WO2020217553A1

WO2020217553A1 - PERSISTENT FLAVOR ENHANCING AGENT COMPRISING p-MENTHA-8-S-GLUTATHIONYL-3-ONE

Info

Publication number: WO2020217553A1
Application number: PCT/JP2019/029261
Authority: WO
Inventors: 祥郎本間; 洋子後藤; 足立　謙次
Original assignee: 小川香料株式会社
Priority date: 2019-04-25
Filing date: 2019-07-25
Publication date: 2020-10-29
Also published as: JP2020180205A; JP6546365B1

Abstract

Provided is a persistent flavor enhancing agent capable of increasing the intensity and improving the persistency of a good flavor of an oral product in the mouth. This persistent flavor enhancing agent is characterized by comprising p-mentha-8-S-glutathionyl-3-one.

Description

Persistent flavor enhancer consisting of p-mentor-8-S-glutationyl-3-one

The present invention relates to a persistent flavor enhancer that can be used to increase the intensity and sustainability of flavors in foods and drinks.
More specifically, the present invention relates to a long-acting flavor enhancer capable of retaining a high-quality flavor expressed in the oral cavity during eating and drinking with an appropriate intensity and time by containing a long-acting flavor enhancer which is a specific compound.

Foods and drinks have a unique aroma and flavor with high palatability, and the aroma and flavor that you feel at the moment you put it in your mouth are good, or the moderate aroma and flavor called afterglow lasts for a long time. It is required to control the expression of flavor so as to match the characteristics of various products, centering on having (hereinafter referred to as "sustainability").
Therefore, it is an extremely important issue in the food and beverage industry to develop a flavor enhancer that meets these requirements.

Expression of aroma and flavor (hereinafter collectively referred to as "flavor") emitted by flavor enhancers added to foods and drinks, chemicals, and oral products (hereinafter collectively referred to as "oral products"). Various methods have been conventionally proposed for control.
For example, chewing gum or the like can be obtained by coating the surface of a core substance containing an aroma component with a hydrophilic polymer to form a matrix (Patent Document 1), or by encapsulating a perfume in cyclodextrin (Patent Document 2). Disclosed are methods of imparting or improving flavor persistence to confectionery.

Further, as a material for enhancing the persistence of the flavor itself, an aroma precursor composition in which a substituent having a furan group or a thiophene group in the molecule is bonded to an SH group such as cysteine or glutathione is reduced to express the aroma. It has been proposed that the aroma of coffee or the like is effectively expressed (Patent Document 3).
However, since this method requires a reducing step, there is still room for improvement in the expression of flavor.

Other methods of using the flavor precursor include, for example, a soft drink containing S- (3-hexane-1-ol) cysteine (Patent Document 4) and a Michael addition reaction product of cysteine and d-pregon (Patent Document). 5), Michael addition reaction product of 4-methyl-3-penten-2-one and glutathione or cysteine (Patent Document 6) have been proposed, but the expression of flavor is controlled according to the characteristics of the oral product. It is extremely difficult to do so. In particular, it has not been realized to retain the flavor for an appropriate period of time and to impart a high-quality persistent flavor called a lingering finish to the oral product.

JP-A-4-228035 Japanese Unexamined Patent Publication No. 3-155753 International Publication No. 00/6328 JP-A-2015-180221 International Publication No. 01/35768 Japanese Unexamined Patent Publication No. 2011-94044

The subject of the present invention is to provide a long-lasting flavor enhancer capable of solving the conventional problems, increasing the intensity of a high-quality flavor in the oral cavity and improving the persistence, and further enhancing the long-lasting flavor. The purpose of the present invention is to provide perfume compositions containing agents, oral products, particularly fruit juice beverages and favorite beverages.

As a result of diligent research to achieve the above object, the present inventors have found that p-mentor-8-S-glutationyl-3-one represented by the following formula (1) is flavored mainly by an enzymatic reaction in the oral cavity. In order to moderately enhance the intensity of flavors such as natural and high-quality richness, umami, and fruitiness, and to improve their sustainability, it is possible to provide a persistent flavor enhancer in the oral cavity such as food and drink. Finding a new fact that it will be possible, and further showing synergistically excellent effects by combining p-mentor-8-S-glutationyl-3-one and p-mentor-8-thiol-3-one. We also found that and completed the present invention.

That is, the present invention is as follows.
[1] A long-acting flavor enhancer, which comprises p-mentor-8-S-glutationyl-3-one represented by the following formula (1).

[2] A fragrance composition containing the long-acting flavor enhancer.
[3] A fragrance composition containing the long-acting flavor enhancer and p-mentor-8-thiol-3-one.
[4] A fragrance composition containing 1 to 100,000 ppm of the long-acting flavor enhancer.
[5] A fragrance composition containing 1 to 100,000 ppm of the long-acting flavor enhancer and 0.0001 to 10,000 ppm of p-mentor-8-thiol-3-one.

[6] An oral product comprising the long-acting flavor enhancer.
[7] An oral product characterized by containing 0.001 to 100 ppm of the long-acting flavor enhancer.
[8] An oral product comprising 0.001 to 100 ppm of the long-acting flavor enhancer and 0.000000001 to 10 ppm of p-mentor-8-thiol-3-one.
[9] An oral product comprising the fragrance composition.
[10] An oral product characterized by containing 0.01 to 1.0% by mass of the fragrance composition.
[11] A method for continuously enhancing the flavor of an oral product, which comprises adding 0.001 to 100 ppm of the sustained flavor enhancer.
[12] A method for continuously enhancing the flavor of an oral product, which comprises adding 0.01 to 1.0% by mass of the flavor composition.

[13] A long-acting flavor enhancer containing p-mentor-8-S-glutathionyl-3-one, which is a reaction product of glutathione and D-pregon, as an active ingredient.
[14] Glutathione and D-pregon are reacted in a solvent in the presence of a base catalyst to obtain a crude product containing p-mentor-8-S-glutathionyl-3-one, and then the crude product is prepared. A method for producing a long-lasting flavor enhancer, which comprises purifying.

[15] A long-acting flavor enhancer containing p-mentor-8-S-glutathionyl-3-one contained in a reaction product of a yeast extract containing glutathione and D-pregon as an active ingredient.
[16] Glutathione-containing yeast extract and D-pregon were reacted in a solvent in the presence of a base catalyst to obtain a crude product containing p-mentor-8-S-glutathionyl-3-one. The method for producing a long-acting flavor enhancer, which comprises purifying the crude product.

When the long-lasting flavor enhancer of the present invention is used in foods and drinks, it is possible to improve the long-lasting taste while increasing the high-quality flavor with an appropriate intensity, and consumers can feel the so-called afterglow. Can be provided to. In other words, it is possible to enhance the flavor of the food and sustain it for a long time, that is, to bring about a state of rising with the passage of time.
Further, the long-acting flavor enhancer of the present invention is easy to handle because it is excellent in solubility in a solvent and stability over time during storage. Further, it can be applied in any manufacturing process of various products to be added, and can be widely applied to various oral products, and is an extremely useful material.

Hereinafter, the present invention will be described in detail according to the embodiment. The long-acting flavor enhancer of the present invention is a compound represented by the above formula (1), that is, p-mentor-8-S-glutationyl-3-one.

Glutathione has been known to react with α and β unsaturated ketones to produce β-ketosulfide (Patent Document 6 and the like), but it has not been known to have a long-lasting flavor-enhancing effect.
The p-mentor-8-S-glutationyl-3-one of the present invention is more soluble in a solvent and more stable over time than, for example, p-mentor-8-S-cystinyl-3-one having a similar structure. In addition to having excellent properties, it also has an excellent flavor-enhancing effect, making it an extremely useful material.

The long-lasting flavor enhancer p-mentor-8-S-glutationyl-3-one of the present invention can be easily produced by the method described in Examples of Patent Document 6 described above.
That is, it is a method in which glutathione, D-pregon and a base catalyst (for example, pyridine) are reacted in a polar solvent such as alcohol to obtain a crude product, and then purified by means such as recrystallization and filtration.

Further, the glutathione used in the present invention may be a yeast extract containing glutathione as well as a synthetic product synthesized by a chemical method. In the present invention, any glutathione obtained by any method can be used, and when a yeast extract containing glutathione is used, the glutathione content is preferably 1% or more, particularly preferably 5% or more, most preferably. Use a yeast extract containing 8% or more of glutathione.

Further, the D-pulegone used in the present invention may be a synthetic product synthesized by a chemical method or one extracted from a plant containing D-pulegone.

In the present invention, when a base catalyst (for example, pyridine) is not used, a crude product containing p-mentor-8-S-glutationyl-3-one can be obtained by reacting at 20 to 70 ° C. for a long time. it can.
The crude product thus obtained can be used as it is as a long-lasting flavor enhancer, but it is purified by means such as recrystallization, filtration, solvent extraction, and a porous adsorbent to p-mentor-8-S-. It is preferable to increase the purity of glutathionyl-3-one before use.

As the porous adsorbent that can be used, activated carbon or a nonionic porous resin adsorbent is preferable because it is inexpensive and can be easily used.
The resin adsorbent is generally an insoluble three-dimensional crosslinked polymer having substantially no functional group such as an ion exchange group. For example, "Amberlite (registered trademark)" whose parent body is styrene-based. "XAD-16" (manufactured by Organo Co., Ltd.), "Sepabeads SP70 (trade name)" (manufactured by Mitsubishi Chemical Corporation) or "Diaion HP20 (trade name)" (Mitsubishi Chemical Co., Ltd.), which is a styrene-divinylbenzene copolymerization system. , Etc., but are not limited to these.

The long-acting flavor enhancer of the present invention can be appropriately added at the stage of manufacturing and processing an oral product.
The content varies depending on the type of oral product, product concept, etc., but generally, the p-mentor-8-S-glutationyl-3-one concentration is 0.001 to 100 ppm, preferably 0.005 to 100 ppm, more preferably. Is used at 0.005 to 50 ppm, particularly preferably 0.01 to 10 ppm, and most preferably 0.01 to 5 ppm.

When the long-acting flavor enhancer of the present invention is added to an oral product, it can be diluted with a solvent to further improve the diffusivity of the flavor and the stability of the long-acting flavor enhancer itself over time. .. Examples of such a solvent include ethanol and propylene glycol.
When ethanol is used, an aqueous solution having a concentration of 80 v / v% or less is suitable, and when propylene glycol is used, an aqueous solution of 1% by mass or more is suitable.

The long-acting flavor enhancer of the present invention combines p-mentor-8-S-glutationyl-3-one with p-mentor-8-thiol-3-one, which is known as a synthetic fragrance, as a fragrance composition. When used, it can exhibit an excellent synergistic effect of allowing a strong flavor to be felt in the oral cavity immediately after eating and drinking and even after 1 minute has passed.

Such a synergistic effect is such that p-mentor-8-S-glutationyl-3-one is usually 1-100,000 ppm, preferably 5-100,000 ppm, more preferably 5-50, in the perfume composition. It is exhibited when used at 000 ppm, particularly preferably 10 to 10,000 ppm, most preferably 10 to 5,000 ppm.
On the other hand, p-mentor-8-thiol-3-one is usually 0.0001 to 10,000 ppm, preferably 0.001 to 10,000 ppm, more preferably 0.001 to 1,000 ppm, and particularly preferably 0. It is exhibited when used at 0.01 to 1,000 ppm, most preferably 0.01 to 100 ppm.
In addition, p-mentor-8-thiol-3-one is a compound used in the food and drink field as a synthetic flavor, and a commercially available product can be purchased and used.

The sustained flavor enhancer of the present invention is also preferably used as a flavor composition mixed with a food and drink flavor other than the above-mentioned p-mentor-8-thiol-3-one. Examples of flavors used in this case include "Patent Agency Gazette, Well-known Common Techniques (Fragrances), Part II, Food Flavors" (issued January 14, 2000, Japan Patent Office) and " Perfume (essential oil, essence, concrete, absolute) described in the Patent Office Gazette, a collection of well-known and commonly used techniques (fragrance), Part III, fragrance for cosmetics (issued on June 15, 2001, Japan Patent Office), etc. , Extract, oleoledin, resinoid, recovered flavor, carbon dioxide extracted essential oil, isolated fragrance, synthetic fragrance) and the like.

When the long-acting flavor enhancer of the present invention is added to an oral product as a fragrance composition together with a fragrance, the amount of the fragrance composition added is usually 0.01 to 1.0% by mass, preferably 0.05 to 1. It is used in an amount of 0% by mass, more preferably 0.05 to 0.5% by mass, particularly preferably 0.08 to 0.5% by mass, and most preferably 0.1 to 0.3% by mass.

When the perfume composition of the present invention is added to an oral product, the concentration of p-mentor-8-S-glutationyl-3-one in the oral product is usually 0.001 to 100 ppm, preferably 0.005 to 100 ppm. , More preferably 0.005 to 50 ppm, particularly preferably 0.01 to 10 ppm, most preferably 0.01 to 5 ppm.
On the other hand, the concentration of p-mentor-8-thiol-3-one is usually 0.000000001 to 10 ppm, preferably 0.000001 to 10 ppm, more preferably 0.000001 to 1 ppm, and particularly preferably 0.00001 to 1 ppm. Most preferably, it is exhibited when used at 0.00001 to 0.1 ppm.

The long-acting flavor enhancer of the present invention can be used in various oral products without particular limitation.
The oral products referred to in the present invention refer to various foods and drinks, chemicals and oral hygiene products.
Foods and drinks include, for example, fruits or processed products thereof, vegetables or processed products thereof, seafood or processed products thereof, paste products, cooked foods, delicatessen, snacks, delicacies, processed foods, nutritional foods, tea beverages and Favorite beverages such as coffee beverages, fruit juice beverages, carbonated beverages, soft beverages, functional beverages, alcoholic beverages, ice cream, desserts such as sherbets, desserts such as jelly, pudding, and sheep can, cookies, cakes, chocolate, chewing gum, Examples include confectionery such as buns, confectionery bread, bread such as bread, jams, ramune, tablets, and tablet confectionery. The long-acting flavor enhancer of the present invention is stable in acidic (pH = 3.0) and neutral (pH = 6.0) aqueous solutions, and is a favorite beverage such as coffee beverage, fruit juice beverage, carbonated beverage, and soft drink. Beverages such as beverages, functional beverages and alcoholic beverages are particularly preferred.

In addition, Japanese soup stock, such as broth, seafood, kelp, shiitake, chicken, vegetables and other soup stock and Japanese-style seasonings, or Western soup stock, such as beef, chicken, pork, seafood, vegetables. Dashi stock and Western-style seasonings such as kelp, or Chinese food tan (hot water), for example, soup and Chinese seasonings taken from beef, chicken, pork, seafood, vegetables and the like.
In addition, the long-lasting flavor enhancer can be appropriately blended with a flavor component or a pigment to enhance the flavor and color tone. The flavor component or pigment used in the formulation is not particularly limited, and a known flavor component or pigment can be appropriately blended and used according to the purpose.

Oral hygiene products to which the long-acting flavor enhancer of the present invention is used include, for example, toothpastes such as toothpaste, toothpaste, powdered toothpaste, and liquid toothpaste, mouthwashes such as mouthwash, and mouth refreshing such as troches. Examples of products related to oral care such as agents can be exemplified.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The p-mentor-8-S-glutationyl-3-one and p-mentor-8-S-cystinyl-3-one used in Examples and Comparative Examples were synthesized and obtained in-house as follows.
For p-mentor-8-thiol-3-one, a product sold as a fragrance was obtained and used.
In addition, commercially available products were used for the grape juice drink, grapefruit juice jelly, blueberry yogurt drink, coffee drink, and tea bag used in the test.

[Production Example 1] (Synthesis of p-mentor-8-S-glutationyl-3-one)
Add 8 mL of distilled water and 2 mL of 99% ethanol to glutathione (1 g; 3.3 mmol), D-pregon (0.50 g; 3.3 mmol), and pyridine (0.52 g; 6.6 mmol) and stir at room temperature. did.
After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polar compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer portion.
The obtained aqueous layer is dried under reduced pressure conditions (10 mmHg) at 50 ° C., a small amount of a mixed solvent (ethanol: water = 80: 6) is added to the residue, and the mixture is heated to 50 ° C. to completely dissolve it. After that, it was recrystallized at room temperature and then in a refrigerator.
The resulting crystals were filtered by "Kiriyama Rohto" (registered trademark) manufactured by Kiriyama Glass Co., Ltd., washed with a small amount of ethanol, dried in a desiccator (under reduced pressure conditions), and 181.5 mg (yield 12.1). %) Was obtained.

[Reference Production Example 1] (Synthesis of p-mentor-8-S-cystinyl-3-one)
Add 8 mL of distilled water and 2 mL of 99% ethanol to cysteine (0.44 g; 3.6 mmol), D-pulegone (0.55 g; 3.6 mmol), and pyridine (0.52 g; 6.6 mmol) to room temperature. Stirred.
After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polar compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer portion.
The obtained aqueous layer is dried under reduced pressure conditions (10 mmHg) at 50 ° C., a small amount of a mixed solvent (ethanol: water = 80: 6) is added to the residue, and the mixture is heated to 50 ° C. to completely dissolve it. After that, it was recrystallized at room temperature and then in a refrigerator.
The resulting crystals were filtered off with "Kiriyama Rohto" (registered trademark), washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure conditions) to obtain 210.9 mg (yield 21.3%).
Here, p-mentor-8-S-cystinyl-3-one corresponds to the flavor enhancer (Flavor Freshness Enhancer) disclosed in Patent Document 5.

[Example 1]
To 100 parts by mass of a 50% grape juice beverage, 0.1 part by mass of a 100 ppm aqueous solution of p-mentor-8-S-glutationyl-3-one obtained in Production Example 1 was added, and p-mentor-8-S- A 50% grape juice beverage of the present invention containing 100 ppb (21.8 nmol) of glutathionyl-3-one was obtained.

[Example 2]
To 100 parts by mass of a 50% grape juice beverage, 0.1 part by mass of a 40.5 ppm aqueous solution of p-mentor-8-thiol-3-one was added, and further, p-mentor-8-S-glutationyl-3-one was added. Add 0.1 parts by mass of 100 ppm aqueous solution of p-mentor-8-thiol-3-one to 40.5 ppb (21.8 nmol), and p-mentor-8-S-glutationyl-3-one to 100 ppb (21.8 nmol). A 50% grape juice beverage of the present invention containing 21.8 nmol) was obtained.

[Example 3]
To 100 parts by mass of 50% grape juice beverage, 0.1 part by mass of a 20 ppm aqueous solution of p-mentor-8-thiol-3-one was added, and further, 20 ppm of p-mentor-8-S-glutationyl-3-one was added. Add 0.1 parts by mass of the aqueous solution to add 20 ppb (10.8 nmol) of p-mentor-8-thiol-3-one and 20 ppb (4.4 nmol) of p-mentor-8-S-glutationyl-3-one. A 50% grape juice beverage containing the present invention was obtained.

[Comparative Example 1]
To 100 parts by mass of a 50% grape juice beverage, 0.1 part by mass of a 59.5 ppm aqueous solution of p-mentor-8-S-cystinyl-3-one obtained in Reference Production Example 1 was added to p-mentor-8. A 50% grape juice beverage containing 59.5 ppb (21.8 nmol) of -S-cystinyl-3-one was obtained.

[Comparative Example 2]
To 100 parts by mass of a 50% grape juice beverage, 0.1 part by mass of a 40.5 ppm aqueous solution of p-mentor-8-thiol-3-one was added, and 40.5 ppb of p-mentor-8-thiol-3-one was added. A 50% grape juice beverage containing (21.8 nmol) was obtained.

[Test Example 1]
The 50% grape juice beverages obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were subjected to sensory evaluation by a skilled panel of 5 persons.
The evaluation items were the original richness and fruit juice feeling of grapes, and the strength of the flavor remaining in the oral cavity immediately after drinking, 30 seconds and 60 seconds after drinking was evaluated in the following 7 stages.
The average value of the evaluation results is shown in Table 1.

Feel very strong: 7
Feel strong: 6
Feel a little strong: 5
Feel: 4
Feels a little weak: 3
Feel weak: 2
Feels very weak: 1

From the results in Table 1, the long-lasting flavor enhancer of the present invention (Example 1) has an excellent lasting flavor as compared with the existing p-mentor-8-S-cystinyl-3-one (Comparative Example 1). It was shown to impart sex. Further, while the flavor expression of the existing p-mentor-8-thiol-3-one (Comparative Example 2) is biased toward the initiality, the p-mentor-8-S-glutationyl-3-one and p of the present invention are used. It was also shown that the combination of -mentor-8-thiol-3-one (Examples 2 and 3) showed an excellent flavor enhancing effect on the initiality and persistence of the flavor.

[Example 4]
To 100 parts by mass of commercially available 30% grapefruit juice jelly, 0.1 part by mass of a 100 ppm aqueous solution of p-mentor-8-S-glutationyl-3-one was added to add p-menta-8-S-glutationyl-3-one. A 30% grapefruit juice jelly of the present invention containing 100 ppb was obtained.
When this jelly was edible, the original dark flesh of grapefruit became stronger with the passage of time in the oral cavity.

[Example 5]
To 100 parts by mass of a commercially available blueberry yogurt drink, 0.1 part by mass of a 50 ppm aqueous solution of p-mentor-8-S-glutationyl-3-one was added, and 50 ppb of p-mentor-8-S-glutationyl-3-one was contained. Obtained the blueberry yogurt drink of the present invention.
When this yogurt drink was drunk, the original rich fruitiness of blueberries in the oral cavity became stronger with the passage of time.

[Example 6]
To 100 parts by mass of a commercially available black coffee beverage, 0.1 part by mass of a 250 ppm aqueous solution of p-mentor-8-S-glutationyl-3-one was added, and 250 ppb of p-mentor-8-S-glutationyl-3-one was contained. Obtained the black coffee of the present invention.
When this coffee beverage was drunk, the original richness and umami of black coffee became stronger with the passage of time in the oral cavity, and the aftertaste was masked.

[Example 7]
To 100 parts by mass of a black tea beverage brewed in a commercially available black tea bag, 0.1 part by mass of a 100 ppm aqueous solution of p-mentor-8-S-glutathionyl-3-one was added, and p-mentor-8-S-glutationyl- A black tea beverage of the present invention containing 100 ppb of 3-one was obtained.
When this black tea beverage was drunk, the original richness, tea leaf feeling, and sweetness of black tea became stronger with the passage of time in the oral cavity.

[Manufacturing Example 2]
Yeast extract containing 8% glutathione "Alomild U (trade name)" (manufactured by Kojin Life Science Co., Ltd.) 75 g, 203 g of distilled water, 97.5 g of 95 (v / v)% ethanol, D-pregon (18. 8 g) was added, stirred to be uniform, stored at 40 ° C. for 20 days, and then filtered using 40 g of diatomaceous earth to obtain 271 g as a filtrate.
To the obtained filtrate, 20 g of synthetically adsorbed tree Sepabeads SP70 (manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred at room temperature for 1 hour and then filtered to add 5000 ppm of p-mentor-8-S-glutationyl-3-one. 250 g of a contained ethanol aqueous solution was obtained.

[Example 8]
To 100 parts by mass of a 50% grape juice beverage, p-mentor-8-S-glutationyl-3-one prepared by diluting the ethanol aqueous solution obtained in Production Example 2 with 30 (W / W)% ethanol was added. 0.1 parts by mass of an aqueous ethanol solution containing 100 ppm was added to obtain a 50% grape juice beverage of the present invention containing 100 ppb of p-mentor-8-S-glutationyl-3-one.

[Test Example 2]
The 50% grape juice beverages obtained in Examples 1 and 8 (both containing p-mentor-8-S-glutationyl-3-one 100 ppb) were subjected to sensory evaluation by a panel of three skilled workers.
Using the evaluation method of Test Example 1, the original richness and fruit juice feeling of grapes were evaluated, and the strength of the flavor remaining in the oral cavity immediately after drinking, 30 seconds and 60 seconds after drinking was evaluated. As a result, production using yeast extract was performed. The persistent flavor enhancer of Example 2 was found to have the same flavor persistence as that of the sustained flavor enhancer of Production Example 1.

[Test Example 3]
To 100 parts by mass of a 50% grape juice beverage, p-mentor-8-S-glutationyl-3-one prepared by diluting the ethanol aqueous solution obtained in Production Example 2 with 30 (W / W)% ethanol was added. 0.1 part by mass of an aqueous ethanol solution containing 100 ppm was added, and p-mentor-8-thiol-3-one was further added so that the concentrations in the beverage were 10 ppt, 100 ppt, 1 ppb and 10 ppb.
When this 50% grape juice beverage was drunk, it was compared with the 50% grape juice beverage to which p-mentor-8-S-glutationyl-3-one and p-mentor-8-thiol-3-one were not added. In each of the beverages, the original richness and fruit juice of grapes were strongly felt from immediately after drinking to 60 seconds after drinking in the oral cavity.

[Test Example 4]
The stability of p-mentor-8-S-glutationyl-3-one and p-mentor-8-S-cystinyl-3-one in aqueous solution was evaluated.
For evaluation, 1 ppm aqueous solutions of acidic (pH = 3.0) and neutral (pH = 6.0) were prepared for both compounds and stored at 50 ° C. for 14 days (corresponding to storage at room temperature for 1 year). The residual rate of the compound was measured by high performance liquid chromatography. The results are shown in Table 2.

From the results in Table 2, it can be seen that the long-acting flavor enhancer of the present invention has excellent stability in the acidic and neutral regions as compared with the existing p-mentor-8-S-cystinyl-3-one. Shown.

[Test Example 5]
The solubility of p-mentor-8-S-glutationyl-3-one and p-mentor-8-S-cystinyl-3-one in various solvents was evaluated.
p-mentor-8-S-glutationyl-3-one showed excellent solubility in any of 50% aqueous ethanol solution, propylene glycol, and a mixed solution of 50% propylene glycol and 50% ethanol.
On the other hand, for p-mentor-8-S-cystinyl-3-one, turbidity or precipitation occurred in any of the above solvents.

The long-lasting flavor enhancer of the present invention can enhance the persistence of excellent flavors such as richness, umami, and fruitiness with respect to general-purpose oral products in general. In addition, it is an extremely useful material because it has excellent solubility in a solvent and stability over time.

Claims

A long-lasting flavor enhancer comprising p-mentor-8-S-glutationyl-3-one represented by the following formula (1).
A fragrance composition comprising the long-acting flavor enhancer according to claim 1.
A fragrance composition containing the long-acting flavor enhancer according to claim 1 and p-mentor-8-thiol-3-one.
A fragrance composition containing 1 to 100,000 ppm of the long-acting flavor enhancer according to claim 1.
A fragrance composition comprising 1 to 100,000 ppm of the long-acting flavor enhancer according to claim 1 and 0.0001 to 10,000 ppm of p-mentor-8-thiol-3-one.
An oral product characterized by containing the long-acting flavor enhancer according to claim 1.
An oral product characterized by containing 0.001 to 100 ppm of the long-acting flavor enhancer according to claim 1.
An oral product characterized by containing 0.001 to 100 ppm of the long-acting flavor enhancer according to claim 1 and 0.000000001 to 10 ppm of p-mentor-8-thiol-3-one.
An oral product comprising the fragrance composition according to any one of claims 2 to 5.
An oral product characterized by containing 0.01 to 1.0% by mass of the fragrance composition according to any one of claims 2 to 5.
A method for continuously enhancing the flavor of an oral product, which comprises adding 0.001 to 100 ppm of the sustained flavor enhancer according to claim 1.
A method for continuously enhancing the flavor of an oral product, which comprises adding 0.01 to 1.0% by mass of the fragrance composition according to any one of claims 2 to 5.
A long-acting flavor enhancer characterized by containing p-mentor-8-S-glutathionyl-3-one, which is a reaction product of glutathione and D-pregon, as an active ingredient.
Glutathione and D-pregon are reacted in a solvent, optionally in the presence of a base catalyst, to give a crude product containing p-mentor-8-S-glutathionyl-3-one, followed by purification of the crude product. 13. The method for producing a long-acting flavor enhancer according to claim 13.
A long-acting flavor enhancer characterized by containing p-mentor-8-S-glutathionyl-3-one contained in a reaction product of a yeast extract containing glutathione and D-pregon as an active ingredient.
Glutathione-containing yeast extract and D-pregon are reacted in a solvent, optionally in the presence of a base catalyst, to give a crude product containing p-mentor-8-S-glutathionyl-3-one, followed by crude production. The method for producing a long-acting flavor enhancer according to claim 15, which comprises purifying a product.