Aroma composition

Abstract

The purpose of the present invention is to provide: an aroma composition containing a compound having an aromatic odor that is useful as a blended aroma starting material and the like; and a product containing this aroma composition. The present invention relates to an aroma composition containing 3-mercapto-3-methylbutanoic acid and an ester thereof.

Description

fragrance composition

[0001] The present invention relates to compounds and fragrance compositions useful as blended fragrance ingredients and the like.

[0002] In recent years, as consumer preferences have diversified, there has been a demand for flavors and aromas that are differentiated from others in the flavorings used in foods and beverages. However, it is sometimes difficult to meet these demands using combinations of conventional flavoring ingredients, and there is a strong demand for new flavoring materials. For example, among the compounds that can be used as flavoring materials, many compounds containing sulfur atoms have been found to contribute greatly to flavorings even in trace amounts, and are considered to be important compounds.

[0003] An object of the present invention is to provide a fragrance composition containing a compound having an odor useful as a blended fragrance ingredient, etc., and a product containing said fragrance composition. As a result of extensive research to solve the above-mentioned problems, the present inventors discovered that the odor and flavor of a fragrance composition can be enhanced by using 3-mercapto-3-methylbutanoic acid and its esters, which have never been used as fragrance components, and thus completed the present invention.

[0004] That is, the present invention relates to the following [1] to [5]: [1] A fragrance composition containing 3-mercapto-3-methylbutanoic acid or an ester thereof represented by the following formula (1): (In formula (1), R represents a hydrogen atom, a methyl group, or an ethyl group.) [2] The flavor composition according to the above [1], which is for use in food or drink. [3] A food or drink, an oral composition, a tobacco product, or a consumer product, which contains the flavor composition according to the above [1] to [2]. [4] A method for producing a food or drink, an oral composition, a tobacco product, or a consumer product, which comprises adding the flavor composition according to the above [1] to [2]. [5] A method for imparting aroma / flavor using 3-mercapto-3-methylbutanoic acid represented by formula (1) or an ester thereof as an active ingredient.

[0005] According to the present invention, a fragrance composition containing compounds having a fragrance useful as a raw material for blended fragrances can be provided.

[0006] The present invention will be described in detail below. In the present invention, the three compounds represented by formula (1) may be collectively referred to as compound (1). (In formula (1), R represents a hydrogen atom, a methyl group, or an ethyl group.) Examples of the compound of formula (1) include 3-mercapto-3-methylbutanoic acid represented by the following formula (1-1), in which R represents a hydrogen atom; methyl 3-mercapto-3-methylbutanoate represented by the following formula (1-2); and ethyl 3-mercapto-3-methylbutanoate represented by the following formula (1-3).

[0007] The compound of formula (1-1) exhibits a roasted aroma accompanied by a tropical fruit-like fruitiness, and the compounds of formula (1-2) and formula (1-3) also exhibit a similar aroma.

[0008] The compound (1-1) of the present invention can be obtained, for example, by the following process. 3,3-Dimethylacrylic acid and p-methoxybenzylthiol (MeOBnSH) are reacted under heating under reflux in a piperidine solvent to form a thiobenzyl adduct (3-((4-methoxybenzyl)thio)-3-methylbutanoic acid). Subsequently, the compound is reacted with anisole in a trifluoroacetic acid (TFA) solvent to debenzylate, thereby obtaining 3-mercapto-3-methylbutanoic acid (1-1).

[0009] The compound (1-1) thus obtained can be purified by distillation, various types of chromatography, etc. Compounds (1-2) and (1-3) are commercially available, and commercially available products can also be used in the present invention. The flavor and fragrance composition of the present invention containing compound (1) and compound (1) have an excellent fragrance and can be used alone or in combination with other components as flavoring components for foods and beverages, oral compositions, tobacco products, etc.

[0010] The flavor and fragrance composition of the present invention and compound (1) can be directly added to foods and beverages in trace amounts to impart or enhance a flavor and aroma, or can be mixed with other ingredients to impart or enhance a flavor and aroma to foods and beverages. Examples of other flavor and fragrance ingredients that can be added include various synthetic flavors, natural flavors, natural essential oils, and plant extracts, such as the natural essential oils, natural flavors, and synthetic flavors described in "Japan Patent Office Gazette, Collection of Well-Known and Commonly Used Techniques (Fragrances) Part II Food Flavors, pp. 88-131, published January 14, 2000." The concentration of compound (1) in the flavor and fragrance composition of the present invention varies depending on the other flavor and fragrance ingredients mixed therein, and cannot be generally determined; however, it is typically within a concentration range of 0.0001 to 100,000 ppm, preferably 0.001 to 10,000 ppm, and more preferably 0.01 to 1,000 ppm, based on the weight of the flavor and fragrance composition.

[0011] When compound (1) is added to a food or drink to enhance its aroma or flavor, the concentration can be in the range of 0.0001 to 100,000 ppb, preferably 0.001 to 10,000 ppb, more preferably 0.01 to 1,000 ppb, based on the weight of the food or drink.

[0012] The fragrance composition of the present invention containing compound (1) may contain, as necessary, commonly used solvents such as water and ethanol; and fixatives such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, Hercolin, triacetin, medium-chain fatty acid triglycerides, and medium-chain fatty acid diglycerides.

[0013] The addition of a flavor composition containing compound (1) or compound (1) itself can enhance or impart the aroma and flavor of foods and beverages. Specific examples of foods and beverages to which the flavor composition of the present invention and compound (1) can be added include beverages such as carbonated drinks, soft drinks, fruit juice drinks, fruit liquors, dairy drinks, lactic acid bacteria drinks, health supplements, soy milk, tea drinks, and coffee; desserts such as ice cream, ice milk, lacto ice cream, frozen desserts, yogurt, pudding, jelly, and dairy desserts; confectioneries such as caramel, candy, tablet candy, crackers, biscuits, cookies, pies, chocolates, snacks, chewing gum, buns, and yokan; soups such as Japanese soups, Western soups, and Chinese soups; breads; jams; flavor seasonings; various instant drinks; and various instant foods. The amount of flavor composition added to food or drink varies depending on the type and form of the product, but can usually be in the concentration range of 0.0001 to 5%, preferably 0.001 to 5%, based on the weight of the food or drink.

[0014] Oral compositions that can be scented or flavored with the flavor composition of the present invention and compound (1) include, for example, dentifrices, mouthwashes, mouthwashes, lozenges, chewing gums, etc. The amount of the flavor composition added to the oral composition varies depending on the type and form of the product, but is usually preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the oral composition.

[0015] Tobacco products that can be scented and flavored with the flavor composition of the present invention and compound (1) include cigarettes, electronic cigarettes, etc. The amount of the flavor composition added to a tobacco product varies depending on the type and form of the product, but can be, for example, preferably 0.00001 to 90% by mass, more preferably 0.0001 to 50% by mass, based on the total mass of the tobacco leaf portion.

[0016] Specific examples of consumer products include fragrance products such as perfume, eau de parfum, eau de toilette, and eau de cologne; basic cosmetics such as facial cleansing cream, cleansing cream, emulsion, lotion, and serum; finishing cosmetics such as lipstick, lip balm, eyeliner, mascara, eye shadow, eyebrow pencil, eye pack, nail enamel, and enamel remover; hair cosmetics such as pomade, brilantine, setting lotion, hair stick, hair solid, hair oil, hair treatment, hair cream, hair tonic, hair liquid, hair spray, bandolin, hair tonic, and hair dye; sunscreen cosmetics such as tanning products and sunscreen products; medicated cosmetics such as antiperspirants, aftershave lotions and gels, permanent wave agents, medicated soaps, medicated shampoos, and medicated skin cosmetics; hair care products such as shampoos, rinses, rinse-in shampoos, conditioners, treatments, and hair packs; Soaps such as toilet soap, bath soap, perfumed soap, transparent soap, synthetic soap, etc.; body cleansers such as body soap, body shampoo, hand soap, face cream, etc.; bath additives such as bath salts (bath salts, bath tablets, bath liquid, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jellies, bath cubes, etc.; detergents such as heavy-duty laundry detergents, light-duty laundry detergents, liquid detergents, laundry soaps, compact detergents, powdered soaps, etc.; fabric softeners such as softeners and furniture care products; cleaning agents such as cleansers, house cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mold removers, drain cleaners, etc.; kitchen detergents such as kitchen soap, synthetic kitchen soap, and dish detergent; bleaches such as oxidation bleaches (chlorine bleaches, oxygen bleaches, etc.), reduction bleaches (sulfur bleaches, etc.), and optical bleaches; aerosols such as spray types and powder sprays; Examples include deodorizers and air fresheners in solid, gel, and liquid types (water-based and oil-based), daily necessities and miscellaneous items such as tissue paper and toilet paper, quasi-drugs such as liquid bath additives, mouthwash, and repellents (mist spray type, water-based liquid type), and pharmaceuticals such as medicated cosmetics and medicated lotions.

[0017] The amount of the fragrance composition of the present invention and compound (1) added to a consumer product may be in the concentration range of 0.0001 to 100,000 ppb, preferably 0.001 to 10,000 ppb, more preferably 0.01 to 1,000 ppb, based on the weight of the consumer product.

[0018] Furthermore, all of the compounds (1-1), (1-2), and (1-3) are useful as fragrance components, and any compound or mixture of compounds can be used in the fragrance composition of the present invention.

[0019] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0020] [Measurement Instruments] The analytical instruments used in the examples are as follows: NMR measurement device: 400 / 54 Premium Shielded NMR (Agilent Technologies) Gas chromatograph mass spectrometer: GCMS-QP2010 (Shimadzu Corporation) Gas chromatograph-time-of-flight mass spectrometer: 8890 GC System (GC) + JMS-T2000GC AccuTOFtm GC-Alpha (mass spectrometer) (JEOL) High-performance liquid chromatograph pump: LC-20A (Shimadzu Corporation) Detector: SPD-M20A (GL Sciences) Separation column: YMC-TriartC18 ExRS (YMC Corporation)

[0021] (Example 1) Synthesis of Compound (1-1) (1) Synthesis of 3-((4-methoxybenzyl)thio)-3-methylbutanoic acid 3,3-Dimethylacrylic acid (10.01 g, 0.10 mol) was dissolved in 25 ml of piperidine, and p-methoxybenzylthiol (15.42 g, 0.10 mol) was added. The mixture was heated to reflux and reacted for 10 hours. GC analysis confirmed a conversion rate of 95.5%. 1 mol / L hydrochloric acid was added to acidify the mixture to pH 2, and the mixture was extracted with ethyl acetate. The solvent was recovered under reduced pressure, and the resulting solid was recrystallized from hexane to obtain 17.01 g of 3-((4-methoxybenzyl)thio)-3-methylbutanoic acid (yield: 66.9%, GC purity: 99.2%).

[0022] (2) Synthesis of 3-mercapto-3-methylbutanoic acid The compound obtained in (1) above (9.24 g, 0.036 mol) was dissolved in trifluoroacetic acid (61.3 g) under ice cooling, and anisole (5.92 g, 0.054 mol) was added, followed by a reaction at room temperature for 12 hours. GC analysis confirmed a conversion rate of 100%. Trifluoroacetic acid was recovered under reduced pressure, and the resulting crude product was purified by distillation to obtain 3.12 g of 3-mercapto-3-methylbutanoic acid (1-1) (yield: 63.9%, GC purity: 100%). <3-Mercapto-3-methylbutanoic acid> 1H NMR (400 MHz, CDCl3) δ: 2.71 (s, 3H), 2.35 (s, 2H), 2.05 (s, 1H), 1.53 (s, 6H) 13C NMR (100 MHz, CDCl3) δ: 176.98, 50.20, 41.23, 32.48 HRMS (+): calculated C6H12O2S ([M]+) 134.0396; found, 134.0395 Furthermore, using methyl 3,3-dimethylacrylate and ethyl 3,3-dimethylacrylate instead of 3,3-dimethylacrylic acid, the same reaction as in Example 1 was carried out to obtain methyl 3-mercaptothio-3-methylbutanoate and ethyl 3-mercapto-3-methylbutanoate.

[0023] Methyl 3-mercapto-3-methylbutanoate can be purchased from Enamine Ltd. (URL: https: / / enaminestore.com / catalog / EN300-3191463), and ethyl 3-mercapto-3-methylbutanoate can be purchased from LGC Limited (URL: https: / / www.lgcstandards.com / US / en / p / TRC-M253975).

[0024] The spectral data for these compounds are as follows: <Methyl 3-mercapto-3-methylbutanoate> 1H NMR (400 MHz, CDCl3) δ: 3.69 (s, 3H), 2.65 (s, 2H), 2.33 (s, 1H), 1.51 (s, 6H) 13C NMR (100 MHz, CDCl3) δ: 171.18, 51.43, 50.18, 41.55, 32.53 HRMS (+): calculated C6H12O2S ([M]+) 148.0553; found, 148.0552 <Ethyl 3-mercapto-3-methylbutanoate> 1H NMR (400 MHz, CDCl3) δ: 4.16 (q, 2H), 2.63 (s, 2H), 2.33 (s, 1H), 1.50 (s, 6H) 13C NMR (100MHz, CDCl3) δ: 170.72, 60.32, 50.42, 41.60, 32.55, 14.23 HRMS (+): calcd C7H14O2S ([M]+) 162.0709; found, 162.0709

[0025] (Example 2) Production of coffee flavor composition Coffee flavor composition (1) was prepared according to the following recipe using methyl 3-mercapto-3-methylbutanoate (compound (1-2)). For comparison, coffee flavor composition (2) was prepared according to the following recipe.

[0026] Coffee flavor compositions (1) and (2) prepared according to the above formulations were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (1) imparted a natural roasted flavor reminiscent of freshly brewed coffee and was far superior to flavor composition (2). The same results were obtained when 3-mercapto-3-methylbutanoic acid (compound (1-1)) and ethyl 3-mercapto-3-methylbutanoate (compound (1-3)) obtained in Example 1 were used.

[0027] (Example 3) Preparation of Green Tea Fragrance Composition Green tea fragrance composition (3) was prepared using compound (1-2) according to the following recipe. For comparison, green tea fragrance composition (4) was prepared according to the following recipe.

[0028] The green tea flavor compositions (3) and (4) prepared according to the above formulations were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (3) was far superior to flavor composition (4), imparting the greenness and umami flavor of tea leaves. The same was true when compound (1-1) and compound (1-3) were used.

[0029] Example 4: Preparation of black tea fragrance composition Using compound (1-2), black tea fragrance composition (5) was prepared according to the following recipe. For comparison, black tea fragrance composition (6) was prepared according to the following recipe.

[0030] The black tea flavor compositions (5) and (6) prepared according to the above formulations were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (5) imparted a broader, sweeter fragrance than flavor composition (6), and was far superior to flavor composition (6). The same was true when compound (1-1) and compound (1-3) were used.

[0031] (Example 5) Preparation of grapefruit flavor composition Grapefruit flavor composition (7) was prepared using compound (1-2) according to the following recipe. For comparison, grapefruit flavor composition (8) was prepared according to the following recipe.

[0032] Grapefruit flavor compositions (7) and (8) prepared according to the above formulations were each added to water at a concentration of 0.1%, and a sensory test was conducted by eight expert panelists. All panelists pointed out that flavor composition (7) imparted a more natural and fresh fruity flavor than flavor composition (8), and was far superior to flavor composition (8). The same was true when compound (1-1) and compound (1-3) were used.

[0033] (Example 6) Preparation of grapefruit flavor composition Grapefruit flavor composition (9) was prepared using compound (1-2) according to the following recipe. For comparison, grapefruit flavor composition (10) was prepared according to the following recipe.

[0034] Grapefruit flavor compositions (9) and (10) prepared according to the above formulations were each added to water at a concentration of 0.1%, and a sensory test was conducted by eight expert panelists. All panelists pointed out that flavor composition (9) imparted a more natural and fresh fruity flavor than flavor composition (10), and was far superior to flavor composition (10). The same was true when compound (1-1) and compound (1-3) were used.

[0035] Example 7: Preparation of grape fragrance composition Grape fragrance composition (11) was prepared using compound (1-2) according to the following recipe. For comparison, grape fragrance composition (12) was prepared according to the following recipe.

[0036] Grape flavor compositions (11) and (12) prepared according to the above formulations were each added to water at a concentration of 0.1%, and a sensory test was conducted by eight expert panelists. All panelists pointed out that flavor composition (11) imparted a richer, more natural fruity flavor than flavor composition (12), and was far superior to flavor composition (12). The same was true when compound (1-1) and compound (1-3) were used.

[0037] (Example 8) Production of passion fruit flavor composition Using compound (1-2), a passion fruit flavor composition (13) was prepared according to the following recipe. For comparison, a passion fruit flavor composition (14) was prepared according to the following recipe.

[0038] Passion fruit flavor compositions (13) and (14) prepared according to the above formulations were each added to water at a concentration of 0.1%, and a sensory test was conducted by eight expert panelists. All panelists pointed out that flavor composition (13) imparted a natural, ripe fruit juice flavor and was far superior to flavor composition (14). The same was true when compound (1-1) and compound (1-3) were used.

[0039] (Example 9) Addition to a Commercially Available Coffee Drink Compound (1-2) was added at 10 ppb to a commercially available coffee drink, and a sensory test was conducted by six expert panelists. All panelists pointed out that the addition of compound (1-2) imparted a natural, freshly brewed roasted flavor and a fragrant roasted taste, making the drink far superior. The same was true when compound (1-1) and compound (1-3) were used.

[0040] (Example 10) Addition to Commercially Available Green Tea Beverages Compound (1-2) was added at 5 ppb to a commercially available green tea beverage, and a sensory test was conducted by six expert panelists. All panelists pointed out that the addition of compound (1-2) imparted the greenness and umami flavor of tea leaves, making the beverage significantly superior. The same results were obtained when compound (1-1) and compound (1-3) were used.

[0041] (Example 11) Addition to a commercially available black tea beverage Compound (1-2) was added at 5 ppb to a commercially available black tea beverage, and a sensory test was conducted by six expert panelists. All panelists pointed out that the addition of compound (1-2) imparted a broad, sweet aroma and astringent taste, making the beverage far superior. The same was true when compound (1-1) and compound (1-3) were used.

[0042] Example 12 Addition to Commercially Available Grapefruit Juice Drink Compound (1-2) was added at 1 ppb to a commercially available grapefruit juice drink, and a sensory test was conducted by eight expert panelists. All panelists pointed out that the addition of compound (1-2) gave the drink a truly fruity taste, freshness, and a refreshing feel, which was far superior to the original. The same was true when compound (1-1) and compound (1-3) were used.

[0043] (Example 13) Addition to a commercially available grape juice drink Compound (1-2) was added at 10 ppb to a commercially available grape juice drink, and a sensory test was conducted by eight expert panelists. All panelists pointed out that the addition of compound (1-2) imparted a rich, natural pulpy texture to the drink, making it far superior. The same was true when compound (1-1) and compound (1-3) were used.

Claims

1. A fragrance composition containing 3-mercapto-3-methylbutanoic acid or its ester represented by the following formula (1): (In formula (1), R represents a hydrogen atom, a methyl group, or an ethyl group.) 2. The flavor composition according to claim 1, which is for use in food and beverage products.

3. A food or drink, oral composition, tobacco product, or consumer product containing the flavor composition according to claims 1 or 2.

4. A method for producing a food or drink, an oral composition, a tobacco product, or a consumer product, which comprises adding the flavor composition according to claims 1 or 2.

5. A method for imparting fragrance and flavor using 3-mercapto-3-methylbutanoic acid represented by formula (1) or its ester as an active ingredient.

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