added, and S- (4-methyl-2-pentanone-4-yl) glutathione was 10 ppb (2.5 nmol) and S- (4-methyl-2-pentanone- The green tea beverage of the present invention containing 4.7 ppb (2.5 nmol) of 4-yl) cysteine was obtained. When this was drunk, the firm and rich green incense inherent in green tea in the oral cavity persisted for a long time.

(Example 13)
43 parts by weight of anhydrous silicic acid, 1.2 parts by weight of sodium carboxymethylcellulose, 2.2 parts by weight of propylene glycol, 23 parts by weight of sorbite solution (60%), 1.4 parts by weight of sodium lauryl sulfate, 0.1 parts of methyl parahydroxybenzoate A toothpaste consisting of part by mass, 0.3 part by mass of sodium benzoate, 1.0 part by mass of green tea extract, 0.2 part by mass of sodium saccharin, and 27.6 parts by mass of purified water was obtained according to a conventional method. 0.1 parts by mass of a 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of this toothpaste, and S- (4-methyl-2-pentanone-4-yl) was added. ) A toothpaste of the present invention containing 20 ppb (5 nmol) of glutathione was obtained. When this product was used, the firm green scent inherent in green tea in the oral cavity became stronger over time.

(Example 14)
Ethanol 15 parts by weight, glycerin 10 parts by weight, polyoxyethylene hydrogenated castor oil 2.0 parts by weight, saccharin sodium 0.15 parts by weight, sodium benzoate 0.15 parts by weight, sodium dihydrogen phosphate 0.1 parts by weight, green tea A mouthwash comprising 1.0 part by mass of extract and 71.6 parts by mass of purified water was obtained according to a conventional method. 0.1 parts by mass of a 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of this mouthwash, and S- (4-methyl-2-pentanone-4- I) A mouthwash of the present invention containing 20 ppb (5 nmol) of glutathione was obtained. When this product was used, the firm green scent inherent in green tea in the oral cavity became stronger over time.

(Comparative Example 1)
0.1 parts by mass of a 10 ppm aqueous solution of 4-mercapto-4-methylpentan-2-one is added to 100 parts by mass of green tea extract, and 6.5 ppb (5 nmol) of 4-mercapto-4-methylpentan-2-one is added. The green tea beverage of the present invention contained was obtained.

[Test Example 1]
Table 1 shows the results of sensory evaluation of each of the green tea beverages obtained in Examples 1 and 12 and Comparative Example 1 using a panel of five people. Seven levels of “strong: 7 to weak: 1” regarding the strength of the flavor (green tea with a firm and rich green tea inherent in the green tea) remaining in the oral cavity after 30 or 60 seconds of drinking each green tea beverage It was evaluated with.

  By adding the persistent fragrance imparting agent of the present invention to oral products such as foods and drinks, it is possible to improve the persistence of good quality fragrance in the oral cavity, and further, a fragrance composition containing the persistent fragrance imparting agent, food and drink Products, products for oral cavity, and particularly excellent tea beverages can be provided.

Claims (9)

An organic compound represented by the following general formula _(1), R 1 -SH is glutathione, and R ₂ is 4-methyl-2-pentanone-4-yl group, 1-hexanol-3-yl A persistent fragrance imparting agent composition comprising an organic compound which is a group or a 1-hexanal-3-yl group.
R ₁ -S-R ₂ (1) The organic compound represented by said general formula (1) is S- (4-methyl-2-pentanone-4-yl) glutathione, The persistent fragrance | flavor imparting agent composition of Claim 1 characterized by the above-mentioned. In addition to the organic compound represented by the general formula (1), the organic compound represented by the following general formula (2) ₁ -SH is cysteine and R ₂ The organic compound is a 4-methyl-2-pentanon-4-yl group, a 1-hexanol-3-yl group or a 1-hexanal-3-yl group. A long-lasting flavor enhancer composition.
R ₁ -S-R ₂     (2) The fragrance | flavor composition containing the persistent fragrance | flavor imparting agent composition in any one of Claims 1-3. Food / drink containing the persistent fragrance | flavor imparting agent composition in any one of Claims 1-3. The product for oral cavity containing the persistent fragrance | flavor imparting agent composition in any one of Claims 1-3. A tea beverage containing the persistent fragrance imparting agent composition according to any one of claims 1 to 3. The manufacturing method of the tea drink characterized by adding the persistent fragrance | flavor imparting agent composition in any one of Claims 1-3.   The method for producing a tea beverage according to claim 8, wherein the addition amount is 0.0001 ppb to 10,000 ppm.