JP4841208B2 - Flavor and fragrance composition - Google Patents

Description

  The present invention relates to a flavor and fragrance composition comprising S-alkyl (R) -2-methylbutanethioate as an active ingredient.

  Conventionally, most of the compounds used as flavor and fragrance components in foods and beverages and cosmetics are racemic, and for example, S-alkyl 2-methylbutanethioate is found in natural products, particularly in fruits and beer. Are known to exist as racemates (Non-Patent Documents 1 to 13). Of these racemic S-alkyl 2-methylbutanethioates, S-methyl 2-methylbutanethioate has been conventionally used for the purpose of giving a fermented odor of food and a sense of ripeness of fruits. ing.

  However, these racemic 2-methylbutanethioic acid S-alkyls are satisfied for the time of giving an excellent fermentation odor and fruit ripeness, but they are still not sufficient.

  On the other hand, in relation to the analysis of cheese aroma components, S-methyl (S) -2-methylbutanethioate and racemic S-methyl 2-methylbutanethioate were analyzed by gas chromatography, A report has been made on aroma (Non-Patent Document 14). In addition, in the analysis of hop aroma components, the aroma of racemic 2-methylbutanethioate S-methyl has been reported (Non-patent Document 8).

  According to these documents, the aroma of racemic 2-methylbutanethioate S-methyl is wild strawberry (Non-patent document 14) or Cooked vegetable, Sulphury, Soapy / fatty (Non-patent document 8). (S) -2-Methylbutanethioate S-methyl aroma is described as rubbery (Non-Patent Document 14).

  However, none of these reports mentions the aroma of S-alkyl (R) -2-methylbutanethioate, such as S-methyl (R) -2-methylbutanethioate.

Food Chemistry (2000), 69 (3), 319-330 Journal of the Institute of Brewing (1983), 89 (2), 87-91 Proceedings of the Congress-European Brewery Convention (1981), 18th, 161-8 Proceedings of the Congress-European Brewery Convention (1979), 17th, 79-89 Proceedings of the Congress-European Brewery Convention (1981), 17th, 91-104 Technical Quarterly-Master Brewers Association of the Americas (1981), 18 (1), 26-30 Organic Magnetic Resonance (1979), 12 (10), 557-60 Proceedings of the Analytical Division of the Chemical Society (1976), 13 (7), 215-17 Journal of Organic Chemistry (1973), 38 (24), 4239-43 Flavor and Fragrance Journal (1996), 11 (5), 295-303 Tetrahedron Letters (1971), (30), 2837-8 Development in Food Science (1988), 18 (Flavors Fragrances), 573-85 32nd Annual Meeting on Fragrances, Terpenes and Essential Oil Chemistry, 31-33, (October 24, 1988) Lebensmittel-Wissenschaft und-Technologie (1979), 12 (5), 258-61

  The present invention has been made against the background of the above-described prior art, and has been made for the purpose of providing an excellent flavor and fragrance composition having high palatability that can satisfy the demand for diversifying flavoring products.

  The present invention intends to solve the above problems by the following (1) to (13).

(1) A flavor and fragrance composition comprising S-alkyl (R) -2-methylbutanethioate as an active ingredient.

(2) The optical purity of S-alkyl (R) -2-methylbutanethioate is 50% e.e. e. The flavor and fragrance composition described in (1) above.

(3) The flavor and fragrance composition according to (1) or (2), which is a flavor composition.

(4) A flavor composition comprising S-alkyl (R) -2-methylbutanethioate at a concentration of 10 ⁻⁶ to 10 ⁷ ppb.

(5) A product flavored by the flavor composition according to (4).

(6) The flavored product according to (5), wherein the flavored product is one selected from foods and drinks, oral compositions and pharmaceuticals.

(7) A flavored product obtained by adding S-alkyl (R) -2-methylbutanethioate at a concentration of 10 ⁻⁹ to 10 ⁵ ppb.

(8) The flavor and fragrance composition according to (1) or (2), which is a fragrance composition.

(9) A fragrance composition comprising S-alkyl (R) -2-methylbutanethioate at a concentration of 10 ⁻⁶ to 10 ⁷ ppb.

(10) A product fragranced by the fragrance composition according to (9).

(11) Fragranced products include fragrance products, basic cosmetics, finished cosmetics, hair cosmetics, tanning cosmetics, medicated cosmetics, hair care products, soap, body cleaners, bath preparations, detergents, softeners, cleaning agents, kitchen The fragranced product according to (10), which is one kind selected from detergents, bleaches, aerosols, deodorants and fragrances, repellents and sundries.

(12) A fragranced product comprising S-alkyl (R) -2-methylbutanethioate added at a concentration of 10 ⁻⁹ to 10 ⁷ ppb.

(13) A method for enhancing, improving or modulating flavor and aroma, which comprises adding S-alkyl (R) -2-methylbutanethioate.

  That is, as a result of intensive studies by the inventors of the present invention in the above situation, (R) -2-R is not a racemic 2-methylbutanethioate S-alkyl which is widely used in the market. A flavor and fragrance composition characterized by containing S-alkyl methylbutanethioate as an active ingredient has a flavor and fragrance reminiscent of a strong fresh passion fruit, and other flavor and fragrance ingredients used. It has been found that it is excellent in harmony, and imparts a clean and fresh, highly-flavored flavor and fragrance, which has been insufficient with similar compounds derived from natural or processed foods and drinks known so far. He continued his research and completed the present invention.

  The flavor and fragrance composition of the present invention containing (R) -2-methylbutanethioate S-alkyl as an active ingredient has a flavor and fragrance reminiscent of a strong fresh passion fruit, and other flavors and It is excellent in harmony with fragrance ingredients, and imparts a clean and fresh, highly-preferred flavor and fragrance, which has been insufficient with similar compounds derived from natural or processed foods and drinks so far known. The flavor and fragrance composition of the present invention can be used in a wide range of food materials, food additives, insurance hygiene materials, etc. in addition to the above-mentioned flavored product and fragranced product of the present invention.

  The present invention is described in detail below.

  In the flavor and fragrance composition of the present invention, S-alkyl (R) -2-methylbutanethioate is used as an essential component. Specific examples of the (R) -2-methylbutanethioic acid S-alkyl include, for example, (R) -2-methylbutanethioic acid S-methyl ester, S-ethyl ester, Sn-propyl ester. , S-isopropyl ester, S-butyl ester, S-2-methylpropyl ester, S-pentyl ester, S-2-methylbutyl ester, S-3-methylbutyl ester, S-hexyl ester, S-cis-3 -Hexenyl ester, S-heptyl ester, S-octyl ester, etc. can be mentioned.

  The above (R) -2-methylbutanethioic acid S-alkyl may be used as an essential component or as a mixture of two or more thereof. Among these compounds, the flavor and fragrance composition of the present invention. A preferred compound as an essential component of the product is S-methyl (R) -2-methylbutanethioate.

  The (R) -2-methylbutanethioic acid S-alkyl used in the present invention can be obtained by extraction from a natural product, or can be obtained by optical resolution of a racemate. It can be used, and further, those obtained by a chemical synthesis method can be used. However, when a large amount of (R) -2-methylbutanethioate S-alkyl is used, the chemical synthesis method is used. It is preferable to select the one obtained.

  Examples of the chemical synthesis method of S-alkyl (R) -2-methylbutanethioate include a method of reacting (R) -2-methylbutanoic acid as a raw material with an acid halide and then reacting with alkylthiol. it can.

  Further, as a chemical synthesis method of (R) -2-methylbutanoic acid, the method described in JP-A-63-239245, that is, tiglic acid ((E)- Examples thereof include a method of asymmetric hydrogenation using 2-methyl-2-butenoic acid) as a raw material and using a ruthenium-optically active phosphine complex having a specific absolute configuration as a catalyst.

The above-mentioned chemical synthesis method of (R) -2-methylbutanoic acid will be described in more detail. An autoclave in which tiglic acid is dissolved in a solvent such as methanol and ethanol and substituted with an inert gas is charged with ruthenium-optical activity. Since the phosphine complex is added 1/100 to 1/1000 times the mole of tiglic acid, hydrogenation is carried out by stirring for 1 to 100 hours at a hydrogen pressure of 4 to 125 kg / cm ² and a reaction temperature of 5 to 50 ° C. is there.

  Further, as a hydrogen source, a method described in JP-A-3-157346 which does not use hydrogen gas can be used. However, according to this method, a primary or secondary alcohol is used as a hydrogen donor in a large excess. Will be used. After the reaction, the target (R) -2-methylbutanoic acid can be obtained by distilling off the solvent and distilling the residue under reduced pressure.

Examples of ruthenium-optically active phosphine complexes that can be used include the following.
Ru _x H _y Cl _z [(+)-(R-BINAP)] ₂ (S) _p (1)
{Wherein (+)-(R-BINAP) is (-)-2,2'-bis (diphenylphosphino) -1,1'-binaphthyl or (+)-2,2'-bis (di -P-methylphenylphosphino) -1,1'-binaphthyl and the like, and S represents a tertiary amine. y represents 0 or 1; when y is 0, x is 2, Z is 4, p is 1, and when y is 1, x is 1, Z is 1, and p is 0. }

{Ru [(+)-(X-BINAP)] _q } (OCOR ¹ ) (OCOR ² ) (2)
{In the formula, (+)-(X-BINAP) may be substituted with amino group, acetylamino group or sulfone group at the 5-position and 5'-position of two naphthyl groups, (+)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl optionally substituted with a lower alkyl group at the p-position is shown. R ¹ and R ² represent a lower alkyl group, a halogeno lower alkyl group, a phenyl group which may be substituted by a lower alkyl group, an α-aminoalkyl group or an α-aminophenylalkyl group, or R ¹ and R 2 ² may combine to form an alkylene group. q represents 1 or 2. }

{RuH _l [(+)-(R-BINAP)] _v } Y _w (3)
{Wherein (+)-(R-BINAP) represents the same content as described above. Y represents ClO ₄ , BF ₄ or PF ₆ . l represents 0 or 1; when l is 0, v represents 1, w represents 2, and when l is 1, v represents 2, and w represents 1. }

{Ru [(+)-(BIPHEMP)]} Y ₂ (4)
{Wherein (+)-(BIPHEMP) is (-)-2,2'-dimethyl-6,6'-bis (diphenylphosphino) -1,1'-biphenyl, (-)-2,2 '-Dimethyl-6,6'-bis (di-p-methylphenylphosphino) -1,1'-biphenyl or (-)-2,2'-dimethyl-6,6'-bis (di- p-methoxyphenylphosphino) -1,1'-biphenyl and the like. Y indicates the same content as described above. )

  Any of the ruthenium-optically active phosphine complexes (1) to (3) described above can be obtained by the method described in JP-A-63-239245. The ruthenium-optically active phosphine complex (4) is a complex described in JP-A No. 63-145292.

  In the flavor and fragrance composition of the present invention, the S-alkyl (R) -2-methylbutanethioate obtained as described above has an optical purity of 50% e.e. e. The above is preferable.

  S-methyl (R) -2-methylbutanethioate synthesized according to the method described in JP-A-63-239245 has an optical purity of 88% e.e. e. Although it was obtained with a high purity, it was tested to what optical purity the effect of the (R) isomer appears, and in the present invention, approximately 50% e.e. e. It was found that the effect of the (R) body began to appear with a degree of optical purity. And based on said result, also about other thioesters, optical purity 50% e.e. e. If it is the above, it came to be anticipated that the effect of this invention can be anticipated reliably. Therefore, if it is higher than these optical purities, it can be used as an essential component of the flavor and fragrance composition of the present invention as it is without purification, thereby ensuring the effects of aroma and flavor of various cosmetics and foods and drinks. It turned out to be expected.

  As shown in the following examples, the flavor and fragrance composition of the present invention containing, for example, S-alkyl (R) -2-methylbutanethioate as an active ingredient has a flavor and aroma reminiscent of a strong and fresh passion fruit. The (R) -2-methylbutanethioic acid S-alkyl, which is an active ingredient, exhibits various effects that require flavoring and fragrance application of flavors and fragrance compositions in order to exert effects even in a small amount. Flavor and fragrance can be applied to base materials of cosmetics and foods and drinks, but racemic 2-methylbutanethioate S-methyl is a natural scent, but lacks strength, The effect is not sufficient.

  Furthermore, the flavor and fragrance composition of the present invention containing, for example, S-alkyl (R) -2-methylbutanethioate as an active ingredient is reminiscent of a strong and fresh passion fruit as described above. It has not only flavor and aroma characteristics, but also has a remarkable flavor / fragrance persistence characteristics and stability, and by blending this, a flavor and fragrance composition with high palatability can be provided.

  In the flavor and fragrance composition of the present invention, for example, in addition to an active ingredient such as S-alkyl (R) -2-methylbutanethioate, a commonly used flavor ingredient and fragrance ingredient can be further added. Examples of other flavor components and fragrance components that can be used in addition include various synthetic fragrances, natural essential oils, synthetic essential oils, citrus oils, animal fragrances, etc., especially floral and fruit flavor components and fragrance components. Are preferred, for example Arctander S. et al. "Perfume and Flavor Chemicals", published by the author, Montclair, N .; J. et al. A wide range of flavor and fragrance components can be used, as described in (USA) 1969. Representative examples include α-pinene, limonene, cis-3-hexenol, phenylethyl alcohol, styrylyl acetate, eugenol, rose oxide, linalool, benzaldehyde, muscone, Tesalon (Takasago International Corporation), ethyl butyrate, Examples include 2-methylbutanoic acid.

  Specifically, when the (R) -2-methylbutanethioic acid S-alkyl is added to natural essential oils such as bergamot oil, galvanum oil, lemon oil, geranium oil, lavender oil, mandarin oil, etc., natural essential oil Can be prepared with a new flavor and fragrance composition which has a mild and rich flavor and aroma, and has a high palatability, a diffusibility, a retention and a long-lasting nature.

  Further, for example, prepared from various synthetic fragrances, natural fragrances, natural essential oils, citrus oils, tea extracts, animal fragrances, etc. For example, strawberry, lemon, orange, grapefruit, apple, pineapple, banana, melon, green tea, oolong tea, black tea When added to flavors and fragrance compositions such as, it gives a fruity-like, tropical-like aroma that is mild and rich in naturalness, and also gives a fresh, highly-flavored aroma and diffusibility. Flavor and fragrance compositions can be prepared that enhance retention and persistence.

The amount of active ingredient such as S-alkyl (R) -2-methylbutanethioate for the flavor and fragrance composition of the present invention varies depending on the type and purpose of the flavor and fragrance composition, but generally In the flavor composition, for example, the blending amount in the composition is 10 ⁻⁸ to 10 ⁹ ppb, particularly 10 ⁻⁷ to 10 ⁸ ppb, more preferably 10 ⁻⁶ to 10 ⁷ ppb. In the composition, for example, a blending amount of 10 ⁻⁷ to 10 ⁹ ppb, particularly 10 ⁻⁸ to 10 ⁸ ppb, more preferably 10 ⁻⁵ to 10 ⁷ ppb is preferable in the composition.

  In addition, the flavor and fragrance composition of the present invention may contain one or more commonly used retention agents, such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol. , Benzyl benzoate, triethyl citrate, diethyl phthalate, hercoline, medium chain fatty acid triglyceride, medium chain fatty acid diglyceride and the like.

  Flavors and fragrance compositions containing the above (R) -2-methylbutanethioate S-alkyl alone or the compound and the above-mentioned other components, such as foods and drinks, oral compositions, pharmaceuticals; fragrance products , Basic cosmetics, finishing cosmetics, hair cosmetics, tanning cosmetics, medicated cosmetics, hair care products, soap, body cleaners, bath preparations, detergents, softeners, detergents, kitchen detergents, bleaches, aerosols, deodorants If an appropriate amount capable of imparting the unique flavor and aroma is added to the fragrance and miscellaneous goods, a flavored product and a fragranced product can be provided.

  Examples of flavored products include fruit juice beverages, fruit liquors, milk beverages, carbonated beverages, soft drinks, beverages such as drinks; ice creams, sherbets, iced confections such as ice candy;・ Paste beverages such as Western confectionery, jams, candy, jelly, gums, breads, coffees, cocoa, teas, oolong teas, green teas; soups such as Japanese-style soups, Western-style soups, Chinese soups , Flavor seasonings, various instant beverages or foods, various snack foods, etc .; as oral compositions, for example, toothpastes, oral cleansing agents, mouthwashes, troches, chewing gums, etc .; And various forms such as an external preparation for skin such as an ointment, and an internal preparation.

  Examples of fragranced products include the following:

  Examples of fragrance products include perfume, eau de parfum, eau de toilette, and eau de cologne; As finishing cosmetics, foundation, powder, solid, talcum powder, lipstick, lip balm, blusher, eyeliner, mascara, eye shadow, eyebrow, eye pack, nail enamel, enamel rim bar, etc .; Brillantin, Set Lotion, Hair Steak, Hair Solid, Hair Oil, Hair Treatment, Hair Cream, Hair Nick, Hair Liquid, Hair Spray, Bundling, Hair Tooth, Mention may be made of the hair agent, and the like.

  Examples of suntan cosmetics include suntan products and sunscreen products; examples of medicinal cosmetics include antiperspirants, after shaving lotions and gels, permanent wave agents, medicated soaps, medicated shampoos, medicinal skin cosmetics, etc .; Is a shampoo, rinse, rinse-in shampoo, conditioner, treatment, hair pack, etc .; soap is cosmetic soap, bath soap, perfume soap, transparent soap, synthetic soap, etc .; body soap, body shampoo, hand Soap, etc .; bathing agents such as bath salts (bath salts, bath tablets, bath liquids, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jelly, bath cubes, etc. Can be mentioned.

  Examples of detergents include heavy detergents for clothing, light detergents for clothing, liquid detergents, laundry soaps, compact detergents, powdered soaps, etc .; softeners such as softeners, furniture cares, etc .; House cleaner, toilet cleaner, bathroom cleaner, glass cleaner, mold remover, drainpipe cleaner, etc .; kitchen detergent, kitchen soap, kitchen synthetic soap, dishwasher, etc .; Oxidative bleaches (chlorine bleaches, oxygen bleaches, etc.), reduced bleaches (sulfur bleaches, etc.), optical bleaches, etc .; aerosols include spray types, powder sprays, etc .; Examples of the fragrance include a solid type, a gel type, and a liquid type; examples of the miscellaneous goods include various forms such as tissue paper and toilet paper.

  The flavor and fragrance composition of the present invention containing (R) -2-methylbutanethioate S-alkyl as an active ingredient, food and drink products, oral compositions, pharmaceutical products, etc .; or fragrance products, basic cosmetics, finishing Cosmetics, hair cosmetics, tanning cosmetics, medicinal cosmetics, hair care products, soaps, body cleaners, bath preparations, detergents, softeners, detergents, kitchen detergents, bleaches, aerosols, deodorants and aromatics, sundries, etc. In this state, or in a liquid state in which these are dissolved in polyhydric alcohols such as alcohols, propylene glycol and glycerin; natural gums such as gum arabic and tragacanth; Emulsified with emulsifiers such as sugar fatty acid esters and processed denbuns; natural gums such as gum arabic Powder form coated with excipients such as gelatin and dextrin; solubilized or dispersed using surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants An arbitrary shape can be selected and used depending on the purpose, such as a solubilized or dispersed form; or a microcapsule obtained by treatment with an encapsulating agent.

  Furthermore, the flavor and fragrance composition can be stabilized and sustained-released by inclusion in an inclusion agent such as cyclodextrin, and these can be used in the form of final products such as liquid, solid, powder. It is suitable for a shape, a gel shape, a mist shape, an aerosol shape, etc., and is appropriately selected and used.

The amount of (R) -2-methylbutanethioic acid S-methyl added to flavored products such as foods and drinks, oral compositions, pharmaceuticals, etc. Although it is arbitrarily adjusted depending on the situation, it is generally about 10 ⁻⁹ to 10 ⁵ ppb.

In addition, fragrance products that are fragranced, basic cosmetics, finished cosmetics, hair cosmetics, tanning cosmetics, medicated cosmetics, hair care products, soap, body cleaning agents, bath preparations, detergents, soft finishes, cleaning agents, kitchen use The amount of S-alkyl (R) -2-methylbutanethioate added to detergents, bleaches, aerosols, deodorants, fragrances, sundries, etc. is optional depending on the expected effects and actions. Generally, it is about 10 ⁻⁹ to 10 ⁷ ppb.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited thereto, and may be modified without departing from the scope of the present invention. .

  In addition, the expression of the odor in an Example and a comparative example is referring to the expression described in Motoichi Into, "Actual knowledge of fragrance | flavor" (March 25, 1975), Toyo Keizai Shinposha, page 3. did.

The analysis in this example was performed using the following analytical equipment.
Optical rotation;
Device: DIP-370 (manufactured by JASCO Corporation)
Proton nuclear magnetic resonance spectrum ( ¹ H-NMR);
Equipment: AM-400 type (400MHz) (Brucker)
Internal standard: Tetramethylsilane Infrared absorption spectrum (IR);
Equipment: Nicolet Avatar 360 FT-IR (manufactured by Nicolet Japan)
Mass spectrum (MS);
Instrument: M-80B mass spectrometer (ionization voltage: 20 eV) (manufactured by Hitachi, Ltd.)
Gas chromatograph instrument: HP-5890 (manufactured by Hewlett-Packard Company)
Column: PEG BC-WAX (0.25 mm × 50 m) (manufactured by GL Sciences Inc.)

Synthesis example 1
Production of (R) -2-methylbutanoic acid 0.2 g (2 mmol) of tiglic acid and 20 ml of methanol were placed in a 100 ml stainless steel autoclave previously purged with nitrogen, followed by Ru [(+)-BINAP] (BF ₄ ). ₂ ((+)-BINAP represents (+)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl)) 6.0 mg (0.007 mmol) was added and hydrogen pressure 4 kg / Hydrogenation was carried out by stirring for 12 hours at cm ² and a reaction temperature of 20 ° C., and the solvent was distilled off to obtain 0.2 g (yield 100%) of the desired (R) -2-methylbutanoic acid. The optical rotation was [α] _D ²⁵ = −16.7 ° (neat), and the purity by gas chromatography was 100%. This was reacted with (S) -1-phenylethylamine to synthesize an amide and analyzed by gas chromatography. As a result, the optical purity of (R) -2-methylbutyric acid was 88% e.e. e. Met.

Synthesis example 2
Production of (R) -2-methylbutanoic acid chloride (R) -2-methylbutanoic acid obtained in Synthesis Example 1 {[α] _D ²⁵ = -16.7 ° (neat)} 35.8 g (350 mmol) 50.0 g (420 mmol) of thionyl chloride was added dropwise at 50 ° C. over 3 hours, and then reacted at 80 ° C. for 1 hour. Excess thionyl chloride was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 40.4 g (yield 96%) of (R) -2-methylbutanoic acid chloride.
Boiling point: 35 ° C / 0.1 torr
¹ H-NMR (CDCl ₃ ): 0.98 (t, J = 7.5 Hz, 3H), 1.29 (d, J = 6.9 Hz, 3H), 1.58 to 1.66 (m, 1H) ), 1.79-1.87 (m, 1H), 2.78-2.85 (m, 1H)
¹³ C-NMR: 11.46 (CH ₃ ), 16.88 (CH ₃ ), 26.91 (CH ₂ ), 53.29 (CH), 178.05 (CO)

Synthesis example 3
(R) -2-Methylbutanethioate Production of S-methyl (R) -2-methylbutane obtained in Synthesis Example 2 with stirring in a mixture of 75 g of a 15% methyl mercaptan aqueous solution cooled to 0 ° C. and 100 mL of diethyl ether 16.1 g (120 mmol) of acid chloride was added dropwise over 1 hour. The organic layer was separated, washed with brine, diethyl ether was distilled off, and the residue was concentrated under reduced pressure to give 15.1 g of S-methyl (R) -2-methylbutanethioate (yield 86%). ) As a result of analysis by gas chromatography, the chemical purity was 100% and the optical purity was 88% e.e. e. Met.
Boiling point 32 ° C./5 torr.
[Α] _D ²⁰ = −36.7 ° (neat)
¹ H-NMR (CDCl ₃ ): 0.92 (t, J = 7.5 Hz, 3H), 1.29 (d, J = 6.9 Hz, 3H), 1.43 to 1.52 (m, 1H) ), 1.70 to 1.78 (m, 1H), 2.28 (s, 3H), 2.54 to 2.60 (m, 1H)
¹³ C-NMR: 11.29 (CH ₃ ), 11.58 (CH ₃ ), 17.21 (CH ₃ ), 27.17 (CH ₂ ), 50.04 (CH), 204.22 (CO)

Example 1 Evaluation of flavor and fragrance A perfumer who has more than 5 years of experience using S-methyl (R) -2-methylbutanethioate obtained in the synthesis example and attached to a bottle mouth and filter paper Sensory evaluation was performed by five people. The evaluation results are shown in Table 1.

  As described above, (R) -2-methylbutanethioate (S-methyl) used in the flavor and fragrance composition of the present invention is reminiscent of a strong and fresh passion fruit, which is unique with a clean, fresh and high palatability. On the other hand, the racemic 2-methylbutanethioate S-methyl is a natural scent, but lacks strength and has a slight miscellaneous feeling. Pointed out. In addition, as panelists, we selected 10 professional flavourists (Flavorists, who create food flavors) in their 20s and 30s, a total of 10 people, 8 men and 2 women. “Paneller” in the following comparison between Example 3 and Comparative Example 1 is an agreement.

Example 2
S-methyl (R) -2-methylbutanethioate synthesized according to the method described in JP-A-63-239245 has an optical purity of 88% e.e. e. Although it was obtained with a high degree of purity, it was tested to what degree of optical purity the effect of the (R) isomer appears clearly. (R) -2-methylbutanethioate S-methyl of any optical purity can be prepared by mixing the racemate at an arbitrary ratio, and the optical purity of the effect of the (R) isomer can be clearly and reliably discriminated. 2: Two-point identification method (To identify two samples A and B, first present samples A and B as light samples to the panel, memorize their characteristics, Present as a blind sample, point out the sample that is different from A, and determine whether there is a difference between the two samples from the number of correct answers obtained in several iterations; Shin Sato “Introduction to Sensory Testing” 54 pages (October 16, 1978, published by Nikka Girensha Publishing Co., Ltd.)) were measured.

  As a result, when S-methyl (R) -2-methylbutanethioate is used, the optical purity is 50% e.e. e. If it was above, it turned out that it can be used as it is, without refine | purifying, and the flavor and flavor improvement effect of a flavor and a fragrance composition can be anticipated reliably.

Example 3, Comparative Example 1
Example 3 containing (R) -2-methylbutanethioic acid S-methyl obtained in Synthesis Example to the grapefruit flavor composition shown in Table 2 below and containing the active ingredient at a concentration of 0.01 ppb A flavor composition was prepared. Further, Comparative Example 1 was obtained by adding racemic S-methyl 2-methylbutanethioate. Each flavor composition was subjected to sensory evaluation by five flavorists who had more than 5 years of experience.

  As a result, all of the panelists pointed out that the added Example 3 was given a natural deep freshness not found in Comparative Example 1.

Example 4 Production of shampoo fragrance composition Formulation Example 1
component
Benzyl salicylate 55
L-citronellol 10
Ethyl acetoacetate 5
Galaxolide 50BB ^* (made by IFF) 390
Geraniol 10
Hedion (Fulmenich) 120
Helioboke (manufactured by Takasago International Corporation) 8
Cis-3-hexen-1-ol 10% DPG ^** solution 10
Acetic acid cis-3-hexenyl 10% DPG solution 5
Hexylcinnamic aldehyde 50
β-Yonon 17
Cobanol (Takasago International Corporation) 40
Lemon oil 40
Linaroll 45
Linalyl acetate 45
Nerolidol 55
Phenylethyl alcohol 30
Phenyl ethyl cinnamate 5
Santarex T (manufactured by Takasago International Corporation) 35
Tripral 10% DPG solution (manufactured by IFF) 5
Maltol 1% DPG solution 15
(R) -2-methylbutanethioic acid S-methyl 10 ppm DPG solution 5
Total 1000
* Benzyl benzoate ** Dipropylene glycol

Comparative Example 2
In the formulation of Example 4, it was carried out except that racemic (R) -2-methylbutanethioate S-methyl (R) -2-methylbutanethioate was used instead of 10 ppm DPG solution of S-methyl (R) -2-methylbutanethioate. A shampoo fragrance composition was prepared according to the same formulation as in Example 4.

[Application Example 1] Production of shampoo Using the shampoo fragrance composition prepared in Example 4 and Comparative Example 2, the following components were heated and stirred at 80 ° C until uniform, and then cooled to 35 ° C to prepare a shampoo. did.
Sensory evaluation was performed by five perfumers who have more than 5 years of experience regarding the scent of each shampoo.

[Shampoo composition] (% by mass)
Sodium lauryl sulfate 40.00
N-coconut oil fatty acid acyl-N-
Carboxymethoxyethyl-
N-carboxymethyl
Ethylenediamine disodium 10.00
Palm oil fatty acid diethanolamide (2) 2.00
Butylene glycol 2.00
Citric acid 0.35
Sodium chloride 0.10
Methylparaben 0.20
Propylparaben 0.10
Edetate tetrasodium 0.10
Fragrance composition of Example 4 or Comparative Example 2 0.50
Purified water balance
Total 100.00

[Evaluation results of Example 4 and Comparative Example 2]
As a result of evaluating the shampoo fragrance of Example 4 and Comparative Example 2, the shampoo fragrance based on the formulation of Example 4 containing S-methyl (R) -2-methylbutanethioate was excellent in diffusibility and fresh. All the panelists pointed out that they had a natural feeling.

Example 5 Production of Body-Shampoo Fragrance Composition Formulation Example 2
component
Lemon oil 100
Lime oil 180
Geranil nitrile 10
Aldehyde C-8 10% DPG solution 25
Aldehyde C-10 10% DPG solution 35
Ethyl decanoate 12
Tripar (made by IFF) 3
Isocyclocitral 10% DPG solution (IFF) 25
Styraryl acetate 20
α-Terpineol 30
Linalool 70
Linalyl acetate 50
Geraniol 60
Geranyl acetate 5
Lilianar (Gibodan) 80
Hexylcinnamic aldehyde 120
Mylacaldehyde (made by IFF) 15
Salicylic acid cis-3-hexenyl 15
β-Yonon 25
Heliotropin 5
Tonalid (manufactured by PFW) 30
Dipropylene glycol balance
(R) -2-methylbutanethioic acid S-methyl 10 ppm DPG solution 5
Total 1000

Comparative Example 3
In the formulation of Example 5, Example 5 was used except that (R) -2-methylbutanethioate S-methyl 10 ppm DPG solution was used instead of racemic 2-methylbutanethioate S-methyl. A body shampoo fragrance composition was prepared according to the same formulation.

[Application Example 2] Production of body shampoo Using the fragrance composition for body shampoo prepared in Example 5 and Comparative Example 3, a body shampoo was prepared.
Sensory evaluation was performed by five perfumers who have more than 5 years of experience regarding the aroma of each body shampoo.

[Body shampoo composition] (mass%)
Dibutylhydroxytoluene 0.05
Methylparaben 0.10
Propylparaben 0.10
Edetate tetrasodium 0.10
Potassium chloride 0.20
Glycerin 5.00
Coconut oil fatty acid diethanolamide (2) 3.00
Polyoxyethylene lauryl
Sodium ether acetate (3EO) (30%) 10.00
Palm oil fatty acid amidopropyl betaine solution (34%) 25.00
Potassium myristate (40%) 25.00
Fragrance composition of Example 4 and Comparative Example 3 0.50
Purified water balance
Total 100.00

[Evaluation results of Example 5 and Comparative Example 3]
As a result of evaluating the scent of the body shampoo of Example 5 and Comparative Example 3, the scent of the body shampoo based on the formulation of Example 5 containing (R) -2-methylbutanethioic acid S-methyl is improved in freshness. All the panelists pointed out that they had a sense of citrus.

Example 6 Production of Rose-like Fragrance Composition Formulation Example 3
component
α-Pinene 8
Aldehyde C-16 1
Allyl amyl glycolate 1
Ambret lid (made by IFF) 8
Bergamot 15
Carbitol 100
Cardamom oil 3
L-citronellol 30
β-Damascon 2
Dimethyloctanol 10% DPG solution 4
Dipropylene glycol 29
Dynascon 10% DPG solution 5
Ethyl acetate 10% DPG solution 4
Ethyl acetoacetate 15
Galvanum oil 10% DPG solution 10
Headion (Filmenich) 195
Helioboke (manufactured by Takasago International Corporation) 10
Cis-3-hexen-1-ol 2
Cis-3-hexen-1-ol 10% DPG solution 3
β-Yonon 10
Jasmine Absolute 3
Lime oil 10% DPG solution 5
Linalyl acetate 40
8-Mercaptomenton 10% DPG solution 8
Musk T (manufactured by Takasago International Corporation) 200
Nerolidol 46
Phenylethyl alcohol 17
β-Pinene 117
Rubofix (Filmenich) 12
Rose Absolute 3
Rose oil 10% DPG solution 5
L-rose oxide 10% DPG solution 15
Santarex T (manufactured by Takasago International Corporation) 40
Triplar (made by IFF) 14
Belton (made by Firmenich) 12
Maltol 5
(R) -2-methylbutanethioic acid S-methyl 10 ppm DPG solution 5
Total 1000

Comparative Example 4
Same as Example 6 except that in the formulation of Example 6, racemic 2-methylbutanethioate S-methyl was used instead of 10 ppm DPG solution of (R) -2-methylbutanethioate S-methyl A rose-like fragrance composition was prepared by formulation.

[Application Example 3] Production of Cosmetic Cream A cosmetic cream was prepared using the rose-like fragrance composition prepared in Example 6 and Comparative Example 4.
[Cosmetic cream] (mass%)
Stearyl alcohol 6.0
Stearic acid 2.0
Hydrogenated lanolin 4.0
Squalane 9.0
Octyldecanol 10.0
Glycerin 6.0
Polyethylene glycol 1500 4.0
Polyoxyethylene (25) cetyl ether 3.0
Glucerin monostearate 2.0
Methyl paraben Appropriate amount Ethyl paraben Appropriate amount Fragrance composition of Example 6 or Comparative Example 4 0.1
Purified water balance
Total 100.0

[Evaluation results of Example 6 and Comparative Example 4]
As a result of evaluating the fragrance of the cosmetic cream of Example 6 and Comparative Example 4, the fragrance of the cosmetic cream based on the formulation of Example 6 containing S-methyl (R) -2-methylbutanethioate was very diffusive. All panelists pointed out that they had a natural feeling.

Claims (13)

A flavor and fragrance composition comprising (R) -2-methylbutanethioate S-alkyl as an active ingredient. (R) -2-methylbutanethioic acid S-alkyl has an optical purity of 50% e.e. e. The flavor and fragrance composition according to claim 1 as described above. The flavor and fragrance composition according to claim 1 or 2, which is a flavor composition. A flavor composition comprising (R) -2-methylbutanethioate S-alkyl at a concentration of 10 ⁻⁶ to 10 ⁷ ppb. A product flavored by the flavor composition of claim 4. 6. The flavored product according to claim 5, wherein the flavored product is one selected from foods and drinks, oral compositions and pharmaceuticals. A flavored product comprising S-alkyl (R) -2-methylbutanethioate added at a concentration of 10 ⁻⁹ to 10 ⁵ ppb. The flavor and fragrance composition according to claim 1 or 2, which is a fragrance composition. A fragrance composition comprising (R) -2-methylbutanethioate S-alkyl at a concentration of 10 ⁻⁶ to 10 ⁷ ppb. A product fragranced by the fragrance composition of claim 9. Fragranced products include fragrance products, basic cosmetics, finished cosmetics, hair cosmetics, tanning cosmetics, medicated cosmetics, hair care products, soaps, body cleaners, bath preparations, detergents, softeners, detergents, kitchen detergents, The fragranced product according to claim 10, which is one selected from a bleaching agent, an aerosol agent, a deodorant / fragrance, a repellent, and a sundries. A fragranced product comprising S-alkyl (R) -2-methylbutanethioate added at a concentration of 10 ⁻⁹ to 10 ⁷ ppb. (R) A method for enhancing, improving or modulating the flavor and aroma, characterized by adding S-alkyl 2-methylbutanethioate.