JP2022103542A - Cyclic compound containing oxygen atom and sulfur atom - Google Patents

Abstract

To provide a compound useful for flavoring.SOLUTION: A flavoring composition containing a compound expressed by formula (1) is provided. In the formula, following conditions (i) - (iv) should be satisfied. (i) n represents an integer from 0 to 3. (ii) One of the two broken lines of the five-membered ring is the carbon-carbon double bond and the other is the carbon-carbon single bond, or both lines are single bonds. (iii) One of broken side lines of the five-membered ring is carbon-carbon double bond and the others are single bonds, or all of them are single bonds. (iv) X1 and X2 are an oxide atom and a sulfur atom.SELECTED DRAWING: None

Description

The present invention relates to a cyclic compound containing an oxygen atom and a sulfur atom, and a flavoring composition containing the compound.

In recent years, consumer demands for foods and drinks and cosmetics have become more sophisticated and diversified, but in particular, scents have been attracting attention, and the characteristics of scents have become an important factor in the appeal of products. For example, there is an increasing demand for compounds that can impart characteristic flavors such as persistence and naturalness to the aroma and taste of the product by blending into the product.

Examples of the compound having a heterocycle, an oxygen atom and a sulfur atom in the molecule, such as the compound according to the present invention, include 2-furfurylmethyl sulfide, 2-furfurylmethyl disulfide and methyl (5-methyl-2-). It is known that compounds such as frill) sulfide and methyl (2-methyl-3-furyl) disulfide are effective in imparting a feeling of brewing coffee (Patent Document 1).

However, the development of new compounds that can differentiate from the flavors of existing products by imparting better flavors to various products such as foods and drinks and cosmetics continues to be expected.

Japanese Unexamined Patent Publication No. 2008-259472

An object of the present invention is to provide a novel compound useful for imparting a flavor to an article.

The present inventors diligently searched for an unknown compound effective for imparting a flavor to an article, and found that a cyclic compound containing an oxygen atom and a sulfur atom, which had no known effect of exhibiting a fragrance or imparting a flavor, had a flavor. It was found to be useful for granting. That is, they have found that cyclic compounds containing oxygen atoms and sulfur atoms (specifically, thiophenone compounds and franchion compounds) each have a characteristic aroma and are useful for imparting flavor to articles, and the present invention has been found. It came to. Thus, the present invention provides the following:

[1] A flavor-imparting composition containing a compound represented by the following formula (1).

[In the equation, (i) to (iv) are satisfied: (i) n represents an integer of 0 to 3, and (ii) the two broken lines of the five-membered ring are carbon-carbon double bonds at one place. The other point is a single bond, or both points are single bonds. (Iii) The broken line of the side chain of the five-membered ring is a carbon-carbon double bond at one place. Yes, the other parts are single bonds, or all parts are single bonds, and (iv) X ₁ and X ₂ are one oxygen atom and the other sulfur atom. ]
[2] A consumer good containing the flavoring composition according to [1].
[3] A method for imparting flavor to consumer goods, which comprises blending the flavoring composition according to [1] into consumer goods.
[4] A method for imparting flavor to a flavor-imparting composition, which comprises blending the flavor-imparting composition according to [1] with another flavor-imparting composition.
[5] A compound represented by the following formula (1').

[In the equation, (i) to (iv) are satisfied: (i) n represents an integer of 0 to 3, and (ii) the two broken lines of the five-membered ring are carbon-carbon double bonds at one place. The other point is a single bond, or both points are single bonds. (Iii) The broken line of the side chain of the five-membered ring is a carbon-carbon double bond at one place. Yes, the other parts are single bonds, or all parts are single bonds, and (iv) X ₁ and X ₂ are one oxygen atom and the other sulfur atom. (However, (i) n is 1, (ii) one point of the broken line of the five-membered ring is a carbon-carbon double bond, and the other place is a single bond, and (iii) the side chain. Except for cases where all points of the broken line in (iv) are single bonds, (iv) X ₁ is a sulfur atom, X ₂ is an oxygen atom, and the side chain is bonded to the 5-position of the five-membered ring. )]]

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a compound that can be newly used for imparting flavor to various articles.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In the present specification, "to" means a range including a lower limit value and an upper limit value, and concentration (ppt, ppb, ppm, etc.) and% represent mass concentration and mass%, respectively, unless otherwise specified.

(Compound represented by the formula (1))
Cyclic compounds containing oxygen atoms and sulfur atoms represented by the formula (1) (sometimes referred to simply as the compounds of the formula (1) in the present specification) may have a fragrance or may be applied to various goods such as consumer goods. It is a group of compounds that have never been known to be usable for flavoring, and the usefulness of flavoring applications has been confirmed for the first time by the present inventors.

In the formula (1), (i) to (iv) are satisfied: (i) n represents an integer of 0 to 3, and (ii) the two broken lines of the five-membered ring are carbon-carbon two at one place. It is a double bond, indicating that the other site is a single bond or both sites are single bonds, and (iii) the side chain of the five-membered ring (in this specification, it may be simply a side chain). ) Indicates that one location is a carbon-carbon double bond and the other location is a single bond, or all locations are single bonds, and (iv) X ₁ and X ₂ are , Oxy atom and sulfur atom, respectively, or sulfur atom and oxygen atom, respectively.

In formula (1), when X ₁ and X ₂ are oxygen atoms and sulfur atoms, respectively, it is a francion compound, and when X ₁ and X ₂ are sulfur atoms and oxygen atoms, respectively, it is a thiophenone compound. I can say.

In the formula (1), n is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even more preferably 1. Further, in the formula (1), among the broken lines, preferably, there is one carbon-carbon double bond in the five-membered ring and one in the side chain, n is 1, and 3 of the broken lines in the side chain. There is a double bond between the 4th and 4th positions, or n is 2 and there is one side chain double bond between the 4th and 5th positions. More preferably, the carbon-carbon double bond present in the five-membered ring is present at one position between the 3-position and the 4-position. Further, in the case of a franchion compound, the side chain is preferably bonded to the 4-position of the 5-membered ring.

Preferred specific examples of the compound of the formula (1) are the compound of the following formula (1-1), the compound of the formula (1-2), the compound of the formula (1-3), and the compound of the formula (1-4). Examples include, but are not limited to, compounds. In the compound of formula (1-1), n is 1, there is one double bond between the 3rd and 4th positions of the broken line of the side chain, and the other part is a single bond, which is a five-membered compound. The carbon-carbon double bond present at one location on the ring exists between the 3- and 4-positions, X ₁ and X ₂ are oxygen and sulfur atoms, respectively, and the side chain is the 4-position of the five-membered ring. If it is bound to. In the compound of formula (1-2), n is 1, there is one double bond between the 3rd and 4th positions of the broken line of the side chain, and the other part is a single bond, which is a five-membered compound. The carbon-carbon double bond present at one location on the ring exists between the 3- and 4-positions, X ₁ and X ₂ are sulfur and oxygen atoms, respectively, and the side chain is the 4-position of the five-membered ring. If it is bound to. In the compound of formula (1-3), n is 1, there is one double bond between the 3rd and 4th positions of the broken line of the side chain, and the other part is a single bond, which is a five-membered compound. The carbon-carbon double bond present at one location on the ring exists between the 3- and 4-positions, X ₁ and X ₂ are sulfur and oxygen atoms, respectively, and the side chain is the 3-position of the five-membered ring. If it is bound to. In the compound of formula (1-4), n is 1, there is one double bond between the 3rd and 4th positions of the broken line of the side chain, and the other part is a single bond, which is a five-membered compound. The carbon-carbon double bond present at one location on the ring exists between the 3- and 4-positions, X ₁ and X ₂ are sulfur and oxygen atoms, respectively, and the side chain is the 5-position of the five-membered ring. If it is bound to.

(Example of Production of Compound of Formula (1))
The means for obtaining the compound of the formula (1) is not particularly limited, but can be obtained by, for example, the following general method.

(Synthesis Example 1)
Among the compounds of the formula (1) of the present invention, when X ₁ and X ₂ are oxygen atoms and sulfur atoms, respectively, that is, the franchion compound can be produced, for example, by the reaction pathways shown in the following reaction pathways 1 and 2. I can. That is, it is obtained by replacing the carbonyl oxygen of the lactone compound having a double bond with sulfur using a sulfurizing agent.

The lactone compound having a double bond can be synthesized, for example, according to the method described in Reaction Path 1 below. In the reaction pathway 1, R corresponds to the side chain of the formula (1), is an alkyl group or an alkenyl group having 5 to 8 carbon atoms, and is an isopentyl group, an isohexyl group, or a 3-methyl-2-butenyl group (prenyl group). , 4-Methyl-3-pentenyl group (homoprenyl group), 5-methyl-4-hexenyl group and the like can be mentioned, but a homoprenyl group is preferable.

In the above reaction step, propargyl alcohol A having a protected hydroxyl group (in the formula A, PG represents a protecting group) is used as a raw material, and ethoxycarbonylated with an arbitrary base and ethyl chloroformate and unsaturated having a triple bond. Let it be ester B. Ethyl chloroformate does not necessarily have to be an ethyl ester, and any alkyl ester such as methyl or propyl may be used. The obtained unsaturated ester B is subjected to a Z-selective conjugate addition reaction by adding a Grignard reagent in the presence of a copper reagent to obtain an unsaturated ester C having a double bond. Deprotection of the obtained unsaturated ester C proceeds to cyclization, and the desired lactone compound can be obtained. Hereinafter, a general manufacturing method will be described for each step, but the present invention is not limited thereto. The hydroxyl group-protected propargyl alcohol A used as a starting material for the above reaction may be synthesized according to a general method or a commercially available product. Examples of the protecting group include an acetal-based protecting group such as an ethoxyethyl (EE) group and a tetrahydropyranyl (THP) group, and a silyl-based protecting group such as a t-butyldimethylsilyl (TBS) group. EE groups are preferred. The base used for the ethoxycarbonylation reaction is not particularly limited, but n-butyllithium is preferable. The Grignard reagent used for the conjugate addition reaction can be prepared from the corresponding alkyl halides and magnesium. The alkyl halide may be synthesized according to a general method or a commercially available product. Examples of the copper reagent used include copper bromide dimethyl sulfide complex, copper bromide, and copper iodide, but copper bromide dimethyl sulfide complex is preferable. The deprotection conditions may be appropriately selected depending on the type of protecting group used. Acetal-based protecting groups such as EE groups are generally deprotected by acid hydrolysis, but are not particularly limited. Examples of the acid used for acid hydrolysis include hydrochloric acid and sulfuric acid, but hydrochloric acid is preferable. As deprotection progresses, it proceeds to cyclization and is converted into the target substance D, that is, a lactone compound having a double bond.

In the reaction pathway 1, the reaction pathway is the case where the side chain is at the 4-position of the lactone ring, but in the case of the lactone compound having the side chain at the 3-position of the lactone ring, Biosci. Biotechno. Biochem. , 66 (1), pp. For lactone compounds that can be synthesized with reference to the method described in 135-140 (2002) and have a side chain at the 5-position of the lactone ring, Bioscii. Biotechno. Biochem. , 84 (8), pp. It can be synthesized with reference to the method described in 1560-1569 (2020).

Next, the carbonyl oxygen of the lactone compound having a double bond obtained by the reaction pathway 1 is replaced with sulfur by using a sulfurizing agent according to the following reaction pathway 2, and the target product E, that is, the compound of the formula (1) is obtained. One embodiment of the franthione compound is obtained. The sulfurizing agent used is not particularly limited, but Lawesson's reagent is preferable.

(Synthesis Example 2)
Further, among the compounds of the formula (1), in the case of a francion compound having a side chain at the 4-position of the five-membered ring, as an alternative method, the carbonyl oxygen of the lactone precursor F is sulfurized as shown in the following reaction pathway 3. It can also be manufactured by substituting with and then cyclizing.

The precursor F used as a starting material for the above reaction may be a product synthesized according to a general method or a commercially available product. For example, J. Agric. Food. Chem. 2019, 67, pp. It can be synthesized according to the method described in 7410-7415. The protecting group (PG) of the lactone precursor F is an acetal-based protecting group such as an ethoxyethyl (EE) group or a tetrahydropyranyl (THP) group, or a silyl-based protecting group such as a t-butyldimethylsilyl (TBS) group. However, the EE group is preferable. The R of the lactone precursor F corresponds to the side chain of the formula (1) and is an alkyl group or an alkenyl group having 5 to 8 carbon atoms, and is an isopentyl group, an isohexyl group, a prenyl group, a homoprenyl group, 5-methyl-4-. Although a hexenyl group and the like can be mentioned, a homoprenyl group is preferable. Examples of R ₂ of the lactone precursor include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like, but an ethyl group is preferable. When a sulfur atom is introduced into the lactone precursor by the method described above and then the lactone precursor is deprotected, it proceeds to cyclization and is converted into a target product. Deprotection conditions should be selected according to the type of protecting group used. Acetal-based protecting groups such as EE groups are generally deprotected by acid hydrolysis, but are not particularly limited. Examples of the acid used for acid hydrolysis include hydrochloric acid and sulfuric acid, but hydrochloric acid is preferable.

(Synthesis Example 3)
Among the compounds of the formula (1) of the present invention, when X ₁ and X ₂ are sulfur atoms and oxygen atoms, respectively, that is, the thiophenone compound can be produced, for example, by the reaction pathways shown in the following reaction pathways 4 and 5. .. That is, it is obtained by oxidizing the corresponding thiophene. Hereinafter, a general manufacturing method will be described, but the present invention is not limited thereto.

The thiophene K or L used as a starting material for the above reaction may be synthesized according to a general method or a commercially available product. For example, in the case of thiophene K, Bull. Chem. Soc. Jpn. 1983,56, pp. According to the method described in 1446-1449, for thiophene L, Recl. Trav. Chim. Pays-Bas. 1977, 96, pp. It can be synthesized according to the method described in 18-22. R of thiophene K and L corresponds to the side chain of the formula (1) and is an alkyl group or an alkenyl group having 5 to 8 carbon atoms, and is an isopentyl group, an isohexyl group, a prenyl group, a homoprenyl group, 5-methyl-4-. Although a hexenyl group and the like can be mentioned, a homoprenyl group is preferable. The method of oxidation is not particularly limited, but an oxidation method via a boric acid ester is preferable. Specifically, thiophene is first treated with a base to deprotonate, then reacted with a boric acid ester, and the obtained boric acid ester is treated with an oxidizing agent to obtain the target product H, I or J, that is, the formula (1). ) Is converted into a thiophenone compound, which is one aspect of the compound. Examples of the base to be used include n-butyllithium, lithium diisopropylamide, Grignard reagent and the like, but n-butyllithium is preferable. Examples of the borate ester to be used include trimethyl borate and tributyl borate, but trimethyl borate is preferable. Examples of the oxidizing agent to be used include hydrogen peroxide solution, oxone, oxygen and the like, but hydrogen peroxide solution is preferable.

Each compound of formula (1) is itself sulfur-like, metallic, sesame-like, aged aroma (sweet aroma of ripe fruit, sweet and fragrant sensation like aged wine or whiskey), rubber-like, waxy. (Wax or wax-like), oily (oil-like), chicken-like, lactone-like (feeling including sweetness, creaminess, etc. as felt from lactone compounds), herb-like, citrus-like fragrance-like characteristics It exhibits a typical aroma, and by blending it with various articles, it is possible to impart a flavor to the blending target. Although the compounding target is not particularly limited, consumer goods such as flavoring compositions (details will be described later), foods and drinks, cosmetics, and pharmaceutical hygiene products can be exemplified.

As used herein, flavor means one or more sensations that can be varied by aroma, typically sensations that include odor and / or taste. As used herein, the term "imparting flavor" includes adding or enhancing the flavor, and may be, for example, improving the flavor as a result of the addition. Furthermore, as a result of the addition of flavor, sensations other than the sense of smell and / or taste, such as coldness, warmth, texture (also called texture such as throat, hardness, viscosity, etc.), carbonation and spiciness, etc. It may be one that enhances, suppresses, or improves sensation, etc. Further, in the present specification, the flavor of food and drink may be referred to as flavor.

(Flavor-imparting composition of the present invention)
The flavor-imparting composition of the present invention contains one or more of the compounds of the formula (1) in a predetermined amount, and is blended with various articles to impart flavor to the articles (the definition of flavor-imparting is as described above. ) Can be done.

As an example of the flavor-imparting composition of the present invention, a composition capable of imparting aroma to various articles, that is, a so-called flavor; various extracts capable of imparting aroma and / or taste to various articles; Other food additives that can be used; additives that can impart aroma and / or taste to various cosmetics and pharmaceutical hygiene products; and the like, but are not limited thereto.

The flavor-imparting composition of the present invention may contain any component in addition to the compound of the formula (1), but may be substantially composed of only the compound of the formula (1). When the flavor-imparting composition of the present invention contains components other than the compound of the formula (1), the concentration of the compound of the formula (1) in the flavor-imparting composition depends on the blending target of the flavor-imparting composition and the aroma characteristics. Can be decided arbitrarily. In the present specification, the concentration is the final concentration unless otherwise specified.

As an example of the concentration, when the flavor-imparting composition of the present invention does not substantially contain components other than the compound of the formula (1) and its solvent (specific examples will be described later), the range is 0.1% to 100%. Can be exemplified inside. Preferred examples are 1% -100%, 10% -100%, 20% -100%, 50% -100%, 70% -100%, 80% -100%, 90% -100%, 95% -100%. , And in the range of 99% to 100%, and substantially 100%.

As an example of the concentration, 0.001 ppm to 1% with respect to the total mass of the flavor-imparting composition, particularly when the flavor-imparting composition contains other components capable of imparting flavor in addition to the compound of the formula (1). , Preferably in the range of 0.1 ppm to 1%. More specifically, the lower limit is 0.001 ppm, 0.01 ppm, 0.1 ppm, 1 ppm, 10 ppm, 100 ppm, or 0.1%, and the upper limit is 1%, 0.1%, 100 ppm, 10 ppm. 1, 1 ppm, 0.1 ppm, or 0.01 ppm can be within the range of any combination of these lower limit values and upper limit values, but is not limited thereto. Although it depends on the formulation and fragrance tone of the flavor-imparting composition, if the concentration of the compound of the formula (1) in the flavor-imparting composition is less than 0.001 ppm, it may be felt that the compounding effect is low. If it exceeds 1%, the scent derived from the compound of the formula (1) is strong and may make the aroma characteristics of the flavor-imparting composition to be blended unfavorable. May formulate the compound of the formula (1) at a concentration below the lower limit or at a concentration higher than the upper limit.

Further, as an example of any other compound or component that may be further contained in addition to the compound of the formula (1) in the flavor-imparting composition of the present invention, each kind of fragrance compound or fragrance composition, oil-soluble pigments, etc. Vitamin, functional substances, fish meat extracts, livestock meat extracts, plant extracts, yeast extracts, animal and plant proteins, animal and plant protein decomposition products, starch, dextrins, sugars, amino acids, nucleic acids, organic acids, solvents, etc. Can be exemplified. For example, "Patent Agency Gazette, Well-known and Conventional Techniques (Fragrances) Part II Food Flavors, published on January 14, 2000", "Survey on the actual use of food flavoring compounds in Japan" (2000 Health Science Research) Described in the report, Japan Fragrance Industry Association, published in March 2001), and "Synthetic Fragrance Chemistry and Product Knowledge" (December 20, 2016, supplementary new edition issued, edited by Synthetic Fragrance Editorial Committee, Chemical Industry Daily). Examples include natural essential oils, natural fragrances, and synthetic fragrances.

Other examples of synthetic fragrance compounds include hydrocarbon compounds such as monoterpenes such as α-pinene, β-pinene, myrcene, camphene and limonene, sesquiterpenes such as valencene, sedren, caryophyllene and longifolene, 1,3,5. -Undecatorien and the like.

Alcohol compounds include saturated or unsaturated alcohols such as butanol, pentanol, 3-octanol, hexanol, (Z) -3-hexene-1-ol, pranol, 2,6-nonazienol, linalol, geraniol, citronellol, tetrahydro. Examples thereof include terpene alcohols such as milsenol, farnesol, nerolidol, sedrol and terpineol, and aromatic alcohols such as benzyl alcohol, phenylethyl alcohol and cinnamyl alcohol.

Examples of the aldehyde compound include saturated or unsaturated aldehydes such as acetaldehyde, hexanal, octanal, decanal, (E) -2-hexenal and 2,4-octadienal, citroneral, hydroxycitroneral, citral, myrtenal and perylaldehyde. Examples thereof include aromatic aldehydes such as terpenaldehyde, benzaldehyde, cinnamaldehyde, amylcinnamaldehyde, vanillin, ethyl vanillin, heliotropin, and p-tolylaldehyde.

Examples of the ketone compound include saturated or unsaturated ketones such as 2-heptanone, 2-undecanone, 1-octene-3-one and acetoin, diacetyl, 2,3-pentandione, maltor, ethylmaltor, cycloten, 2,5-. Diketones such as dimethyl-4-hydroxy-3 (2H) -furanone and terpene ketones such as hydroxyketones, carboxylics, menthone and nutcatons, and ketones derived from terpene decomposition products such as α-ionone, β-ionone and β-damasenone. Examples include aromatic ketones such as raspberry ketone.

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

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

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

Acid compounds include saturated or unsaturated fatty acids such as acetic acid, buty acid, octanoic acid, isobaric acid, caproic acid, stearic acid, oleic acid, linolenic acid and linolenic acid.

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

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

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

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

The flavor-imparting composition of the present invention can be prepared by blending the compound of the formula (1) with an appropriate solvent or dispersion medium by a known method.

Examples of the form of the flavor-imparting composition of the present invention include a solution in which the compound of the formula (1) and other components are dissolved in a water-soluble or oil-soluble solvent, an emulsified preparation, a powder preparation, and other solid preparations (solid fat, etc.). preferable.

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

Further, in order to prepare an emulsified preparation, the compound of the formula (1) can be obtained by emulsifying with a water-soluble solvent and an emulsifier. The method for emulsifying the compound of the formula (1) is not particularly limited, and each kind of emulsifier conventionally used for foods and drinks, for example, fatty acid monoglyceride, fatty acid diglyceride, fatty acid triglyceride, propylene glycol fatty acid ester, and the like. Sucrose fatty acid ester, polyglycerin fatty acid ester, lecithin, chemical starch, sorbitan fatty acid ester, Kiraya extract, Arabic gum, tragant gum, guar gum, karaya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, casein glaya saponin, An emulsified solution having excellent stability can be obtained by emulsifying using an emulsifying agent such as sodium caseinate using a homomixer, a colloid mill, a rotary disk-type homogenizer, a high-pressure homogenizer, or the like. The amount of these emulsifiers to be used is not strictly limited and can be changed over a wide range depending on the type of emulsifier to be used, etc., but usually, about 0. A range of 01 to about 100 parts by mass, preferably about 0.1 to about 50 parts by mass is suitable. In addition to water, such water-soluble solvent solutions include polyhydric alcohols such as glycerin, propylene glycol, sorbitol, martitol, sucrose, glucose, trehalose, sugar solutions, and reduced water candy in order to stabilize emulsification. One type or a mixture of two or more types can be blended.

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

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

(Use for various articles)
The flavor-imparting composition containing the compound of the formula (1) of the present invention can be blended and used in various articles. By imparting flavor to various articles, articles with flavor are manufactured. Therefore, in the present invention, the method for imparting flavor to various articles can be said to be a method for producing articles to which flavor is imparted. Here, the various articles to be blended in the present invention may be those in the process of being manufactured by the producer, or may be those that have been put on the market and can be used by consumers. For example, by blending the flavor-imparting composition of the present invention with various consumer goods such as foods and drinks, cosmetics, and health and hygiene products, the flavor-imparting consumer goods can be produced, and the flavor-imparting composition of the present invention can be blended. May be performed during the production of the producer's consumer goods, or may be performed by the consumer for the marketed consumer goods. Further, a new flavor-imparting composition may be produced by blending the flavor-imparting composition of the present invention with another flavor-imparting composition to further impart the flavor, and this new flavor-imparting composition may be produced. The imparting composition can also be used in the production of various articles as the flavor-imparting composition of the present invention. For example, the flavoring composition containing the compound of the formula (1) may be blended with various consumer goods such as foods and drinks, cosmetics, pharmaceutical hygiene products, or various articles such as other flavoring compositions. Good, one or more water-soluble fragrances, emulsified flavoring compositions, arbitrary fragrance compounds, natural essential oils (for example, "Patent Agency Gazette, Well-known and Conventional Techniques (Fragrance)" Part II Food fragrances mentioned above. , "Survey on the actual use of food flavoring compounds in Japan", and "Flavoring compounds described in" Synthetic perfume chemistry and commercial knowledge "), may be blended in various articles together with one or more selected from.

Foods and drinks to which the flavor-imparting composition containing the compound of the formula (1) of the present invention can be blended are not particularly limited, and examples thereof include lemon, orange, grapefruit, lime, mandarin, black tea, kabosu, sudachi, hassaku, and iyokan. Various citrus flavors such as yuzu, shikuwasa, and golden citrus; various fruits such as strawberry, blueberry, raspberry, apple, cherry, plum, apricot, peach, pineapple, banana, melon, mango, papaya, kiwi, pear, grape, muscat, and giant peak. Flavor; Milk flavor such as milk, yogurt, butter; Vanilla flavor; Green tea, Matcha, Roasted tea, Black tea, Karyu tea, Pual tea, Herb tea, etc. Various tea flavors; Coffee flavor; Cola flavor; Cacao flavor; Cocoa flavor; Spare mint, Various mint flavors such as peppermint; cinnamon, chamomile, cardamon, caraway, cumin, clove, pepper, coriander, Japanese pepper, perilla, ginger, staranis, thyme, pepper, nutmeg, basil, majorum, rosemary, laurel, wasabi , Various spices or herbs such as Japanese pepper; Various nut flavors such as almond, cashew nut, walnut; Various alcoholic beverages such as wine, brandy, whiskey, lamb, gin, liqueur, Japanese sake, shochu, beer; Carrot, tomato , Vegetable flavors such as black tea; foods and drinks having one or more of the flavors such as. That is, it may be a food or drink that makes you feel only one kind of the above flavors, or it may be a food or drink that makes you feel two or more kinds of flavors, and the plurality of kinds of flavors may be similar or different, for example, the former. 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 are those that make you feel citrus flavors such as lemon and milk flavors (citrus). Flavored lactic acid bacteria beverages, etc.), mint-flavored, citrus-flavored, and cola-flavored beverages (such as mint or lemon-flavored cola beverages), depending on the compound of formula (1) or the flavoring composition containing it. It may be any flavor that can be flavored.

Examples of flavors that can be preferably used include various fruit flavors typified by citrus; beer flavor; various tea flavors typified by black tea and green tea; milk flavor; oil flavor; chocolate flavor; cocoa flavor; ginger and perilla. Various spice or herb flavors; livestock meat flavors; egg flavors and the like can be mentioned, but are not limited thereto. In the case of a franchion compound such as the compound of the formula (1-1), the aging feeling of fruits, wine, whiskey, etc., and the heating of foods and drinks (typically roasted, baked, steamed, etc.) Coffee, sesame, chocolate, cacao, various cooked products (for example, dumplings, fried rice, tonkatsu) because it has the effect of giving a feeling of roasted food and making you feel more impressive flavors such as fragrance from the top of the flavor. , Foods and drinks such as baked goods, breads, kinako, and black beer, and cosmetics and health products with aromas such as these can be exemplified. Among the thiophenone compounds such as the compounds of the formulas (1-2) to (1-4), foods and drinks having an oily feeling using animal or vegetable oils and fats, foods and drinks having a waxy feeling like citrus peel, and foods and drinks having a waxy feeling. Various foods and drinks using cosmetics or pharmaceutical hygiene products, soups and soups derived from animal food materials (chicken soup, consomme, pork bone soup, etc.), various foods and drinks using eggs, various foods and drinks using livestock meat, Examples thereof include foods and drinks using edible plants (particularly herbs), cosmetics or pharmaceutical hygiene products, foods and drinks using tea leaves (for example, black tea, oolong tea, puer tea, green tea, etc.), cosmetics or pharmaceutical hygiene products. ..

More specific food and drink examples include senbei, hail, soup stock, rice cakes, buns, sardines, bean paste, sheep cans, water sheep cans, broth, jelly, castella, candy balls, biscuits, crackers, potato chips, cookies, etc. Confectionery such as pie, pudding, butter cream, custard cream, cream puff, waffle, sponge cake, donuts, chocolate, chewing gum, caramel, candy, peanut paste or other pastes; bread, udon, ramen, Chinese noodles, sushi , Gomoku rice, fried rice, pilaf, dumpling skin, shumai skin, okonomiyaki, octopus, etc., breads, noodles, rice, other grains; Pickles and pickles such as their pickles; fish such as mackerel, sardines, saury, salmon, tuna, bonito, whales, curry, squid, ayu, squid such as surumeika, spear squid, crested squid, firefly squid Kind, octopus such as Madako, Iidako, shrimp such as car shrimp, button shrimp, sardine shrimp, black tiger prawn, crabs such as taraba crab, zuwai crab, cotton crab, kegani, shellfish such as asari, hamaguri, scallop, oyster, mussels, etc. Seafood; Canned, boiled fish, soup stock, broth, fish paste products (chikuwa, broth, broth, crab broth, etc.), fried foods, tempura, and other processed foods and drinks; chicken, pork, beef, and sheep , Horse meat and other livestock meat; curry, stew, beef stew, hayashi rice sauce, meat sauce, marbo tofu, hamburger, dumplings, pot rice base, soup stock (corn soup, tomato soup, consomme soup, etc.), meat dumplings, simmered sardines, Processed foods and drinks using livestock meat such as canned livestock meat; tabletop salt, seasoning salt, soy sauce, powdered soy sauce, miso, powdered miso, moromi, dashi, sprinkle, ochazuke no moto, margarine, mayonnaise, dressing, vinegar, three cups of vinegar, Powdered sushi vinegar, Chinese broth, Tentsuyu, Mentsuyu (Konbu dashi or bonito dashi, etc.), Sauce (Nakano sauce, Tomato sauce, etc.), Ketchup, Grilled meat sauce, Curry roux, Stew base, Soup stock, Dashi stock (Dashi stock) Seasonings such as kelp dashi or bonito dashi), complex seasonings, new mirin, mixed powder such as fried powder and octopus broth, animal or vegetable dashi flavored foods and drinks to which these seasonings are added Dairy products such as cheese, yogurt, butter; Boiled vegetables, Boiled Chikuzen, Oden, Hot pot, etc.; Homecoming lunch ingredients and side dishes; fruit juice drinks such as apples, grapes, citrus fruits (grapefruit, orange, lemon, etc.) and refreshing drinks with fruit juice, fruit meat drinks and fruit drinks with fruit grains; tomatoes, peppers, celery , Uri, Nigauri, carrot, potato, asparagus, warabi, zenmai and other vegetables, vegetable-based beverages containing these vegetables, vegetable-containing foods and drinks such as vegetable soup; coffee, cocoa, green tea, tea, crow dragon tea, refreshing beverages , Beverages such as cola beverages and lactic acid bacteria beverages; beverages containing raw medicines and herbs; cola beverages, fruit juice beverages, dairy beverages, non-alcoholic beverages and beer-taste beverages including so-called "third beer" (also beer-flavored beverages) Functional beverages such as sports drinks, honey beverages, vitamin supplement beverages, mineral supplement beverages, nutritional drinks, nourishing drinks, lactic acid bacteria beverages; alcohol-taste beverages with various alcoholic beverages (beer flavor, plum wine flavor, chewy flavor, etc.) Non-alcoholic beverages; other brewed liquors (foaming) or liqueurs such as wine, shochu, awamori, sake, beer, chuhai, cocktail drinks, sparkling liquor, fruit liquor, medicinal liquor, so-called "third beer" Effervescent) and the like, or alcoholic beverages containing these; and the like.

Cosmetics or pharmaceutical hygiene products to which a flavor-imparting composition containing the compound of the formula (1) of the present invention can be blended are not particularly limited, and examples thereof include perfumes such as eau deodorant, eau de toilette, eau de parfum, and parfum; shampoo, rinse, and so on. Hair care products such as hair conditioners (hair cream, pomade, etc.); cosmetics such as foundations, lipsticks, lip creams, lip glosses, soaps, cosmetic emulsions, cosmetic creams, cosmetic gels, beauty liquids, packs; Deodorant products such as sweat sprays, deodorant sheets, deodorant creams, and deodorant sticks; bathing agents such as inorganic salts, refreshing, carbon dioxide, skin care, enzyme, and raw medicines; tanning cosmetics such as suntan products and sunscreen products. Kind: Health and hygiene such as face soaps and face wash creams, body soaps and body soaps, laundry soaps, laundry detergents, disinfectant detergents, deodorant detergents, softeners, kitchen detergents, cleaning detergents, etc. Deodorants for use; health and hygiene materials such as toothpaste, tissue paper, and toilet paper; fragrance deodorants for indoors and cars, fragrance products such as room fragrances; and the like. The fragrance tone that can be used is not particularly limited, and may be any fragrance tone that can improve the flavor by the compound of the formula (1) or the flavor-imparting composition containing the same, for example, a sweet fragrance containing a fragrant nuance. It can be suitably used for tones, for example, incense tones reminiscent of caramel and baked goods. In addition, it may be used for citrus tone, floral tone, fruity tone, green tone, ozone tone and the like.

In the present invention, the concentration of the compound of the formula (1) in various consumer goods such as foods and drinks, cosmetics, pharmaceutical hygiene products, etc. containing the flavor-imparting composition of the present invention, and other articles such as other flavor-imparting compositions is , Can be arbitrarily determined according to the flavor of the article, the degree of desired effect, and the like.

As an example of the concentration, if it is another flavor-imparting composition, the concentration described in the above-mentioned "flavor-imparting composition of the present invention" can be adopted.

As an example of the concentration, in the case of food and drink, the concentration of the compound of the formula (1) may be in the range of 1 ppt to 1 ppm with respect to the total mass of the food or drink. More specifically, the lower limit is set to 1 pt, 10 pt, 100 pt, 1 ppb, 10 ppb, 100 ppb, and the upper limit is set to 1 ppm, 100 ppb, 10 ppb, 1 ppb, 100 pt, 10 pt. Within, but not limited to, any combination. As an example of a preferable concentration, the concentration of the compound of the formula (1) of the present invention is 10 pt to 10 ppb, 10 pt to 100 ppb, 100 pt to 10 ppb, 100 pt to 100 ppb, 1 ppb to 10 ppb, 1 ppb to 100 ppb with respect to the total mass of the food or drink. Therefore, it can be selected according to the flavor characteristics of the food and drink, but is not limited thereto. Although it depends on the type and flavor of the food and drink, if the concentration of the compound of the formula (1) in the food and drink is less than 1 ppt, the effect of improving the flavor may be felt to be low, and if it exceeds 1 ppm, it may be felt. In some cases, the aroma of the compound itself is prominent and the flavor of the food or drink to be blended is unfavorable.

In the case of cosmetics, the concentration of the compound of the formula (1) of the present invention may be in the range of 1 ppt to 1% with respect to the total mass of the cosmetics. More specifically, the lower limit is 1 pt, 10 pt, 100 pt, 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, 0.1%, and the upper limit is 1%, 0.1%, 100 ppm, 10 ppm. Any combination of these lower and upper limits can be mentioned, but is not limited to, as any of 1 ppm, 100 ppb, 10 ppb, 1 ppb, 100 ppt, and 10 ppt. As an example of a preferable concentration, the concentration of the compound of the formula (1) of the present invention is 100 ppb to 100 ppm, 1 ppm to 100 ppm, 1 ppm to 0.1%, 10 ppm to 0.1% with respect to the total mass of the cosmetic product. From each range, it can be selected according to the aroma characteristics of the cosmetic product, but is not limited thereto. Although it depends on the type of cosmetics and the aroma, if the concentration of the compound of the formula (1) of the present invention in the cosmetics is less than 1 ppt, the aroma improving effect may be felt to be low or unchanged. Yes, if it exceeds 1%, it may make the aroma of the cosmetic product to be blended unfavorable.

The compound of the formula (1) of the present invention can impart a good aroma or taste to various articles, for example, can enhance the aroma of the top and / or enhance the thickness and finish of the taste from the middle to the last. .. As an example of a specific effect, for example, by blending an effective amount of the compound of the formula (1) of the present invention into an article such as a food or drink or a cosmetic, an animal or plant material used in the food or drink or a cosmetic may be used. Natural feeling, fresh feeling, fruit juice feeling, freshness, volume feeling (feeling that the taste is enhanced with the aroma and the whole flavor is swollen), richness, oily feeling, fragrance, flesh feeling At least one of these is enhanced to give a cored flavor, which has the effect of maintaining a good balance (also called afterglow).

Further, the flavor-imparting composition of the present invention results in bitterness, astringency, astringency (collectively referred to as astringent taste), off-flavors such as protein odor, and irritation caused by alcohol (typically). It can also be used to mask unpleasant tastes such as burning or burning, which is a hot or burning sensation felt in the mouth or throat when eating alcohol-containing foods and drinks. That is, the flavor-imparting composition of the present invention may be blended into foods and drinks in which astringent taste, protein odor, etc. may be prominent and may be perceived as a strange taste and an offensive odor, and excessive irritation of alcohol may be a problem, and the flavor of the food or drink may be added. It can be used to mask prominent offensive odors and unpleasant odors by imparting richness and / or thickness of taste. Examples of such foods and drinks include foods and drinks containing a high amount of protein, and more specifically, various high-nutrient foods such as protein drinks, concentrated liquid foods, and high-nutrient drinks, and alternatives using vegetable proteins. Meat (also referred to as vegetable meat) can be mentioned, and other examples include, but are not limited to, beverages having a relatively high alcohol concentration and alcoholic beverages having a flavor that makes it easy to feel the stimulus of alcohol. .. In order to obtain the masking effect, the concentration of the compound of the formula (1) in the food or drink can be adjusted. For example, by blending the food or drink with a slightly higher concentration in the above-mentioned concentration range of 1 ppt to 1 ppm, it is possible to sufficiently impart richness and volume, and a sufficient masking effect can be obtained. As an example of the concentration range in which the masking effect can be easily obtained, the lower limit is 0.01 ppb, 0.1 ppb, 1 ppb, 10 ppb, 20 ppb, 50 ppb, 100 ppb, 200 ppb, 500 ppb, and the upper limit is 1 ppm, 500 ppb, 200 ppb, 100 ppb. , 50 ppb, 20 ppb, 10 ppb, 1 ppb, 0.1 ppb, and the concentration range may be any combination thereof, and specific examples thereof include 0.1 ppb to 100 ppb or 1 ppb to 200 ppb, but are limited thereto. However, it may be determined according to the desired degree of masking effect and the flavor of the food or drink to be blended.

(Compound represented by the formula (1'))
The present invention also provides a cyclic compound represented by the following formula (1'), which contains an oxygen atom and a sulfur atom (in the present specification, it may be simply referred to as a compound of the formula (1')).

In equation (1'), (i) to (iv) are satisfied: (i) n represents an integer of 0 to 3, and (ii) the broken line of the five-membered ring is a carbon-carbon double bond at one place. (Iii) The broken line of the side chain of the five-membered ring is one carbon-carbon double bond. Yes, the other parts are single bonds, or all parts are single bonds, and (iv) X ₁ and X ₂ are one oxygen atom and the other sulfur atom. (However, (i) n is 1, (ii) one point of the broken line of the five-membered ring is a carbon-carbon double bond, and the other place is a single bond, and (iii) the side chain. Except for cases where all points of the broken line in (iv) are single bonds, (iv) X ₁ is a sulfur atom, X ₂ is an oxygen atom, and the side chain is bonded to the 5-position of the five-membered ring. )
Each compound represented by the formula (1') is a novel compound which has not been described in the prior art. The compound of the formula (1') is included in the compound of the above-mentioned formula (1), and can be effectively used for flavoring as described above.

In the formula (1'), the preferred embodiment is the same as the preferred embodiment in the formula (1). That is, in the formula (1'), n is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even more preferably 1. Further, in the formula (1'), among the broken lines, preferably, there is one carbon-carbon double bond in the five-membered ring and one in the side chain, n is 1, and the broken line in the side chain. There is a double bond between the 3rd and 4th positions, or n is 2 and there is a side chain double bond between the 4th and 5th positions. More preferably, the carbon-carbon double bond at one location on the five-membered ring is between the 3- and 4-positions. Further, in the case of a franchion compound, the side chain is preferably bonded to the 4-position of the 5-membered ring.

Preferred specific examples of the compound of the formula (1') are the compound of the following formula (1'-1), the compound of the formula (1'-2), the compound of the formula (1'-3), and the compound of the formula (1'-3). '-4) compounds can be mentioned, but are not limited thereto. The compound of the formula (1'-1), the compound of the formula (1'-2), the compound of the formula (1'-3), and the compound of the formula (1'-4) are each of the formula (1-1). It is the same as the compound, the compound of the formula (1-2), the compound of the formula (1-3), and the compound of the formula (1-4).

The compound of the formula (1') can be produced by the same method as the above-mentioned method for producing the compound of the formula (1).

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these.

[Example 1]
As an example of the compound of the formula (1), the compounds of the following formulas (1-1) to (1-4) were synthesized.

Example 1 (1): Synthesis of compound of formula (1-1) (4- (4-methyl-3-pentenyl) furan-2 (5H) -thione) First, J. Agric. Food. Chem. 2019, 67, pp. 4- (4-Methyl-3-pentenyl) furan-2 (5H) -one (Compound α) was synthesized according to the method described in 7410-7415, and then synthesized according to the following reaction route.

Compound α (1.00 g, 6.02 mmol), dehydrated toluene (60 mL), and Lawesson's reagent (2.44 g, 6.03 mmol) were placed in a 300 mL eggplant flask and heated to reflux under an argon atmosphere for 10 hours.

After cooling the reaction solution, silica gel (4.0 g) was added and concentrated under reduced pressure to obtain a crude product (7.05 g). This crude product was subjected to flash silica gel column chromatography twice (1st time: SiO ₂ : 60 g, hexane: ethyl acetate = 30: 1 and 2 times: SiO ₂ : 50 g, hexane: ethyl acetate = 100: 1 → 70: 1 → 50: 1) Purification and further purification with Kugel roll (oven temperature: ~ 250 ° C./0.27 kPa) to obtain 131 mg (yield 12%) of the compound of formula (1-1) as a yellow oil. rice field. The obtained compound of the formula (1-1) was designated as the product 1 of the present invention. The physical characteristic values of the obtained compound of the formula (1-1) were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ1.62 (s, 3H), 1.70 (s, 3H), 2.29 (q, J = 7.2 Hz, 2H), 2.45 (t, J = 7.2Hz, 2H), 5.06 (m, 2H), 5.07 (m, 1H), 6.36 (m, 1H).
¹³ C-NMR (100MHz, CDCl ₃ ): δ17.8, 25.6, 25.8, 27.8, 82.6, 121.8, 129.7, 134.0, 168.8, 214.5 ..
IR (total reflection measurement method): 2967, 2912, 2853, 1605, 1433, 1375, 1362, 1327, 1274, 1227, 1211, 1158, 1142, 1092, 978, 892, 855, 829, 804 cm ^-1 .
DART-TOFMS: m / z calcd. for C ₁₀ H ₁₅ O ₁ S ₁ [M + H] ⁺ 183.0838, found 183.0831.

Example 1 (2): Compounds of formula (1-2) (4- (4-methyl-3-pentenyl) thiophene-2 (5H) -on) and compounds of (1-3) (3- (4- (4-) Synthesis of Methyl-3-pentenyl) Thiophene-2 (5H) -On) First, Bull. Chem. Soc. Jpn. 1983,56, pp. 3- (4-Methyl-3-pentenyl) thiophene (Compound β) was synthesized according to the method described in 1446-1449, and then synthesized according to the following reaction pathway.

Compound β (1.50 g, 9.02 mmol) and dehydrated diethyl ether (Et ₂ O, 25 mL) were placed in a 100 mL three-necked flask and stirred under an argon atmosphere. To this, n-butyllithium (n-BuLi, 1.58 M hexane solution, 6.30 mL, 9.95 mmol) was added over 15 minutes at room temperature (rt), and then the mixture was heated under reflux for 30 minutes. After cooling the reaction solution to −78 ° C., trimethyl borate (B (OMe) ₃ , 1.20 mL, 10.7 mmol) was added over 10 minutes, and the mixture was stirred at the same temperature for 4 hours. After raising the temperature of the reaction solution to room temperature, hydrogen peroxide solution ( _{H2O 2 ,} 35%, 1.50 mL, 17.4 mmol) was added, and the mixture was heated under reflux for 1 hour.

After cooling the reaction solution, water was added and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to give a crude product (1.23 g). This crude product was purified by flash silica gel column chromatography (SiO ₂ : 60 g, hexane: ethyl acetate = 40: 1) to obtain 716 mg of the compound of the formula (1-2) and the compound of the formula (1-3). 151 mg was obtained. In order to further purify these, for the compound of formula (1-2), further flash silica gel column chromatography (SiO ₂ : 60 g, hexane: ethyl acetate = 50: 1) and cougel roll (oven setting: ~ 235 ° C / /). Purification was carried out at 0.27 kPa) to obtain 413 mg (yield 25%) of the high-purity target product as a colorless oil. The compound of formula (1-3) is further purified by flash silica gel column chromatography (SiO ₂ : 60 g, hexane: ethyl acetate = 50: 1) and cougel roll (oven temperature: ~ 210 ° C./0.13 kPa). A high-purity target product was obtained as a colorless oil in an amount of 134 mg (yield 8%). The obtained compound of the formula (1-2) was designated as the product 2 of the present invention, and the compound of the formula (1-3) was designated as the product 3 of the present invention. The physical property values of the obtained compound of the formula (1-2) and the compound of the formula (1-3) were as follows.

Physical characteristics of the compound of formula (1-2)
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ1.62 (s, 3H), 1.70 (s, 3H), 2.30 (q, J = 7.6 Hz, 2H), 2.50 (t, J = 7.6Hz, 2H), 3.98 (s, 2H), 5.09 (m, 1H), 6.11 (m, 1H).
¹³ C-NMR (100MHz, CDCl ₃ ): δ17.7, 25.6, 26.3, 32.2, 39.9, 122.0, 128.4, 133.7, 171.8, 200.0 ..
IR (total reflection measurement method): 2967, 2912, 2855, 1670, 1627, 1442, 1403, 1377, 1142, 1092, 878, 850, 836, 770, 656 cm ^-1 .
DART-TOFMS: m / z calcd. for C ₁₀ H ₁₅ O ₁ S ₁ [M + H] ⁺ 183.0838, found 183.0838.
Physical characteristics of the compound of formula (1-3)
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ1.59 (s, 3H), 1.69 (d, J = 0.8 Hz, 3H), 2.22 (q, J = 7.2 Hz, 2H), 2.35 (m, 2H), 3.95 (m, 2H), 5.09 (m, 1H), 7.16 (m, 1H).
¹³ C-NMR (100MHz, CDCl ₃ ): δ17.7, 25.6, 26.2, 26.5, 35.1, 122.9, 132.9, 145.4, 146.9, 200.5 ..
IR (total reflection measurement method): 2966, 2913, 2854, 1667, 1642, 1436, 1410, 1376, 1106, 1012, 986, 902,864,826,804,773,613,521 cm ^-1 .
DART-TOFMS: m / z calcd. for C ₁₀ H ₁₅ O ₁ S ₁ [M + H] ⁺ 183.0838, found 183.0851.

Example 1 (3): Synthesis of compound of formula (1-4) (5- (4-methyl-3-pentenyl) thiophene-2 (5H) -on) First, Recl. Trav. Chim. Pays-Bas. 1977, 96, pp. 2- (4-Methyl-3-pentenyl) thiophene (compound γ) was synthesized according to the method described in 18-22, and then synthesized according to the following reaction pathway.

Compound γ (1.50 g, 9.02 mmol) and dehydrated diethyl ether (25 mL) were placed in a 100 mL three-necked flask, and the mixture was stirred under an argon atmosphere. To this, n-butyllithium (1.58 M hexane solution, 6.30 mL, 9.95 mmol) was added over 15 minutes at room temperature, and then the mixture was heated under reflux for 30 minutes. The reaction mixture was cooled to −78 ° C., trimethyl borate (1.20 mL, 10.7 mmol) was added over 10 minutes, and the mixture was stirred at the same temperature for 4 hours. After raising the temperature of the reaction solution to room temperature, hydrogen peroxide solution (35%, 1.50 mL, 17.4 mmol) was added, and the mixture was heated under reflux for 1 hour.

After cooling the reaction solution, water was added and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to give a crude product (1.28 g). This crude product was subjected to flash silica gel column chromatography twice (1st time: SiO ₂ : 60 g, hexane: ethyl acetate = 50: 1, 2nd time: SiO ₂ : 60 g, hexane: ethyl acetate = 100: 1 → 20: 1) Purification was further carried out by further purification with a cougel roll (oven temperature: ~ 230 ° C./0.27 kPa) to obtain 524 mg (yield 32%) of the compound of the formula (1-4) as a colorless oil. The obtained compound of the formula (1-4) was designated as the product 4 of the present invention. The physical characteristic values of the obtained compound of the formula (1-4) were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ1.62 (s, 3H), 1.71 (d, J = 0.8 Hz, 3H), 1.75 (m, 1H), 2.01 (m, 1H), 2.19 (q, J = 7.2Hz, 2H), 4.47 (tt, J = 2.4,6.8Hz, 1H), 5.11 (m, 1H), 6.28 ( dd, J = 2.4,6.0 Hz, 1H), 7.43 (dd, J = 2.4,6.0 Hz, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ17.7, 25.7, 26.6, 34.4, 54.2, 122.3, 132.0, 133.7, 158.7, 200.0 ..
IR (total reflection measurement method): 2966, 2913, 2852, 1673, 1605, 1437, 1377, 1337, 1125, 1079, 823,790, 662,642,614 cm ^-1 .
DART-TOFMS: m / z calcd. for C ₁₀ H ₁₅ O ₁ S ₁ [M + H] ⁺ 183.0838, found 183.0847.

[Example 2] Aroma characteristics of the synthesized compound of the formula (1) Each compound of the formula (1) obtained in Examples 1 (1) to (3) (that is, formulas (1-1) to (1). The aroma of each compound) of -4) was evaluated. In the aroma evaluation, each compound of the formula (1) was blended with 99% ethanol so as to have a concentration of 1% by mass to obtain the flavor-imparting composition of the present invention (Products 2-1 to 2-4 of the present invention). Five well-trained panelists with more than 10 years of experience sniffed and commented on the perceived aroma. Typical comments are shown in Table 1 below. In addition, in Table 1, as a comparative product, the fragrance of furfuryl methyl sulfide, which is known as a fragrance compound, was also commented on the fragrance that can be smelled and felt. Furfuryl methyl sulfide is a compound known to be contained in coffee, having a heterocycle, an oxygen atom and a sulfur atom in the molecule, like the compound of the formula (1).

As shown in Table 1, the product 2 of the present invention containing each compound (products 1 to 4) of the formulas (1-1) to (1-4), which is a compound of the formula (1) of the present invention, respectively. Each of -1 to 2-4 exhibited a characteristic aroma, and therefore, it could be blended with various articles to impart a flavor. It also has characteristics that the comparative furfuryl methyl sulfide does not have, and it can be said that each compound of the formula (1) of the present invention can impart a flavor different from that of the comparative compound.

[Example 3] Effect of blending into fruit flavoring composition A basic blended flavor composition having an orange-like scent was prepared according to the general formulation shown in Table 2 below.

In this orange-like basic blended fragrance composition, each compound of the formula (1) obtained in Examples 1 (1) to (3) was added, and the concentration thereof was 0.1% with respect to the total mass of the basic blended fragrance composition. The flavor-imparting compositions of the present invention (Products 3-1 to 3-4 of the present invention) were obtained. Then, using the above-mentioned basic blended fragrance composition as a control product, the aroma of the flavor-imparting composition of the present invention was evaluated by seven well-trained panelists with 10 years or more of experience. As a result, all seven panelists stated that all of the flavor-imparting compositions of the present invention had a markedly enhanced orange peel-like waxy and oily feeling, a freshness like freshly squeezed orange fruit, and an aroma finish. I answered.

[Example 4] Effect of blending fruit-like scent into detergent Prepare a commercially available liquid detergent for tableware with orange scent, and each compound of the formula (1) obtained in Examples 1 (1) to (3). (Each compound of the formula (1-1) to the formula (1-4)) was blended so as to have the concentration shown in Table 3 below to prepare the detergent of the present invention (Product 4-1 to the present invention). 4-12). A sensory evaluation was performed on the aroma of these liquid dish detergents during actual dishwashing. Specifically, the aroma of the present invention was compared with the aroma of the control by five well-trained panelists with more than 15 years of experience, using a commercially available liquid detergent for dishes with an orange scent as a control. Regarding the aroma when washing dishes with detergent, the natural feeling is scored as "significantly improved" = 4 points, "improved" = 3 points, "slightly improved" = 2 points, "no change" = 1 point. At the same time, he was allowed to freely comment on what he felt about the change in aroma when compared with the control product. Here, the natural feeling means a natural orange scent that is reminiscent of orange fruits and has an enhanced scent, which is similar to that of an actual orange juice. The average aroma evaluation result is shown in Table 3.

As shown in Table 3, it was confirmed that each compound of the formula (1) can impart a flavor to the detergent having an orange scent and further improve its natural feeling. Further, it was confirmed that the flavor-imparting effect can be obtained at least in the concentration range of 10 ppb to 1000 ppm in the detergent.

[Example 5] Effect of blending into fruit-flavored foods and drinks Each compound of the formula (1) obtained in Example 1 (each compound of the formula (1-1) to the formula (1-4)) was added to a commercially available marmalade. To obtain the fruit-flavored foods and drinks of the present invention by blending them so as to have the concentrations shown in Table 4 below. Then, the natural feeling of the fruit-flavored food and drink of the present invention was sensory-evaluated using a commercially available marmalade as a control product. Specifically, 10 panelists with more than 10 years of well-trained experience were given "significantly improved" = 4 points, "improved" = 3 points, and "slightly improved" in terms of natural feeling compared to the control product. "= 2 points," no change "= 1 point, and freely commented on the change in flavor felt compared to the control product. Here, the natural feeling means a natural flavor that is reminiscent of the orange fruit, which is the material, and has an enhanced flavor, as if more orange was used. Table 4 below shows the average scores and typical comments of the 10 panelists.

As shown in Table 4, it was confirmed that each compound of the formula (1) can impart a flavor to orange-flavored foods and drinks and further improve its natural feeling. Further, it was confirmed that the flavor-imparting effect can be obtained at least in the concentration range of 0.1 ppb to 1 ppm in foods and drinks.

[Example 6] Effect of blending into a beer-taste beverage In a commercially available non-alcoholic beer-taste beverage, each compound of the formula (1) obtained in Example 1 (formula (1-1) to formula (1-4) Each compound) was blended so as to have the concentration shown in Table 5 below to obtain a fruit-flavored food or drink of the present invention. Then, the natural feeling of the fruit-flavored food and drink of the present invention was sensory-evaluated using a commercially available beer-taste beverage as a control product. Specifically, 10 panelists with more than 10 years of well-trained experience were asked to "significantly improve" = 4 points, "improve" = 3 points, and "slightly improve" the beer feeling compared to the control product. "= 2 points," no change "= 1 point. Here, the feeling of beer means that it resembles ordinary beer. The average scores and typical comments of the 10 panelists are shown in Table 5 below.

As shown in Table 5, it was confirmed that each compound of the formula (1) can impart a flavor to beer-flavored foods and drinks and further improve its natural feeling. Further, it was confirmed that the flavor-imparting effect can be obtained at least in the concentration range of 0.1 ppb to 1 ppm in foods and drinks.

[Example 7] Example of use of the compound of the formula (1-1) As an example of the compound of the formula (1) of the present invention, an example of the use of the compound of the formula (1-1) will be described. As shown in Table 6 below, the compound of formula (1-1) was blended into various commercially available foods and drinks with various flavors, and the commercially available products were used as control products for five well-trained panelists with more than 15 years of experience. We commented on the change in flavor when compared to the control product. Typical comments are shown in Table 6 below.

As shown in Table 6, the compound of the formula (1-1) (franchion compound) can impart flavor to articles having various flavors other than those shown in Examples 3 to 5, and can improve the flavor. confirmed. In addition, it gives a feeling of ripening of fruits, heating of food and drink (typically roasted, roasted, steamed, roasted), and an impressive flavor such as aroma from the top of the flavor. The effect of making you feel stronger was also confirmed. In addition to the items listed in Table 6 above, chocolate, cacao, general cooked items (for example, high-temperature cooked items such as dumplings, fried rice, tonkatsu, and fried foods), baked goods, breads, kinako, and dark beer are also available. It can be exemplified as an article whose flavor can be enhanced by blending the compound of the formula (1-1).

[Example 8] Example of use of the compound of the formula (1-2) As an example of the compound of the formula (1) of the present invention, an example of the use of the compound of the formula (1-2) will be described. As shown in Table 7 below, the compound of formula (1-2) was added to various commercially available foods and drinks with various flavors, and the commercially available products were used as control products for five well-trained panelists with more than 15 years of experience. We commented on the change in flavor when compared to the control product. Typical comments are shown in Table 7 below.

As shown in Table 7, it was confirmed that the compound of the formula (1-2) (thiophenone compound) can impart flavor to articles having various flavors other than those shown in Examples 3 to 5, and can improve the flavor. Was done. It was also confirmed that the effect of imparting richness was particularly excellent. In addition to those listed in Table 7 above, foods and drinks with an oily feeling using animal or vegetable oils and fats, foods and drinks with a waxy feeling like citrus peel, cosmetics or pharmaceutical hygiene products, animal foods Various foods and drinks using soup and soup (chicken soup, consomme, pork bone soup, etc.) derived from the ingredients, various foods and drinks using eggs, various foods and drinks using livestock meat, etc. are compounds of formula (1-2). It can be exemplified as an article whose flavor can be enhanced by the combination of the above.

[Example 9] Example of use of the compound of the formula (1-3) As an example of the compound of the formula (1) of the present invention, an example of the use of the compound of the formula (1-3) will be described. As shown in Table 8 below, the compound of formula (1-3) was added to various commercially available foods and drinks with various flavors, and five well-trained panelists with more than 15 years of experience were asked to use the commercially available product as a control product. We commented on the change in flavor when compared to the control product. Typical comments are shown in Table 8 below.

As shown in Table 8, it was confirmed that the compound of the formula (1-3) (thiophenone compound) can impart flavor to articles having various flavors other than those shown in Examples 3 to 5, and can improve the flavor. Was done. It was also confirmed that it is particularly excellent in enhancing the overall flavor after the middle and adding richness. In addition to those listed in Table 8 above, foods and drinks with an oily feeling using animal or vegetable oils and fats, foods and drinks with a waxy feeling like citrus peel, cosmetics or pharmaceutical hygiene products, and edible foods. Foods and drinks using plants (especially herbs), cosmetics or medicinal hygiene products, foods and drinks using tea leaves (for example, black tea, oolong tea, Pu'er tea, green tea, etc.), cosmetics or medicinal hygiene products, etc. are formulas (1). It can be exemplified as an article whose flavor can be enhanced by blending the compound of -3).

[Example 10] Example of use of the compound of the formula (1-4) As an example of the compound of the formula (1) of the present invention, an example of the use of the compound of the formula (1-4) will be described. As shown in Table 9 below, the compound of formula (1-4) was added to various commercially available foods and drinks with various flavors, and the commercially available products were used as control products for five well-trained panelists with more than 15 years of experience. We commented on the change in flavor when compared to the control product. Typical comments are shown in Table 9 below.

As shown in Table 9, it was confirmed that the compound of the formula (1-4) (thiophenone compound) can impart flavor to articles having various flavors other than those shown in Examples 3 to 5, and can improve the flavor. Was done. It was also confirmed that it is particularly excellent in enhancing the overall flavor after the middle and adding richness. In addition to those listed in Table 9 above, foods and drinks with an oily feeling using animal or vegetable oils and fats, foods and drinks with a flavor having a waxy feeling and / or a feeling of fruit juice like citrus peel, cosmetics or pharmaceutical hygiene. Goods, foods and drinks using edible plants (especially herbs), cosmetics or pharmaceutical hygiene products, foods and drinks using tea leaves (eg black tea, oolong tea, puer tea, green tea, etc.), cosmetics or pharmaceutical hygiene products, etc. However, it can be exemplified as an article whose flavor can be enhanced by a compound in the formulation of the formula (1-4).

[Example 11] Effect of blending into a protein beverage In a commercially available protein beverage, each compound of the formula (1) obtained in Examples 1 (1) to (3) (formula (1-1) to formula (1-). Each compound) of 4) was blended so that the concentration thereof was 100 ppb with respect to the total mass of the protein beverage to obtain the protein beverage of the present invention (products 11-1 to 11-4 of the present invention). Then, using a commercially available protein beverage as a control product, four panelists with more than 10 years of well-trained experience answered about the change in flavor of the protein beverage of the present invention as compared with the control product. As a result, all four panelists found that the protein beverage of the present invention had a more voluminous flavor than the commercially available protein beverage of the control product, and the peculiar bitterness and astringency felt in the high-concentration protein was reduced. The answer was that the so-called protein odor became weaker and the overall satisfaction after drinking increased.

Claims (5)

A flavor-imparting composition containing a compound represented by the following formula (1).

[In the equation, (i) to (iv) are satisfied: (i) n represents an integer of 0 to 3, and (ii) the broken line of the five-membered ring is a carbon-carbon double bond at one place. The other is a single bond, or both are single bonds. (Iii) The broken line of the side chain of the five-membered ring is one carbon-carbon double bond, and the other. Indicates that the location of is a single bond, or that all locations are single bonds, and (iv) X ₁ and X ₂ are one oxygen atom and the other sulfur atom. ] A consumer good containing the flavoring composition according to claim 1. A method for imparting flavor to consumer goods, which comprises blending the flavoring composition according to claim 1 into consumer goods. A method for imparting flavor to a flavor-imparting composition, which comprises blending the flavor-imparting composition according to claim 1 with another flavor-imparting composition. A compound represented by the following formula (1').

[In the equation, (i) to (iv) are satisfied: (i) n represents an integer of 0 to 3, and (ii) the broken line of the five-membered ring is a carbon-carbon double bond at one place. The other is a single bond, or both are single bonds. (Iii) The broken line of the side chain of the five-membered ring is one carbon-carbon double bond, and the other. Indicates that the part of (iv) is a single bond or is a single bond, and (iv) X ₁ and X ₂ are one of which is an oxygen atom and the other of which is a sulfur atom. (However, (i) n is 1, (ii) one point of the broken line of the five-membered ring is a carbon-carbon double bond, and the other place is a single bond, and (iii) the side chain. Except for cases where all points of the broken line in (iv) are single bonds, (iv) X ₁ is a sulfur atom, X ₂ is an oxygen atom, and the side chain is bonded to the 5-position of the five-membered ring. )]]