JP7543343B2 - Sulfur-containing compound and flavor-imparting composition using same - Google Patents

Description

The present invention relates to novel sulfur-containing compounds, flavoring compositions and consumer goods, as well as a method for flavoring a flavoring composition and a method for flavoring a consumer good.

In recent years, consumer demands for various items such as food and beverages, fragrances and cosmetics, medicines, and health and hygiene products (hereinafter sometimes referred to as consumer goods) also extend to the fragrance of these consumer goods. For example, with regard to fragrances, which are one of the raw materials for food and beverages, conventionally proposed fragrance compounds alone are not sufficient to meet these demands, and the challenge is to develop fragrance compositions that have unprecedented and unique fragrance and flavor characteristics, and that are excellent not only in fragrance and flavor characteristics but also in their long-lasting properties. With regard to fragrances and cosmetics, as consumer preferences become more diverse, there is a demand for the development of a wide variety of fragrances and cosmetics.

To date, several proposals have been made to improve aroma. For example, Patent Document 1 describes that a dairy flavoring composition containing ethyl thioacetate and/or methyl thiobutyrate, which are sulfur-containing compounds, imparts a milk or dairy product-like flavor that is full of naturalness and highly palatable.

JP 2005-15685 A

However, according to the inventor's investigations, the sulfur-containing compound described in Patent Document 1 is a compound that is easily volatile, has poor durability, and has problems such as being limited in the targets to which it can be added. Therefore, there is a need for the development of a new sulfur-containing compound that can be widely applied to consumer goods, as well as the development of a new flavoring composition and consumer goods using this compound.

In view of the above, the object of the present invention is to provide a novel sulfur-containing compound, a flavoring composition, and a consumer product, as well as a method for flavoring a flavoring composition and a method for flavoring a consumer product.

The inventors conducted intensive research to solve the above problems and discovered that the novel sulfur-containing compounds described below have aroma characteristics such as fermented milk-like, heated milk-like, oily, fatty, milky, roasted, and creamy aromas, and that the addition of the sulfur-containing compounds themselves or flavor-imparting compositions containing the sulfur-containing compounds to consumer goods can impart, improve, or enhance flavors, leading to the completion of the invention of this application.

Thus, the following is a brief overview of the representative inventions disclosed in this application.

[1] A sulfur-containing compound represented by the following formula (1):

[In formula (1), n represents an integer of 0 to 2, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 2 to 5 carbon atoms, a furfuryl group, or a p-mentha-1-en-8-yl group, and R ³ represents a hydrogen atom or a methyl group.]
[2] A flavoring composition comprising the sulfur-containing compound according to [1].
[3] A consumer product comprising the sulfur-containing compound according to [1] or the flavoring composition according to [2].
[4] A method for imparting flavor to a flavor-imparting composition, comprising the step of adding the sulfur-containing compound according to [1] or the flavor-imparting composition according to [2] to another flavor-imparting composition.
[5] A method for imparting flavor to a consumer good, comprising the step of adding the sulfur-containing compound according to [1] or the flavor imparting composition according to [2] to the consumer good.

The present invention provides novel sulfur-containing compounds, flavoring compositions and consumer goods, as well as a method for flavoring a flavoring composition and a method for flavoring a consumer good.

Hereinafter, an embodiment of the present invention will be described in detail. In this specification, "~" means a range including a lower limit and an upper limit, and "concentration (ppm, ppb, ppt)" and "%" mean "mass concentration" and "mass percent concentration", respectively, unless otherwise specified. In addition, in this specification, "flavor" means one or more senses that can be changed by aroma (aroma), typically including the sense of smell and/or taste. In this specification, the term "flavoring (imparting flavor)" includes adding a new flavor and/or enhancing a flavor, and also includes those that improve the flavor as a result of imparting or enhancing a flavor. Furthermore, the term "flavoring (imparting flavor)" also includes those that enhance, suppress, or improve sensations other than the sense of smell and/or taste as a result of imparting flavor, such as coolness, warmth, texture (also called texture, such as smoothness, hardness, viscosity, etc.), and stimulating sensations such as carbonation and spiciness. In this specification, the flavor of food and drink is sometimes called flavor. In addition, in this specification, "adding" includes at least one of simply adding to an object by spraying, dripping, etc., and mixing with an object.

(Compound)
A compound according to one embodiment of the present invention (hereinafter, sometimes referred to as the present compound) is a compound represented by the following formula (1).

[In formula (1), n represents an integer of 0 to 2, R ¹ represents a hydrogen atom (H) or a linear or branched alkyl group having 1 to 9 carbon atoms, R ² represents a hydrogen atom (H), a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 2 to 5 carbon atoms, a furfuryl group, or a p-mentha-1-en-8-yl group, and R ³ represents a hydrogen atom or a methyl group.]

Examples of the compound of the present invention include 5-formyloxyhexanethioic S-acid represented by the following formula (2) (n=1, ^R1 is a methyl group, ^R2 is a hydrogen atom (H), and ^R3 is a hydrogen atom (H)), 5-formyloxydecanethioic S-acid represented by the following formula (3) (n=1, ^R1 is a pentyl group, ^R2 is a hydrogen atom (H), and ^R3 is a hydrogen atom (H)), S-methyl 4-formyloxybutanethioate represented by the following formula (4) (n=0, ^R1 is a hydrogen atom (H), ^R2 is a methyl group, and ^R3 is a hydrogen atom (H)), and S-methyl 5-formyloxypentanethioate represented by the following formula (5) (n=1, ^R1 is a hydrogen atom (H), R S-butan-2-yl 4-formyloxybutanethioate represented by formula (6) (n=0, R ¹ is a hydrogen atom (H), R ² is a butan-2-yl group, and R ³ is a hydrogen atom (H)); S-2-methylbut- ³ -en-2-yl 4-formyloxybutanethioate represented by formula (7) (n=0, R ¹ is a hydrogen atom (H), R 2 is a 2-methylbut-3-en-2-yl group, and R ³ is a hydrogen atom (H)); S-3-methylbut-3-en-1-yl 4-formyloxybutanethioate represented by formula (8) (n=0, R ¹ is a hydrogen atom (H), R ² is a 2-methylbut-3-en-2-yl group, and R 3 is a hydrogen atom (H)); 4-formyloxybutanethioate; n=0, R ¹ is a hydrogen atom (H), R ² is a 3-methylbut-3-en-1-yl group, and R ³ is a hydrogen atom (H); S-furfuryl 4-formyloxybutanethioate represented by formula (9); S-furfuryl 5-formyloxypentanethioate; n=1, R ¹ is a hydrogen atom (H), R ² is a furfuryl group, and R ³ is a hydrogen atom ⁽ H) ^; S-furfuryl 5-formyloxyhexanethioate represented by formula (11) ^; n=0, R ¹ is a methyl group, R ² is a furfuryl group, and R ³ is a hydrogen atom (H); Sp-menth-1-en-8-yl 4-formyloxybutanethioate represented by formula (12) (n=0, R ¹ is a hydrogen atom (H), R ² is a p-menth-1-en-8-yl group, and R ³ is a hydrogen atom (H); S-butan-2-yl 4-formyloxydodecanethioate represented by formula (13) (n=0, R ¹ is an octyl group, R ² is a butan-2-yl group, and R ³ is a hydrogen atom (H); S-butan-2-yl 5-formyloxytetradecanethioate represented by formula (14) (S-butan-2-yl 5-formyloxytetradecanethioate; n=1, R ¹ is a nonyl group, R ² is a butan-2-yl group, and R ³ is a hydrogen atom (H); S-butan-2-yl 4-acetoxybutanethioate represented by formula (15); n=0, R ¹ is a hydrogen atom (H), R ² is a butan- ² -yl group, ^and R ³ is a methyl group; S-furfuryl 4-formyloxydodecanethioate represented by formula (16); S-furfuryl 5-formyloxytetradecanethioate represented by formula (17) ^; Examples of the 6-acetoxyhexanethioic S-acid represented by the formula (10) include S-furfuryl 4-acetoxybutanethioate (n=0, ^R1 is a hydrogen atom (H), ^R2 is a furfuryl group, and ^R3 is a hydrogen atom (H)) represented by the formula (15), S-furfuryl 4-acetoxybutanethioate (n=0, ^R1 is a hydrogen atom (H), ^R2 is a furfuryl group, and ^R3 is a methyl group) represented by the formula (16), 6-formyloxyhexanethioic S-acid (n=2, ^R1 is a hydrogen atom (H), ^R2 is a hydrogen atom (H), and ^R3 is a hydrogen atom (H)) represented by the formula (17), and 6-acetoxyhexanethioic S-acid (n=2, ^R1 is a hydrogen atom (H), ^R2 is a hydrogen atom (H), and ^R3 is a methyl group) represented by the formula (18). Although the acetoxy group is also called an acetyloxy group, in this specification it will be referred to as the "acetoxy group."

The compound can be obtained, for example, by the reaction pathway shown below.

<First step>

[In formula (13), n represents an integer of 0 to 2, R ¹ represents a hydrogen atom (H) or a linear or branched alkyl group having 1 to 9 carbon atoms, and R ³ represents a hydrogen atom (H) or a methyl group.]

In the first step shown in formula (13), γ-lactone (n=0), δ-lactone (n=1) or ε-lactone (n=2) is reacted with benzyl formate ( ^R3 is a hydrogen atom (H)) or benzyl acetate ( ^R3 is a methyl group) to open the intramolecular ester bond and obtain a benzyl ester of formyloxyalkanoic acid ( ^R3 is a hydrogen atom (H)) or a benzyl ester of acetoxyalkanoic acid ( ^R3 is a methyl group).

<Second step>

[In formula (14), n represents an integer of 0 to 2, R ¹ represents a hydrogen atom (H) or a linear or branched alkyl group having 1 to 9 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.]
In the second step shown in formula (14), the benzyl ester of formyloxyalkanoic acid ( ^R3 is a hydrogen atom (H)) or the benzyl ester of acetoxyalkanoic acid ( ^R3 is a methyl group) obtained in the first step is reacted with hydrogen gas using a palladium (Pd) catalyst supported on carbon (hereinafter referred to as a "carbon-supported palladium catalyst") to obtain formyloxyalkanoic acid ( ^R3 is a hydrogen atom (H)) or acetoxyalkanoic acid ( ^R3 is a methyl group).

＜Third step＞

[In formula (15), n represents an integer of 0 to 2, R ¹ represents a hydrogen atom (H) or a linear or branched alkyl group having 1 to 9 carbon atoms, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms.]

In the third step shown in formula (15), the formyloxyalkanoic acid ( ^R3 is a hydrogen atom (H)) or acetoxyalkanoic acid ( ^R3 is a methyl group) obtained in the second step is reacted with an acyl halide to obtain a formyloxyalkanoic anhydride ( ^R3 is a hydrogen atom (H)) or an acetoxyalkanoic anhydride ( ^R3 is a methyl group).

<Step 4>

[In formula (16), n represents an integer of 0 to 2, R ¹ represents a hydrogen atom (H) or a linear or branched alkyl group having 1 to 9 carbon atoms, R ² represents a hydrogen atom (H), a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 2 to 5 carbon atoms, a furfuryl group, or a p-mentha-1-en-8-yl group, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms.]

In the fourth step shown in formula (16), the formyloxyalkanoic anhydride obtained in the third step is reacted with hydrogen sulfide or sodium hydrogen sulfide ( ^R2 is a hydrogen atom (H)), or with a thiol or sodium thiolate (sodium sulfide) ( ^R2 is other than a hydrogen atom (H)), to obtain the compound of the present invention, that is, a formyloxyalkanethioic acid ( ^R2 is a hydrogen atom (H), ^R3 is a hydrogen atom (H)), a formyloxyalkanethioic acid ester ( ^R2 is other than a hydrogen atom (H), ^R3 is a hydrogen atom (H)), an acetoxyalkanethioic acid ( ^R2 is a hydrogen atom (H), ^R3 is a methyl group), or an acetoxyalkanethioic acid ester ( ^R2 is other than a hydrogen atom (H), ^R3 is a methyl group).

The compound obtained by the above synthesis method may be further purified, if necessary, by means of column chromatography or reduced pressure distillation.

As shown in the examples below, the compound exhibits characteristic odors such as sulfur-like, egg-like, meat-like, gas-like, basil-like, tropical, roasted, burnt, green onion-like, citrus-like, and passion fruit-like odors.

In addition, the compound itself has a characteristic odor, but since it can produce lactones over time, it can also be used as a precursor to lactones and the corresponding sulfur-containing compounds.

Flavoring Composition
A flavoring composition according to one embodiment of the present invention (hereinafter, sometimes referred to as the present flavoring composition) contains a predetermined amount of the present compound.

The present inventors have found that the present flavoring composition containing a predetermined amount of the present compound exerts an excellent flavoring effect when added to various articles, as shown in the examples below. That is, the present flavoring composition can impart to various articles to which it is added the freshness and/or richness of milk (dairy products); the freshness, peeliness and/or juiciness of citrus fruits; the pulpiness and/or ripeness of fruits other than citrus fruits; the refreshing bitter aroma and/or malt aroma of beer; the freshness, freshly brewed and/or roasted aroma of various beverages; the fragrant and/or richness of soup; the fragrantness, richness, roasted and/or freshly baked aroma of baked goods; the freshness of various aromas of cosmetic products, and the like.

The present flavoring composition may be composed only of the present compound, or may contain other components as long as it contains a specified amount of the present compound. For example, when the present flavoring composition contains a solvent and/or other aroma components as components other than the present compound, the present flavoring composition itself can be used as a fragrance composition. The concentration of the present compound in the flavoring composition can be determined arbitrarily depending on the object to which the flavoring composition is to be added and the aroma characteristics.

The article to which the present flavoring composition is added is not particularly limited, but examples include other flavoring compositions or consumer goods (food and beverages, cosmetics, medicines, health and hygiene products, etc.). Furthermore, the present flavoring composition can be added to various flavoring compositions, as examples of other flavoring compositions, to impart a flavor to the flavoring composition and improve the flavor of the flavoring composition.

The concentration of the compound in the flavor imparting composition can be determined arbitrarily depending on the target of the flavor imparting composition. Examples of the concentration of the compound include a range of 1 ppb (0.001 ppm) to 100%, preferably 100 ppb (0.1 ppm) to 1%, based on the total mass of the flavor imparting composition. More specifically, the lower limit can be any of 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, 0.1%, 1%, or 10%, and the upper limit can be any of 100%, 10%, 1%, 0.1%, 100 ppm, 10 ppm, 1 ppm, 100 ppb, or 10 ppb, and the range can be any combination of these lower and upper limits, but is not limited to these.

(Fragrance composition)
The flavor composition according to one embodiment of the present invention (hereinafter, sometimes referred to as the flavor composition) is one aspect of the flavor-imparting composition, contains a predetermined amount of the compound, and can be added to various articles for the purpose of imparting flavor. The flavor composition can impart flavor to various articles by adding it to the articles. More specifically, the flavor composition can impart to the various articles to which it is added a fresh feeling and/or rich feeling of milk (dairy products); a fresh feeling, peel feeling, and/or fruit juice feeling of citrus fruits; a pulpy feeling and/or ripe feeling of fruits other than citrus fruits; a refreshing bitter aroma and/or malt aroma of beer flavor; a freshly ground feeling, freshly brewed feeling, and/or roasted feeling of various beverages; a fragrant feeling and/or rich feeling of soup; a fragrant feeling, rich feeling, roasted feeling, and/or freshly baked feeling of baked goods; a fresh feeling of each aroma tone of a cosmetic product, and the like. Specific examples of the present flavor composition include a flavor composition for food and beverages (also referred to as a flavor composition) and a flavor composition for cosmetics (also referred to as a fragrance composition). As mentioned above, examples of products to which the composition is added include consumer goods such as food and beverages, cosmetics, medicines, and health and hygiene products. The form of the present flavor composition is not particularly limited, and examples include a water-soluble flavor composition, an oil-soluble flavor composition, an emulsion flavor composition, and a powder flavor composition.

The concentration of the compound in the present fragrance composition can be determined arbitrarily depending on the target of the fragrance composition, and the amount added can be adjusted based on the concentration of the compound, which is the active ingredient, as in the case of the flavor-imparting composition described above. Examples of the concentration of the compound in the present fragrance composition include a range of 1 ppb (0.001 ppm) to 100%, preferably 100 ppb (0.1 ppm) to 1%, based on the total mass of the fragrance composition. More specifically, the lower limit can be any of 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, 0.1%, 1%, or 10%, and the upper limit can be any of 100%, 10%, 1%, 0.1%, 100 ppm, 10 ppm, 1 ppm, 100 ppb, or 10 ppb, and the range can be any combination of these lower and upper limits, but is not limited to these. Although it depends on the formulation and fragrance tone of the fragrance composition, it is preferable to set the concentration of the compound in the fragrance composition to 100 ppb to 1%, because the effect of adding the compound is noticeable and the scent derived from the compound is not excessively prominent. However, the compound may be added at a concentration below the lower limit or above the upper limit, depending on the fragrance tone of the fragrance composition to which it is added.

In addition to the compound, the fragrance composition may further contain any other compound or ingredient.

Examples of such compounds or ingredients include various kinds of flavor compounds or flavor compositions, oil-soluble dyes, vitamins, functional substances, fish meat extracts, livestock meat extracts, plant extracts, yeast extracts, animal and plant proteins, animal and plant protein hydrolysates, starch, dextrin, sugars, amino acids, nucleic acids, organic acids, solvents, etc. Examples include natural essential oils, natural flavors, and synthetic flavors described in "Japan Patent Office Gazette, Collection of Well-Known and Commonly Used Technologies (Flavors) Part II Food Flavors, published January 14, 2000," "Survey on the Actual Use of Food Flavor Compounds in Japan" (Report on the Ministry of Health, Labour and Welfare's Research in 2000, Japan Flavor and Flavor Manufacturers Association, published March 2001), and "Synthetic Flavors: Chemistry and Product Knowledge" (revised and updated December 20, 2016, edited by the Synthetic Flavors Editorial Committee, Chemical Daily Co., Ltd.).

Specific examples of synthetic fragrance compounds include hydrocarbon compounds such as monoterpenes such as α-pinene, β-pinene, γ-terpinene, myrcene, camphene, and limonene, sesquiterpenes such as valencene, cedrene, caryophyllene, and longifolene, and 1,3,5-undecatriene.

Examples of alcohol compounds include saturated alcohols such as butanol, pentanol, 3-octanol, and hexanol; unsaturated alcohols such as (Z)-3-hexen-1-ol, prenol, and 2,6-nonadienol; terpene alcohols such as linalool, geraniol, citronellol, tetrahydromyrcenol, farnesol, nerolidol, cedrol, α-terpineol, terpinen-4-ol, and borneol; and aromatic alcohols such as benzyl alcohol, phenylethyl alcohol, and cinnamyl alcohol.

Aldehyde compounds include saturated aldehydes such as acetaldehyde, hexanal, octanal, and decanal; unsaturated aldehydes such as (E)-2-hexenal and 2,4-octadienal; terpene aldehydes such as citronellal, hydroxycitronellal, citral, myrtenal, and perillaldehyde; and aromatic aldehydes such as benzaldehyde, cinnamyl aldehyde, vanillin, ethyl vanillin, heliotropin, and p-tolyl aldehyde.

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

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

Examples of ester compounds include aliphatic esters such as ethyl acetate, isoamyl acetate, octyl acetate, ethyl butyrate, ethyl isobutyrate, isoamyl butyrate, ethyl 2-methylbutyrate, ethyl isovalerate, 2-methylbutyl isobutyrate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate, ethyl octanoate, isoamyl isovalerate, and ethyl nonanoate; terpene alcohol esters such as linalyl acetate, geranyl acetate, lavandulyl acetate, terpinyl acetate, and neryl acetate; and aromatic esters such as benzyl acetate, methyl salicylate, methyl cinnamate, cinnamyl propionate, ethyl benzoate, cinnamyl isovalerate, and ethyl 3-methyl-2-phenylglycidate.

Examples of lactone compounds include saturated lactones such as γ-decalactone, γ-dodecalactone, δ-decalactone, and δ-dodecalactone, and unsaturated lactones such as 7-decen-4-olide and 2-decen-5-olide.

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

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

Examples of sulfur-containing compounds include hydrogen sulfide, methanethiol, dimethyl sulfide, dimethyl disulfide, allyl isothiocyanate, 2-butanethiol, 3-methyl-3-butene-1-thiol, 2-methyl-3-butene-1-thiol, 3-methyl-2-butene-1-thiol, 3-methyl-2-butanethiol, 3-methyl-1-butanethiol, 2-methyl-1-butanethiol, 3-mercaptohexanol, 4-mercapto-4-methyl-2-pentanone, 3-mercaptohexyl acetate, 1-p-menthen-8-thiol, p-mentha-8-thiol-3-one, and furfuryl mercaptan.

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, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, and labdanum.

Various animal and plant extracts include herb or spice extracts, fruit and vegetable extracts, coffee, green tea, black tea, or oolong tea extracts, milk or dairy products, and various enzymatic decomposition products thereof using lipase or protease, etc.

The present flavor composition can be prepared by adding the present flavor imparting composition to an appropriate solvent or dispersion medium by a known method.

The preferred form of the flavor composition is a solution in which the flavoring composition or other components are dissolved in a water-soluble or oil-soluble solvent, an emulsion preparation, a powder preparation, or other solid preparations (such as solid fats).

Examples of water-soluble solvents include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, propylene glycol, and dipropylene glycol. Of these, ethanol and glycerin are particularly preferred from the viewpoint of use in food and beverages. Examples of oil-soluble solvents include vegetable oils and fats, animal oils and fats, refined oils and fats (for example, processed oils and fats such as medium-chain fatty acid triglycerides, and short-chain fatty acid triglycerides such as triacetin and tripropionin), various essential oils, and triethyl citrate.

In addition, to prepare an emulsion preparation, the present flavoring composition can be emulsified with a water-soluble solvent and an emulsifier. The method of emulsifying the present flavoring composition is not particularly limited, and an emulsion with excellent stability can be obtained by emulsifying the composition using various types of emulsifiers conventionally used in foods and beverages, such as fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, propylene glycol fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, lecithin, modified starch, sorbitan fatty acid esters, Quillaja extract, gum arabic, tragacanth gum, guar gum, karaya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, Quillaja saponin casein, or sodium caseinate, using a homomixer, colloid mill, rotating disk homogenizer, high-pressure homogenizer, or the like. The amount of these emulsifiers used is not strictly limited and can vary over a wide range depending on the type of emulsifier used, but is usually within the range of about 0.01 to about 100 parts by mass, preferably about 0.1 to about 50 parts by mass, per 1 part by mass of the compound of the present invention. In addition to water, one or a mixture of two or more polyhydric alcohols such as glycerin, propylene glycol, sorbitol, maltitol, sucrose, glucose, trehalose, sugar solution, and reduced starch syrup can be added to the emulsion in order to stabilize the emulsified state.

If desired, the emulsion thus obtained can be dried to produce a powder formulation. When powdering, sugars such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, and reduced starch syrup can also be added as needed. The amounts of these used can be selected as appropriate depending on the properties desired for the powder formulation.

In addition to the above, the fragrance composition may contain, if necessary, ingredients that are commonly used in fragrance compositions. For example, it may contain solvents such as water and ethanol, and fragrance retainers such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, Hercolin, medium-chain fatty acid triglycerides, and medium-chain fatty acid diglycerides.

(Method of imparting flavor to flavor-imparting composition)
A method for imparting flavor to a flavor-imparting composition according to one embodiment of the present invention (hereinafter sometimes referred to as a method for imparting flavor to a flavor-imparting composition according to the present invention) includes a step of adding the present compound or the present flavor-imparting composition to another flavor-imparting composition.

By adding an effective amount of the present compound or the present flavoring composition to another flavoring composition, a flavor can be imparted to the flavoring composition to which it is added. More specifically, the flavoring composition to which the present compound or the present flavoring composition is added can be imparted with the following properties, thereby improving the flavor of the flavoring composition: freshness and/or richness of milk (dairy products); freshness, peel and/or juiciness of citrus fruits; pulp and/or ripeness of fruits other than citrus fruits; refreshing bitterness and/or malt aroma of beer; freshly ground, freshly brewed and/or roasted taste of various beverages; aroma and/or richness of soup; aroma, richness, roasted and/or freshly baked taste of baked goods; freshness of each aroma of cosmetic products, and the like.

In the flavoring method of the present invention, the amount (concentration) of the present flavoring composition (the present compound) added to the flavoring composition to be added may be an effective amount that improves the flavor by the present compound contained as an active ingredient, and may be set arbitrarily according to the type and form of the flavoring composition. When the flavoring composition to be added is a fragrance composition, examples of the concentration of the present compound relative to the fragrance composition are as described above in the section "Fragrance Composition."

In the flavor imparting method of the present invention, the method of adding the present compound or the present flavor imparting composition to another flavor imparting composition is not particularly limited. In addition, the time (timing) of adding the present compound or the present flavor imparting composition to another flavor imparting composition is not particularly limited.

(Consumer Goods)
A consumer good according to an embodiment of the present invention (hereinafter, sometimes referred to as the consumer good) contains a predetermined amount of the compound or the flavoring composition of the present invention. The consumer good can provide a flavored consumer good because an effective amount of the compound or the flavoring composition of the present invention is added to the consumer good. More specifically, the consumer good can be imparted with the freshness and/or richness of milk (dairy products); the freshness, peeliness and/or juiciness of citrus fruits; the pulpiness and/or ripeness of fruits other than citrus fruits; the refreshing bitterness and/or malt aroma of beer; the freshness, freshly brewed and/or roasted taste of various beverages; the aroma and/or richness of soup; the aroma, richness, roasted and/or freshly baked taste of baked goods; and the freshness of each aroma of cosmetic products, thereby improving the aroma. In addition, the consumer product is endowed with at least one of top, middle and last flavors, and in particular with a top aroma and taste sensation (spread).

In the present consumer product, the amount (concentration) of the present flavoring composition (the present compound) added to the consumer product can be determined arbitrarily depending on the flavor of the consumer product due to the present compound contained as an active ingredient and the degree of the desired effect.

As an example of the concentration, in the case of food and beverages, the concentration of the compound of the present invention may be in the range of 10 ppt (0.00001 ppm) to 100 ppm (0.01%), preferably 1 ppb (0.001 ppm) to 10 ppm, relative to the total mass of the food and beverage. More specifically, the lower limit may be any of 10 ppt, 100 ppt, 1 ppb, 10 ppb, 100 ppb, 1 ppm, and the upper limit may be any of 100 ppm, 10 ppm, 1 ppm, 100 ppb, 10 ppb, 1 ppb, and 100 ppt, and the range may be any combination of these lower and upper limits. As examples of preferred concentrations, the concentration of the compound of the present invention can be selected from 10 ppt (0.00001 ppm) to 1 ppb (0.001 ppm), 10 ppt (0.00001 ppm) to 1 ppm, 100 ppt (0.0001 ppm) to 10 ppb (0.01 ppm), 1 ppb (0.001 ppm) to 100 ppb (0.1 ppm), 10 ppb (0.01 ppm) to 1 ppm, and 10 ppb (0.01 ppm) to 10 ppm based on the total mass of the food or beverage, but is not limited to these.

Although it depends on the type and flavor of the food or beverage, it is preferable to set the concentration of the compound in the food or beverage to 1 ppb (0.001 ppm) to 10 ppm, since the effect of the addition is noticeable and the aroma derived from the compound is not excessively prominent. However, the compound may be added at a concentration below the lower limit or above the upper limit depending on the flavor of the food or beverage to which it is added.

In the case of a cosmetic product, the concentration of the compound in question may be within the range of 1 ppb (0.001 ppm) to 0.1% relative to the total mass of the cosmetic product. More specifically, the lower limit may be any of 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, and 100 ppm, and the upper limit may be any of 0.1%, 100 ppm, 10 ppm, 1 ppm, 100 ppb, and 10 ppb, and the range may be any combination of these lower and upper limits, but is not limited thereto. As a preferred example of the concentration, the concentration of the compound in question may be selected from the ranges of 10 ppb (0.01 ppm) to 10 ppm, 100 ppb (0.1 ppm) to 100 ppm, and 1 ppm to 0.1% relative to the total mass of the cosmetic product according to the fragrance characteristics of the cosmetic product, but is not limited thereto. Although it depends on the type and fragrance of the cosmetic product, it is preferable to set the concentration of the compound in the cosmetic product to 10 ppb (0.01 ppm) to 100 ppm, since the effect of the addition is noticeable and the fragrance derived from the compound is not excessively prominent. However, the compound may be added at a concentration below the lower limit or above the upper limit depending on the fragrance of the cosmetic product to which it is added.

The flavoring composition (the compound) may be added to a consumer product by itself, or may be added to the consumer product together with one or more selected from one or more water-soluble flavors, emulsified flavor compositions, any flavor compounds, and natural essential oils (for example, the flavor compounds described in the above-mentioned "Japan Patent Office Gazette, Collection of Well-Known and Commonly Used Technology (Flavors) Part II Food Flavors," "Survey on the Actual Use of Food Flavor Compounds in Japan," and "Synthetic Flavors: Chemistry and Product Knowledge").

Foods and beverages to which the present flavoring composition (the present compound) can be added are not particularly limited, but examples include various citrus flavors such as lemon, orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, hassaku, iyokan, yuzu, shikuwasa, and kumquat; various fruit flavors such as strawberry, blueberry, raspberry, apple, cherry, plum, apricot, peach, pineapple, banana, melon, mango, papaya, kiwi, pear, grape, muscat, and Kyoho; dairy flavors such as milk, yogurt, and butter; vanilla flavor; various tea flavors such as green tea, black tea, oolong tea, and herbal tea; coffee flavor; cola flavor; cacao flavor; cocoa flavor; various mint flavors such as spearmint and peppermint; cinnamon, chamomile, cardamom, caraway, cumin, clove, pepper, coriander, Japanese pepper, shiso, ginger, star anise, Spice or herb flavors such as thyme, chili pepper, nutmeg, basil, marjoram, rosemary, laurel, garlic, and wasabi; nut flavors such as almond, cashew nut, and walnut; alcohol flavors such as wine, brandy, whiskey, rum, gin, liqueur, sake, shochu, and beer; vegetable flavors such as onion, celery, carrot, tomato, and cucumber; and livestock flavors such as chicken, duck, pork, beef, lamb, and horse meat. Examples of foods and beverages that have one or more of the following flavors include meat flavors; various seafood and seaweed flavors such as red fish such as tuna, white fish such as mackerel, sea bream, salmon and horse mackerel, freshwater fish such as sweetfish, trout and carp, shellfish such as turban shells, clams, Japanese mussels and mussels, various crustaceans such as shrimp and crab, and various seaweeds such as wakame seaweed and kelp; various grain flavors such as rice, barley, wheat and malt; and various oil and fat flavors such as beef tallow, chicken oil and lard, and various fish oils. That is, the food or drink may be one that gives the impression of only one of the above flavors, or may be one that gives the impression of two or more flavors, and the multiple flavors may be the same or different. For example, an example of the former is a food or drink that gives the impression of multiple fruit flavors such as banana, peach, and apple flavors (so-called mixed fruit flavors), and an example of the latter is one that gives the impression of a citrus flavor such as lemon and a milk flavor (such as a citrus-flavored lactobacillus drink), or one that gives the impression of a mint flavor, a citrus flavor, and a cola flavor (such as a mint or lemon-flavored cola drink).

More specific examples of food and drink include rice crackers, arare, okoshi, mochi, manju, uiro, bean paste, yokan, mizuyokan, kingyoku, jelly, castella, candy, biscuits, crackers, potato chips, cookies, pies, puddings, butter cream, custard cream, cream puffs, waffles, sponge cakes, donuts, chocolate, chewing gum, caramel, candy, peanut paste or other pastes, etc. Sweets; bread, udon, ramen, Chinese noodles, sushi, gomoku rice, fried rice, pilaf, gyoza wrappers, shumai wrappers, okonomiyaki, takoyaki, and other breads, noodles, rice, and other grains; pickles such as bran pickles, pickled plums, fukujin pickles, bettara pickles, senmaizuke, rakkyo, miso pickles, takuan pickles, and the bases for these pickles; fish such as mackerel, sardines, pacific saury, salmon, tuna, bonito, whale, flounder, sand lance, sweetfish, flying squid, spear squid Seafood such as squid, firefly squid, and other squid; octopus such as common octopus and Japanese octopus; shrimp such as kuruma shrimp, button shrimp, spiny lobster, and black tiger shrimp; crabs such as king crab, snow crab, blue crab, and hairy crab; shellfish such as clams, mussels, scallops, oysters, and mussels; canned foods, boiled fish, tsukudani, surimi, fish paste products (chikuwa, kamaboko, fried kamaboko, crab leg kamaboko, etc.), fries, tempura, and other processed seafood foods and drinks; chicken, pork, beef Meat, lamb, horse meat, and other livestock meat; curry, stew, beef stew, hayashi rice sauce, meat sauce, mapo tofu, hamburger steak, dumplings, kamameshi seasonings, soups (corn soup, tomato soup, consommé soup, etc.), meatballs, braised pork, canned meat, and other processed foods and drinks using livestock meat; table salt, seasoning salt, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hishio, furikake, ochazuke seasonings, margarine, mayonnaise, dressing, vinegar, sanbaizu, powdered Seasonings such as vinegared sushi, Chinese seasonings, tempura sauce, noodle sauce (kelp stock or bonito stock, etc.), sauces (medium-thick sauce, tomato sauce, etc.), ketchup, yakiniku sauce, curry roux, stew base, soup base, dashi stock base (kelp stock or bonito stock, etc.), compound seasonings, new mirin, mixed flours such as fried chicken flour and takoyaki flour, and animal or vegetable dashi-flavored foods and beverages with these seasonings added; dairy products such as cheese, yogurt, and butter; beer yeast. Various yeasts such as yeast, baker's yeast, and lactic acid bacteria are used in fermentation products using various microorganisms; simmered vegetables, Chikuzen-ni, oden, hotpots, and other simmered dishes; take-out bento box ingredients and side dishes; fruit juice drinks and soft drinks containing fruit juice, such as apples, grapes, and citrus fruits (grapefruit, oranges, lemons, etc.), fruit pulp drinks, and fruit drinks containing fruit pieces; vegetables such as tomatoes, bell peppers, celery, melons, bitter melons, carrots, potatoes, asparagus, bracken, and fern, and vegetables containing these vegetables. Examples of such beverages include vegetable-containing foods and beverages such as vegetable drinks and vegetable soups; coffee, cocoa, green tea, black tea, oolong tea, soft drinks, cola drinks, carbonated drinks (ciders with various flavors such as citrus flavors), and lactobacillus drinks; beverages containing herbal medicines and herbs; functional beverages such as cola drinks, fruit juice drinks, dairy drinks, beer-flavored drinks including non-alcoholic beer and so-called "third beer" that uses less malt than beer, sports drinks, honey drinks, vitamin supplement drinks, mineral supplement drinks, nutritional drinks, nutritious drinks, and lactobacillus drinks; non-alcoholic beverages such as alcohol-flavored drinks with various alcoholic beverage flavors (beer flavor, plum wine flavor, chuhai flavor, etc.); wine, shochu, awamori, sake, beer, chuhai, cocktail drinks, happoshu, fruit wine, yakumi shu, other brewed alcoholic beverages (sparkling) or liqueurs (sparkling), or alcoholic beverages containing these; etc.

Cosmetics to which the present flavoring composition (the present compound) can be added are not particularly limited, but examples include perfumes such as eau de cologne, eau de toilette, eau de parfum, and parfum; hair care products such as shampoo, rinse, and hair styling products (hair cream, pomade, etc.); cosmetics such as foundation, lipstick, lip balm, lip gloss, lotion, cosmetic emulsion, cosmetic cream, cosmetic gel, beauty serum, and pack; and deodorant products such as antiperspirant spray, deodorant sheet, deodorant cream, and deodorant stick. bath additives such as inorganic salts, cooling agents, carbon dioxide gas, skin care agents, enzyme agents, and herbal medicines; tanning cosmetics such as suntan products and sunscreen products; health and hygiene detergents such as face soap and face wash, body soap, laundry soap, laundry detergent, disinfectant detergent, deodorant detergent, fabric softener, kitchen detergent, and cleaning detergent; health and hygiene materials such as toothpaste, tissue paper, and toilet paper; aromatic products such as deodorizers for indoor and car use, and room fragrances; etc.

There are no limitations on the fragrance tone that can be used with the present flavoring composition (the present compound), and any fragrance tone that can be improved by the present flavoring composition (the present compound) may be used.

(Method of imparting flavor to consumer goods)
A method for imparting flavor to consumer goods according to one embodiment of the present invention (hereinafter sometimes referred to as the method for imparting flavor to consumer goods according to the present invention) includes a step of adding the present compound or the present flavor imparting composition to a consumer good.

By adding an effective amount of the flavor-imparting composition (the compound) to consumer goods such as food and beverages and fragrances and cosmetics, it is possible to impart a flavor to the consumer goods. More specifically, the flavor-imparting composition can impart the freshness and/or richness of milk (dairy products); the freshness, peeliness and/or juiciness of citrus fruits; the pulpiness and/or ripeness of fruits other than citrus fruits; the refreshing bitter flavor and/or malty aroma of beer; the freshness and/or freshly brewed and roasted flavors of various beverages; the fragrant and/or richness of soup; the fragrant, richness, roasted and/or freshly baked flavors of baked goods; and the freshness of each aroma of fragrances and cosmetics to the consumer goods, thereby improving the flavor of the consumer goods. Furthermore, by adding an effective amount of the present flavor-imparting composition (the present compound) to consumer goods such as food and beverages and fragrances and cosmetics, it is possible to impart one or more of the top, middle, and last flavors, particularly the top aroma and taste sensation (broadness).

In the present method of imparting flavor to consumer goods, the amount (concentration) of the present flavor imparting composition (the present compound) added to the consumer goods may be an effective amount that improves the flavor by the present compound contained as an active ingredient, and may be set arbitrarily depending on the type and form of the consumer goods. In this case, examples of the concentration of the present compound in the consumer goods are as described above in the "Consumer Goods" section.

In the method of flavoring consumer goods, the method of adding the present compound or the present flavoring composition to the consumer goods is not particularly limited. In addition, the time (timing) of adding the present compound or the present flavoring composition to the consumer goods is not particularly limited.

The present invention will be explained in more detail below with reference to examples. Note that the present invention is not limited to these examples.

[Example 1] Synthesis examples of the subject compound The subject compound was synthesized according to the following examples.

<Example 1-1-1: Synthesis of benzyl 5-formyloxyhexanoate>

δ-Hexalactone (22.8 g, 0.20 mol), benzyl formate (272.2 g, 2.0 mol), and p-toluenesulfonic acid (0.96 g, 5.0 mmol) were placed in a 500 mL two-neck flask and stirred overnight at room temperature. The reaction solution was washed successively with a mixed aqueous solution of sodium bicarbonate (sodium bicarbonate) and salt (sodium chloride), and saturated saline, and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and the resulting filtrate was distilled under reduced pressure to recover benzyl formate (203.5 g). The distillation residue (54.0 g) was distilled under reduced pressure to obtain the desired benzyl 5-formyloxyhexanoate (31.3 g) (yield 63%).

<Example 1-1-2: Synthesis of 5-formyloxyhexanoic acid>

Benzyl 5-formyloxyhexanoate (12.5 g, 50.0 mmol), ethyl acetate (50 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.63 g) were placed in a 200 mL flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the resulting filtrate was used directly in the next step.

<Example 1-1-3: Synthesis of 5-formyloxyhexanethio S-acid>

In a nitrogen atmosphere, crude 5-formyloxyhexanoic acid (50.0 mmol) (total amount of filtrate after reaction) obtained in the previous step and triethylamine (Et ₃ N, 6.1 g, 60.0 mmol) were placed in a 300 mL four-neck flask and stirred under ice water cooling. Pivaloyl chloride (PivCl, 6.6 g, 55.0 mmol) was added dropwise to the mixture under ice water cooling and stirred for 2 hours. Next, triethylamine (50 mL) was added while stirring under ice water cooling, and hydrogen sulfide was blown in for 1.5 hours under ice water cooling, and then for 1.5 hours while warming to room temperature. After the blowing of hydrogen sulfide was terminated, the mixture was stirred overnight at room temperature. A 30% aqueous citric acid solution was added to the mixture under ice water cooling, and the aqueous layer obtained by liquid separation was extracted with ethyl acetate. The organic layers were combined, washed with saturated saline, and dried over anhydrous magnesium sulfate. The crude product (15.4 g) obtained by vacuum concentration was purified by silica gel column chromatography, and the purified product was purified by distillation under reduced pressure to obtain the target 5-formyloxyhexanethio S-acid (4.5 g). The distilled product contained 1.8% pivalic acid, which was removed under reduced pressure to obtain the present invention product 1-1 (4.4 g). The yield from benzyl 5-formyloxyhexanoate was 50%.

<<Physical properties of product 1-1 of the present invention>>
¹ H NMR (CDCl ₃ , 400 MHz) δ 8.02 (s, 1 H), 4.97-5.06 (m, 1 H), 4.26 (br s, 1 H), 2.60-2.64 (m, 2 H), 1.52-1.76 (m, 4 H), 1.23 (d, 3 H, J=6.4 Hz).
^13C NMR ( _CDCl3 , 100MHz) δ 197.2, 160.7, 45.1, 34.7, 20.9, 19.9.
MS (EI, 70eV) m/z 115 (100), 97 (71), 73 (24), 71 (11), 69 (87), 55 (58), 45 (28), 43 (19), 41 (31).

<Example 1-2-1: Synthesis of benzyl 5-formyloxydecanoate>

δ-Decalactone (8.5 g, 0.05 mol), benzyl formate (68.1 g, 0.50 mol) and p-toluenesulfonic acid (0.24 g, 1.3 mmol) were placed in a 100 mL three-neck flask and stirred overnight at room temperature. The reaction solution was diluted with diethyl ether (Et ₂ O), washed with saturated sodium bicarbonate water and saturated saline in that order, and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, and the resulting concentrated residue (65.1 g) was distilled under reduced pressure to recover benzyl formate (48.8 g). The distillation residue (15.4 g) was purified by silica gel column chromatography to obtain the desired benzyl 5-formyloxydecanoate (11.2 g) (yield 73%).

<Example 1-2-2: Synthesis of 5-formyloxydecanoic acid>

Benzyl 5-formyloxydecanoate (3.1 g, 10.0 mmol), ethyl acetate (9 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.16 g) were placed in a 30 mL two-neck flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the resulting filtrate was concentrated under reduced pressure and dried under reduced pressure (up to 40°C) to obtain the desired 5-formyloxydecanoic acid (2.1 g) (crude yield 97%).

<Example 1-2-3: Synthesis of 5-formyloxydecanethio S-acid>

In a nitrogen atmosphere, the crude 5-formyloxydecanoic acid (2.0 g, 9.3 mmol) obtained in the previous step and diethyl ether (Et ₂ O, 20 mL) were placed in a 50 mL flask and stirred under ice-water cooling. Triethylamine (0.94 g, 9.3 mmol) was added dropwise thereto and stirred under ice-water cooling for 0.5 hours. Next, pivaloyl chloride (1.2 mL, 9.3 mmol) was added dropwise thereto under ice-water cooling for 15 minutes and stirred under ice-water cooling for 1 hour. The reaction solution was filtered through a filter paper to obtain 36.8 g of filtrate.

The filtrate (35.9 g) was placed in a 200 mL four-neck flask, and hydrogen sulfide was bubbled in at room temperature for 1 hour. Triethylamine (10 mL) was then added, and hydrogen sulfide was bubbled in at room temperature for 1 hour. A 15% aqueous citric acid solution and citric acid were added in turn to the reaction solution that had been left overnight, and the liquids were separated. The organic layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. The crude product (3.1 g) obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain a purified product (1.22 g). 0.52 g of this was purified by distillation to obtain the desired product, 5-formyloxydecanethio S-acid (0.41 g), as a yellow oil (this is referred to as product 1-2 of the present invention). The yield from 5-formyloxydecanoic acid was 44%.

<<Physical properties of product 1-2 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.07 (s, 1H), 4.94-5.01 (m, 1H), 4.66 (br s, 1H), 2.56-2.67 (m, 2H), 1.46-1.75 (m, 6H), 1.21-1.34 (m, 6H), 0.86 (t , 3H, J=6.8Hz).
^13C NMR ( _CDCl3 , 100MHz) δ 197.2, 160.9, 45.2, 33.9, 32.9, 31.5, 24.8, 22.5, 20.9, 13.9.
MS (EI, 70eV) m/z 171 (56), 153 (100), 135 (55), 111 (24), 97 (33), 83 (44), 81 (16), 71 (20), 69 (73), 57 (22), 55 (68), 43 (28), 41 (31).

<Example 1-3-1: Synthesis of benzyl 4-formyloxybutanoate>

γ-Butyrolactone (12.9 g, 0.15 mol), benzyl formate (204.2 g, 1.5 mol), and p-toluenesulfonic acid (0.71 g, 3.75 mmol) were placed in a 300 mL two-neck flask and stirred at room temperature for approximately 8 days. The reaction solution was washed successively with saturated sodium bicarbonate water and saturated saline, and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and the resulting filtrate was distilled under reduced pressure to recover benzyl formate (184.6 g). The distillation residue (15.0 g) was distilled under reduced pressure to obtain the desired benzyl 4-formyloxybutanoate (11.3 g) (yield 34%).

<Example 1-3-2: Synthesis of 4-formyloxybutanoic acid>

Benzyl 4-formyloxybutanoate (8.9 g, 40.0 mmol), ethyl acetate (40 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.45 g) were placed in a 100 mL flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the resulting filtrate was used directly in the next step.

<Example 1-3-3: Synthesis of S-methyl 4-formyloxybutanethioate>
The filtrate and triethylamine (4.9 g, 48 mmol) were added to a 300 mL three-neck flask and cooled with ice water. Pivaloyl chloride (5.3 g, 44 mmol) was added, and the mixture was stirred at the same temperature for 3 hours. A 15% aqueous solution of sodium methanethiolate (aq. NaSMe, 28.0 g, 60 mmol, 1.5 eq.) was added to the reaction solution at once and the mixture was stirred overnight at room temperature. Water (150 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated aqueous ammonium chloride solution (100 mL), water (100 mL), saturated aqueous sodium bicarbonate solution (100 mL), and saturated aqueous sodium chloride solution (100 mL) in sequence, then dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue (3.42 g) was purified by silica gel column chromatography, and the main fraction was Kugelrohr distilled (120° C./0.1 kPa) to obtain the target thioester as a colorless oily substance (1.49 g, 9.19 mmol, this is the present invention product 1-3). The yield from benzyl 4-formyloxybutanoate was 23%.

<<Physical properties of products 1-3 of the present invention>>
¹ H NMR (CDCl ₃ , 400 MHz) δ 8.05 (s, 1H), 4.20 (dt, 2H, J=0.8Hz, 6.4Hz), 2.67 (t, 2H, J=7.2Hz), 2.28 (s, 3H), 1.66-1.79 (m, 4H).
^13C NMR ( _CDCl3 , 100MHz) δ 199.4, 161.0, 63.3, 43.1, 27.7, 22.0, 11.6.
MS (EI, 70eV) m/z 162 (3), 115 (100), 87 (88), 75 (19), 69 (12), 47 (10), 45 (41), 43 (53), 41 (27), 31 (19).

<Example 1-4-1: Synthesis of benzyl 5-formyloxypentanoate>

δ-valerolactone (10.0 g, 0.10 mol), benzyl formate (136.1 g, 1.0 mol) and p-toluenesulfonic acid (0.48 g, 2.5 mmol) were placed in a 200 mL two-neck flask and stirred overnight at room temperature. The reaction solution was washed successively with saturated sodium bicarbonate water and saturated saline, and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and the resulting filtrate (166.2 g) was distilled under reduced pressure to recover benzyl formate (117.4 g). The distillation residue (22.4 g) was distilled under reduced pressure to obtain the desired benzyl 5-formyloxypentanoate (16.2 g) (yield 68%).

<Example 1-4-2: Synthesis of 5-formyloxypentanoic acid>

Benzyl 5-formyloxypentanoate (8.0 g, 33.9 mmol), ethyl acetate (36 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.4 g) were placed in a 100 mL flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the resulting filtrate was concentrated under reduced pressure and dried under reduced pressure (up to 40°C) to obtain the desired 5-formyloxypentanoic acid (4.9 g).

<Example 1-4-3: Synthesis of S-methyl 5-formyloxypentanethioate>
By the same method as in Example 1-3-3, the target S-methyl 5-formyloxypentanethioate was obtained as a colorless oily substance (1.8 g, yield 31%, this is the present invention product 1-4).

<<Physical properties of products 1-4 of the present invention>>
¹ H NMR (CDCl ₃ , 400 MHz) δ 8.03 (s, 1H), 4.15 (t, 2H, J=6.0Hz), 2.57 (t, 2H, J=6.8Hz), 2.31 (s, 3H), 2.00-2.08 (m, 2H).
^13C NMR ( _CDCl3 , 100MHz) δ 198.7, 160.8, 62.6, 39.9, 24.4, 11.6.
MS (EI, 70eV) m/z 176 (0.6), 130 (10), 129 (100), 101 (78), 83 (64), 75 (18), 59 (21), 55 (82), 43 (21), 41 (8), 31 (12).

<Example 1-5-1: Synthesis of benzyl 4-formyloxybutanoate>
Benzyl 4-formyloxybutanoate was synthesized in the same manner as in Example 1-3-1.

<Example 1-5-2: Synthesis of 4-formyloxybutanoic acid>

In a 200 mL two-neck flask, benzyl 4-formyloxybutanoate (8.9 g, 40 mmol), ethyl acetate (40 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.45 g) were sequentially placed and stirred for 2 days under a hydrogen atmosphere. The reaction solution was filtered through Celite and washed with ethyl acetate, after which the filtrate was subjected to the subsequent reaction.

<Example 1-5-3: Synthesis of S-butan-2-yl 4-formyloxybutanethioate>
The above-mentioned solution and triethylamine (4.9 g, 48 mmol) were added to a 300 mL three-neck flask and cooled with ice water. Pivaloyl chloride (5.3 g, 44 mmol) was added and stirred at the same temperature for 1 hour. Triethylamine (7.1 g, 70 mmol) and 2-butanethiol (4.32 g, 48 mmol) were added to the reaction solution and stirred at room temperature for 4 days. Saturated sodium bicarbonate water (150 mL) was added to the reaction solution, and it was extracted with ethyl acetate. The organic phase was washed with water and saturated saline in order, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue (7.45 g) was purified by silica gel column chromatography, and the main fraction (4.38 g) was Kugelrohr distilled (145° C./0.3 kPa) to obtain the target thioester as a colorless oily substance (3.71 g, 18.2 mmol, this is the present invention product 1-5). The yield from benzyl 4-formyloxybutanoate was 45%.

<<Physical properties of products 1-5 of the present invention>>
¹ H NMR (CDCl ₃ , 400 MHz) δ 8.05 (s, 1 H), 4.19 (br t, 2 H, J = 6.8 Hz), 3.52 (qui, 1 H, J = 6.8 Hz), 2.63 (t, 2 H, J = 6.8 Hz), 2.03 (qui, 2 H, J=6.8Hz), 1.56-1.63 (m, 2H), 1.28 (d, 3H, J=6.8Hz), 0.94 (t, 3H, J=7.6Hz).
^13C NMR ( _CDCl3 , 100MHz) δ 198.5, 160.9, 62.7, 41.0, 40.3, 29.4, 24.4, 20.8, 11.4.
MS (EI, 70eV) m/z 204 (1), 149 (12), 148 (12), 115 (23), 87 (100), 57 (14), 45 (16), 43 (31), 41 (16).

<Example 1-6-1: Synthesis of benzyl 4-formyloxybutanoate>
Benzyl 4-formyloxybutanoate was synthesized in the same manner as in Example 1-3-1.

<Example 1-6-2: Synthesis of 4-formyloxybutanoic acid>

In a 200 mL two-neck flask, benzyl 4-formyloxybutanoate (8.9 g, 40 mmol), ethyl acetate (40 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.45 g) were sequentially placed and stirred under a hydrogen atmosphere for 48 hours. The reaction solution was filtered through Celite and washed with ethyl acetate, after which the filtrate was subjected to the subsequent reaction.

<Example 1-6-3: Synthesis of S-2-methylbut-3-en-2-yl 4-formyloxybutanethioate>
The filtrate and triethylamine (4.9 g, 48 mmol) were added to a 300 mL three-neck flask and cooled with ice water. Pivaloyl chloride (5.3 g, 44 mmol) was added and stirred at the same temperature for 3 hours. Triethylamine (9.8 g, 96 mmol), 4-dimethylaminopyridine (DMAP, 0.25 g, 2 mmol) and 2-methylbut-3-ene-2-thiol (4.1 g, 40 mmol) were added to the reaction solution and stirred overnight at room temperature. Water was added to the reaction solution and extracted with ethyl acetate. The organic phase was washed with saturated aqueous ammonium chloride solution, water, saturated aqueous sodium bicarbonate (100 mL) and saturated saline (100 mL) in that order, then dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography, and the main fraction was Kugelrohr distilled (150° C./0.1 kPa) to obtain the target thioester as a colorless oil (2.84 g, 13.1 mmol, this is the present invention product 1-6). The yield from benzyl 4-formyloxybutanoate was 33%.

<<Physical properties of products 1-6 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.03 (s, 1H), 6.08 (dd, 1H, J = 17.6Hz, 6.4Hz), 5.16 (d, 1H, J = 17.6Hz), 5.05 (d, 1H, J = 6.4Hz), 4.17 (br t, 2H, J=6.8Hz), 2.55 (br t, 2H, J=6.8Hz), 1.98 (qui, 2H, J=6.8Hz), 1.54 (s, 6H).
^13C NMR ( _CDCl3 , 100MHz) δ 198.1, 160.8, 142.7, 112.8, 62.7, 51.3, 40.4, 26.8, 24.1.
MS (EI, 70eV) m/z 216 (3), 170 (7), 101 (11), 87 (19), 69 (100), 45 (6), 43 (10), 41 (30).

<Example 1-7-1: Synthesis of benzyl 4-formyloxybutanoate>
Benzyl 4-formyloxybutanoate was synthesized in the same manner as in Example 1-3-1.

<Example 1-7-2: Synthesis of 4-formyloxybutanoic acid>

Benzyl 4-formyloxybutanoate (8.9 g, 40 mmol), ethyl acetate (40 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.45 g) were sequentially placed in a 200 mL two-neck flask and stirred under a hydrogen atmosphere for 16 hours. The reaction solution was filtered through Celite and washed with ethyl acetate, after which the filtrate was subjected to the subsequent reaction.

<Example 1-7-3: Synthesis of S-3-methylbut-3-en-1-yl 4-formyloxybutanethioate>
The above-mentioned solution and triethylamine (4.9 g, 48 mmol) were placed in a 300 mL three-neck flask and cooled with ice water. Pivaloyl chloride (5.3 g, 44 mmol) was then added, and the mixture was stirred at the same temperature for 3 hours. Triethylamine (7.1 g, 70 mmol) and 3-methylbut-3-ene-1-thiol (4.08 g, 40 mmol) were added to the reaction solution, and the mixture was stirred at room temperature for 3 days. Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phase was washed successively with saturated sodium bicarbonate water and saturated saline, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue (5.89 g) was purified by silica gel column chromatography, and the main fraction was Kugelrohr distilled (150° C./0.1 kPa) to obtain the desired thioester as a colorless oily substance (4.85 g, 22.4 mmol, this is the present invention product 1-7). The yield from benzyl 4-formyloxybutanoate was 56%.

<<Physical properties of products 1-7 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.05 (s, 1H), 4.79 (s, 1H), 4.72 (s, 1H), 4.20 (t, 2H, J = 6.4Hz) 3.01 (t, 2H, J = 7.6Hz), 2.66 (t, 2H, J = 7.6Hz) ), 2.27 (t, 2H, J=7.6Hz), 1.99-2.07 (m, 2H), 1.59 (s, 3H).
^13C NMR ( _CDCl3 , 100MHz) δ 198.3, 160.8, 143.4, 111.7, 62.6, 40.1, 37.3, 27.1, 24.3, 22.2.
MS (EI, 70eV) m/z 216 (3), 170 (12), 102 (29), 101 (52), 100 (14), 87 (100), 69 (29), 68 (25), 67 (16), 45 (28), 43 (47), 41 (32).

<Example 1-8-1: Synthesis of benzyl 4-formyloxybutanoate>
Benzyl 4-formyloxybutanoate was synthesized in the same manner as in Example 1-3-1.

<Example 1-8-2: Synthesis of 4-formyloxybutanoic acid>

Benzyl 4-formyloxybutanoate (8.9 g, 40.0 mmol), ethyl acetate (40 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.45 g) were placed in a 100 mL flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the resulting filtrate was used directly in the next step.

<Example 1-8-3: Synthesis of S-furfuryl 4-formyloxybutanethioate>

In a nitrogen atmosphere, the crude 4-formyloxybutanoic acid (40.0 mmol) and triethylamine (4.9 g, 48.0 mmol) obtained in the previous step were placed in a 300 mL four-neck flask and stirred under ice-water cooling. Pivaloyl chloride (5.3 g, 44.0 mmol) was added dropwise to the mixture over 20 minutes under ice-water cooling and stirred for 1.5 hours. Next, triethylamine (40 mL) was added under ice-water cooling and stirring, and furfuryl mercaptan (5.5 g, 48.0 mmol) was added dropwise over 0.5 hours and stirred overnight while warming to room temperature. The resulting reaction solution was washed successively with saturated aqueous sodium carbonate solution and saturated saline, and dried over anhydrous magnesium sulfate. After concentrating under reduced pressure, the resulting crude product (9.9 g) was purified by silica gel column chromatography, and the purified product was purified by distillation under reduced pressure using a Kugelrohr distiller to obtain the desired S-furfuryl 4-formyloxybutanethioate (5.3 g) (this product is designated as Product 1-8 of the present invention). The yield from benzyl 4-formyloxybutanoate was 58%.

<<Physical properties of products 1-8 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.00 (s, 1H), 7.30 (dd, 1H, J = 1.6Hz, 0.8Hz), 6.27 (dd, 1H, J = 3.2Hz, 1.6Hz), 6.19 (dd, 1H, J = 3.2Hz, 0.8 Hz), 4.17 (br t, 2H, J = 6.4Hz), 4.14 (s, 2H), 2.66 (t, 2H, J = 7.2Hz), 1.99-2.07 (m, 2H).
^13C NMR ( _CDCl3 , 100MHz) δ 197.1, 160.8, 150.2, 142.3, 110.6, 108.0, 62.6, 40.0, 25.7, 24.2.
MS (EI, 70eV) m/z 228 (18), 182 (13), 114 (10), 113 (15), 87 (17), 81 (100), 53 (10), 45 (11), 43 (12).

<Example 1-9-1: Synthesis of benzyl 5-formyloxypentanoate>
Benzyl 5-formyloxypentanoate was synthesized in the same manner as in Example 1-4-1.

<Example 1-9-2: Synthesis of 5-formyloxypentanoic acid>
Benzyl 5-formyloxypentanoate (8, 8.0 g, 33.9 mmol), ethyl acetate (36 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.4 g) were placed in a 100 mL flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the resulting filtrate was concentrated under reduced pressure and dried under reduced pressure (up to 40°C) to obtain the desired 5-formyloxypentanoic acid (4.9 g).

<Example 1-9-3: Synthesis of S-furfuryl 5-formyloxypentanethioate>

In a nitrogen atmosphere, the crude 5-formyloxypentanoic acid (4.9 g, 36.0 mmol) obtained in the previous step and diethyl ether (140 mL) were placed in a 200 mL four-neck flask and stirred under ice-water cooling. Triethylamine (4.4 g, 43.2 mmol) was added dropwise over 5 minutes and stirred under ice-water cooling for 0.5 hours. Next, a solution of pivaloyl chloride (4.8 g, 39.6 mmol) in diethyl ether (30 mL) was added dropwise over 0.5 hours under ice-water cooling and stirred under ice-water cooling for 1 hour. The mixture was filtered through a paper filter (rinsed with 50 mL of diethyl ether) to obtain 137.7 g of filtrate.

The filtrate (137.7 g) and triethylamine (36 mL) were placed in a 300 mL four-neck flask and stirred under ice-water cooling. A solution of furfuryl mercaptan (4.9 g, 43.2 mmol) in diethyl ether (10 mL) was added dropwise and stirred at the same temperature for 2.5 hours, and then stirred at room temperature overnight. The resulting reaction solution was washed successively with saturated aqueous sodium carbonate and saturated saline, and dried over anhydrous magnesium sulfate. The crude product (10.3 g) obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain a purified product (5.5 g). This was purified by distillation under reduced pressure to obtain the desired S-furfuryl 5-formyloxypentanethioate (3.6 g) (this product is referred to as product 1-9 of the present invention). The yield from benzyl 5-formyloxypentanoate was 42%.

<<Physical properties of products 1-9 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.02 (s, 1H), 7.30 (dd, 1H, J = 1.6Hz, 0.8Hz), 6.27 (dd, 1H, J = 3.2Hz, 1.6Hz), 6.19 (dd, 1H, J = 3.2Hz, 0 .8Hz), 4.14 (t, 2H, J=6.4Hz), 4.13 (s, 2H), 2.60 (t, 2H, J=7.2Hz), 1.64-1.80 (m, 4H).
^13C NMR ( _CDCl3 , 100MHz) δ 197.6, 1601.0, 150.4, 142.2, 110.6, 107.9, 63.3, 43.0, 27.7, 25.6, 21.8.
MS (EI, 70eV) m/z 242 (30), 196 (11), 114 (12), 113 (17), 101 (26), 83 (19), 81 (100), 55 (21), 53 (11).

<Example 1-10-1: Synthesis of benzyl 5-formyloxyhexanoate>
δ-Hexalactone (11.4 g, 0.10 mol), benzyl formate (136.1 g, 1.0 mol) and p-toluenesulfonic acid (0.48 g, 2.5 mmol) were placed in a 200 mL two-neck flask and stirred overnight at room temperature. The reaction solution was washed with saturated sodium bicarbonate water and saturated saline, and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and the resulting filtrate was distilled under reduced pressure to recover benzyl formate (120.8 g). The distillation residue (23.4 g) was distilled under reduced pressure to obtain the desired benzyl 5-formyloxyhexanoate (16.3 g) (yield 65%).

<Example 1-10-2: Synthesis of 5-formyloxyhexanoic acid>
Benzyl 5-formyloxyhexanoate (16.0 g, 63.9 mmol), ethyl acetate (64 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.8 g) were placed in a 200 mL flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the resulting filtrate was concentrated under reduced pressure and dried under reduced pressure (up to 40° C.) to obtain the desired 5-formyloxyhexanoic acid (10.3 g).

<Example 1-10-3: Synthesis of S-furfuryl 5-formyloxyhexanethioate>

In a nitrogen atmosphere, the crude 5-formyloxyhexanoic acid (5.0 g, 31.2 mmol) obtained in the previous step and diethyl ether (140 mL) were placed in a 200 mL four-neck flask and stirred while cooling with ice water. Triethylamine (3.8 g, 37.4 mmol) was added dropwise to the mixture and stirred for 15 minutes while cooling with ice water. Next, a solution of pivaloyl chloride (4.1 g, 34.3 mmol) in diethyl ether (30 mL) was added dropwise over 0.5 hours while cooling with ice water, and stirred for 1 hour while cooling with ice water. The mixture was then filtered through a paper filter (rinsed with 50 mL of diethyl ether).

The filtrate and triethylamine (31 mL) were placed in a 300 mL four-neck flask and stirred under ice-water cooling. A solution of furfuryl mercaptan (4.3 g, 37.4 mmol) in diethyl ether (10 mL) was added dropwise and stirred at the same temperature for 2.5 hours, and then stirred at room temperature overnight. The resulting reaction solution was washed successively with saturated aqueous sodium carbonate and saturated saline, and dried over anhydrous magnesium sulfate. The crude product (8.9 g) obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain a purified product (5.5 g). This was purified by distillation under reduced pressure to obtain the desired S-furfuryl 5-formyloxyhexanoate (5.0 g) (this product is referred to as product 1-10 of the present invention). The yield from benzyl 5-formyloxyhexanoate was 63%.

<<Physical properties of products 1-10 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.01 (s, 1H), 7.30 (dd, 1H, J = 2.0Hz, 0.8Hz), 6.27 (dd, 1H, J = 3.2Hz, 2.0Hz), 6.19 (br d, 1H, J = 3.2Hz), 4.98-5.23 (m, 1H) 4.13 (s, 2H), 2.57 (t, 2H, J=7.2Hz), 1.52-1.77 (m, 4H), 1.23 (d, 3H, J=6.8Hz).
¹³ C NMR (CDCl ₃ , 100 MHz) δ 197.7, 160.7, 150.4, 142.2, 110.5, 107.9, 70.3, 43.2, 34.8, 25.6, 21.2, 19.9.
MS (EI, 70eV) m/z 256 (13), 210 (29), 129 (14), 115 (14), 113 (9), 112 (15), 101 (10), 97 (20), 81 (100), 69 (30), 55 (13), 53 (10).

<Example 1-11-1: Synthesis of benzyl 4-formyloxybutanoate>
Benzyl 4-formyloxybutanoate was synthesized in the same manner as in Example 1-3-1.

<Example 1-11-2: Synthesis of 4-formyloxybutanoic acid>

In a 200 mL two-neck flask, benzyl 4-formyloxybutanoate (8.9 g, 40 mmol), ethyl acetate (40 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.09 g) were sequentially placed and stirred under a hydrogen atmosphere for 6 hours. The reaction solution was filtered through Celite and washed with ethyl acetate, after which the filtrate was subjected to the subsequent reaction.

<Example 1-11-3: Synthesis of Sp-mentha-1-en-8-yl 4-formyloxybutanethioate>
The above-mentioned solution and triethylamine (4.9 g, 48 mmol) were added to a 300 mL three-neck flask and cooled with ice water. Pivaloyl chloride (5.3 g, 44 mmol) was added and stirred at the same temperature for 3 hours. Triethylamine (9.8 g, 96 mmol), 4-dimethylaminopyridine (0.25 g, 2 mmol) and p-mentha-1-ene-8-thiol (thioterpineol, 6.8 g) were added to the reaction solution and stirred at room temperature overnight. Water was added to the reaction solution and extracted with ethyl acetate. The organic phase was washed with water, saturated sodium bicarbonate solution and saturated saline in that order, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography, and the main fraction was distilled under reduced pressure (136-137°C/0.2 kPa) to obtain the desired thioester as a colorless oily substance (4.38 g, 15.4 mmol, this is the present invention product 1-11). The yield based on benzyl 4-formyloxybutanoate was 39%.

<<Physical properties of products 1-11 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.04 (s, 1H), 5.35 (dd, 1H, J = 3.2Hz, 2.0Hz), 4.18 (t, 2H, J = 7.2Hz), 2.56 (t, 2H, J = 7.2Hz), 1.80-2.12 (m, 8H), 1.63 (br s, 3H), 1.47 (s, 3H), 1.46 (s-3H).
¹³ C NMR (CDCl ₃ , 100 MHz) δ 199.0, 160.9, 134.0, 120.3, 62.8, 55.7, 42.8, 40.8, 31.1, 26.9, 24.9, 24.5, 24.4, 24.3, 23.2.
MS (EI, 70eV) m/z 284 (0.1), 170 (12), 169 (100), 137 (16), 136 (68), 121 (66), 107 (11), 95 (17), 93 (49), 87 (14), 81 (40), 75 (11), 69 (14), 43 (11 ), 41(13).

<Example 1-12-1: Synthesis of benzyl 4-formyloxydodecanoate>

γ-Dodecalactone (9.92 g, 50 mmol), benzyl formate (34.04 g, 250 mmol) and p-toluenesulfonic acid (0.48 g) were placed in a 200 mL recovery flask and stirred at room temperature for 24 hours. After diluting the reaction solution with hexane (100 mL), the organic phase was washed successively with saturated sodium bicarbonate water, tap water and saturated saline, and concentrated under reduced pressure. The residue was distilled under reduced pressure to recover the excess benzyl formate. The distillation residue (9.89 g) was purified by silica gel column chromatography to obtain the desired 4-formyloxydodecanoate benzyl as a colorless oily substance (0.43 g, 1.28 mmol) (yield 2%).

<Example 1-12-2: Synthesis of 4-formyloxydodecanoic acid>

Benzyl 4-formyloxydodecanoate (4.29 g, 12.8 mmol), 99% ethanol (20 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.06 g) were placed in a 100 mL two-neck flask and stirred at room temperature under a hydrogen atmosphere for 2 hours. The reaction solution was filtered through Celite, and the resulting filtrate was concentrated under reduced pressure to obtain crude 4-formyloxydodecanoic acid as a white solid (2.95 g, 12.1 mmol, 94%).

<Example 1-12-3: Synthesis of S-butan-2-yl 4-formyloxydodecanethioate>

In a 100 mL two-neck flask, the crude 4-formyloxydodecanoic acid (1.42 g) obtained in the previous step and methylene chloride (20 mL) were placed, followed by triethylamine (1.18 g) and pivaloyl chloride (0.88 g) under ice-water cooling, and stirring at the same temperature for 1 hour. Additional triethylamine (1.18 g) was added to the reaction solution, followed by 2-butanethiol (0.65 g) and stirring for 1 hour under ice-water cooling, followed by stirring overnight at room temperature. Tap water and diethyl ether were added to the resulting reaction solution, followed by stirring. After separating the lower layer, the organic phase was washed with saturated saline and dried over anhydrous magnesium sulfate. After drying, the solution was filtered and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired 4-formyloxydodecanethioic acid S-butan-2-yl (0.87 g, 2.75 mmol, yield 47%, referred to as product 1-12 of the present invention).

<<Physical properties of products 1-12 of the present invention>>
¹ H NMR (CDCl ₃ , 400 MHz) δ 8.08 (s, 1H), 4.91-5.04 (m, 1H), 3.45-3.55 (m, 1H), 2.54-2.59 (m, 2H), 1.84-2.04 (m, 2H), 1.24-1.64 (m, 16H), 0 95 (t, 3H, J=7.6Hz) 0.86-0.89 (m, 6H).
^13C NMR ( _CDCl3 , 100MHz) δ 198.8, 160.8, 73.2, 40.2, 39.9, 34.0, 31.8, 29.4, 29.4, 29.4, 29.2, 26.5, 25.1, 22.6, 20.8, 14.1, 11.4.
MS (EI, 70eV) m/z 316 (2), 199 (100), 181 (87), 163 (71), 111 (22), 97ZZ (51), 85 (21), 83 (46), 69 (30), 57 (39), 55 (43), 43 (23), 41 (25).

<Example 1-13-1: Synthesis of benzyl 5-formyloxytetradecanoate>

δ-Tetradecalactone (11.32 g, 50 mmol), benzyl formate (34.04 g) and p-toluenesulfonic acid (0.48 g) were added in order to a 200 mL recovery flask and stirred at room temperature for 23 hours. After diluting the reaction solution with hexane, the organic phase was washed with saturated sodium bicarbonate water, tap water and saturated saline, and concentrated under reduced pressure. The residue was distilled under reduced pressure (up to 76°C/0.2 kPa) to recover excess benzyl formate, and the residue (17.14 g) was purified by silica gel column chromatography to obtain the desired benzyl 5-formyloxytetradecanoate as a colorless oily substance (12.65 g, 34.9 mmol, 70%).

<Example 1-13-2: Synthesis of 5-formyloxytetradecanoic acid>

Benzyl 5-formyloxytetradecanoate (1.16 g, 3.2 mmol), 99% ethanol (20 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.08 g) were sequentially placed in a 100 mL two-neck flask and stirred overnight at room temperature under a hydrogen atmosphere. After filtering the reaction solution through Celite, the filtrate was concentrated under reduced pressure to obtain crude 5-formyloxytetradecanoic acid.

<Example 1-13-3: Synthesis of S-butan-2-yl 5-formyloxytetradecanethioate>

5-formyloxytetradecanoic acid (1.00 g), dichloromethane (10 mL), and triethylamine (0.74 g) were sequentially placed in a 100 mL two-neck flask, cooled with ice water, pivaloyl chloride (0.55 g) was added, and the mixture was stirred at the same temperature for 1 hour. Additional triethylamine (0.74 g) was added to the reaction solution, and 2-butanethiol (0.41 g) was added dropwise, and the mixture was stirred at room temperature overnight. Water was added to the reaction solution, and the mixture was extracted with diethyl ether. The organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product (2.71 g) was purified by silica gel column chromatography to obtain the desired 5-formyloxytetradecanethioic acid S-butan-2-yl as a slightly yellow oily substance (0.60 g, yield 47%, this is the present invention product 1-13).

<<Physical properties of product 1-13 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.08 (s, 1H), 4.99 (br qui, 1H, J = 6.0Hz), 3.50 (sex, 1H, J = 6.8Hz) 2.52 (t, 2H, J = 7.2Hz), 1.22-1.80 (m, 2 2H), 0.95 (t, 3H, J=7.6Hz) 0.88 (t, 3H, J=6.8Hz).
¹³ C NMR (CDCl ₃ , 100 MHz) δ 199.3, 161.0, 73.8, 43.6, 40.8, 33.9, 33.1, 31.9, 29.5, 29.4, 29.3, 26.5, 25.2, 22.7, 21.3, 20.8, 14.1, 11.4.
MS (EI, 70eV) m/z 344 (1), 227 (49), 209 (100), 191 (44), 111 (25), 109 (23), 97 (41), 95 (22), 83 (35), 71 (19), 69 (38), 57 (38), 55 (46), 43 (24), 4 1 (25).

<Example 1-14-1: Synthesis of benzyl 4-acetoxybutanoate>

γ-Butyrolactone (8.61 g, 100 mmol), benzyl acetate (75.1 g, 500 mmol) and p-toluenesulfonic acid (0.95 g) were sequentially placed in a 200 mL recovery flask and stirred at room temperature for 24 hours. After diluting the reaction solution with hexane, the organic phase was washed with saturated sodium bicarbonate water, tap water and saturated saline, and concentrated under reduced pressure. The residue was distilled under reduced pressure to recover the excess benzyl acetate (71.8 g), and the residue was purified by silica gel column chromatography to obtain the desired benzyl 4-acetoxybutanoate as a colorless oily substance (3.50 g, 14.8 mmol, yield 14%).

<Example 1-14-2: Synthesis of 4-acetoxybutanoic acid>

Benzyl 4-acetoxybutanoate (2.36 g, 10 mmol), 99% ethanol (20 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.12 g) were sequentially placed in a 100 mL two-neck flask and stirred at room temperature under a hydrogen atmosphere for 2 hours. The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure and subjected to the subsequent reaction.

<Example 1-14-3: Synthesis of S-butan-2-yl 4-acetoxybutanethioate>
The filtrate was placed in a 100 mL two-neck flask, dissolved in ethyl acetate (20 mL), and then triethylamine (1.8 mL) and pivaloyl chloride (1.32 g) were added in sequence under ice-water cooling, and the mixture was stirred at the same temperature for 1 hour. Additional triethylamine (2.6 mL) and 2-butanethiol (0.90 g) were added to the reaction solution, and the mixture was stirred at the same temperature for 1 hour and at room temperature overnight. Tap water was added to the reaction solution, and the mixture was stirred to separate the lower layer. The organic phase was washed with saturated sodium bicarbonate water and saturated saline in sequence, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired S-butan-2-yl 4-acetoxybutanethioate as a pale yellow oily substance (0.47 g, 2.15 mmol, this is the present invention product 1-14). The yield from benzyl 4-acetoxybutanoate was 22%.

<<Physical properties of product 1-14 of the present invention>>
^1H NMR ( _CDCl3 , 400MHz) δ 4.06 (t, 2H, J = 6.4Hz), 3.49 (sex, 1H, J = 6.8Hz), 2.59 (t, 2H, J = 7.2Hz), 2.02 (s, 3H), 1.97 (qui, 2H, J = 6 .8Hz), 1.57 (qui, 2H, J=7.2Hz), 1.26 (d, 2H, J=6.8Hz), 0.93 (t, 3H, J=6.8Hz).
^13C NMR ( _CDCl3 , 100MHz) δ 198.7, 171.0, 63.3, 40.9, 40.5, 29.5, 24.5, 20.9, 20.8, 11.4.
MS (EI, 70eV) m/z 218 (1), 129 (29), 88 (6), 87 (100), 57 (6), 43 (31), 41 (6).

<Example 1-15-1: Synthesis of benzyl 4-formyloxydodecanoate>
Benzyl 4-formyloxydodecanoate was synthesized in the same manner as in Example 1-12-1.

<Example 1-15-2: Synthesis of 4-formyloxydodecanoic acid>
4-Formyloxydodecanoic acid was synthesized in the same manner as in Example 1-12-2.

<Example 1-15-3: Synthesis of S-furfuryl 4-formyloxydodecanethioate>

In a 100 mL two-neck flask, the crude 4-formyloxydodecanoic acid (1.53 g) obtained in the previous step and methylene chloride (20 mL) were placed, followed by triethylamine (1.27 g) and pivaloyl chloride (0.94 g) under ice-water cooling, and stirring at the same temperature for 1 hour. Additional triethylamine (1.27 g) was added to the reaction solution, followed by furfuryl mercaptan (0.89 g) and stirring under ice-water cooling for 1 hour, and then stirring at room temperature overnight. Tap water and diethyl ether were added to the resulting reaction solution and stirred, and after separating the lower layer, the organic phase was washed with saturated saline and dried over anhydrous magnesium sulfate. After drying, the solution was filtered and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired 4-formyloxydodecanethioic acid S-furfuryl (1.63 g, 4.79 mmol, yield 77%, this is the present invention product 1-15).

<<Physical properties of product 1-15 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.04 (s, 1H), 7.32 (brd, 1H, J = 1.6Hz), 6.28 (dd, 1H, J = 3.2Hz, 1.6Hz), 6.20 (br d, 1H, J = 3.2Hz), 4.97-5. 03 (m, 1H) 4.17 (d, 1H, J = 14.8Hz), 4.13 (d, 1H, J = 14.8Hz), 2.55-2.66 (m, 2H), 1.86-2.06 (m, 2H), 1.24-1.75 (m, 14H), 0.88 (t, 3H, J = 6.8Hz).
^13C NMR ( _CDCl3 , 100MHz) δ 197.3, 160.8, 150.3, 142.2, 110.6, 107.9, 73.1, 39.5, 33.9, 31.8, 31.6, 29.4, 29.3, 29.2, 29.2, 25.6, 25.1, 22. 6,14.1.
MS (EI, 70eV) m/z 340 (8), 294 (30), 213 (19), 114 (9), 113 (10), 112 (14), 97 (13), 83 (13), 82 (11), 81 (100), 69 (11), 55 (15), 43 (9).

<Example 1-16-1: Synthesis of benzyl 5-formyloxytetradecanoate>
Benzyl 5-formyloxytetradecanoate was synthesized in the same manner as in Example 1-13-1.

<Example 1-16-2: Synthesis of 5-formyloxytetradecanoic acid>

Benzyl 5-formyloxytetradecanoate (1.16 g, 3.2 mmol), 99% EtOH (20 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.08 g) were sequentially placed in a 100 mL two-neck flask and stirred overnight at room temperature under a hydrogen atmosphere. The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure and subjected to the subsequent reaction.

<Example 1-16-3: Synthesis of S-furfuryl 5-formyloxytetradecanethioate>
The filtrate was placed in a 100 mL two-neck flask, dissolved in ethyl acetate (20 mL), and then triethylamine (1.4 mL) and pivaloyl chloride (0.90 g) were added in sequence under ice-water cooling, and the mixture was stirred at the same temperature for 1 hour. Additional triethylamine (2.8 mL) and furfuryl mercaptan (0.99 g) were added to the reaction solution, and the mixture was stirred at the same temperature for 1 hour and at room temperature overnight. Tap water was added to the reaction solution, and the mixture was stirred to separate the lower phase. The organic phase was washed with saturated sodium bicarbonate water and saturated saline in sequence, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired S-furfuryl 5-formyloxytetradecanethioate as a pale yellow oily substance (0.28 g, 0.76 mmol, this is the product of the present invention 1-16). The yield from benzyl 5-formyloxytetradecanoate was 24%.

<<Physical properties of product 1-16 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 8.08 (s, 1H), 7.32 (dd, 1H, J = 2.0Hz, 0.8Hz), 6.28 (dd, 1H, J = 3.2Hz, 2.0Hz), 6.20 (dd, 1H, J = 3.2Hz, 0.8 Hz), 4.98 (br qui, 1H, J=6.0Hz), 4.15 (s, 2H), 2.58 (t, 2H, J=6.8Hz), 1.23-1.80 (m, 20H), 0.88 (t, 3H, J=6.8Hz).
^13C NMR ( _CDCl3 , 100MHz) δ 197.7, 160.9, 150.4, 142.2, 110.6, 107.9, 73.7, 43.3, 33.9, 33.0, 31.9, 29.5, 29.5, 29.4, 29.3, 25.6, 25.2, 22. 7, 21.1, 14.1.
MS (EI, 70eV) m/z 368 (5), 322 (25), 241 (41), 213 (22), 209 (11), 114 (16), 13 (13), 112 (19), 97 (13), 83 (13), 82 (16), 81 (100), 69 (16), 55 (19), 43(11).

<Example 1-17-1: Synthesis of benzyl 4-acetoxybutanoate>
Benzyl 4-acetoxybutanoate was synthesized in the same manner as in Example 1-14-1.

<Example 1-17-2: Synthesis of 4-acetoxybutanoic acid>

Benzyl 4-acetoxybutanoate (2.36 g, 10 mmol), 99% ethanol (20 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.12 g) were sequentially placed in a 100 mL two-neck flask and stirred at room temperature under a hydrogen atmosphere for 2 hours. The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure and subjected to the subsequent reaction.

<Example 1-17-3: Synthesis of S-furfuryl 4-acetoxybutanethioate>
The filtrate was added to a 100 mL two-neck flask, dissolved in ethyl acetate (20 mL), and then triethylamine (1.8 mL) and pivaloyl chloride (1.32 g) were added in sequence under ice-water cooling, and the mixture was stirred at the same temperature for 1 hour. Additional triethylamine (2.6 mL) and furfuryl mercaptan (1.14 g) were added to the reaction solution, and the mixture was stirred at the same temperature for 1 hour and at room temperature overnight. Tap water was added to the reaction solution, and the mixture was stirred to separate the lower phase. The organic phase was washed with saturated sodium bicarbonate water and saturated saline in sequence, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired S-furfuryl 4-acetoxybutanethioate as a pale yellow oily substance (0.36 g, 1.46 mmol, this is the present invention product 1-17). The yield from benzyl 4-acetoxybutanoate was 15%.

<<Physical properties of product 1-17 of the present invention>>
^1H NMR (CDCl ₃ , 400MHz) δ 7.31 (br d, 1H, J = 1.6Hz), 6.28 (dd, 1H, J = 3.2Hz, 1.6Hz), 6.20 (br d, 1H, J = 3.2Hz), 4.15 (s, 2H) 4.08 (t, 2H, J=6.4Hz), 2.66 (t, 2H, J=7.6Hz), 1.97-2.04 (m, 5H).
^13C NMR ( _CDCl3 , 100MHz) δ 197.2, 170.9, 150.3, 142.2, 110.6, 107.9, 63.1, 40.2, 25.6, 24.3, 20.8.
MS (EI, 70eV) m/z 242 (15), 182 (30), 156 (12), 129 (27), 113 (20), 87 (86), 81 (100), 53 (13), 43 (47).

<Example 1-18-1: Synthesis of benzyl 6-formyloxyhexanoate>

ε-caprolactone (23.65 g), benzyl formate (141.05 g), and p-toluenesulfonic acid (2.00 g) were added in order to a 300 mL recovery flask and allowed to react overnight at room temperature. After washing the reaction solution with 5% sodium bicarbonate water and saturated saline, the organic phase was distilled under reduced pressure to obtain the desired benzyl 6-formyloxyhexanoate as a colorless oily substance (25.28 g).

<Example 1-18-2: Synthesis of 6-formyloxyhexanoic acid>

Benzyl 6-formyloxyhexanoate (6.0 g), ethyl acetate (15 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.15 g) were sequentially placed in a 300 mL recovery flask and stirred under a hydrogen atmosphere for 48 hours. The reaction solution was filtered through Celite and washed with ethyl acetate, after which the filtrate was subjected to the subsequent reaction.

<Example 1-18-3: Synthesis of 6-formyloxyhexanethio S-acid>
The filtrate and triethylamine (4.9 g) were placed in a 300 mL three-neck flask and cooled with ice water. Pivaloyl chloride (4.4 g) was then added and stirred at the same temperature for 30 minutes. Triethylamine (4.9 g) was added to the reaction solution, hydrogen sulfide was blown in for 2 hours under ice water cooling, and the mixture was stirred overnight at room temperature. A 15% aqueous citric acid solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phase was washed successively with tap water and saturated saline, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue (10.84 g) was distilled under reduced pressure to obtain a distillate as a mixture of thioacid and carboxylic acid (2.15 g), which was then purified by silica gel column chromatography and dried in vacuum to obtain the desired 6-formyloxyhexanethio S-acid as a pale yellow oily substance (1.01 g, 5.7 mmol, this is the product of the present invention 1-18). The yield from benzyl 6-formyloxyhexanoate was 24%.

<<Physical properties of product 1-18 of the present invention>>
¹ H NMR (CDCl ₃ , 400 MHz) δ 8.05 (s, 1H), 4.14-4.19 (m, 2H), 2.63 (t, 2H, J=7.2Hz), 1.64-1.74 (m, 4H), 1.38-1.48 (m, 2H).
^13C NMR ( _CDCl3 , 100MHz) δ 197.4, 161.1, 63.5, 45.4, 28.1, 25.1, 24.8.
MS (EI, 70eV) m/z 115 (68), 97 (56), 73 (19), 69 (100), 55 (47), 42 (11), 41 (73), 31 (15), 29 (11).

<Example 1-19-1: Synthesis of benzyl 6-acetoxyhexanoate>

ε-caprolactone (25.0 g), benzyl acetate (164.5 g), and p-toluenesulfonic acid (2.20 g) were sequentially placed in a 300 mL recovery flask and allowed to react overnight at room temperature. After washing the reaction solution with 5% sodium bicarbonate water and saturated saline, the organic phase was distilled under reduced pressure to obtain the desired benzyl 6-acetoxyhexanoate as a colorless oily substance (6.0 g).

<Example 1-19-2: Synthesis of 6-acetoxyhexanoic acid>

Benzyl 6-acetoxyhexanoate (6.0 g), ethyl acetate (15 mL), and carbon-supported palladium catalyst (5% Pd-C, wet type, 0.15 g) were sequentially placed in a 300 mL recovery flask and stirred under a hydrogen atmosphere for 48 hours. The reaction solution was filtered through Celite and washed with ethyl acetate, after which the filtrate was subjected to the subsequent reaction.

<Example 1-19-3: Synthesis of 6-acetoxyhexanethio S-acid>
The filtrate and triethylamine (4.9 g) were placed in a 300 mL three-neck flask and cooled with ice water. Pivaloyl chloride (4.4 g) was then added and stirred at the same temperature for 30 minutes. Triethylamine (4.9 g) was added to the reaction solution, hydrogen sulfide was blown in for 2 hours under ice water cooling, and the mixture was stirred overnight at room temperature. A 15% aqueous citric acid solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phase was washed successively with tap water and saturated saline, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue (10.84 g) was distilled under reduced pressure to obtain a distillate as a mixture of thioacid and carboxylic acid (2.15 g), which was then purified by silica gel column chromatography and dried in vacuum to obtain the desired 6-acetoxyhexanethio S-acid as a pale yellow oily substance (2.04 g, 10.7 mmol, this is the product of the present invention 1-19). The yield from benzyl 6-acetoxyhexanoate was 47%.

<<Physical properties of product 1-19 of the present invention>>
¹ H NMR (CDCl ₃ , 400MHz) δ 4.05 (t, 2H, J=6.8Hz) 2.63 (t, 2H, J=7.2Hz), 2.04 (s, 3H), 1.60-1.80 (m, 4H), 1.34-1.47 (m, 2H).
^13C NMR ( _CDCl3 , 100MHz) δ 197.5, 171.2, 64.1, 45.5, 28.2, 25.2, 24.9, 21.0.
MS (EI, 70eV) m/z 115 (100), 97 (43), 73 (13), 69 (42), 55 (28), 43 (67), 41 (22).

Example 2: Odor characteristics of the present compound The odor evaluation of the present compound was carried out by the following procedure. 1% ethanol solutions of the present invention products 1-1 to 1-19 synthesized in Example 1 were prepared, respectively, and named the present invention products 2-1 to 2-19. The present invention products 2-1 to 2-19 were smelled by five well-trained panelists with 10 years or more of experience, and they were asked to comment on the odors they perceived. Representative comments are shown in Table 1.

Example 3 Effect of Addition to Flavor Composition (Milk-like) According to the formulation in Table 2, a milk-based blend flavor composition was prepared.

The flavor compositions of the present invention, Products 1-1 to 1-19, diluted with ethanol as necessary, were added to a milk-based blended flavor composition so that the concentration of the present compound in the milk-based blended flavor composition was the concentration shown in Table 3, to prepare the flavor compositions of the present invention, Products 3-1 to 3-57. Then, sensory evaluation was performed on the obtained flavor compositions of the present invention, Products 3-1 to 3-57, by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the aroma of the present invention, Products 3-1 to 3-57, in comparison with a control product, a milk-based blended flavor composition to which none of Products 1-1 to 1-19 of the present invention was added.

The results of the sensory evaluation are shown in Table 3.

As shown in Table 3, it was confirmed that the flavoring composition containing the compound of the present invention imparts a fresh and rich flavor to the milk-like flavor composition.

Example 4 Effect of Addition to Fragrance Composition (Grapefruit-like) According to the formulation in Table 4, a grapefruit-based blended fragrance composition was prepared.

To a grapefruit-based blended fragrance composition, the present invention products 1-1 to 1-19 were added as flavor-imparting compositions, diluted with ethanol as necessary, so that the concentration of the present compound in the grapefruit-based blended fragrance composition was the concentration shown in Table 5, to prepare the fragrance compositions of the present invention products 4-1 to 4-57. Then, the obtained fragrance compositions of the present invention products 4-1 to 4-57 were subjected to a sensory evaluation by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the aroma of the present invention products 4-1 to 4-57 in comparison with a grapefruit-based blended fragrance composition to which none of the present invention products 1-1 to 1-19 was added, which was used as a control product.

The results of the sensory evaluation are shown in Table 5.

As shown in Table 5, it was confirmed that the flavoring composition containing the compound of the present invention imparts a fresh feeling and a peeling feeling to the grapefruit-like flavor composition.

Example 5 Effect of Addition to Food and Drink (Mango Flavored Beverage) Invention Products 1-1 to 1-19, diluted with ethanol as necessary, were added as flavor-imparting compositions to a commercially available beverage containing 30% mango juice (hereinafter referred to as mango-based beverage) so that the concentrations of the present compound in the mango-based beverage were as shown in Table 6, to prepare mango-flavored beverages of Invention Products 5-1 to 5-57.

The resulting mango-flavored beverages, Invention Products 5-1 to 5-57, were subjected to a sensory evaluation by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the difference in flavor between Invention Products 5-1 to 5-57 and a control product, a mango-based beverage to which no Invention Products 1-1 to 1-19 were added.

The results of the sensory evaluation are shown in Table 6.

As shown in Table 6, it was confirmed that the flavor imparting composition containing the compound of the present invention imparts a pulpy, ripe, and juicy feel to the mango-flavored beverage, improving the flavor of the mango-flavored beverage. As shown in Invention Products 5-31 to 5-33, it was confirmed that the flavor imparting composition containing S-p-mentha-1-en-8-yl 4-formyloxybutanethioate (Invention Product 1-11) is compatible with the aroma of mango and has the effect of imparting a juicy feel over a wide concentration range.

[Example 6] Effect of Addition to Food and Beverage (Beer-Flavored Beverage) The present invention products 1-1 to 1-19 were added as flavor-imparting compositions, diluted with ethanol as necessary, to commercially available non-alcoholic beer so that the concentration of the present compound in the non-alcoholic beer was the concentration shown in Table 7, to prepare beer-flavored beverages of the present invention products 6-1 to 6-19.

The resulting beer-flavored beverages, Products 6-1 to 6-19 of the present invention, were subjected to a sensory evaluation by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the difference in flavor between Products 6-1 to 6-19 of the present invention and a non-alcoholic beer to which none of Products 1-1 to 1-19 of the present invention was added, which was used as a control product.

The results of the sensory evaluation are shown in Table 7.

As shown in Table 7, it was confirmed that the flavor imparting composition containing the present compound imparts a refreshing bitter flavor and malty aroma to the beer-flavored beverage, improving the flavor of the beer-flavored beverage.

[Example 7] Effect of Addition to Food and Beverage (Coffee-Flavored Beverage) The present invention products 1-1 to 1-19, diluted with ethanol as necessary, were added as flavor-imparting compositions to commercially available black coffee so that the concentrations of the present compounds in the black coffee were as shown in Table 8, to prepare coffee-flavored beverages of the present invention products 7-1 to 7-57.

The resulting coffee-flavored beverages, Products 7-1 to 7-57 of the present invention, were subjected to a sensory evaluation by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the difference in flavor between Products 7-1 to 7-57 of the present invention and a control product, black coffee to which none of Products 1-1 to 1-19 of the present invention had been added.

The results of the sensory evaluation are shown in Table 8.

As shown in Table 8, it was confirmed that the flavor imparting composition containing the compound of the present invention imparts a freshly ground, freshly brewed, and roasted flavor to a coffee-flavored beverage, thereby improving the flavor of the coffee-flavored beverage. As shown in Products 7-31 to 7-33 of the present invention, it was confirmed that the flavor imparting composition containing S-p-mentha-1-en-8-yl 4-formyloxybutanethioate (Product 1-11 of the present invention) is compatible with the aroma of coffee and has the effect of imparting a freshly ground, freshly brewed, and fragrant flavor over a wide concentration range.

Example 8 Effect of Addition to Foods and Beverages (Various Favourite Beverages (Black Tea, Barley Tea, Cocoa)) The flavouring compositions containing the present invention products 1-1 to 1-19, diluted with ethanol as necessary, were added to commercially available unsweetened black tea, barley tea, and cocoa so that the concentrations of the present compound in each commercially available product were as shown in Table 9, to prepare favourite beverages of the present invention products 8-1 to 8-57.

Then, the obtained beverages of the present invention products 8-1 to 8-57 were subjected to a sensory evaluation by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the difference in flavor between the present invention products 8-1 to 8-57 and each of the commercial products to which none of the present invention products 1-1 to 1-19 was added, which were used as controls.

The results of the sensory evaluation are shown in Table 9.

As shown in Table 9, it was confirmed that the flavoring composition containing the compound of the present invention imparts the bitterness and/or aroma of tea leaves to a beverage of choice, improving the flavor of the beverage of choice.

Example 9 Effect of Addition to Food and Drink (Soup) The present invention products 1-1 to 1-19, diluted with ethanol as necessary, were added as flavor-imparting compositions to commercially available onion consommé soup (retort cooked product) so that the concentrations of the present compound in the onion consommé soup were as shown in Table 10, to prepare soups of the present invention products 9-1 to 9-19.

Then, a sensory evaluation was conducted on the obtained soups of the present invention products 9-1 to 9-19 by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was conducted by having the panelists comment on the difference in flavor between the present invention products 9-1 to 9-19 and an onion consommé soup to which none of the present invention products 1-1 to 1-19 was added, which was used as a control product.

The results of the sensory evaluation are shown in Table 10.

As shown in Table 10, it was confirmed that the flavor imparting composition containing the present compound imparts savory flavor, richness, roasted meat flavor, and/or spicy flavor to soup, improving the flavor of the soup.

[Example 10] Effect of Addition to Food and Drink (Ice Cream) According to the recipe in Table 11, ice cream (base) was prepared.

The flavor-imparting compositions of the present invention, 1-1 to 1-19, diluted with ethanol as necessary, were added to ice cream (base) so that the concentration of the present compound in the ice cream (base) was the concentration shown in Table 12, to prepare ice creams of the present invention, 10-1 to 10-19.

The resulting ice creams of the present invention products 10-1 to 10-19 were subjected to a sensory evaluation by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the difference in flavor between the present invention products 10-1 to 10-19 and an ice cream (base) containing none of the present invention products 1-1 to 1-19 as a control product.

The results of the sensory evaluation are shown in Table 12.

As shown in Table 12, it was confirmed that the flavoring composition containing the present compound imparts a milk-like freshness to ice cream and improves the flavor of ice cream.

[Example 11] Effect of Addition to Food and Drink (Cookies) According to the recipe in Table 13, cookie dough was prepared.

The flavor-imparting compositions of the present invention, 1-1 to 1-19, diluted with ethanol as necessary, were added to the prepared cookie dough so that the concentration of the present compound in the cookie dough was the concentration shown in Table 14, and the cookie dough was baked at 220°C for 7 minutes to prepare cookies of the present invention, 11-1 to 11-19.

The resulting cookies of the present invention products 11-1 to 11-19 were subjected to a sensory evaluation by 15 well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the difference in flavor between the present invention products 11-1 to 11-19 and the control product, which was a cookie baked under the above conditions without adding any of the present invention products 1-1 to 1-19.

The results of the sensory evaluation are shown in Table 14.

As shown in Table 14, it was confirmed that the flavor imparting composition containing the present compound imparts to cookies a savory flavor (like burnt butter), a rich egg flavor, a roasted wheat flavor, and/or a freshly baked flavor, thereby improving the flavor of the cookies.

[Example 12] Effect of Addition to Cosmetics (Kitchen Detergents) The present invention products 1-1 to 1-19 were added as flavoring compositions to commercially available kitchen detergents with orange, berry, rose, and peach fragrances so that the concentrations of the present compounds in the kitchen detergents were the concentrations shown in Table 15, to prepare kitchen detergents of the present invention products 12-1 to 12-76. Then, sensory evaluation was performed on the obtained kitchen detergents of the present invention products 12-1 to 12-76 by five well-trained panelists (with 10 years or more of experience). The sensory evaluation was performed by having the panelists comment on the difference in odor when comparing the above-mentioned kitchen detergents to which the present invention product was not added with the control product and the products of the present invention 12-1 to 12-76 with the control product.

The results of the sensory evaluation are shown in Table 15.

As shown in Table 15, it was confirmed that the flavoring composition containing the compound of the present invention is useful for improving the odor of detergents with citrus, fruit, or floral odors. It was also confirmed that the flavoring composition containing S-p-mentha-1-en-8-yl 4-formyloxybutanethioate (Product 1-11 of the present invention) is compatible with detergents with orange, berry, rose, and peach odors, and has a fresh feeling imparting effect over a wide concentration range of 0.001 to 1 ppm, including the concentrations shown in Table 15.

Claims (5)

A compound represented by the following formula (1):

[In formula (1), n represents an integer of 0 to 2, R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 2 to 5 carbon atoms, a furfuryl group, or a p-mentha-1-en-8-yl group, and R ³ represents a hydrogen atom or a methyl group.] A flavoring composition comprising the compound according to claim 1. A consumer product comprising the compound of claim 1 or the flavoring composition of claim 2. A method for imparting flavor to a flavor imparting composition, comprising the step of adding the compound according to claim 1 or the flavor imparting composition according to claim 2 to another flavor imparting composition. A method for flavoring a consumer product, comprising the step of adding the compound according to claim 1 or the flavoring composition according to claim 2 to the consumer product.