JP7332568B2 - 3-Methyl-3-butene-1-thiol as a flavoring agent - Google Patents

Description

The present invention relates to 3-methyl-3-butene-1-thiol and flavoring agents.

In recent years, consumer demand for various products such as food, beverages, cosmetics, pharmaceuticals, and hygiene products has extended to the quality of product flavor. Needs are growing.

For example, many compounds containing sulfur atoms (sulfur-containing compounds) are found in foods as trace aroma components, and are considered to be important compounds for reproducing the natural flavor of foods.
Examples of typical sulfur-containing compounds found in nature include thiols such as 2-furylmethanethiol (furfurylmercaptan) and 3-methyl-2-butene-1-thiol, which volatilize coffee. As ingredients, 1-p-mentene-8-thiol (thioterpineol) has been found as an important volatile component in grapefruit, and 2-methylfuran-3-thiol has been found as a volatile component in beef soup, which are used as flavoring agents. It is widely used as a chemical compound. In addition, some compounds having a mercapto group (also called a thiol group or a sulfanyl group) and a carboxylic acid ester group in the molecule are known, and specific examples include 3-mercapto-4-methyl Pentyl acetate is described as presenting a rhubarb-like aroma and increasing in hops aged 51 days or more from flowering. Patent Document 2 describes that 3-mercapto-3-methylbutyl formate can be used to enhance specific flavors such as freshly roasted sesame. Patent Document 3 discloses that 3-mercapto-3-methylbutyl acetate can impart a freshly brewed feeling to coffee in combination with other sulfur-containing compounds such as 2-furfurylmethylsulfide and 2-furfurylmethyldisulfide. is described.

Each sulfur-containing compound has its own flavor quality and intensity, but conventional sulfur-containing compounds alone are limited in flavor. Therefore, for the reason of wanting to obtain a more natural flavor and the reason of responding to various consumer demands for product flavor, the search for a new compound useful as a flavor-imparting agent has been continued.

WO2018/139153 JP 2010-148412 A JP 2008-259472 A

An object of the present invention is to provide compounds useful as flavoring agents.

As a result of intensive research by the present inventors in order to solve the above problems, 3-methyl-3-butene-1-thiol represented by formula (1), which is a compound whose use in imparting flavor has not been known in the past, has been found. , It has been found that when blended in various articles such as food and drink, cosmetics, and health and hygiene products, it exhibits an excellent flavoring effect for a wide range of flavors, and is extremely useful as a flavoring compound.
3-Methyl-3-butene-1-thiol has been conventionally used as a synthetic raw material (China Patent Application Publication 109306221 and Japanese Patent Application Publication 1998-109972) and as one of the materials related to the chemical reaction mechanism (Tetrahedron Letters (1975), ( 41), 3551-4), but it was a completely unknown compound in terms of its flavor properties and its use as a flavor imparting agent or fragrance.
Thus, the present invention provides the following.
[1] A flavor imparting agent containing 3-methyl-3-butene-1-thiol represented by the following formula (1) as an active ingredient.

[2] A fragrance composition containing the flavor-imparting agent according to [1].
[3] Consumer goods containing the flavor-imparting agent of [1] or the fragrance composition of [2].
[4] A method for imparting flavor to a flavoring composition, comprising blending the flavoring agent of [1] into the flavoring composition.
[5] A method for imparting flavor to consumer goods, comprising blending the flavor imparting agent of [1] or the flavor composition of [2] into consumer goods.

ADVANTAGE OF THE INVENTION By this invention, the compound which can be used as a new flavor imparting agent can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with specific examples. In the present specification, "-" means a range including the lower and upper limits, and concentration, ppm, ppb, ppt, and % each represent mass concentration unless otherwise specified.

(How to obtain 3-methyl-3-butene-1-thiol)
3-Methyl-3-butene-1-thiol can be obtained from known available raw materials by combining various known synthetic reactions. It can be obtained by carrying out a halogenation reaction using -1-ol as a starting material, reacting the resulting halide with potassium thioacetate, and then cleaving the acetyl group with a reducing agent. The obtained 3-methyl-3-butene-1-thiol may be further purified by known methods such as column chromatography and vacuum distillation, if necessary.

3-Methyl-3-butene-1-thiol itself can impart flavor to various articles by blending it into various articles as a flavor imparting agent. The present inventors have found that this compound itself exhibits a roasted aroma similar to coffee, grilled meat, and freshly baked bread, but as described below, not only does it have a roasted aroma similar to coffee, roasted meat, and freshly baked bread, but it is also very The present inventors discovered the high usefulness of being effective in imparting various flavors, and arrived at the present invention.

The articles to be blended are not particularly limited, but consumer goods such as food and drink, cosmetics, and medical hygiene products can be exemplified. Furthermore, the compound of the present invention can be blended into various perfume compositions to impart fragrance to the composition.

As used herein, flavor means one or more of the senses that may be altered by scent, typically including smell and taste. As used herein, the term "adding flavor" includes newly adding or enhancing the flavor, and for example, the flavor may be improved as a result of the addition. Furthermore, as a result of imparting flavor, sensations other than olfactory and gustatory sensations, such as cold sensation, warm sensation, texture (such as throat, hardness, viscosity, etc., also referred to as texture), stimulating sensation such as carbonic acid and hotness, etc. may be enhanced, suppressed, or improved. Moreover, in the context of food and drink, flavor can be rephrased as flavor.

(Perfume composition of the present invention)
The fragrance composition of the present invention can be used for the purpose of imparting flavor, contains an effective amount of a flavor imparting agent consisting of 3-methyl-3-butene-1-thiol, and can be blended into various articles. Specific examples thereof include fragrance compositions for food and drink (also referred to as flavor compositions) and fragrance compositions for cosmetics (also referred to as fragrance compositions). Examples of articles to be blended include, as described above, consumer goods such as food and drink, cosmetics, and medical hygiene products. The form of the perfume composition of the present invention is not particularly limited, and examples thereof include a water-soluble perfume composition, an oil-soluble perfume composition, an emulsified perfume composition, and a powdered perfume composition. The flavor of the fragrance composition is not particularly limited, but specific examples and examples of particularly preferred flavors will be described in detail in the section (Use for various articles) below.

The concentration of 3-methyl-3-butene-1-thiol in the fragrance composition of the present invention can be arbitrarily determined according to the desired fragrance of the fragrance composition, the fragrance to be blended, the application, and other characteristics. Examples of such concentrations include 0.1 ppt to 10%, preferably 10 ppt to 5%, more preferably 0.1 ppb to 1%, based on the total weight of the perfume composition. More specifically, the lower limit is 0.1 ppt, 1 ppt, 10 ppt, 100 ppt, 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, 1000 ppm, 1%, or 5%, and the upper limit is 10%, 5 %, 1%, 1000 ppm, 100 ppm, 10 ppm, 1 ppm, 100 ppb, 10 ppb, 1 ppb, 100 ppt, 10 ppt, 1 ppt within any combination of these lower and upper limits, but these is not limited to Although it depends on the formulation and fragrance tone of the perfume composition, when the concentration of formula 3-methyl-3-butene-1-thiol in the perfume composition is less than 0.1 ppt, 3-methyl-3-butene -It may be felt that the blending effect of 1-thiol is low, and if it exceeds 10%, the scent derived from 3-methyl-3-butene-1-thiol is strong and is not preferable for the flavor characteristics of the fragrance composition to be blended. Although it may be felt that it imparts deterioration, it may be blended at a concentration below the lower limit or above the upper limit depending on the fragrance tone of the fragrance composition to be blended.

Also, the perfume composition of the present invention may contain any other compound or ingredient in addition to 3-methyl-3-butene-1-thiol. Examples of such compounds or ingredients include various flavor compounds or flavor compositions, oil-soluble pigments, vitamins, functional substances, fish extracts, livestock meat extracts, plant extracts, yeast extracts, animal and plant proteins. , animal and plant protein decomposition products, starch, dextrin, saccharides, amino acids, nucleic acids, organic acids, solvents and the like. For example, "Patent Office Gazette, Collection of Well-known and Commonly Used Techniques (Fragrance) Part II Food Flavors, Issued on January 14, 2000", "Survey on the Usage of Food Flavoring Compounds in Japan" (2000 Welfare Science Research Report, Japan Perfumery Industry Association, published March 2001) and "Synthetic Perfume Chemistry and Product Knowledge" (published December 20, 2016, enlarged new edition, edited by the Synthetic Perfume Editorial Committee, The Chemical Daily) natural essential oils, natural fragrances, synthetic fragrances, and the like.

Specific examples of synthetic fragrance compounds include hydrocarbon compounds such as monoterpenes such as α-pinene, β-pinene, γ-terpinene, myrcene, camphene and limonene; sesquiterpenes such as valencene, cedrene, caryophyllene and longifolene; 3,5-undecatriene and the like.

Alcohol compounds include saturated or unsaturated alcohols such as butanol, pentanol, 3-octanol, hexanol, (Z)-3-hexen-1-ol, prenol, 2,6-nonadienol, linalool, geraniol, citronellol, tetrahydro Examples include terpene alcohols such as myrcenol, farnesol, nerolidol, cedrol, α-terpineol, terpinen-4-ol and borneol, and aromatic alcohols such as benzyl alcohol, phenylethyl alcohol and cinnamyl alcohol.
Aldehyde compounds include saturated or unsaturated aldehydes such as acetaldehyde, hexanal, octanal, decanal, (E)-2-hexenal, and 2,4-octadienal, citronellal, hydroxycitronellal, citral, myrtenal, perillaldehyde, and the like. aromatic aldehydes such as terpenealdehyde, benzaldehyde, cinnamylaldehyde, vanillin, ethylvanillin, heliotropine, and p-tolylaldehyde.

Ketone compounds include saturated or unsaturated ketones such as 2-heptanone, 2-undecanone, 1-octen-3-one, acetoin, 6-methyl-5-hepten-2-one (methylheptenone), diacetyl, 2,3 - diketones and hydroxyketones such as pentanedione, maltol, ethyl maltol, cyclotene, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, terpene ketones such as carvone, menthone, nootkatone, α-ionone, β- Examples include ketones derived from terpene decomposition products such as ionone and β-damascenone, and aromatic ketones such as raspberry ketone.

Furan or ether compounds include furfuryl alcohol, furfural, rose oxide, linalool oxide, menthofuran, theaspirane, estragole, eugenol, 1,8-cineole, and the like.

Ester compounds include ethyl acetate, isoamyl acetate, octyl acetate, ethyl butyrate, ethyl isobutyrate, isoamyl butyrate, ethyl 2-methylbutyrate, ethyl isovarate, 2-methylbutyl isovarate, ethylhexano Aliphatic esters such as ate, allylhexanoate, ethylheptanoate, ethylcaprylate, isoamylisovalerate, and ethylnonanoate; linalyl acetate, geranyl acetate, lavandulyl acetate, terpinyl acetate, neryl acetate, etc. Aromatic esters such as terpene alcohol esters, benzyl acetate, methyl salicylate, methyl cinnamate, cinnamyl propionate, ethyl benzoate, cinnamyl isovarate, ethyl 3-methyl-3-phenyl glycidate.

The lactone compounds include saturated or unsaturated lactones such as γ-decen-decenate, γ-dodecalactone, δ-decen-decenate, δ-dodecalactone, 7-decen-4-olide, 2-decene-5-olide.

Acid compounds include saturated or unsaturated fatty acids such as acetic acid, butyric acid, isovaleric acid, caproic acid, octanoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and the like.

Nitrogen-containing compounds include indole, skatole, pyridine, methyl anthranilate, and trimethylpyrazine.

Sulfur-containing compounds include methanethiol, dimethylsulfide, dimethyldisulfide, allyl isothiocyanate, 3-methyl-2-butene-1-thiol, 3-methyl-2-butanethiol, 3-methyl-1-butanethiol, 2 -methyl-1-butanethiol, 3-mercaptohexanol, 4-mercapto-4-methyl-2-pentanone, 3-mercaptohexyl acetate, p-mentha-8-thiol-3-one and furfuryl mercaptan. .

Natural essential oils include sweet orange, bitter orange, petitgrain, lemon, bergamot, mandarin, grapefruit, lime, neroli, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, hyacinth, lilac, geranium, Jasmine, ylang-ylang, anise, cloves, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, labdanum, etc.

Various animal and plant extracts include herb or spice extracts, coffee, green tea, black tea, or oolong tea extracts, milk or processed milk products, and various enzymatic decomposition products thereof such as lipase and/or protease.
The perfume composition of the present invention can be prepared by blending 3-methyl-3-butene-1-thiol with an appropriate solvent or dispersion medium by a known method.
Examples of the form of the perfume composition of the present invention include solutions in which 3-methyl-3-butene-1-thiol and other components are dissolved in a water-soluble or oil-soluble solvent, emulsified formulations, powder formulations, and other solid formulations (solid fats). etc.) are preferred.

Examples of water-soluble solvents include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, and propylene glycol. Among these, ethanol or glycerin is particularly preferable from the viewpoint of use in foods and drinks. Oil-soluble solvents include vegetable oils, animal oils, refined oils (for example, processed oils such as medium-chain fatty acid triglycerides and short-chain fatty acid triglycerides such as triacetin and tripropionin), various essential oils, and triethyl citrate. etc. can be exemplified.
In addition, an emulsified formulation can be obtained by emulsifying 3-methyl-3-butene-1-thiol with a water-soluble solvent and an emulsifier. The method for emulsifying 3-methyl-3-butene-1-thiol is not particularly limited, and various types of emulsifiers conventionally used in food and drink, such as fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, Propylene glycol fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, lecithin, modified starch, sorbitan fatty acid ester, quillaya extract, gum arabic, tragacanth gum, guar gum, karaya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin , casein quillayasaponin, sodium caseinate, etc., and emulsification using a homomixer, a colloid mill, a rotating disk-type homogenizer, a high-pressure homogenizer, or the like, an emulsified liquid having excellent stability can be obtained. The amount of these emulsifiers to be used is not strictly limited, and can vary over a wide range depending on the type of emulsifier used. about 0.01 to about 100 parts by mass, preferably about 0.1 to about 50 parts by mass. In order to stabilize the emulsification, such a water-soluble solvent liquid contains, in addition to water, polyhydric alcohols such as glycerin, propylene glycol, sorbitol, maltitol, sucrose, glucose, trehalose, sugar solution, and reduced starch syrup. One type or a mixture of two or more types can be blended.

Moreover, the emulsion thus obtained can be made into a powder formulation by drying if desired. At the time of pulverization, saccharides such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, reduced starch syrup, etc., can be added as appropriate. The amount of these agents to be used can be appropriately selected according to the desired properties of the powder formulation.

The perfume composition of the present invention may further contain ingredients commonly used in perfume compositions, if desired. For example, solvents such as water and ethanol, and fragrances such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hakoline, medium chain fatty acid triglyceride, medium chain fatty acid diglyceride. A retention agent may be included.

(Use for various articles)
The flavor-imparting agent of the present invention and the fragrance composition of the present invention containing it can be used by blending in various articles or fragrance compositions used therefor.

For example, the flavor-imparting agent of the present invention and the flavoring composition containing it may itself be blended in food or drink, or may be one or more water-soluble flavorings, emulsified flavoring compositions, or any Flavoring compounds, natural essential oils (for example, the above-mentioned "Patent Office Gazette, Collection of Well-known and Commonly Used Techniques (Fragrance) Part II Food Flavoring", "Survey on the Usage of Food Flavoring Compounds in Japan", and "Synthetic Flavoring Chemistry and Product Knowledge Fragrance compounds described in ”), may be blended in various articles in combination with one or more selected from.

Food and drink that can be blended with the flavor imparting agent of the present invention or the flavor composition of the present invention containing it is not particularly limited, but examples include coffee flavor; freshly baked bread flavor; roasted butter flavor; beer flavor; Roasted meat flavor; Hojicha flavor; Roasted grain tea flavor; Cola flavor; Cacao flavor; Cocoa flavor; Citrus flavor; various fruit flavors such as strawberry, blueberry, raspberry, apple, cherry, plum, apricot, peach, pineapple, banana, melon, mango, papaya, kiwi, pear, grape, muscat grape, and Kyoho grape (excluding the citrus mentioned above) Milk flavors such as milk, yogurt and butter; Vanilla flavor; Various tea flavors such as green tea, black tea, oolong tea and herbal tea; Various mint flavors such as spearmint and peppermint; Various spices or herbal flavors such as pepper, coriander, Japanese pepper, perilla, ginger, star anise, thyme, capsicum, nutmeg, basil, marjoram, rosemary, laurel, garlic, wasabi; various nut flavors such as almonds, cashews, walnuts. wine, brandy, whiskey, rum, gin, liqueur, sake, shochu, and other alcoholic beverage flavors; celery, carrot, tomato, cucumber, and other vegetable flavors; chicken, duck, pork, beef, mutton, horse meat, and other meat Flavor: red fish such as tuna, white fish such as mackerel, sea bream, salmon and horse mackerel, freshwater fish such as sweetfish, trout and carp, shellfish such as turban shells, clams, clams and freshwater clams, various crustaceans such as shrimp and crab, wakame seaweed , seaweed such as kelp, various seafood and seaweed flavors; various grain flavors such as rice, barley, wheat, malt, etc.; livestock oils and fats such as beef tallow, chicken oil, lard, and various fish oils Food and drink having one or more of flavors such as various oil and fat flavors such as. That is, it may be a food or drink that makes you feel only one of the above flavors, or it may be a food or drink that makes you feel two or more flavors, and the plurality of flavors may be the same or different. Examples of fruit flavors include those that make you feel multiple fruit flavors such as banana, peach and apple flavors (so-called mixed fruit flavors), and examples of the latter include those that make you feel citrus flavors such as lemon and milk flavors (citrus Flavored lactic acid bacteria drink, etc.), and those with mint flavor, citrus flavor, and cola flavor (mint or lemon flavored cola drink, etc.).

In particular, the flavor-imparting agent of the present invention or the flavor composition of the present invention containing it is excellent for various foods and drinks such as coffee flavor, freshly baked bread flavor, roast butter flavor, beer flavor, onion flavor and grilled meat flavor. A fragrance effect can be exhibited.

For example, it is possible to enhance the aroma of top notes such as roasted aroma and dry roasted feeling drifting from the surface of coffee beans, increase freshness, and further enhance the preferable sourness of coffee. In addition, the freshly baked bread flavor has the sweetness of freshly roasted bread, the roasted butter flavor has a sweet and fragrant top flavor like burnt butter, and the beer flavor has a crisp malty top flavor of malt. The onion flavor can be given a sweet and fragrant top flavor when the onion is fried to a caramel color, and the yakiniku flavor can be given a sweet and fragrant flavor of freshly grilled meat. can.

Furthermore, for example, various citrus or fruit flavors, fruit juice feeling, pulp feeling (a sensation that reminds you of the fiber quality and texture of the pulp), pericarp feeling (a feeling that you feel when you eat the peel, such as bitterness, oily, fibrous, etc.) One or more senses of), matured feeling (for example, a feeling that aging has progressed, such as ripe fruit, matured wine or whiskey), bitterness, body, and freshness. Various livestock meat or seafood flavors have a juicy feeling (e.g., moist meat or a feeling reminiscent of meat juice), a fatty feeling derived from livestock or seafood, and a cooking feeling (reminiscent of the aroma and richness that can be felt when eating cooked food). It is possible to impart one or more flavors such as a feeling of elasticity), a feeling of body, a feeling of freshness, and a feeling of thickness (for example, a feeling of elasticity reminiscent of meat and a feeling reminiscent of fiber), and a body feeling derived from nuts for various nut flavors. , a feeling of fat and oil, a texture reminiscent of real nuts, or a natural feeling. In particular, it can effectively add one or more of juiciness such as fruit juice and gravy, body, and fatness to food and drink, and comprehensively improve the texture, satisfaction, naturalness, thickness, etc. of food and drink. It is possible to increase the palatability of food and drink.

Here, in this specification, the body feeling includes the feeling that the flavor is firm, mellow and plump, and brings volume and strength to the overall taste. The fresh feeling is reminiscent of natural raw materials such as fruits, vegetables, and leaves that have a flavor that can contribute to various flavors, or immediately after processing them (freshly picked, freshly cut, freshly ground, freshly shaved, It includes the sense of reminiscent of the flavor felt in freshly slapped paper, etc.). Thickness includes the feeling that the flavor is not monotonous and that various flavors are felt in a well-balanced manner.
More specific examples of food and drink include senbei, arare rice crackers, rice cakes, rice cakes, steamed buns, uiro, red bean paste, yokan, mizu yokan, kingyoku, jelly, castella, hard candy, biscuits, crackers, potato chips, cookies, 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, Gomoku rice, fried rice, pilaf, gyoza skin, shumai skin, okonomiyaki, takoyaki, and other breads, noodles, rice; Pickles such as those pickle bases; Fish such as mackerel, sardines, saury, salmon, tuna, bonito, whale, flatfish, sand eel, sweetfish, squid such as flying squid, spear squid, crest squid, firefly squid, common octopus, Octopus such as octopus, prawns such as tiger prawns, botan prawns, spiny lobsters and black tigers, crabs such as king crabs, snow crabs, blue crabs and horse crabs, shellfish such as clams, clams, scallops, oysters and mussels; Processed seafood foods such as canned foods, boiled fish, tsukudani, surimi, fish paste products (chikuwa, kamaboko, fried kamaboko, crab leg kamaboko, etc.), fried foods, tempura; chicken, pork, beef, mutton, horse meat, etc. Meat: Curry, stew, beef stew, hayashi rice sauce, meat sauce, mapo tofu, hamburg steak, dumplings, kamameshi mix, soups (corn soup, tomato soup, consommé soup, etc.), meatballs, braised cubes, canned meat, etc. Processed foods and drinks using livestock meat; Table salt, Seasoning salt, Soy sauce, Powdered soy sauce, Miso, Powdered miso, Moromi, Hishio, Furikake, Ochazuke mix, Margarine, Mayonnaise, Dressing, Vinegar, Sanbaizu, Powdered sushi vinegar, Chinese food Nomoto, tempura sauce, noodle soup (kelp or bonito stock, etc.), sauce (chuno sauce, tomato sauce, etc.), ketchup, yakiniku sauce, curry roux, stew mix, soup stock, dashi stock (kelp or bonito stock) Dashi, etc.), seasonings such as compound seasonings, new mirin, mixed flour such as fried chicken powder and takoyaki powder, animal or plant-based dashi-flavored foods and drinks with these seasonings added; cheese, yogurt , butter and other dairy products; various yeasts such as brewer's yeast and baker's yeast; various microbial fermented products such as lactic acid bacteria; , Fruit juice drinks such as citrus fruits (grapefruit, orange, lemon, etc.), soft drinks containing fruit juice, fruit pulp drinks and fruit drinks containing fruits; Vegetables such as bracken and fern, vegetable drinks containing these vegetables, vegetable-containing food and drink such as vegetable soup; coffee, cocoa, green tea, black tea, oolong tea, soft drinks, cola drinks, carbonated drinks (various flavors such as citrus flavor cider, etc.), lactic acid beverages, and other beverages; beverages containing herbal medicines and herbs; Functional drinks such as honey drinks, vitamin supplement drinks, mineral supplement drinks, nutrition drinks, nutrition drinks, lactic acid drinks; wine, shochu, awamori, sake, beer, chuhai, cocktail drinks, low-malt beer, fruit wine, spiced wine, so-called "third beer" and other brewed alcoholic beverages (sparkling) or liqueurs (sparkling), or alcoholic beverages containing these;

Cosmetics to which the flavoring agent of the present invention and the fragrance composition of the present invention containing it can be blended are not particularly limited, but examples include perfumes such as eau de cologne, eau de toilette, eau de parfum, and parfum; shampoos, rinses, and hair styling. Hair care products such as cosmetics (hair cream, pomade, etc.); Cosmetics such as foundation, lipstick, lip balm, lip gloss, lotion, cosmetic milky lotion, cosmetic cream, cosmetic gel, serum, pack agent; Antiperspirant Deodorant products such as sprays, deodorant sheets, deodorant creams, and deodorant sticks; bath agents such as inorganic salt-based, refreshing, carbon dioxide-based, skin care, enzyme-based, and herbal medicine-based products; sunscreen products such as suntan products and sunscreen products. ;Facial cleansers such as face soaps and cleansing creams, body soaps and soaps, laundry soaps, laundry detergents, disinfectant detergents, deodorant detergents, softeners, kitchen detergents, cleaning detergents, etc. for health and hygiene Detergents; Health and hygiene materials such as toothpaste, tissue paper, and toilet paper; Fragrance products such as deodorants for rooms and cars, and room fragrances;

The flavor-imparting agent of the present invention or the flavoring composition of the present invention containing it is not particularly limited, and the flavor can be improved by the flavoring agent of the present invention or the perfume composition containing the same. Any scent tone may be used, but citrus tone, floral tone, fruity tone, green tone, woody tone, moss tone, tropical flower tone, and the like can be suitably used. More specifically lemon, orange, grapefruit, lime, yuzu, kabosu, strawberry, raspberry, apple, pineapple, mango, peach, banana, melon, grape, papaya, kiwi, grapes, rose, jasmine, lily of the valley, hyacinth. , lilac, plumeria, etc., but not limited to these. For example, when blended in various floral-scented articles, it is possible to increase the lively freshness and splendor of flowers.

In the present invention, the concentration of 3-methyl-3-butene-1-thiol in various articles such as food, beverages and cosmetics can be arbitrarily determined according to the flavor of the article and the desired degree of flavoring effect.

As an example of the concentration, in the case of food and drink, the concentration of 3-methyl-3-butene-1-thiol is 0.001ppt to 1000ppm, preferably 0.01ppt to 100ppm, relative to the total weight of the food and drink. Preferably, it is within the range of 0.1 ppt to 10 ppm.

More specifically, the lower limit is 0.001ppt, 0.01ppt, 0.1ppt, 1ppt, 10ppt, 100ppt, 1ppb, 10ppb, 100ppb, 1ppm, 10ppm or 100ppm, and the upper limit is 1000ppm, 100ppm or 10ppm. , 1 ppm, 100 ppb, 10 ppb, 1 ppb, 100 ppt, 10 ppt, 1 ppt, 0.1 ppt, 0.01 ppt within any combination of these lower and upper limits. Examples of preferred concentrations include 0.1 ppt to 10 ppm, 1 ppt to 1 ppm, 10 ppt to 100 ppb, and 100 ppt to 10 ppb as the concentration of 3-methyl-3-butene-1-thiol relative to the total weight of the food and drink. However, it is not limited to these. Although it depends on the type and flavor of the food and drink, if the concentration of 3-methyl-3-butene-1-thiol in the food and drink is less than 0.001 ppt, it may be felt that the blending effect is low. , When it exceeds 1000 ppm, it may be felt that the aroma of 3-methyl-3-butene-1-thiol itself is prominent and gives an unfavorable alteration to the flavor of the food and drink to be blended, but the flavor of the food and drink etc. Depending on the situation, the concentration may be lower than the lower limit or higher than the upper limit.

In the case of cosmetics, the 3-methyl-3-butene-1-thiol concentration is 0.001ppt to 1%, preferably 0.01ppt to 1000ppm, more preferably 0.1ppt to the total weight of the cosmetics. Within the range of 100 ppm can be mentioned. More specifically, the lower limit is 0.001ppt, 0.01ppt, 0.1ppt, 1ppt, 10ppt, 100ppt, 1ppb, 10ppb, 100ppb, 1ppm, 10ppm, 100ppm, or 1000ppm, the upper limit is 1%, any of 1000 ppm, 100 ppm, 10 ppm, 1 ppm, 100 ppb, 10 ppb, 1 ppb, 100 ppt, 10 ppt, 1 ppt, 0.1 ppt, 0.01 ppt within any combination of these lower and upper limits, but It is not limited to these. Examples of preferred concentrations include the concentration of 3-methyl-3-butene-1-thiol with respect to the total mass of the cosmetic, from each range of 100ppt to 1000ppm, 10ppb to 100ppm, and 100ppb to 10ppm. It can be selected depending on the characteristics, but is not limited to these. Although it depends on the type and fragrance of the cosmetic, if the concentration of 3-methyl-3-butene-1-thiol in the cosmetic is less than 0.001 ppt, 3-methyl-3-butene-1- It may be felt that the effect of thiol blending is low or there is no change, and if it exceeds 1%, the fragrance of 3-methyl-3-butene-1-thiol itself is prominent and is preferable for the fragrance of the cosmetic product to be blended. However, depending on the fragrance of cosmetics, it may be blended at a concentration below the lower limit or above the upper limit.

For example, by adding an effective amount of 3-methyl-3-butene-1-thiol to foods, beverages, cosmetics, and other products, in addition to a light roasted feeling, it reminds us of the animal and plant materials used in foods, beverages, cosmetics, etc. Natural feeling, fruit juice, fruit skin, gravy, flesh (including texture and thickness of meat), freshness, maturity (including fully ripe or moderately ripe), gorgeousness, freshness The texture, richness, body, thickness, etc. are enhanced, and it is possible to maintain a good balance. Any one or more of the top, middle, and last flavors can be enhanced, for example, one or more of top flavor strength, middle and last flavor depth, body feeling, and persistence (also referred to as lingering sound) can be enhanced. be able to. In particular, the thickness of the top and middle flavor can be enhanced.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. In addition, this invention is not limited to these.

[Example 1] Synthesis of 3-methyl-3-butene-1-thiol 3-methyl-3-butene-1-thiol was synthesized by the following steps.
(First step)

3-Methyl-3-buten-1-ol (a) (20 g, 232 mmol) and acetonitrile (MeCN) (1000 ml) were placed in a 2 L round-bottomed flask and cooled at 10° C. with stirring. Triphenylphosphine (PPh ₃ ) (72.9 g, 278 mmol) and carbon tetrabromide (CBr ₄ ) (92.2 g, 278 mmol) were sequentially introduced into the system. After stirring at room temperature for 3.0 hours and confirming disappearance of 3-methyl-3-buten-1-ol (a) by gas chromatography, the reaction solution was added to water (3000 ml) and stirred for 30 minutes. After the aqueous layer was extracted with hexane, the resulting organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After the organic layer was filtered by suction, the filtrate was concentrated under normal pressure, and the resulting concentrate was used in the next step as it was without purification. It was confirmed by gas chromatography that the resulting concentrate contained 1-bromo-3-methyl-3-butene (b).
(Second step)

Potassium thioacetate (AcSK) (34.44 g, 300 mmol) and N,N-dimethylformamide (DMF) (150 ml) were placed in a 1 L eggplant flask and stirred at 0 to 10°C. An N,N-dimethylformamide (50 ml) solution of 1-bromo-3-methyl-3-butene (b) (equivalent to 232 mmol) obtained as the atmospheric concentrate in the first step was added dropwise into the system, and the reaction was continued for 16 hours. After stirring, disappearance of raw materials was confirmed by gas chromatography. After adding water (600 ml) to the system and stirring for 30 minutes, the aqueous layer was extracted with hexane. The resulting organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After suction filtration, the filtrate was concentrated under normal pressure, and the obtained concentrate was purified by silica gel chromatography (300 g, hexane:diethyl ether=30:1). Fractions containing 1-acetylthio-3-methyl-3-butene (c) with high purity (confirmed by gas chromatography) were concentrated under atmospheric pressure to obtain a solution of 1-acetylthio-3-methyl-3-butene (c). (50 g) was obtained. This product was used in the next step without further purification.
(Third step)

Lithium aluminum hydride (LAH) (2.2 g, 58 mmol) and diethyl ether (Et ₂ O) (50 ml) were placed in a 500 ml eggplant flask and stirred at 0 to 10°C. 1-Acetylthio-3-methyl-3-butene (c) (12.5 g, corresponding to 58 mmol) in an amount of 1/4 of the normal pressure concentrate obtained in Step 2 was dropped into the system. After stirring at the same temperature for 2.0 hours, disappearance of 1-acetylthio-3-methyl-3-butene (c) was confirmed by gas chromatography, and 50% aqueous Rochelle salt solution (100 ml) was added to the system. It was added dropwise while maintaining the temperature from 0 to 10°C. Then, the mixture was stirred overnight while warming to room temperature, and the aqueous layer was extracted with diethyl ether. An aqueous solution of potassium hydroxide (16 g of potassium hydroxide and 100 ml of water) was allowed to act on the resulting organic layer twice to transfer the target compound to the aqueous layer as a potassium salt. Citric acid monohydrate (50 g) was added to the resulting aqueous layer to acidify the liquid. A crude product obtained by liquid separation of the released organic layer was distilled under reduced pressure to obtain 3-methyl-3-butene-1-thiol [formula (1)] (0.76 g). The combined yield of the first to third steps was 13%. The resulting 3-methyl-3-butene-1-thiol of formula (1) was designated as Product 1 of the present invention.
The obtained 3-methyl-3-butene-1-thiol exhibited a light roasted aroma and bread-like aroma, and its physical properties were as follows.

¹ H-NMR (CDCl3, 400 MHz): 1.43 (1H, t, J = 7.8 Hz), 1.72 (3H, s), 2.34 (2H, t, J = 7.2 Hz), 2 .64 (2H, dt, J=7.2, 7.8 Hz), 4.75 (1 H, s), 4.83 (1 H, s).
¹³ C-NMR (CDCl3, 100 MHz): 21.926, 22.612, 41.874, 112.057, 143.090.

[Example 2] Use example (1) of the compound of formula (1): Formulation in a coffee-like flavor composition A basic blended flavor composition exhibiting a coffee-like flavor was prepared according to the general formulation shown in Table 1 below. prepared.

To the resulting coffee-like basic blended flavor composition, the present invention product 1 (compound of formula (1)) obtained in Example 1 was blended so as to have the concentration shown in Table 2 below. were prepared (present invention products 2 to 5). Sensory evaluation was performed on the obtained perfume composition by 14 panelists with 10 years or more of experience. In the sensory evaluation, the basic perfume composition was used as a control product, and the scent compared with the control product was scored from the following viewpoints. The average score is shown in Table 2 below.
(Evaluation criteria) Roast feeling 4 points: Remarkably increased compared to the control product 3 points: Increased compared to the control product 2 points: Slightly increased compared to the control product 1 point: Same as the control product

As shown in Table 2, it was confirmed that all of the products 2 to 5 of the present invention have an enhanced roast feeling and a more excellent and desirable aroma by blending the compound of formula (1).

[Example 3] Comparison between the compound of formula (1) and 3-methyl-2-butene-1-thiol -Butene-1-thiol (a known perfume compound structurally similar to the compound of formula (1)) was added at 1 ppm to prepare a product (comparative product 1). Sensory evaluation was carried out on the product 4 of the present invention and the comparative product 1 by seven panelists with 10 years or more of experience, and they were asked to freely comment on the flavor of each perfume. Representative comments are listed in Table 3 below.

As shown in Table 3, it was confirmed that 3-methyl-2-butene-1-thiol, which is a known perfume compound, and the compound of formula (1) differ greatly in aroma properties.

[Example 4] Usage example (2) of compound of formula (1): Formulation in butter-like flavor composition A basic blended flavor composition exhibiting a butter-like flavor was prepared according to the general formulation shown in Table 4 below. prepared.

To the obtained butter-like basic blended fragrance composition, the present invention product 1 (compound of formula (1)) obtained in Example 1 was added at 0.01 ppm with respect to the total mass of the butter-like basic blended fragrance composition. were added to prepare the perfume composition of the present invention (Invention Product 6). Seven panelists with 10 or more years of experience were asked to comment on changes in the flavor of the obtained flavor composition, with a butter-like basic blended flavor composition as a control. As a result, all seven panelists evaluated that the product 6 of the present invention had an enhanced aroma reminiscent of the sweet and fragrant top of roast butter compared to the control product, and had a highly palatable buttery flavor. .

[Example 5] Use example (3) of compound of formula (1): Formulation in coffee beverage Drip extraction was performed with ion-exchanged water). Then, after adding 6 g of sodium bicarbonate to this coffee extract, no addition, present invention product 1 (compound of formula (1)) obtained in Example 1, or 3-methyl-2-butene-1-thiol is blended and adjusted so that the concentration is as shown in Table 5 below, and the total amount is adjusted to 10 L with ion-exchanged water. Sugar-free black coffee beverages of the invention (Products 7 to 13 of the invention) were obtained.
The obtained coffee beverage of the present invention was sensory evaluated by 14 panelists with 10 years or more of experience. In the sensory evaluation, the additive-free beverage was used as a control product, and the flavor of the beverage of the present invention compared with the control product was scored from the following viewpoints, and the subjects were asked to freely comment on the flavor of each beverage. The average score and representative comments obtained are shown in Table 5 below.
(Evaluation Criteria) Dry roasted feeling and favorable sourness reminiscent of freshly ground coffee beans 4 points: Remarkably increased compared to the control product 3 points: Increased compared to the control product 2 points: Control Slightly increased compared to the product 1 point: Same as the control product

As shown in Table 5, it was confirmed that all of the products 7 to 13 of the present invention were imparted with an excellent flavor in terms of roast feeling by blending the compound of the formula (1). In particular, the effect was remarkable within the range of 0.1 ppb to 10 ppb. It was also confirmed that 3-methyl-2-butene-1-thiol and the compound of formula (1) differ greatly in aroma characteristics.

[Example 6] Use example (4) of the compound of formula (1): Blended into bread 140 g wheat flour (strong flour), 5 g yeast, 0.2 g yeast food, emulsifier (fatty acid monoglyceride and tartaric acid monoglyceride) 1 g, sugar 2 g and 80 g of water was mixed and kneaded using a kneader for 3 minutes at low speed and 3 minutes at high speed. After kneading, the mixture was fermented at room temperature (25° C.) for 3 hours to obtain medium seeds.
Next, 60 g of wheat flour (strong flour), 12 g of sugar, 4 g of salt, 4 g of skimmed milk powder, 8 g of unsalted butter, 48 g of water, and the present invention product 1 obtained in Example 1 (compound of formula (1)) were added to the medium dough. was added in an amount to give the concentration shown in Table 5 relative to the total amount (inventive product 1 was not added to the control product), and kneaded using a kneader for 3 minutes at low speed and 3 minutes at high speed to obtain seeds. After that, the seeds were placed in a bowl, wrapped and left for 20 minutes. The mixture was again degassed, re-rolled, packed in a baking mold, and fermented at 38°C and 85% humidity for 70 minutes. After that, they were baked in an oven at 200° C. for 35 minutes, cooled, and removed from the molds to prepare loaves of bread (control products and products 14 to 18 of the present invention).
The obtained control product and the bread of the present invention were sensory evaluated by 14 panelists with 10 years or more of experience. In the sensory evaluation, the subjects were asked to rate the flavor of each loaf of bread of the present invention compared to the control product from the following viewpoints, and to freely comment on the flavor of each loaf of bread. The average score and representative comments obtained are shown in Table 6 below.
(Evaluation criteria) Sweet and fragrant top note like roast butter and aroma of freshly baked bread 4 points: Remarkably increased compared to the control product 3 points: Increased compared to the control product 2 points: Slightly increased compared to the control product Increased 1 point: Same as control product

As shown in Table 6, it was confirmed that in any of the products 14 to 18 of the present invention, the addition of the compound of formula (1) imparted an excellent flavor to the bread. In particular, the effect was remarkable within the range of 0.1 ppb to 10 ppb.

[Example 7] Use example (5) of the compound of formula (1): Incorporation into beer-flavored beverage compound) was added at 0.1 ppb to the total mass of a commercially available beer beverage to prepare a beer-flavored beverage of the present invention (Inventive Product 19).
Regarding the flavor of the obtained beer-flavored beverage of the present invention, seven panelists with 10 years or more of experience were asked to comment on changes in flavor compared to a commercially available beer-flavored non-alcoholic beverage. As a result, all of the seven panelists found that the product 19 of the present invention had an enhanced aroma reminiscent of a crisp, malty top derived from malt compared to the control product, making the beverage more palatable. and evaluated.

[Example 8] Use example (6) of the compound of formula (1): Incorporation into onion dressing The present invention product 1 obtained in Example 1 (compound of formula (1)) was added to a commercially available onion dressing. was added at 1 ppb to the total mass of the onion dressing to prepare the onion dressing of the present invention (Inventive Product 20). Regarding the flavor of the obtained onion dressing of the present invention, seven panelists with 10 or more years of experience were asked to comment on changes in flavor compared to a commercially available onion dressing. As a result, all of the seven panelists found that compared to the control product, the product 20 of the present invention had a roasted onion-like aroma reminiscent of the sweet and fragrant top when the onion was fried to a caramel color. It was evaluated that it became a highly effective dressing.

[Example 9] Example of use of the compound of formula (1) (7): Incorporation into yakiniku sauce The present invention product 1 (compound of formula (1)) obtained in Example 1 was added to commercially available yakiniku sauce. was added at 10 ppb to the total mass of the grilled meat sauce to prepare the grilled meat sauce of the present invention (Inventive Product 21). Regarding the flavor of the obtained yakiniku sauce of the present invention, seven panelists with 10 or more years of experience were asked to comment on changes in flavor compared to a commercially available yakiniku sauce. As a result, all of the seven panelists found that product 21 of the present invention had an enhanced aroma reminiscent of freshly grilled yakiniku-like fragrant roast feeling compared to the control product, and became a more palatable yakiniku sauce. and evaluated.

Claims (5)

A flavor imparting agent containing 3-methyl-3-butene-1-thiol represented by the following formula (1) as an active ingredient.

A perfume composition containing the flavor-imparting agent according to claim 1 . A consumer product comprising the flavor imparting agent according to claim 1 or the flavoring composition according to claim 2. A method for imparting flavor to a flavoring composition, comprising blending the flavoring agent according to claim 1 into a flavoring composition. A method of flavoring a consumer good, comprising incorporating the flavoring agent of claim 1 or the flavor composition of claim 2 into the consumer good.