JP6824926B2 - Food and beverage flavor improver - Google Patents

Description

The present invention relates to a food and drink flavor improving agent, and more particularly to a food and drink flavor improving agent containing 3-methylbutano-1,3-dithiol as an active ingredient.

In recent years, consumer demands for the flavor of foods and drinks have diversified, and in various flavors, there are demands for a natural feeling and demands for improving satisfaction including taste, richness, and volume. However, in response to such demands, it may be difficult to increase the amount of food and drink raw materials used due to health consciousness and cost issues. Therefore, there has been a demand for a perfume compound or composition capable of enhancing flavor and natural feeling in a well-balanced manner and imparting richness and satisfaction.

Some of the flavor compounds not only add or enhance the odor, but also enhance the richness, thickness, and volume of food and drink, as if they also act on the taste, and use abundant raw materials. There is something that makes me feel. It can be said that such a flavor compound is a very useful compound from the viewpoint of palatability and manufacturing cost in these days when food and drink are strongly natural-oriented and health-oriented, and the development of such a flavor compound is awaited. ..

For example, a compound that enhances the richness of a specific flavor, such as a compound that can enhance the richness of milk flavor (see Patent Document 1), is known.

In addition, some compounds have been identified from food and drink raw materials in the thiols to which the active ingredient of the flavor improving agent of the present invention belongs. For example, there is a document describing that alkanedithiols such as 1,2-ethanedithiol, 2,3-butanedithiol, and 1,6-hexanedithiol are useful for imparting a cooked meat-like aroma (Patent Documents). 2), 1,1-ethanedithiol (see Non-Patent Document 1) has been identified as a volatile component of cooked beef, and 1-pentanethiol (see Non-Patent Document 2) has been identified from Asatsuki.

However, the above compounds and conventional methods are monotonous in terms of aroma and flavor quality and strength, and are not sufficient in terms of enhancing richness and overall satisfaction, and can be used. For at least one reason, such as the limited number of foods and drinks, the demand for improving the flavor of diversified foods and drinks has not been sufficiently met, and the development of new flavor improving agents has been expected.

3-Methylbutane-1,3-dithiol, which is the active ingredient of the flavor improving agent of the present invention, is thioacetate as one of the compounds listed in the literature on a method for producing various thiols or thioacetates by biological conversion. Although it is described that it can be obtained by the decomposition of (see Patent Document 3), no specific aroma characteristics are known.

Japanese Unexamined Patent Publication No. 2017-018025 Japanese Unexamined Patent Publication No. 50-12277 International Publication No. 01/77359

J. Agric. Food Chem. 1991, Vol. 39, p. 336-343 J. Food Sci. 1983, Vol. 48, p. 1858-1859

An object of the present invention is to provide a novel flavor improving agent capable of improving the flavor of foods and drinks and a flavor composition containing the same.

As a result of diligent studies to solve the above problems, the present inventors surprisingly add 3-methylbutano-1,3-dithiol, whose aroma characteristics have not been known at all, to foods and drinks or to blend them. It has been found that by blending an effective amount into a fragrance composition, an unprecedentedly good flavor can be obtained.

Thus, the present invention provides:
[1] A flavor improving agent for foods and drinks containing 3-methylbutano-1,3-dithiol represented by the formula (1) as an active ingredient.

[2] A perfume composition containing the flavor improving agent according to [1].
[3] The fragrance composition according to [2], wherein the concentration of the compound represented by the formula (1) is 1 ppt to 1000 ppm.
[4] A food or drink with improved flavor, wherein the flavor improving agent or flavor composition is blended with 0.001 ppt to 100 ppb as a compound represented by the formula (1).
[5] A method for improving the flavor of food or drink, which comprises blending the flavor improving agent or flavor composition into food or drink at a concentration of 0.001 ppt to 100 ppb as a compound represented by the formula (1).

So far, nothing has been confirmed about 3-methylbutane-1,3-dithiol (which may be referred to as the compound of the present invention in the present specification) in terms of its aroma characteristics and its compounding effect. The present inventors have found a completely unexpected and surprising effect that this compound significantly improves the flavor of foods and drinks. Therefore, according to the present invention, it is possible to provide a novel flavor improving agent capable of improving the flavor of food and drink. The flavor improving agent of the present invention is useful as a compounding material for flavor compositions that can improve the flavor of consumer goods such as foods and drinks and other articles to enhance palatability.

Embodiments of the present invention will be described in more detail.

(Flavor improver of the present invention)
The flavor improving agent of the present invention is characterized by containing a compound represented by the following formula (1), that is, 3-methylbutano-1,3-dithiol as an active ingredient.

As a result of blending the flavor improving agent of the present invention, the flavor of foods and drinks having various flavors is remarkably improved. As a result, when eating or drinking a food or drink containing the flavor improving agent of the present invention or a food or drink containing a flavor composition containing the flavor improving agent of the present invention, the aroma and / or taste is enhanced and the body feeling is enhanced. Increased, mellowness enhanced, satisfaction enhanced, volume increased, taste thickness enhanced, taste (eg umami) enhanced, flavor lingering more One or more of longer lasting, enhanced aroma and / or taste of food and drink ingredients, enhanced mellowness, enhanced naturalness, improved overall flavor balance, etc. By the effect of, the flavor of the flavor composition and food and drink can be improved. The flavor means a comprehensive sense of aroma and taste.

The form of the flavor improving agent of the present invention is not particularly limited, and a solution, emulsified preparation, powder preparation, or other solid preparation in which the active ingredient 3-methylbutane-1,3-dithiol is dissolved in a water-soluble or oil-soluble solvent ( It may be solid fat, etc.).

(Method for producing 3-methylbutano-1,3-dithiol)
3-Methylbutano-1,3-dithiol, which is the active ingredient of the flavor improving agent of the present invention, may be obtained by any method. For example, it can be obtained by chemical synthesis by a production method according to the following reaction route. The reagents and various conditions (temperature, time, etc.) described in the following reaction pathways may be appropriately changed as long as the desired reaction proceeds.

First, an alkylthio group is introduced into the aldehyde (3-methyl-2-butenal) of the formula (2) by a nucleophilic addition reaction, and then a hydroxyl group, which is a portion into which the thiol group is introduced, is generated by a reduction reaction.

In the formula of the reaction pathway 1, R represents an arbitrary alkyl group, but is preferably an inert group (so-called protecting group), and for example, a benzyl group can be exemplified. As the nucleophile, any compound can be used as long as the reaction proceeds, and for example, triethylamine, pyridine, 2,6-lutidine, N, N-diisopropylethylamine (DIPEA) and the like can be exemplified, and triethylamine is preferable. The reaction temperature is not particularly limited and may be, for example, 25 ° C. (about room temperature) or lower, but the lower the temperature, the longer the reaction time, so about room temperature is preferable.

The reducing agent used in the subsequent reduction reaction is not particularly limited, and examples thereof include sodium borohydride and lithium aluminum hydride. The solvent in the reduction reaction is arbitrary as long as it does not cause a reaction with the reaction substrate, and examples thereof include methanol, ethanol, and isopropyl alcohol.

Then, a protecting group is introduced into the hydroxyl group of the compound of the formula (3) to obtain the mesylate of the formula (4). In the formula, a mesylate group is introduced as a protecting group, but other protecting groups such as a tosyl group may also be used. This reaction may be carried out in any organic solvent that does not react with the reaction substrate, and examples thereof include ether-based solvents such as diethyl ether and dichloromethane. The reaction temperature is not particularly limited, but is usually carried out between 0 ° C. and 25 ° C. (about room temperature).

Then, the mesylate moiety in the mesylate of the formula (4) is alkylthiolated to obtain the alkyldithiol compound of the formula (5). In the formula, R'is an arbitrary alkyl group like R in the reaction pathway 1, preferably an inactive group, for example a benzyl group. The strong base for alkyl thiolation is not particularly limited, and examples thereof include sodium hydride and potassium hydride. The organic solvent that can be used in this reaction is arbitrary as long as it does not react with the reaction substrate, and examples thereof include N, N-dimethylformamide (DMF), tetrahydrofuran (THF), and dimethyl sulfoxide (DMSO). The reaction temperature is usually about 0 to 20 ° C.

Next, as the reaction pathway 4, the alkyldithiol compound of the formula (5) obtained in the reaction pathway 3 is reduced to obtain the target compound, 3-methylbutane-1,3-dithiol of the formula (1).

The reduction reaction is not particularly limited, but the Birch reaction can be preferably used. In the case of the Birch reaction, an alkali metal such as sodium or lithium can be reacted with the compound of the formula (5) in a low temperature solvent such as liquid ammonia to reduce the alkylthio group to a thiol group.

The obtained 3-methylbutano-1,3-dithiol may be appropriately purified by vacuum distillation or column chromatography.

In the above reaction route, the reaction time may be determined while monitoring the progress of the reaction by gas chromatography, thin layer chromatography or the like. Further, after completion of the reaction, the desired reaction product may be extracted with an organic solvent, dried, and the solvent may be removed to obtain a purified product. The organic solvent used for extraction is not particularly limited, and but dichloromethane, diethyl ether, hexane and the like can be exemplified. The obtained organic solvent may be appropriately washed (for example, sodium thiosulfate water, water, sodium carbonate water, etc.). The drying method is not particularly limited, but the drying may be carried out using an anhydrous product such as anhydrous magnesium sulfate or silica gel. The solvent can be generally removed by distilling off the solvent with a rotary evaporator or the like.

(Fragrance composition of the present invention)
The flavor compound of the present invention contains a predetermined amount of 3-methylbutano-1,3-dithiol represented by the formula (1), and can be blended in foods and drinks. The type of the fragrance composition of the present invention is not particularly limited, and examples thereof include water-soluble fragrance compositions, oil-soluble fragrance compositions, emulsified fragrance compositions, and powder fragrance compositions.

The flavor composition of the present invention can be blended with foods and drinks and used at least for the purpose of improving the flavor of the foods and drinks. For example, when the flavor composition of the present invention exhibits a citrus-like scent, the flavor may be improved and the citrus-like scent may be imparted by adding the flavor composition to the food or drink.

The concentration of 3-methylbutano-1,3-dithiol in the fragrance composition of the present invention can be arbitrarily determined according to the compounding target of the fragrance composition. As an example of the concentration, 1 ppt to 1000 ppm, preferably 10 ppt to 100 ppm (in the present specification, all "-" means a range including a lower limit value and an upper limit value) with respect to the total mass of the fragrance composition. Within the range. More specifically, the lower limit is 1 pt, 10 pp, 100 pp, 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, and the upper limit is 1000 ppm, 100 ppm, 10 ppm, 1 ppm, 100 ppb, 10 ppb, 1 ppb, Any combination of these lower limit value and upper limit value can be set as any of 100 ppt and 10 ppt, but is not limited thereto. Further, as an example of a preferable concentration range, it can be selected from each range of 100 ppb to 1000 ppm, 100 ppb to 100 ppm, 1 ppm to 100 ppm, and 1 ppm to 1000 ppm according to the aroma characteristics of the fragrance composition, but is not limited thereto. .. Although it depends on the formulation and fragrance tone of the fragrance composition, if the concentration of 3-methylbutano-1,3-dithiol in the fragrance composition is less than 1 ppt, the flavor of the fragrance composition may vary depending on the person. It may be felt that the improving effect is low, and if it exceeds 1000 ppm, the fragrance derived from 3-methylbutano-1,3-dithiol is strong depending on the person, and the fragrance composition to be blended has an unfavorable alteration in aroma and / or flavor characteristics. May feel like giving.

Further, the fragrance compound of the present invention may contain any other compound or component in addition to 3-methylbutano-1,3-dithiol.

Examples of such compounds or ingredients are various fragrance compounds or compositions, oil-soluble pigments, vitamins, functional substances, fish extracts, livestock extracts, vegetable extracts, yeast extracts, animal and plant proteins. Classes, animal and plant proteolytic products, starch, dextrin, sugars, amino acids, nucleic acids, organic acids, solvents and the like can be exemplified. For example, "Patent Agency Gazette, Well-known and Conventional Techniques (Fragrances) Part II Food Flavors, published on January 14, 2000", "Fact-finding Survey on the Use of Food Fragrance Compounds in Japan" (2000 Health Science Research) Described in the report, Japan Fragrance Industry Association, published in March 2001), and "Synthetic Fragrance Chemistry and Product Knowledge" (December 20, 2016, supplemented new edition, edited by Synthetic Fragrance Editing Committee, Chemical Industry Daily) Examples include natural essential oils, natural fragrances, and synthetic fragrances.

Examples of synthetic fragrance compounds include monoterpenes such as α-pinene, β-pinene, myrcene, camphene and limonene, sesquiterpenes such as Valensen, sedren, cariophyllene and longifolene, 1,3,5-un Examples include hydrocarbons.

Examples of the alcohol compound include linear / saturated alkanols such as butanol, pentanol, 3-octanol and hexanol, and linear / unsaturated alcohols such as (Z) -3-hexene-1-ol, plenol and 2,6-nonazienol. , Linalool, geraniol, citronellol, tetrahydromilsenol, farnesol, nerolidol, sedrol and other terpenal alcohols, benzyl alcohol, phenylethyl alcohol, cinnamyl alcohol and other aromatic alcohols.

Examples of the aldehyde compound include linear / saturated aldehydes such as acetaldehyde, hexanal, octanal, decanal, and hydroxycitroneral, linear / unsaturated aldehydes such as (E) -2-hexenal, and 2,4-octadienal, and citronellal. , Terpenaldehyde such as citral, myltenal, perylaldehyde, aromatic aldehyde such as benzaldehyde, cinnamylaldehyde, vanillin, ethyl vanillin, heliotropin, p-tolylaldehyde.

Examples of the ketone compound include linear / saturated and unsaturated ketones such as 2-heptanone, 2-undecanone, 1-octen-3-one, and acetoin, diacetyl, 2,3-pentandione, maltor, ethylmaltor, cycloten, and 2 , 5-Dimethyl-4-hydroxy-3 (2H) -Franone and other linear and cyclic diketones and hydroxyketones, carboxylics, menthons, nutcatons and other terpene ketones, α-ionone, β-ionone, β-damasenone and other terpenes. Examples include aromatic ketones such as ketones and raspberry ketones derived from decomposition products.

Examples of the furan or ether compound include furfuryl alcohol, furfural, rose oxide, linalool oxide, mentofran, theaspirane, estragole, eugenol, 1,8-cineole and the like.

Ester compounds include ethyl acetate, isoamyl acetate, ethyl butyrate, ethyl isobutyrate, isoamyl butyrate, ethyl 2-methylbutyrate, ethyl 3-methylbutyrate, 2-methylbutyl isobutyrate, ethyl hexanoate, allyl hexanoate, ethyl heptate. , Alius esters such as ethyl caproate, isoamyl isovalerate, ethyl nonanoate, terpenic alcohol esters such as linaryl acetate, geranyl acetate, lavandryl acetate, terpenyl acetate, benzyl acetate, methyl salicylate, methyl silicate, cinnamyl propionate. , Ethyl benzoate, cinnamyl isovalerate, ethyl 3-methyl-2-phenylglycidate and other aromatic esters.

Examples of the lactone compound include saturated lactones such as γ-decalactone, γ-dodecalactone, δ-decalactone and δ-dodecalactone, and unsaturated lactones such as 7-decene-4-olid and 2-decene-5-olid. ..

Examples of the acid compound include saturated and unsaturated fatty acids such as acetic acid, butyric acid, octanoic acid, isobaric acid, caproic acid, stearic acid, oleic acid, linoleic acid and linolenic acid.

Examples of the nitrogen-containing compound include indole, skatole, pyridine, alkyl-substituted pyrazine, methyl anthranilate, and trimethylpyrazine.

Examples of sulfur-containing compounds include methanethiol, dimethyl sulfide, dimethyl disulfide, allyl isothiocyanate, 3-methyl-2-butene-1-thiol, 3-methyl-2-butanethiol, 3-methyl-1-butanethiol, and 2 -Methyl-1-butanethiol, flufuryl mercaptan and the like.

Natural essential oils include sweet orange, bitter orange, petitgrain, lemon, bergamot, mandarin, neroli, peppermint, spearmint, lavender, matricaria, rosemary, eucalyptus, sage, basil, rose, hyacinth, lilac, geranium, jasminum, Iran Iran. , Anis, cloves, ginger, nutmeg, cardamon, sugi, hinoki, vetiver, mint, lovedanum, etc.

Examples of various animal and plant extracts include extracts of herbs or spices, extracts of coffee, green tea, black tea, or oolong tea, milk or processed dairy products, and various enzymatic decomposition products such as lipases and / or proteases thereof.

The fragrance composition of the present invention can be prepared by blending the compound of the present invention with an appropriate solvent or dispersion medium by a known method.

The fragrance composition of the present invention includes a solution in which 3-methylbutane-1,3-dithiol and other components are dissolved in a water-soluble or oil-soluble solvent, an emulsified preparation, a powder preparation, and other solid preparations (solid fat, etc.). Etc. are preferable.

Examples of the water-soluble solvent include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, propylene glycol and the like. Of these, ethanol or glycerin is particularly preferable from the viewpoint of use in foods and drinks. Examples of the oil-soluble solvent include vegetable fats and oils, animal fats and oils, refined fats and oils (for example, processed fats and oils such as medium-chain fatty acid triglycerides, short-chain fatty acid triglycerides such as triacetin and tripropionin), various essential oils, and triethylcitrate. Etc. can be exemplified.

Further, in order to prepare an emulsified preparation, 3-methylbutano-1,3-dithiol can be obtained by emulsifying with a water-soluble solvent and an emulsifier. The method for emulsifying 3-methylbutane-1,3-dithiol is not particularly limited, and various types of emulsifiers conventionally used in foods and drinks, such as fatty acid monoglyceride, fatty acid diglyceride, fatty acid triglyceride, and propylene glycol. Fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, lecithin, chemical starch, sorbitan fatty acid ester, Kiraya extract, Arabic gum, tragant gum, guar gum, Karaya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, casein An emulsified solution having excellent stability can be obtained by emulsification treatment using an emulsifier such as Kiraya saponin or sodium caseinate using a homomixer, a colloid mill, a rotary disk type homogenizer, a high-pressure homogenizer or the like. The amount of these emulsifiers used is not strictly limited and can be changed over a wide range depending on the type of emulsifier used, etc., but usually, with respect to 1 part by mass of 3-methylbutano-1,3-dithiol, A range of about 0.01 to about 100 parts by mass, preferably about 0.1 to about 50 parts by mass is suitable. In addition to water, such water-soluble solvent solutions include polyhydric alcohols such as glycerin, propylene glycol, sorbitol, maltitol, sucrose, glucose, trehalose, sugar solutions, and reduced water candy in order to stabilize emulsification. One type or a mixture of two or more types can be blended.

Further, the emulsion thus obtained can be made into a powder preparation by drying if desired. At the time of pulverization, sugars such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, and reduced starch syrup can be appropriately added as needed. The amount of these to be used can be appropriately selected according to the characteristics desired for the powder formulation and the like.

The fragrance composition of the present invention may further contain components usually used in the fragrance composition, if necessary. For example, solvents such as water and ethanol, and fragrances such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzylbenzoate, triethylcitrate, diethylphthalate, harcholine, medium-chain fatty acid triglyceride, and medium-chain fatty acid diglyceride are retained. The agent can be contained.

(Use of the flavor improving agent or flavor composition of the present invention in foods and drinks)
The flavor improving agent and flavor composition of the present invention can be used by blending with various foods and drinks or flavor compositions used therein.

The flavor improver or flavor composition of the present invention may be blended alone in a flavor composition or a food or drink, or one or more water-soluble flavors, emulsified flavor compositions, any flavor compound, natural Essential oils (for example, described in "Patent Agency Gazette, Well-known and Conventional Techniques (Fragrances) Part II Food Flavors", "Fact-finding Survey on the Use of Food Fragrance Compounds in Japan", and "Synthetic Fragrance Chemistry and Product Knowledge" Perfume compound), may be blended together with one or more selected from.

Foods and drinks to which the flavor improving agent or fragrance composition of the present invention can be blended are not particularly limited, and examples thereof include lemon, orange, grapefruit, lime, mandarin, black tea, kabos, sudachi, hassaku, iyokan, yuzu, shikuwasa, and golden citrus. Various citrus flavors such as strawberry, blueberry, raspberry, apple, cherry, plum, apricot, peach, pineapple, banana, melon, mango, papaya, kiwi, pear, grape, muscat, giant peak and other fruit flavors; milk, yogurt , Butter and other milk flavors; vanilla flavors; green tea, black tea, oolong tea, herb tea and other tea flavors; coffee flavors; cacao flavors; cocoa flavors; spice mint, peppermint and other mint flavors; cinnamon, chamomile, cardamon, caraway , Cumin, cloves, pepper, coriander, sunshaw, perilla, ginger, staranis, thyme, pepper, nutmeg, basil, majorum, rosemary, laurel, wasabi and other spices or herbal flavors; almonds, cashew nuts, walnuts Various nut flavors; various liquor flavors such as wine, brandy, whiskey, lamb, gin, liqueur, Japanese sake, shochu, beer; vegetable flavors such as carrot, tomato, cucumber ;; beverages having one or more flavors such as ..

More specific examples of food and drink include rice crackers, hail, okonomiyaki, rice cakes, buns, sardines, bean paste, sheep cans, water sheep cans, brocade balls, jelly, castella, candy balls, biscuits, crackers, potato chips, cookies, etc. Confectionery such as pie, pudding, butter cream, custard cream, cream puff, waffle, sponge cake, donut, chocolate, chewing gum, caramel, candy, peanut paste and other pastes; bread, udon, ramen, Chinese noodles, sushi, Breads such as Gomoku rice, fried rice, pilaf, dumpling skin, Shumai skin, okonomiyaki, takoyaki, etc., noodles, rice; rice crackers, plum pickles, Fukujin pickles, betta pickles, thousand pickles, rakkyo, miso pickles, takuan pickles, and Pickles such as those pickles; fish such as mackerel, sardines, saury, salmon, tuna, bonito, whale, curry, squid, sweetfish, squid such as sulmeika, spear squid, crested squid, firefly squid, madako, Octopus such as octopus, shrimp such as car shrimp, button shrimp, rice cracker, black tiger prawn, crabs such as taraba crab, zuwai crab, cotton crab, and kegani, and seafood such as asari, hamaguri, scallop, oyster, and mussels;
Processed seafood such as canned, boiled fish, boiled soybeans, ground meat, marine products (chikuwa, sardines, fried sardines, crab foot sardines, etc.), fried foods, tempura, etc.; chicken, pork, beef, sheep, horse meat, etc. Livestock meat; curry, stew, beef stew, hayashi rice sauce, meat sauce, marbo tofu, hamburger, dumplings, pot rice base, soups (corn soup, tomato soup, consomme soup, etc.), meat dumplings, boiled meat, canned meat, etc. Processed foods and drinks using livestock meat; tabletop salt, seasoning salt, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hisoshio, sprinkle, Ochazuke no Moto, margarine, mayonnaise, dressing, vinegar, three cups vinegar, powdered sushi vinegar, Chinese Nomoto, Tentsuyu, Mentsuyu (Konbu-dashi or Katsu-dashi, etc.), Sauce (Nakano sauce, Tomato sauce, etc.), Ketchup, Grilled meat sauce, Curry roux, Stew-no-moto, Soup-no-moto, Dashi-no-moto (Konbu-dashi or eel Dashi, etc.), complex seasonings, new mirin, mixed powders such as fried powder and takoyaki powder, and other seasonings, animal or vegetable flavored foods and drinks to which these seasonings are added; cheese, yogurt , Butter and other dairy products; Boiled vegetables, Chikuzen boiled, Oden, pots and other boiled foods; Take-out lunch ingredients and side dishes; Apples, grapes, citrus fruits (grapefruit, orange, lemon, etc.) and other fruit juices and juices Beverages and soft drinks with fruit juice, fruit meat drinks and fruit drinks with fruit grains; vegetables such as tomatoes, peppers, celery, uri, niggauri, carrots, potatoes, asparagus, warabi, zenmai, and vegetables including these vegetables Beverages, vegetable-containing foods and drinks such as vegetable soups; favorite beverages such as coffee, cocoa, green tea, tea, crow dragon tea, soft drinks, wine, beer, non-alcoholic beer; beverages containing raw medicines and herbs; cola beverages, fruit juice beverages, Milk drinks, beer-taste drinks, sports drinks, honey drinks, vitamin-supplemented drinks, mineral-supplemented drinks, nutritional drinks, nourishing drinks, lactic acid bacteria drinks, various alcoholic beverages (beer flavor, plum wine flavor, chewy flavor, etc.) Non-alcoholic beverages; Chuhai, cocktail drinks, sparkling liquor, fruit liquor, seasoned liquor, other brewed liquor (foaming) such as so-called "third beer" or alcoholic beverages such as liqueur (foaming); Can be mentioned.

In the present invention, the concentration of 3-methylbutano-1,3-dithiol in various foods and drinks can be arbitrarily determined according to the flavor of the foods and drinks and the degree of desired effect. For example, an example of the concentration is in the range of 0.001 ppt to 100 ppb with respect to the total mass of food and drink. More specifically, the lower limit is 0.001 ppt, 0.01 ppt, 0.1 ppt, 1 ppt, 10 ppt, 100 ppt, 1 ppb, 10 ppb, and the upper limit is 100 ppb, 10 ppb, 1 ppb, 100 ppt, 10 ppt, 1 ppt. As any of 1, 1 ppt, 0.1 ppt, and 0.01 ppt, the range of any combination of these lower limit value and upper limit value can be mentioned, but is not limited thereto. As an example of a preferable concentration, the concentration of the compound of the present invention is 0.1 ppt to 10 ppb, 0.1 ppt to 100 ppb, 1 ppt to 10 ppb, 1 pt to 100 ppb, 10 pt to 10 ppb, 10 pt to 100 ppb, based on the total mass of the food or drink. It can be selected from the ranges of 100 pt to 10 ppb and 100 pt to 100 ppb according to the flavor characteristics of the food and drink, but is not limited thereto. Although it depends on the type and flavor of the food and drink, if the concentration of the compound of the present invention in the food and drink is less than 0.001 ppt, some people who eat and drink may feel that the effect of improving the flavor is low, and 100 ppb. If it exceeds the above, some people who eat and drink may feel that the flavor of the food or drink to be blended is unfavorably altered.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited thereto. Further, the concentration described in the examples means a mass concentration unless otherwise specified.

[Example 1] Synthesis of 3-methylbutano-1,3-dithiol 3-methylbutano-1,3-dithiol was synthesized by the following method.

A flask was charged with 3-methyl-2-butenal (also known as senesioaldehyde) of the formula (2) (manufactured by Kuraray, 16.8 g, 200.0 mmol) and triethylamine (1.0 g, 10.0 mmol), and stirred under ice-water cooling. did. Benzyl mercaptan (BnSH, 24.8 g, 200.0 mmol) was added dropwise into the system. After completion of the dropping, the mixture was stirred at room temperature for 24 hours, methanol (20.0 g) was added, and NaBH ₄ (1.9 g, 30.1 mmol) was added into the system. After completion of the addition, the mixture was stirred at room temperature for 2 hours, water and diethyl ether were added to separate the organic layer, and the organic layer was washed with saturated brine, dried and concentrated in order to obtain a concentrate. The obtained concentrate was subjected to distillation to obtain an alcohol compound of the formula (3) in a yield of 85.1% and a purity of 98.4%.

Next, the alcohol compound of the formula (3) (21.1 g, 100.0 mmol), triethylamine (15.3 g, 151.0 mmol) and diethyl ether (250 mL) were charged in a flask, and the mixture was stirred under ice-water cooling. A mixed solution of methanesulfonyl chloride (MsCl, 13.8 g, 120.0 mmol) and diethyl ether (50 mL) was added dropwise to the system. After completion of the dropping, the mixture was stirred at the same temperature for 5 hours. The reaction solution was washed successively with water and saturated brine, and concentrated with an evaporator to obtain a crude product of the mesylate compound of the formula (4).

Next, N, N-dimethylformamide (DMF) (220.0 g) and sodium hydride (60%, 5.2 g, 128.7 mmol) were charged in a flask, and the mixture was stirred under ice-water cooling. Benzyl mercaptan (14.7 g, 118.0 mmol) was added dropwise to the system, and the mixture was stirred at the same temperature for 30 minutes. Then, a mixed solution of the crude product of the mesylate compound of the formula (4) obtained in the previous step (assumed to be 30.9 g and 107.3 mmol) and DMF (20 g) was added dropwise, and the mixture was stirred at the same temperature for 1 hour. .. Water was added and the mixture was extracted with hexane, and the organic layer was washed with water again and then concentrated by an evaporator to obtain a crude product of the bisbenzylthioether of the formula (5).

Liquid ammonia was charged into the flask, 6.0 g (261.1 mmol) of metallic sodium was added at −60 ° C., and the mixture was stirred at the same temperature. A mixed solution of the crude product of bisbenzylthioether of the formula (5) obtained in the previous step (20.0 g, assuming 63.2 mmol) and diethyl ether (20 mL) was added dropwise to the system, and the temperature was the same. Stirred. After stopping the reaction by adding a saturated aqueous solution of ammonium chloride, the mixture was stirred overnight at room temperature to evaporate and remove ammonia. Diethyl ether and water were added to the obtained reaction product to separate the organic layer, which was then washed successively with water and saturated brine. The obtained organic layer was concentrated by an evaporator to obtain a concentrate. The obtained concentrate was subjected to distillation to obtain 3-methylbutano-1,3-dithiol of the formula (1) in a yield of 19.1% (3 steps) and a purity of 98.3%.

The physical property data of the compound obtained by the above method was as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ ppm
2.63-2.69 (m, 2H), 1.87-1.91 (m, 2H), 1.38 (s, 6H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ ppm
51.3, 44.38, 32.61, 20.61
MS (EI, 7eV) m / z 27 (4), 41 (43), 47 (27), 55 (12), 57 (14), 59 (9), 61 (27), 69 (90), 75 (31), 87 (20), 89 (3), 102 (55), 103 (15), 136 (100), 137 (8), 138 (9).
The 3-methylbutano-1,3-dithiol synthesized as described above was used as the flavor improving agent of the present invention in the following examples.

[Example 2] Effect of addition to various fruit-flavored foods and drinks An orange-like basic blended flavor composition and a pineapple-like basic blended flavor composition were prepared according to the general formulations shown in the table below.

An appropriate amount of an ethanol solution containing 0.1% of the flavor improving agent (3-methylbutane-1,3-dithiol) of the present invention was added to each of the obtained basic blended flavor compositions to obtain the flavor improving agent of the present invention. , 10 ppt, 1 ppb, 1 ppm, and 10 ppm, respectively, to prepare a fragrance composition of the present invention. Then, 15 well-trained panelists were asked to use each basic blended fragrance composition as a comparative product (the orange-like basic blended fragrance composition was designated as comparative product 1 and the pineapple-like basic blended fragrance composition was designated as comparative product 2). The volume of the scent became very strong = 4 points, clearly strengthened = 3 points, slightly strengthened = 2 points, no change = 1 point, and a strange taste = 0 points. Let me comment on the fragrance. Table 3 shows the average results of the 15 panelists.

Then, using the perfume composition of the product of the present invention 2, 3, 4, 5, 6 as the perfume composition of the present invention, the mass of 3-methylbutane-1,3-dithiol in the juice was added to a commercially available orange juice. The fruit-flavored beverage of the present invention was obtained by blending so that the concentrations were 0.001 ppt, 0.01 ppt, 1 ppt, 1 ppb, and 10 ppb. Similarly, the flavor compositions of the products of the present invention 7, 8, 9, 10 and 11 were blended with commercially available pineapple juice at the same concentrations as in the case of orange juice to obtain the beverage of the present invention.

Each fruit juice beverage was sensory evaluated by 15 well-trained panelists. In the sensory evaluation, it was clear that the panelists were very strong in terms of "richness", "afterglow" and "favorability", with the additive-free juice as a comparative product, and the flavor compared with the comparative product = 4 points. The score was given as 3 points for strengthening, 2 points for slightly stronger, 1 point for no change, and 0 points for feeling a strange taste, and comments on the flavor. Here, the voluminous feeling means a favorable feeling with a feeling of satisfaction, which is rich in overall thickness, richness, and eating response. Table 4 shows the average results of the 15 panelists.

As shown in Table 4, according to the present invention, the richness and finish of fruit-flavored foods and drinks are enhanced, the volume feeling is satisfactorily enhanced, and a well-balanced flavor is obtained, and as a result, the palatability of various fruit beverages is enhanced. It was confirmed that it could be significantly improved.

[Example 3] Effect of addition to various milk-flavored foods and drinks In a commercially available coffee beverage containing milk or a commercially available yogurt-flavored beverage, 3-methylbutane-1,3-dithiol is listed in the table below with respect to the total mass of each beverage. The milk-flavored beverage of the present invention was obtained by blending so as to have a concentration of. These beverages of the present invention were subjected to sensory evaluation by 15 well-trained panelists. In the sensory evaluation, when compared with the commercial product without the addition of the fragrance composition, the "richness", "afterglow", and "favorability" were very strong = 4 points, and clearly stronger = 3 The score was given as points, slightly stronger = 2 points, no change = 1 point, and a strange taste = 0 points, and comments were made regarding the flavor. Table 5 shows the average results of the 15 panelists.

As shown in Table 5, the milk-flavored beverage of the present invention has a markedly enhanced richness and finish as compared with the comparative product, and also has enhanced volume, body feeling, good milk fat feeling, mellowness and the like. It was evaluated that it felt like this, and it was confirmed that it was a highly palatable beverage.

[Example 4] Effect of addition to various beer-flavored beverages Commercially available non-alcoholic beer and low-malt beer are prepared as commercially available beer-flavored beverages, and the flavor improver of the present invention (Product 1 of the present invention) is described in the table below. The beer-flavored beverage of the present invention was obtained by blending to a concentration. On the other hand, as a comparative example, 3-methyl-1-butanethiol, which is a thiol compound, was blended so as to have the concentration shown in Table 6 below to obtain a comparative beer-flavored beverage. This compound is known to have been identified from beer.

Next, sensory evaluation was performed by 15 well-trained panelists using commercially available non-alcoholic beer beverages and low-malt beer containing nothing as controls. In the sensory evaluation, "richness", "drinking", "afterglow", and "favorability" were scored using the following criteria, and comments on the flavor were entered. Table 6 shows the average results of the 15 panelists.
(Sensory evaluation score standard)
0: Lower than control product, 1: Equivalent, 2: Slightly enhanced, 3: Clearly enhanced, 4: Significantly enhanced

As shown in Table 6, the beer-flavored beverage of the present invention has a markedly enhanced richness, volume, responsiveness, and aftertaste as compared with the comparative product, and also has a good hop-like bitterness and taste. It was evaluated that it felt like a hop, and it was confirmed that it was a very palatable beverage with the same richness and satisfaction as real beer. In addition, carbonation stimulation and throat sensation were also good.

[Example 5] Effect of addition to foods having a soup stock A commercially available corn soup and soup for oden are prepared, and the flavor improving agent of the present invention (Product 1 of the present invention) is blended so as to have the concentration shown in Table 7 below. Then, the soup stock flavored food of the present invention was obtained. On the other hand, as a comparative example, methanethiol, which is a thiol compound, was blended so as to have the concentrations shown in Table 7 below to obtain comparative corn soup and soup for oden. It is described in JP-A-2004-135522 that this compound can be used in a perfume composition for fish section.

Next, sensory evaluation was performed by 15 well-trained panelists using commercially available corn soup containing nothing and soup for oden as controls. In the sensory evaluation, "richness", "drinking", "afterglow", and "favorability" were scored using the following criteria, and comments on the flavor were entered. Table 7 shows the average results of 15 panelists.
(Sensory evaluation score standard)
0: Lower than control product, 1: Equivalent, 2: Slightly enhanced, 3: Clearly enhanced, 4: Significantly enhanced

As shown in Table 7, the dashi-flavored food of the present invention has a markedly enhanced richness, volume, drinkability, and lingering finish as compared with the comparative product, and the enhanced taste enhances the body feeling and enhances the mellowness. It was evaluated that there was a feeling of satisfaction as if the ingredients were used abundantly, and it was confirmed that the food was very palatable.

[Example 6] Effect of addition to coffee flavor A commercially available black coffee is prepared, and the flavor improving agent of the present invention (product 1 of the present invention) is blended so as to have the concentration shown in Table 8 below, and the coffee beverage of the present invention is prepared. Got On the other hand, as a comparative example, methanethiol, which is a thiol compound, was blended so as to have the concentration shown in Table 8 below to obtain a comparative coffee beverage. It is described in JP-A-2006-20526 that this compound can be used in a coffee flavoring composition.

Next, sensory evaluation was performed by 15 well-trained panelists using black coffee containing nothing as a control product. In the sensory evaluation, "richness", "drinking", "afterglow", and "favorability" were scored using the following criteria, and comments on the flavor were entered. Table 8 shows the average results of 15 panelists.
(Sensory evaluation score standard)
0: Lower than control product, 1: Equivalent, 2: Slightly enhanced, 3: Clearly enhanced, 4: Significantly enhanced

As shown in Table 8, the coffee beverage of the present invention has significantly enhanced richness, volume, response to drinking, and afterglow, as well as umami and aroma, and improved balance as compared with the comparative product. It was confirmed that the beverage was highly palatable.

Claims (5)

A flavor improving agent for foods and drinks containing 3-methylbutano-1,3-dithiol represented by the formula (1) as an active ingredient.

A flavor composition containing the flavor improving agent according to claim 1. The fragrance composition according to claim 2, wherein the concentration of the compound represented by the formula (1) is 1 ppt to 1000 ppm. A food or drink with improved flavor, wherein the flavor improving agent according to claim 1 or the flavor composition according to claim 2 or 3 is blended with 0.001 ppt to 100 ppb as a compound represented by the formula (1). Goods. A method for improving the flavor of a food or drink, which comprises blending the flavor improving agent or a flavor composition into a food or drink at a concentration of 0.001 ppt to 100 ppb as a compound represented by the formula (1).