Flavor improvers and pungency enhancers

Abstract

To provide a new compound useful for enhancing the flavor and spiciness of an article [Solution] We provide a flavor improving agent containing a compound represented by formula (1) as an active ingredient, and a flavor composition containing the flavor improving agent. The wavy line in formula (1) indicates that the (Z) and (E) isomers may be contained in any ratio. n is 1 to 9. TIFF2026042558000018.tif33111

Description

[Technical Field]

[0001] The present invention relates to flavor improvers, particularly pungency enhancers, consumable products containing them, and methods of incorporating them into consumable products. [Background technology]

[0002] Recently, consumer demands for foods, beverages, and cosmetics have become more sophisticated and diverse, with particular attention being paid to fragrance, and fragrance characteristics becoming an important factor in the appeal of products. For example, there is a growing demand for compounds that, when blended into products, can impart distinctive flavors, such as long-lasting and natural aromas, to the fragrance and taste of the products.

[0003] In particular, in recent years, the spiciness imparted to consumer goods such as foods and beverages by chili peppers, wasabi, mustard, pepper, Japanese pepper, ginger, etc. can enhance the flavor of the consumer goods, enhance the flavor by enjoying the spiciness itself, stimulate appetite, etc. Therefore, consumer goods such as spicy foods and beverages are enjoyed in a wide variety of ways in various cultural spheres.

[0004] Technologies related to pungent compounds have been investigated. For example, Patent Document 1 describes an efficient method for producing a ginger extract with a high content of shogaol, which has a strong pungent taste. Specifically, it describes that an extract with a high shogaol content can be produced by adding an organic acid to the ginger extract and then dehydrating it under reduced pressure. Patent Document 2 describes the extraction of hydroxysanshool from the oil extract of plants of the genus Zanthoxylum using an aqueous ethanol solution with an ethanol concentration of 35 to 65% by mass. Hydroxysanshool is useful as a pungent component with a strong numbing sensation unique to plants of the genus Zanthoxylum. Patent Document 3 describes that processed wasabi products to which isothiocyanates have been added can be imparted with the distinctive aroma of real wasabi and a pungent taste that evokes the authenticity of freshly grated wasabi.

[0005] However, these methods result in a change in flavor due to the addition of pungent components, and do not provide the flavor or spiciness desired by consumers. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-152130 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-103901 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-5414 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a novel compound that is useful for improving the flavor and enhancing the pungency of products. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have discovered that 1-(4-hydroxy-3-methoxyphenyl)-5-alken-3-one, which has not previously been known as a flavor compound, is useful for flavor enhancement. Specifically, they have discovered that 1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one and its analogs can achieve the above-mentioned problems of improving the flavor and enhancing the pungency of products, and have thus completed the present invention.

[0009] Thus, the present invention provides the following: [1] A flavor improver containing a compound represented by the following formula (1) as an active ingredient:

[0010] [ka]

[0011] [The wavy line in formula (1) indicates that the (Z) isomer and the (E) isomer may be contained in any ratio. n is an integer of 1 to 9.] [2] The flavor improver according to [1], which is a pungency enhancer. [3] A flavor composition containing the flavor improver according to [1]. [4] A pungent composition containing the flavor improver according to [2]. [5] A consumer product containing the flavor improver according to [1] or [2]. [6] A consumer product containing the flavor composition according to [3] and / or the pungent composition according to [4]. [7] A method for improving the flavor of consumer goods, comprising blending the flavor improver according to [1] into the consumer goods. [8] A method for enhancing the spiciness of a product containing a pungent component, comprising blending the flavor improver described in [2] into the product. [9] A compound represented by the following formula (2):

[0012] [ka]

[0013] [The wavy line in formula (2) indicates that the (Z) isomer and the (E) isomer may be contained in any ratio. n is 2 to 9.] [Effects of the Invention]

[0014] The present invention provides novel compounds that can be used to enhance the flavor and spiciness of various products. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in more detail below with reference to specific examples. In this specification, the symbol "to" indicates a range including a lower limit and an upper limit, and concentrations (ppt, ppb, ppm, etc.) and % indicate mass concentrations and mass %, respectively, unless otherwise specified.

[0016] (Compound represented by formula (1)) 1-(4-hydroxy-3-methoxyphenyl)-5-alken-3-ones represented by formula (1) (sometimes simply referred to as compounds of formula (1) in this specification) are a group of compounds that were previously unknown to have any fragrance or pungent taste, or to be usable for improving the flavor or enhancing the pungency of various products such as consumer goods, and the present inventors have been the first to confirm their usefulness for flavor improvement purposes.

[0017] [ka]

[0018] [The wavy line in formula (1) indicates that the (Z) isomer and the (E) isomer may be contained in any ratio. n is an integer of 1 to 9.]

[0019] The compound of the present invention, that is, the compound of formula (1), exhibits the effects of the present invention when used alone as the (Z) isomer shown in formula (3) or the (E) isomer shown in formula (4), but also exhibits the effects of the present invention when used as a mixture of the (Z) isomer and the (E) isomer.

[0020] [ka]

[0021] [n in formula (3) is 1 to 9.]

[0022] [ka]

[0023] [n in formula (4) is 1 to 9.]

[0024] Any compound of formula (1) can exhibit the effects of the present invention, but among them, compounds that particularly exhibit the effects of the present invention include 1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one, 1-(4-hydroxy-3-methoxyphenyl)undec-5-en-3-one, 1-(4-hydroxy-3-methoxyphenyl)dodec-5-en-3-one, 1-(4-hydroxy-3-methoxyphenyl)tridec-5-en-3-one, and 1-(4-hydroxy-3-methoxyphenyl)tetradec-5-en-3-one. Furthermore, the effects of the present invention can be fully exerted by using (E)-1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one, (E)-1-(4-hydroxy-3-methoxyphenyl)dodec-5-en-3-one, (E)-1-(4-hydroxy-3-methoxyphenyl)tetradec-5-en-3-one, (Z)-1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one, (Z)-1-(4-hydroxy-3-methoxyphenyl)dodec-5-en-3-one, or (Z)-1-(4-hydroxy-3-methoxyphenyl)tetradec-5-en-3-one.

[0025] (Compound represented by formula (2)) 1-(4-hydroxy-3-methoxyphenyl)-5-alken-3-one represented by formula (2) (sometimes simply referred to as the compound of formula (2) in this specification) was not only completely unknown to have a fragrance or a pungent taste, or to be usable for enhancing the flavor or spiciness of various products such as consumer goods, but it was also previously unknown as a compound.

[0026] [ka]

[0027] [The wavy line in formula (2) indicates that the (Z) isomer and the (E) isomer may be contained in any ratio. n is 2 to 9.]

[0028] (Method for producing the compound represented by formula (1)) The method for obtaining the compound of formula (1) of the present invention is not particularly limited, but it can be produced, for example, according to the following reaction route.

[0029] [ka]

[0030] [The wavy lines in the above reaction pathways indicate the (Z) or (E) isomer. n is 1 to 9.] That is, the hydroxyl group of methyl hydroferulate is protected with a tert-butyldimethylsilyl group, and aldehyde 2 is prepared via DIBAL reduction. 2-Alken-1-ol is brominated to prepare compound 3, and compound 4 is prepared via a Barbier reaction using compound 2 and compound 3. Compound 2 is added to compound 4 and an allylic rearrangement reaction is carried out to obtain compound 5. This is further oxidized with 2-iodoxybenzoic acid to obtain compound 6, which is then deprotected to obtain compound 1 of formula (1).

[0031] In particular, when it is desired to efficiently obtain the (E) isomer of formula (1), it can be produced, for example, according to the following reaction route.

[0032] [ka]

[0033] [The reaction pathway n is 1 to 9.]

[0034] That is, compound 3 in the above reaction formula and (-)-menthone are used to carry out a Grignard reaction to prepare compound 7. Compound 2 is added to compound 7 to carry out an allylic rearrangement reaction to obtain compound 5. Compound 5 is oxidized with 2-iodoxybenzoic acid to obtain compound 6. Then, deprotection is carried out to obtain compound 1 of formula (1), which is mainly composed of the (E) isomer.

[0035] (flavor improver) As used herein, flavor refers to one or more senses that can be changed by aroma, typically including smell and / or taste. In this specification, the term "flavor improvement" refers not only to pure flavor improvement, but also to the addition or enhancement of the flavor. Furthermore, flavor improvement may result in the enhancement, suppression, or improvement of senses other than smell and / or taste, such as coolness, warmth, texture (e.g., smoothness in the throat, hardness, viscosity, etc., also referred to as texture), and stimulating sensations such as pungency. In this specification, the flavor of a food or beverage may also be referred to as flavor.

[0036] The flavor improver of the present invention contains a predetermined amount of one or more compounds of formula (1), and can be blended into various articles to improve the flavor of the articles (the definition of flavor improvement is as described above).

[0037] The flavor improver of the present invention has a ginger-like odor, but when added to consumer goods, it usually does not significantly affect the flavor of the consumer goods themselves, although this depends on the concentration of the added agent. The flavor improver of the present invention also has a slightly sour odor.

[0038] (Spicy flavor enhancer) One aspect of flavor improvement according to the present invention is pungency enhancement. As used herein, the term "pungency enhancement" encompasses further improving the pungency of a product containing a pungent component, as well as raising a reduced pungency to normal or even higher levels. For example, if the pungency is improved when the enhancer of the present invention is applied to a normal amount of a pungent component, a product containing half the amount of the pungent component can be perceived as being at least as pungent as a product containing the full amount. In some cases, the term "pungency enhancement" refers to a phenomenon or effect in which a certain substance or condition makes a food or dish appear more spicy. This phenomenon occurs due to the interaction of the pungent component with other components or conditions, and is therefore induced by the addition of components other than the pungent enhancer of the present invention. Furthermore, the pungent enhancer of the present invention has the effects of being less irritating than other pungent components, exhibiting a slower onset of pungency than normal pungent components, and providing a longer-lasting pungency.

[0039] (Fragrance composition) The fragrance composition of the present invention contains a predetermined amount of one or more compounds of formula (1), and can be blended into various articles to improve the flavor of the articles (the definition of flavor improvement is as described above).

[0040] Examples of the fragrance composition of the present invention include, but are not limited to, compositions that can improve the scent of various items, i.e., so-called fragrances; various extracts that can improve the scent and / or taste of various items; other food additives that can improve the scent and / or taste of various foods and beverages; and additives that can improve the scent and / or taste of various cosmetics, medical and sanitary products.

[0041] The fragrance composition of the present invention may contain any component other than the compound of formula (1), but may also consist essentially of the compound of formula (1). When the fragrance composition of the present invention contains components other than the compound of formula (1), the concentration of the compound of formula (1) in the fragrance composition can be determined as desired depending on the intended use and fragrance characteristics of the fragrance composition. In this specification, concentration refers to the final concentration unless otherwise specified.

[0042] A preferred concentration range for the flavor improving agent of formula (1) contained in the flavor composition of the present invention is, for example, 10 ppb to 10%, and preferably 100 ppb to 1%, based on the total mass of the flavor composition. More specifically, the lower limit may be any of 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, 0.1%, or 1%, and the upper limit may be any of 10%, 1%, 0.1%, 100 ppm, 10 ppm, 1 ppm, or 100 ppb, and the range may 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, if the concentration of the compound of formula (1) in the fragrance composition is less than 10 ppb, the blending effect may be perceived as low, and if it exceeds 10%, the scent derived from the compound of formula (1) may be strong, making the fragrance characteristics of the fragrance composition to be blended undesirable. However, depending on the fragrance tone of the fragrance composition to be blended, the compound of formula (1) may be blended at a concentration below the lower limit or above the upper limit.

[0043] In addition to the compound of formula (1), the flavor composition of the present invention may further contain other optional compounds or components, such as various flavor compounds or flavor compositions, oil-soluble colorants, vitamins, functional substances, fish extracts, meat extracts, plant extracts, yeast extracts, animal and plant proteins, animal and plant protein hydrolysates, starch, dextrin, sugars, amino acids, nucleic acids, organic acids, and solvents. Examples of such compounds include natural essential oils, natural flavors, and synthetic flavors described in "Patent Office Gazette, Collection of Well-Known and Commonly Used Techniques (Fragrances) Part II: Food Flavors, published January 14, 2000," "Survey on the Actual Use of Food Flavoring Compounds in Japan" (Report of the Ministry of Health, Labour and Welfare's Research on 2000, Japan Flavor and Flavor Manufacturers' Association, published March 2001), and "Synthetic Flavors: Chemistry and Product Knowledge" (revised and expanded edition published December 20, 2016, edited by the Synthetic Flavors Editorial Committee, Chemical Daily Co., Ltd.).

[0044] Other examples of synthetic fragrance compounds include hydrocarbon compounds such as monoterpenes such as α-pinene, β-pinene, myrcene, camphene, and limonene, sesquiterpenes such as valencene, cedrene, caryophyllene, and longifolene, and 1,3,5-undecatriene.

[0045] Examples of alcohol compounds include saturated or unsaturated alcohols such as butanol, pentanol, 3-octanol, hexanol, (Z)-3-hexen-1-ol, prenol, and 2,6-nonadienol; terpene alcohols such as linalool, geraniol, citronellol, tetrahydromyrcenol, farnesol, nerolidol, cedrol, and terpineol; and aromatic alcohols such as benzyl alcohol, phenylethyl alcohol, and cinnamyl alcohol.

[0046] Examples of aldehyde compounds include saturated or unsaturated aldehydes such as acetaldehyde, hexanal, octanal, decanal, (E)-2-hexenal, and 2,4-octadienal; terpene aldehydes such as citronellal, hydroxycitronellal, citral, myrtenal, and perillaldehyde; and aromatic aldehydes such as benzaldehyde, cinnamaldehyde, amylcinnamaldehyde, vanillin, ethyl vanillin, heliotropin, and p-tolylaldehyde.

[0047] Examples of ketone compounds include saturated or unsaturated ketones such as 2-heptanone, 2-undecanone, 1-octen-3-one, and acetoin; 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 degradation products such as α-ionone, β-ionone, and β-damascenone; and aromatic ketones such as raspberry ketone.

[0048] Examples of furan or ether compounds include furfuryl alcohol, furfural, rose oxide, linalool oxide, menthofuran, theaspirane, estragole, eugenol, and 1,8-cineole.

[0049] Examples of the ester compound include aliphatic esters such as ethyl acetate, isoamyl acetate, ethyl butyrate, ethyl isobutyrate, isoamyl butyrate, ethyl 2-methylbutyrate, ethyl 3-methylbutyrate, 2-methylbutyl isobutyrate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate, ethyl caproate, isoamyl isovalerate, and ethyl nonanoate; terpene alcohol esters such as linalyl acetate, geranyl acetate, lavandulyl acetate, and terpenyl acetate; and aromatic esters such as benzyl acetate, benzyl butyrate, methyl salicylate, benzyl salicylate, methyl cinnamate, cinnamyl propionate, ethyl benzoate, cinnamyl isovalerate, and ethyl 3-methyl-2-phenylglycidate.

[0050] Examples of the lactone compound include saturated or unsaturated lactones such as γ-decalactone, γ-dodecalactone, δ-decalactone, δ-dodecalactone, 7-decen-4-olide, and 2-decen-5-olide.

[0051] Examples of the acid compound include saturated or unsaturated fatty acids such as acetic acid, butyric acid, octanoic acid, isovaleric acid, caproic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.

[0052] Examples of the nitrogen-containing compound include indole, skatole, pyridine, alkyl-substituted pyrazine, methyl anthranilate, and trimethylpyrazine.

[0053] Examples of sulfur-containing compounds include methanethiol, dimethyl sulfide, dimethyl disulfide, allyl isothiocyanate, 3-methyl-2-butene-1-thiol, 3-methyl-2-butanethiol, 3-methyl-1-butanethiol, 2-methyl-1-butanethiol, and furfuryl mercaptan.

[0054] 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.

[0055] Examples of various animal and plant extracts include herb or spice extracts, coffee, green tea, black tea, or oolong tea extracts, milk or dairy products, and various enzymatic decomposition products thereof using lipase and / or protease.

[0056] The fragrance composition of the present invention can be prepared by blending the compound of formula (1) in an appropriate solvent or dispersion medium by a known method.

[0057] The fragrance composition of the present invention is preferably in the form of a solution in which the compound of formula (1) or other components are dissolved in a water-soluble or oil-soluble solvent, an emulsion preparation, a powder preparation, or other solid preparation (such as solid fat).

[0058] Examples of water-soluble solvents include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, and propylene glycol. Among these, ethanol and glycerin are particularly preferred from the viewpoint of use in foods and beverages. Examples of oil-soluble solvents include vegetable oils and fats, animal oils and fats, refined oils and fats (e.g., 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.

[0059] In addition, to prepare an emulsion preparation, the compound of formula (1) can be emulsified with a water-soluble solvent and an emulsifier.The method for emulsifying the compound of formula (1) is not particularly limited, and various emulsifiers that have been 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, casein Quillaja saponin, sodium caseinate, etc. can be used to emulsify using a homomixer, colloid mill, rotating disk homogenizer, high-pressure homogenizer, etc., to obtain an emulsion with excellent stability. 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 part by mass of the compound of formula (1). Furthermore, to stabilize the emulsion, the aqueous solvent solution may contain, 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.

[0060] The emulsion thus obtained can be dried, if desired, to form a powder formulation. When powdering, sugars such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, and reduced starch syrup can also be appropriately blended, if necessary. The amounts of these can be appropriately selected depending on the desired properties of the powder formulation.

[0061] The fragrance composition of the present invention may further contain, if necessary, ingredients commonly used in fragrance compositions, such as solvents such as water and ethanol, and fragrance retention agents 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.

[0062] (Pungent composition) The pungent composition of the present invention contains a predetermined amount of one or more compounds of formula (1) and can be incorporated into various articles to enhance the spiciness of the articles (the definition of spiciness enhancement is as described above).

[0063] Examples of the pungent composition of the present invention include, but are not limited to, compositions that can enhance the spiciness of products containing pungent ingredients, i.e., so-called pungent ingredients; various extracts that can improve the spiciness of various items; other food additives that can improve the spiciness of various foods and beverages; and additives that can improve the spiciness of various cosmetics, pharmaceuticals, and sanitary products.

[0064] The pungent composition of the present invention may contain any component other than the compound of formula (1), but may also consist essentially of the compound of formula (1). When the pungent composition of the present invention contains components other than the compound of formula (1), the concentration of the compound of formula (1) in the pungent composition can be determined arbitrarily depending on the target compound of the pungent composition and the pungent characteristics.

[0065] A preferred concentration range for the pungency-improving agent of formula (1) in the pungency composition of the present invention is 10 ppb to 1%, preferably 100 ppb to 0.1%, based on the total mass of the pungency composition. More specifically, the lower limit can be 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, or 0.1%, and the upper limit can be 1%, 0.1%, 100 ppm, 10 ppm, 1 ppm, or 100 ppb. The range can be any combination of these lower and upper limits, but is not limited to these. Depending on the formulation of the pungency composition, a concentration of the compound of formula (1) in the pungency composition below 10 ppb may result in a perceived lack of effectiveness, while a concentration above 1% may result in an overly strong pungency of formula (1), affecting the flavor characteristics of the product to which it is added. Depending on the flavor characteristics of the pungent composition to be blended, the compound of formula (1) may be blended at a concentration below the lower limit or above the upper limit.

[0066] In addition to the compound of formula (1), examples of other optional compounds or components that may be contained in the pungent composition of the present invention include various types of pungent components or pungent compositions, oil-soluble pigments, 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.

[0067] Examples of pungent components include capsaicin, allyl isothiocyanate, piperine, sanshool, diallyl disulfide, and gingerol.

[0068] The pungent composition of the present invention is preferably in the form of a solution in which the compound of formula (1) or other components are dissolved in a water-soluble or oil-soluble solvent, an emulsion preparation, a powder preparation, or other solid preparation (such as solid fat).

[0069] Examples of water-soluble solvents include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, and propylene glycol. Among these, ethanol and glycerin are particularly preferred from the viewpoint of use in foods and beverages. Examples of oil-soluble solvents include vegetable oils and fats, animal oils and fats, refined oils and fats (e.g., 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.

[0070] In addition, to prepare an emulsion preparation, the compound of formula (1) can be emulsified with a water-soluble solvent and an emulsifier.The method for emulsifying the compound of formula (1) is not particularly limited, and various emulsifiers that have been 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, casein Quillaja saponin, sodium caseinate, etc. can be used to emulsify using a homomixer, colloid mill, rotating disk homogenizer, high-pressure homogenizer, etc., to obtain an emulsion with excellent stability. 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 part by mass of the compound of formula (1). Furthermore, to stabilize the emulsion, the aqueous solvent solution may contain, 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.

[0071] The emulsion thus obtained can be dried, if desired, to form a powder formulation. When powdering, sugars such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, and reduced starch syrup can also be appropriately blended, if necessary. The amounts of these can be appropriately selected depending on the desired properties of the powder formulation.

[0072] (Use in various items) A flavor improver containing the compound of formula (1) of the present invention as an active ingredient (hereinafter also referred to as flavor improver) and a fragrance composition containing said compound (hereinafter also referred to as the fragrance composition of the present invention) can be added in a predetermined amount to various articles having a flavor and / or fragrance. Examples of articles to which they can be added include fragrance compositions and consumer goods such as foods and beverages, cosmetics, and health and hygiene products. By adding the flavor improver or fragrance composition of the present invention to various articles having a flavor and / or fragrance, the natural feeling and freshness can be enhanced, and the fragrance and / or flavor can be improved.

[0073] The flavor improving agent or flavor composition of the present invention may be blended alone into articles such as consumer goods, or may be blended together with one or more selected from one or more water-soluble flavors, emulsified flavor compositions, arbitrary flavor compounds, and natural essential oils (for example, flavor compounds described in the aforementioned "Patent Office Gazette, Collection of Well-Known and Commonly Used Techniques (Fragrances) Part II Food Flavors," "Survey on the Actual Use of Food Flavoring Compounds in Japan," and "Synthetic Flavors: Chemistry and Product Knowledge").

[0074] Examples of foods and beverages that can be blended with the flavor improver or flavor composition of the present invention include citrus-flavored fruits such as oranges such as navel orange, Valencia orange, and bergamot; grapefruits such as orangelo and grapefruit; acidic citrus fruits such as lemon, lime, kabosu, sudachi, yuzu, shikuwasa, and daidai; mandarin orange, unshu mandarin, and ponkan; miscellaneous citrus fruits such as hassaku, kumquat, and sweetie; tangors such as iyokan; and pomelo; strawberry, blueberry, raspberry, apple, Fruit flavors such as cherry, plum, apricot, peach, pineapple, banana, melon, mango, papaya, kiwi, pear, grape, muscat, and Kyoho grapes; dairy flavors such as milk, yogurt, and butter; vanilla flavor; tea flavors such as green tea, black tea, and oolong tea; coffee flavor; cocoa flavor; mint flavors such as spearmint and peppermint; cinnamon, chamomile, cardamom, caraway, cumin, cloves, pepper, coriander, Japanese pepper, shiso, ginger, star anise, thyme, chili pepper, nutmeg, basil, and marjoram. These include foods and beverages with flavors such as various spice flavors such as corn, rosemary, laurel, and wasabi; various nuts such as almonds, cashew nuts, and walnuts; meat flavors such as beef, pork, and chicken; seafood flavors such as salmon, sardines, clams, shijimi clams, scallops, shrimp, crab, kelp, wakame seaweed, and nori seaweed; and alcoholic beverage flavors such as wine, brandy, whiskey, rum, gin, liqueur, sake, shochu, and beer. More specifically, carbonated drinks such as cola drinks, carbonated drinks with fruit juice, carbonated drinks with dairy products, and beer-flavored drinks are also included. Food beverages such as drinks, honey drinks, soy milk, vitamin supplement drinks, mineral supplement drinks, energy drinks, nutritious drinks, lactic acid bacteria drinks, and dairy drinks; beverages such as green tea, black tea, oolong tea, herbal tea, and coffee drinks; alcoholic beverages such as chuhai, cocktail drinks, sparkling wine, fruit wine, condiment wine, and other brewed alcoholic beverages (sparkling) or liqueurs (sparkling), including so-called "third beer"; desserts such as ice cream, lacto ice cream, frozen desserts, yogurt, pudding, jelly, and daily desserts, as well as mixes for making them;Examples include confectioneries such as caramel, candy, tablets, crackers, biscuits, cookies, pies, chocolates, and snacks, as well as mixes such as cake mixes for making them; general foods such as bread, soup, and various instant foods; condiments such as dressings, sauces, ponzu sauces, and spreads; and processed fruit products such as jams.

[0075] Furthermore, examples of cosmetics and health and hygiene products that can be blended with the flavor improving agent or fragrance composition of the present invention include cosmetics and health and hygiene products with fragrance tones such as bergamot, geranium, rose, bouquet, hyacinth, lilac, iris, orchid, and floral. More specific examples include perfumes; hair care products such as shampoo, conditioner, hair cream, and pomade; cosmetics such as eyeshadow and lipstick; health and hygiene detergents such as face soap, body soap, laundry soap, laundry detergent, disinfectant detergent, and deodorizing detergent; health and hygiene materials such as toothpaste, tissue paper, and toilet paper; and aromatic products such as room fresheners and car colognes.

[0076] In the present invention, the amount of the compound of formula (1) added to consumer goods such as foods and beverages and cosmetics, i.e., the concentration in the consumer goods, can be determined arbitrarily depending on the intended use and aroma or flavor of the consumer goods. For foods and beverages, the concentration range can be 10 ppt to 0.1%, preferably 100 ppt to 100 ppm, based on the total mass of the food or beverage. More specifically, the lower limit can be any of 10 ppt, 100 ppt, 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, and 100 ppm, and the upper limit can be any of 0.1%, 100 ppm, 10 ppm, 1 ppm, 100 ppb, 10 ppb, 1 ppb, and 100 ppt, and the range can be any combination of these lower and upper limits, but is not limited to these. In the case of cosmetics, the concentration range can be 100 ppt to 100 ppm, preferably 1 ppb to 10 ppm, relative to the total mass of the cosmetic. More specifically, the lower limit can be any of 100 ppt, 1 ppb, 10 ppb, 100 ppb, 1 ppm, and 10 ppm, and the upper limit can be any of 100 ppm, 10 ppm, 1 ppm, 100 ppb, 10 ppb, and 1 ppb, and the range can be any combination of these lower and upper limits, but is not limited to these.

[0077] Although it depends on the purpose of use, form, or aroma or flavor of each product, if the amount is less than 10 ppt for food and beverages or less than 100 ppt for fragrances and cosmetics, the flavor improving effect may not be felt due to the small amount, and if the amount exceeds 1000 ppm for food and beverages or 100 ppm for fragrances and cosmetics, the balance of the aroma and / or flavor of the product to which it is added may be disrupted, giving an odd sensation.

[0078] (For use in products containing pungent ingredients) The pungent component-containing product of the present invention is a product containing a pungent component, typically an edible product containing a pungent component. Examples of the target product include foods and beverages; oral medicines; oral medicines; oral care products such as toothpaste and mouthwash (including pharmaceuticals and quasi-drugs), and preferably foods and beverages.

[0079] Specific examples of foods and beverages include confectioneries such as rice crackers, biscuits, pretzels, cakes, chocolates, gum, candies, gummy candies, and tablet candies containing the aforementioned spicy ingredients; snack foods such as potato chips; soups such as instant soup and instant miso soup; frozen cooked foods such as frozen hamburgers and frozen takoyaki; chilled cooked foods such as chilled meatballs and chilled gyoza; other cooked foods such as tamagoyaki and corn dogs; alcoholic beverages such as chuhai and non-alcoholic chuhai; chilled desserts such as chilled pudding and fruit sauce; ice cream; frozen desserts such as soft mixes and ice creams; dry desserts such as dried jellies and dessert bases; frozen cooked rice products; cooked rice products such as risotto; noodles such as cup noodles, instant noodles, chilled ramen, and frozen pasta; other staple foods such as prepared bread and okonomiyaki mix; chili pepper paste, yuzu pepper, tom yum Paste, powdered wasabi, wasabi paste, powdered mustard, mustard paste, powdered pepper, salt and pepper, powdered Japanese pepper, garlic powder, grated garlic, grated ginger, dressings, yakiniku sauce, pickled vegetables, chili oil, chili bean paste, mayonnaise, and other condiments; ready-to-eat curry, pasta sauce, fried rice mix, and other seasonings; pickles, wasabi-marinated vegetables, seasoned bamboo shoots, and other agricultural processed products; hams; livestock products such as salad chicken; fish paste products; kelp tsukudani, spicy mentaiko Examples of such products include processed seafood products such as egg; dairy oil products such as margarines and cheeses; fruit drinks such as fruit juice drinks and vegetable drinks; carbonated drinks such as cola and ginger ale; dairy drinks such as lactic acid bacteria drinks and yogurt drinks; beverages such as coffee, tea, and jelly drinks; health drinks such as drinks, functional soft drinks, and sports drinks; other beverages such as soft drinks and flavored water; and beverages such as portioned coffee and premixed drinks.

[0080] Examples of oral medications include lozenges, drinks, granules, powders, tablets, capsules, etc., which contain the aforementioned spicy ingredients; examples of oral medications include sprays, ointments, pastes, etc., which contain the aforementioned spicy ingredients; and examples of oral care products include liquid toothpastes, toothpastes, mouthwashes, breath fresheners, etc., which contain the aforementioned spicy ingredients.

[0081] In the present invention, the amount of the compound of formula (1) added to a pungent ingredient-containing product, i.e., the concentration in the pungent ingredient-containing product, can be determined arbitrarily depending on the intended use and pungent characteristics of the pungent ingredient-containing product. Examples of concentrations range from 10 ppt to 0.1%, preferably 100 ppt to 100 ppm, based on the total mass of the pungent ingredient-containing product. More specifically, the lower limit can be any of 10 ppt, 100 ppt, 1 ppb, 10 ppb, 100 ppb, 1 ppm, 10 ppm, and 100 ppm, and the upper limit can be any of 0.1%, 100 ppm, 10 ppm, 1 ppm, 100 ppb, 10 ppb, 1 ppb, and 100 ppt, and the range can be any combination of these lower and upper limits, but is not limited to these. [Example]

[0082] The present invention will be explained in more detail below with reference to examples, although the present invention is not limited to these examples.

[0083] In the examples, the crude reaction products and purified products were measured using the following analytical instruments.

[0084] GC measurement: GC-2025 (manufactured by Shimadzu Corporation) GC columns for GC measurement: GL Sciences TC-1 (length 30 m, inner diameter 0.53 mm, liquid layer thickness 1.50 micrometers), GL Sciences TC-1701 (length 30 m, inner diameter 0.53 mm, liquid layer thickness 1.00 micrometers) GC / MS measurement: 5973N (manufactured by Agilent) GC column for GC / MS measurement: GL Sciences TC-1701 (length 30 m, inner diameter 0.25 mm, liquid layer thickness 0.25 micrometers) NMR measurement: ECZ400S (manufactured by JEOL Ltd.)

[0085] Example 1-1: Synthesis of 3-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]propanal (Compound 2) Methyl hydroferulate (6.2 g, 29.6 mmol), imidazole (2.46 g, 38.2 mmol), DMF (40 mL), and dichloromethane (100 mL) were added to a 500 mL recovery flask and cooled to 0°C with stirring. tert-Butyldimethylchlorosilane (5.36 g, 35.6 mmol) was added to the mixture, and the mixture was stirred overnight while gradually warming to room temperature. After the reaction was complete, water (100 mL) was added to the reaction mixture and stirred for 15 minutes. After liquid-liquid partitioning, ethyl acetate (100 mL) was added to the aqueous layer to extract the organic matter. The organic layer and the ethyl acetate extract were mixed, and the mixture was washed with water (100 mL) and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate=3:1) to give a TBS-protected methyl hydroferulate (9.5 g, 29.3 mmol) in a yield of 99%.

[0086] Under a nitrogen stream, a 500 mL four-neck flask was charged with the TBS-protected compound (9.0 g, 27.8 mmol) and dichloromethane (50 mL), cooled to -78 °C, and stirred. To this mixture was added a 1.03 M n-hexane solution of diisobutylaluminum hydride (41 mL). After the addition, the mixture was stirred at -78 °C for 3 hours. After the reaction was complete, a Rochelle salt solution (200 mL) was added, and the mixture was stirred while gradually raising the temperature to 5 °C. The reaction mixture was partitioned, and ethyl acetate (100 mL) was added to the aqueous layer to extract the organic matter. The organic layer and the ethyl acetate extract were mixed, washed with water (100 mL) and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The mixture was purified by silica gel chromatography (hexane:ethyl acetate = 4:1) to obtain compound 2 (6.6 g, 22.5 mmol) in an 81% yield.

[0087] Example 1-2: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]dec-5-en-3-ol (Compound 5, n=1) Under a nitrogen atmosphere, magnesium (1.0 g, 42.9 mmol), iodine (one piece), and dry tetrahydrofuran (5 mL) were added to a 300 mL three-neck flask and stirred at room temperature. A small amount of 1,2-dibromoethane was added to the mixture, and the mixture was heated with a heat gun. When the color of the iodine in the solution disappeared, heating with the heat gun was stopped, and a solution of (-)-menthone (4.0 g, 25.9 mmol) and (E)-1-bromo-2-heptene (3.56 g, 20.0 mmol, can be synthesized by the method described in the non-patent document J. Agric. Food Chem. 68, 7, 2116-2123 (2020)) dissolved in tetrahydrofuran (100 mL) was added dropwise to the reaction solution. After the addition was complete, the mixture was stirred at room temperature for 2 hours. After the reaction was complete, 1N aqueous hydrochloric acid (100 mL) was added, stirred, and then extracted with ethyl acetate (300 mL). The resulting organic layer was washed twice with water (100 mL) and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated using an evaporator to obtain Compound 7 (n=1) (6.6 g).

[0088] Compound 7 (n = 1) (8.3 g), compound 2 (2.0 g, 6.8 mmol), and dichloromethane (20 mL) were added to a 200 mL recovery flask and stirred at room temperature. p-Toluenesulfonic acid (0.2 g, 1.0 mmol) was added to the mixture and stirred at room temperature for 2 days. After the reaction was completed, water (20 mL) and ethyl acetate (100 mL) were added to the reaction solution to extract the organic matter. The resulting organic layer was washed with water (100 mL) twice and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The mixture was purified by silica gel chromatography (hexane:ethyl acetate = 6:1) to give compound 5 (n = 1) (1.4 g, 3.6 mmol) in a two-step yield of 53%.

[0089] Example 1-3: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]dec-5-en-3-one (Compound 6, n=1) Compound 5 (n = 1) (2.5 g, 6.4 mmol) and dimethyl sulfoxide (30 mL) were added to a 200 mL recovery flask and stirred at room temperature. 2-Iodoxybenzoic acid (2.99 g, 10.7 mmol) was added to the mixture and stirred at room temperature for 4.5 hours. After the reaction was completed, water (100 mL) and ethyl acetate (100 mL) were added and stirred. The resulting organic layer was washed twice with aqueous sodium thiosulfate (50 mL), water (100 mL), and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate = 6:1) to give compound 6 (2.0 g, 5.1 mmol, E / Z = 95:5) in 80% yield.

[0090] Example 1-4: Synthesis of 1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one (Compound 1, n=1) Compound 6 (2.0 g, 5.1 mmol), acetic acid (0.7 g, 10.8 mmol), and tetrahydrofuran (40 mL) were added to a 200 mL recovery flask and stirred at 0 °C. Tetrabutylammonium fluoride-tetrahydrofuran solution (1 M, 6.25 mL) was added to the mixture and stirred at 0 °C for 2 h. After the reaction was complete, 2 N aqueous hydrochloric acid (5 mL), water (10 mL), and ethyl acetate (200 mL) were added and stirred. The resulting organic layer was washed twice with water (100 mL) and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate = 2:1) to give compound 1 (n = 1) (1.3 g, 4.7 mmol, E / Z = 89:11) in 92% yield.

[0091] Physical properties data of 1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one (compound 1) 1 H-NMR (400MHz, CDCl3): δ6.82(d,J=8.0Hz,1H),6.65-6.68(m,2H),5.43-5.57(m,3H),3.87(s,3 H),3.06-3.14(m,2H),2.70-2.84(m,4H),2.01(m,2H),1.26-1.37(m,4H),0.88(t,J=6.8Hz,3H). 13 C-NMR (100MHz, CDCl3): δ208.90,146.45,143.95,135.51,133.12,121.65,120 .84,114.37,111.11,55.95,47.20,44.07,32.34,31.42,29.53,22.26,13.99. MS(EI,70eV):m / z41(5),55(10),65(3),77(5),91(10),94(6),107(5),122(13),137(100),151(14)179(15),205(13),276(M+,86)

[0092] Examples 1-5: Preparation of 1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one (Product 1 of the Invention) and isolation of (E)-1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one (Product 2 of the Invention) and (Z)-1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one (Product 3 of the Invention) 1-(4-Hydroxy-3-methoxyphenyl)dec-5-en-3-one (Product 1 of the present invention) was prepared by isolating (E)-1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one (Product 2 of the present invention) and (Z)-1-(4-hydroxy-3-methoxyphenyl)dec-5-en-3-one (Product 3 of the present invention) from Compound 1 (n=1) using the following preparative HPLC conditions, and then mixing Products 2 and 3 of the present invention in a 1:1 ratio.

[0093] (Preparative HPLC conditions) Equipment: High-performance liquid chromatograph (Shimadzu Nexera) Column: Kinetex F5 (5 μm, 21.2 mm × 250 mm) Eluent: methanol / ultrapure water = 650 / 350 Flow rate: 8.0mL / min Oven temperature: 25℃ Detector: UV 210 nm

[0094] The fractions of Invention Products 2 and 3 were concentrated under reduced pressure and then extracted with ethyl acetate. The extract solutions of Invention Products 2 and 3 were washed twice each with ultrapure water and saturated saline, and then dried over sodium sulfate. The extract solutions of Invention Products 2 and 3 were filtered through paper and then concentrated under reduced pressure. After three hours of vacuum drying, 451.6 mg of Invention Product 2 (recovery rate: 92.9%) and 40.5 mg of Invention Product 3 (recovery rate: 66.1%) were obtained.

[0095] The purity of Invention Products 2 and 3 was confirmed by HPLC chromatography, and the results showed that both Invention Products 2 and 3 were 97% pure.

[0096] (HPLC measurement conditions) Equipment: High-performance liquid chromatograph (Shimadzu Nexera) Column: Kinetex F5 (5 μm, 4.6 mm × 250 mm) Eluent: A: Ultrapure water B: Methanol Flow rate: 0.4mL / min Gradient conditions: Bconc.65% Oven temperature: 25℃ Detection: UV 210 nm

[0097] Example 2-1: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]-4-ethenyldecan-3-ol (Compound 4, n=3) Compound 2 (4.64 g, 14.0 mmol) and zinc powder (1.80 g, 28.0 mmol) were added to a 100 mL flask and cooled to 0°C. Saturated aqueous ammonium chloride solution (15 mL) was added and rapidly stirred. 1-Bromona-2-ene (5.74 g, 28.0 mmol, can be synthesized by the method described in the non-patent document J. Agric. Food Chem. 68, 7, 2116-2123 (2020)) dissolved in tetrahydrofuran (30 mL) was added dropwise. After stirring for 2 hours, the organic layer was separated after filtration through Celite. The aqueous layer was washed with diethyl ether (50 mL), and the combined organic layer was dried over magnesium sulfate and concentrated. Purification by silica gel chromatography (hexane:ethyl acetate = 20:1) gave compound 4 (n = 3) (3.54 g, 59.2% yield) as a diastereomeric mixture.

[0098] Example 2-2: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]dodec-5-en-3-ol (Compound 5, n=3) Compound 2 (0.244 g, 0.829 mmol), compound 4 (n = 3) (3.48 g, 8.29 mmol), p-toluenesulfonic acid monohydrate (0.158 g, 0.829 mmol), and methylene chloride (30 mL) were placed in a 100 mL flask and stirred overnight at room temperature. Sodium carbonate (3 g) and saturated aqueous sodium carbonate (15 mL) were added, followed by transfer to a separatory funnel. Water (50 mL) and ethyl acetate (30 mL) were added to obtain an organic layer. The mixture was dried over magnesium sulfate and concentrated under reduced pressure. Purification by silica gel chromatography (hexane:ethyl acetate = 20:1) afforded compound 5 (n = 3) (2.30 g, 65.1% yield) as a diastereomeric mixture.

[0099] Example 2-3: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]dodec-5-en-3-one (Compound 6, n=3) Compound 5 (n = 3) (2.27 g, 5.40 mmol) and dimethyl sulfoxide (30 mL) were added to a 300 mL recovery flask and stirred at room temperature. 2-Iodoxybenzoic acid (3.02 g, 10.8 mmol) was added to the mixture and stirred at room temperature for 3 days. After the reaction was completed, water (100 mL) and ethyl acetate (100 mL) were added and stirred. The resulting organic layer was washed with aqueous sodium thiosulfate solution (50 mL × 2), water (100 mL), and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate = 9:1) to give compound 6 (n = 3) (yield 1.83 g, 71.9%, E:Z = 59:41).

[0100] Example 2-4: Synthesis of 1-(4-hydroxy-3-methoxyphenyl)dodec-5-en-3-one (Compound 1, n=3: Invention Product 4) Compound 6 (n = 3) (1.63 g, 3.38 mmol), acetic acid (0.467 g, 7.77 mmol), and tetrahydrofuran (35 mL) were added to a 200 mL recovery flask and stirred at 0 °C. Tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution, 4.60 mL) was added to the mixture and stirred at 0 °C for 30 minutes. After the reaction was completed, 2 mol / L hydrochloric acid (3.3 mL), water (7 mL), and ethyl acetate (140 mL) were added and stirred. The resulting organic layer was washed with water (50 mL × 2) and saturated brine (50 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate = 9:1) to obtain product 4 (yield 1.05 g, 88.9%, E:Z = 59:41).

[0101] Physical properties of 1-(4-hydroxy-3-methoxyphenyl)dodec-5-en-3-one (Product 4) 1 H-NMR (400MHz, CDCl3): δ6.82(d,J=8.0Hz,1H),6.65-6.69(m,2H),5.43-5.62(m,3H),3.86(s,3 H),3.06-3.14(m,2H),2.70-2.85(m,4H),2.00(m,2H),1.26-1.36(m,8H),0.87(t,J=6.8Hz,3H). 13 C-NMR (100MHz, CDCl3): δ209.03,208.48,146.48,143.98,135.61,134.07,133.15,133.10,121.67,120.87,120.72,114.42 ,111.14,55.97,47.25,44.31,44.13,42.09,32.71,31.83,29.63,29.57,29.41,29.29,29.07,28.97,27.63,22.75,14.23. MS(EI,70eV):m / z41(4),43(3),55(5),69(2),77(3),91(6),107(3),122(7),137(100),151(8),179(10),205(13),304(M+,41)

[0102] Example 2-5: Isolation of (E)-1-(4-hydroxy-3-methoxyphenyl)dodec-5-en-3-one (Product 5 of the Invention) and (Z)-1-(4-hydroxy-3-methoxyphenyl)dodec-5-en-3-one (Product 6 of the Invention) The present invention products 5 and 6 were isolated from the present invention product 4 using the following preparative HPLC conditions. (Preparative HPLC conditions) Equipment: High-performance liquid chromatograph (Shimadzu Nexera) Column: Kinetex F5 (5 μm, 21.2 mm × 250 mm) Eluent: methanol / ultrapure water = 675 / 325 Flow rate: 9.0mL / min Oven temperature: 25℃ Detector: UV 210 nm

[0103] Fractions of Invention Products 5 and 6 were concentrated under reduced pressure and then extracted with ethyl acetate. The extract solutions of Invention Products 5 and 6 were washed twice each with ultrapure water and saturated saline, and then dried over sodium sulfate. The extract solutions of Invention Products 5 and 6 were filtered through paper, and the solvent was removed by vacuum concentration. Subsequent vacuum drying for 3 hours yielded 227.1 mg of Invention Product 5 (recovery rate: 73.7%) and 153.5 mg of Invention Product 6 (recovery rate: 71.7%).

[0104] The purity of Invention Products 5 and 6 was confirmed by ultra-high performance liquid chromatography. As a result, the purity of Invention Product 5 was 96%, and the purity of Invention Product 6 was 93%.

[0105] (UHPLC measurement conditions) Equipment: Ultra-high performance liquid chromatograph (Shimadzu Nexera) Column: Kinetex F5 (1.7 μm, 2.1 mm × 150 mm) Eluent: A: Ultrapure water B: Methanol Flow rate: 0.25mL / min Gradient conditions: Bconc.67.5% Oven temperature: 25℃ Detection: UV 210 nm

[0106] Example 3-1: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]-4-ethenyldodecan-3-ol (Compound 4, n=5) Compound 2 (2.50 g, 8.50 mmol) and zinc powder (1.11 g, 17.0 mmol) were added to a 100 mL flask and cooled to 0°C. Saturated aqueous ammonium chloride solution (8.5 mL) was added and rapidly stirred. 1-Bromoundeca-2-ene (5.17 g, 17.0 mmol, can be synthesized by the method described in the non-patent document J. Agric. Food Chem. 68, 7, 2116-2123 (2020)) dissolved in tetrahydrofuran (20 mL) was added dropwise. After stirring for 2 hours, the organic layer was separated after filtration through Celite. The aqueous layer was extracted with diethyl ether (50 mL). The combined organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Purification by silica gel chromatography (hexane:ethyl acetate = 20:1) gave compound 4 (n = 5) (yield 2.75 g, 72.2%) as a diastereomeric mixture.

[0107] Example 3-2: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]tetradec-5-en-3-ol (Compound 5, n=5) Compound 2 (0.164 g, 0.559 mmol), compound 4 (n = 5) (4.17 g, 5.59 mmol), p-toluenesulfonic acid monohydrate (0.106 g, 0.559 mmol), and dichloromethane (20 mL) were placed in a 100 mL flask and stirred overnight at room temperature. Sodium carbonate (2 g) and saturated aqueous sodium carbonate (10 mL) were added, followed by transfer to a separatory funnel and extraction with water (30 mL) and ethyl acetate (20 mL) to obtain an organic layer. The mixture was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Purification by silica gel chromatography (hexane:ethyl acetate = 20:1) afforded compound 5 (n = 5) (yield 1.97 g, 78.4%) as a diastereomeric mixture.

[0108] Example 3-3: Synthesis of 1-[4-(tert-butyldimethylsilanoxy)-3-methoxyphenyl]tetradec-5-en-3-one (Compound 6, n=5) Compound 5 (n = 5) (1.66 g, 3.70 mmol) and dimethyl sulfoxide (20 mL) were added to a 200 mL recovery flask and stirred at room temperature. 2-Iodoxybenzoic acid (1.85 g, 6.61 mmol) was added to the mixture and stirred at room temperature overnight. After the reaction was completed, water (100 mL) and ethyl acetate (100 mL) were added and stirred, and the suspension was filtered. The resulting organic layer was washed with aqueous sodium thiosulfate solution (50 mL × 2), water (100 mL), and saturated brine (100 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate = 20:1) to give compound 6 (n = 5) (yield 1.47 g, 89.1%, E:Z = 64:36).

[0109] Example 3-4: Synthesis of 1-(4-hydroxy-3-methoxyphenyl)tetradec-5-en-3-one (Compound 1, n=5: Invention Product 7) Compound 6 (n = 5) (1.48 g, 3.30 mmol), acetic acid (0.400 g, 6.60 mmol), and tetrahydrofuran (30 mL) were added to a 200 mL recovery flask and stirred at 0 °C. Tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution, 4.00 mL) was added to the mixture and stirred at 0 °C for 30 minutes. After the reaction was completed, 2 mol / L hydrochloric acid (3.3 mL), water (6 mL), and ethyl acetate (120 mL) were added and stirred. The resulting organic layer was washed with water (50 mL × 2) and saturated brine (50 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The product was purified by silica gel chromatography (hexane:ethyl acetate = 9:1) to obtain product 7 (yield 0.76 g, 69.1%, E:Z = 64:36).

[0110] Physical properties of 1-(4-hydroxy-3-methoxyphenyl)tetradec-5-en-3-one (Product 7) 1H-NMR (400MHz, CDCl3): δ6.82(d,J=8.0Hz,1H),6.65-6.68(m,2H),5.43-5.62(m,3H),3.87(s,3H) ),3.06-3.14(m,2H),2.70-2.85(m,4H),2.00(m,2H),1.25-1.35(m,12H),0.88(t,J=6.8Hz,3H). 13 C-NMR (100MHz, CDCl3): δ208.98,208.43,146.44,143.94,135.59,134.04,133.11,133.07,121.61,120.83,120.67,114.37,11 1.10,55.94,47.21,44.28,44.09,42.05,32.69,31.97,29.60,29.58,29.54,29.42,29.37,29.30,29.27,27.60,22.76,14.21. MS(EI,70eV): m / z41(2),55(3),91(3),19(2),122(3),137(100),151(3),179(4),332(M + ,8)

[0111] Example 3-5: Isolation of (E)-1-(4-hydroxy-3-methoxyphenyl)tetradec-5-en-3-one (Product 8 of the Invention) and (Z)-1-(4-hydroxy-3-methoxyphenyl)tetradec-5-en-3-one (Product 9 of the Invention) The present invention products 8 and 9 were isolated from the present invention product 7 using the following preparative HPLC conditions. (Preparative HPLC conditions) Equipment: High-performance liquid chromatograph (Shimadzu Nexera) Column: Kinetex F5 (5 μm, 21.2 mm × 250 mm) Eluent: methanol / ultrapure water = 725 / 275 Flow rate: 10.0mL / min Oven temperature: 25℃ Detector: UV 210 nm

[0112] Fractions of present invention product 8 and present invention product 9 were concentrated under reduced pressure and then extracted with ethyl acetate. The extract solutions of present invention product 8 and present invention product 9 were washed twice each with ultrapure water and saturated saline, and then dehydrated by adding sodium sulfate. The extract solutions of present invention product 8 and present invention product 9 were filtered through filter paper, and the solvent was removed by concentration under reduced pressure. After three hours of vacuum drying, 219.5 mg of present invention product 8 (recovery rate: 78.3%) and 127.7 mg of present invention product 9 (recovery rate: 80.9%) were obtained.

[0113] The purity of present invention products 8 and 9 was confirmed by ultra-high performance liquid chromatography. As a result, the purity of both present invention products 8 and 9 was 95%.

[0114] (UHPLC measurement conditions) Equipment: Ultra-high performance liquid chromatograph (Shimadzu Nexera) Column: Kinetex F5 (1.7 μm, 2.1 mm × 150 mm) Eluent: A: Ultrapure water B: Methanol Flow rate: 0.25mL / min Gradient conditions: Bconc.72.5% Oven temperature: 25℃ Detection: UV 210 nm

[0115] Example 4: Flavor characteristics of present invention products 1 to 9 Flavor evaluation (evaluation of flavor characteristics and pungency) was carried out on Invention Products 1 to 9 obtained from the above Examples. For the evaluation of flavor characteristics, each compound of Invention Products 1 to 9 was blended in 99% ethanol to a concentration of 1% by mass to prepare flavor improvers of the present invention (Invention Products 10-1 to 10-9). Five well-trained panelists with over 10 years of experience smelled the products and commented on the flavors they perceived. Representative comments are shown in Table 1 below.

[0116] [Table 1]

[0117] In addition, the pungency of Invention Products 1 to 9 was evaluated. For the pungency evaluation, the flavor improvers (Invention Products 10-1 to 10-9) were further diluted with water to give Invention Products 1 to 9 at a concentration of 10 ppm, which were used as samples (Invention Products 10-10 to 10-18). Additionally, [6]-shogaol at a concentration of 10 ppm was used as a sample for comparison, Product 1. Five well-trained panelists with over 10 years of experience tasted these samples and commented on their pungency. Representative comments are shown in Table 2 below.

[0118] [Table 2]

[0119] Example 5: Pineapple-like blended fragrance composition A pineapple-like compound fragrance composition was prepared according to the formulation in Table 3 below.

[0120] [Table 3]

[0121] Novel pineapple-like blended fragrance compositions (Invention Products 11-1 to 11-9) were prepared by mixing Invention Products 1 to 9 with the above-mentioned pineapple-like fragrance composition (Comparative Product 2) to a concentration of 0.1%. Comparisons were conducted with Comparative Product 1 as a control by five well-trained expert panelists. For the fragrance evaluation, 10 mL of the fragrance composition was placed in a sample bottle (30 mL), and the five well-trained panelists evaluated the fragrance through the bottle opening and using scent strips impregnated with the fragrance composition. As a result, all five expert panelists concluded that Invention Products 11-1 to 11-9 captured the fresh, natural characteristics of pineapple compared to Comparative Product 1, and were also significantly superior in terms of longevity.

[0122] Example 6: Incorporation of pineapple-like compounded flavor composition into sherbet The pineapple-like compounded fragrance composition (Comparative Product 2) and the present invention products 11-1 to 11-9 were added to a sherbet of the following formulation, and the sherbet was prepared by a conventional method. Ten well-trained panelists tasted the sherbet and conducted a sensory evaluation. Sherbet formulation (parts by weight) Sugar: 10, corn syrup (75%): 6, high fructose corn syrup (75%): 5, citric acid (crystalline): 0.1, 20% pineapple juice: 10, products 11-1 to 11-9 of the present invention (or comparative product 2): 0.2, water to make a total of 100.

[0123] These sorbets were subjected to a sensory evaluation by 10 well-trained panelists. As a result, all 10 panelists evaluated that the sorbets containing invention products 11-1 to 11-9 had a more pronounced fresh and natural pineapple flavor than the sorbet containing comparative product 2, and that they also had a stronger umami and sweetness.

[0124] Example 7: Lila-type blended fragrance composition A lila-type blended fragrance composition was prepared according to the formulation in Table 4 below.

[0125] [Table 4]

[0126] Novel lila-type blended fragrance compositions (Inventions 12-1 to 12-9) were prepared by mixing Inventions 1 to 9 with the above-mentioned lila-type fragrance composition (Comparative Product 3) to a concentration of 0.5%. Inventions 12-1 to 12-9 and Comparative Product 3 were compared by five expert panelists. As a result, all five expert panelists recognized that Inventions 12-1 to 12-9 captured the fresh, natural characteristics of lila and were significantly superior in terms of longevity compared to Comparative Product 3.

[0127] Example 8: Blending of Lila-type perfume composition into shampoo A lilac-type blended fragrance composition (Comparative Product 3) and present invention products 12-1 to 12-9 were added to shampoos of the following formulation, and the shampoos were prepared in the usual manner. Ten well-trained panelists washed their hair and conducted a sensory evaluation. Shampoo formulation (parts by mass) Polyoxyethylene sodium lauryl sulfate: 20, coconut oil fatty acid diethanolamide: 5, glycerin: 4, invention products 12-1 to 12-9 (or comparative product 3): 0.2, water to make a total of 100.

[0128] These shampoos were subjected to a sensory evaluation by 10 panelists. As a result, all 10 panelists evaluated that the shampoos containing invention products 12-1 to 12-9 had a fresher, more natural, and more lilac-like characteristic than the shampoo containing comparison product 3.

[0129] Example 9: Effect of blending with ginger ale drinks Each of the compounds of Invention Products 1 to 9 was blended with a commercially available ginger ale beverage at the concentrations shown in Table 5 below to obtain a ginger ale beverage of the present invention. The ginger flavor of the ginger ale beverage of the present invention was then evaluated using a commercially available ginger ale beverage as a control. Specifically, 10 well-trained panelists with 10 or more years of experience were asked to score the ginger flavor compared to the control beverage as follows: "greatly improved" = 4 points, "improved" = 3 points, "slightly improved" = 2 points, and "no change" = 1 point. Here, "ginger flavor" refers to whether the flavor is similar to that of regular ginger.

[0130] [Table 5]

[0131] As shown in Table 5, it was confirmed that each of the compounds of the present inventions 1 to 9 can impart a flavor to ginger-flavored foods and beverages and further improve their natural flavor. It was also confirmed that the flavor-imparting effect can be obtained at least within a concentration range of 0.1 ppb to 100 ppm in foods and beverages.

[0132] Example 10: Evaluation of spiciness by adding to soy sauce Sauces were prepared by dissolving Products 1 to 9 of the present invention in commercially available soy sauce for sashimi at the concentrations shown in Table 6. Using the commercially available soy sauce for sashimi as the control, ten well-trained panelists tasted each soy sauce for sashimi and conducted a sensory evaluation of its spiciness. The samples were scored relative to the control product as follows: 1: no difference from the control product; 2: slightly spicier than the control product; 3: spicier than the control product; 4: stronger spiciness than the control product; and 5: very stronger spiciness than the control product. The average scores of the ten panelists are shown in Table 6.

[0133] [Table 6]

[0134] As shown in Table 6, it was confirmed that each compound of Invention Products 1 to 9 can impart a pungent taste to soy sauce and further improve the pungent taste. Furthermore, it was confirmed that the pungent taste gradually increases after consumption. It was also confirmed that the pungent taste-imparting effect can be obtained at least within the concentration range of 0.1 ppb to 100 ppm in foods and beverages.

[0135] Example 11: Evaluation of spiciness by adding to noodle soup Noodle soups were prepared according to the recipes in Table 7 below, and Invention Products 1 to 9 were added thereto at 1 ppm to prepare the invention products (designated Invention Products 15-1 to 15-9).

[0136] [Table 7]

[0137] Five well-trained panelists tasted the present invention products 15-1 to 15-9 using an additive-free noodle soup as a control product, and evaluated their spiciness. As a result, all five panelists found the present invention products 15-1 to 15-9 to be more preferable than the control product, with a particular preference for the spiciness gradually increasing.

[0138] Example 12: Evaluation of the pungency of ginger ale beverages Present invention products 16-1 to 16-9 were prepared by adding 1 ppm of each of the compounds of present invention products 1 to 9 to a commercially available ginger ale beverage. Five well-trained panelists tasted the present invention products 16-1 to 16-9, using the commercially available ginger ale beverage as a control, and evaluated their pungency. All five panelists evaluated the present invention products 16-1 to 16-9 as being more palatable than the control, with a particularly favorable pungency-increasing effect, and as being delicious and good.

[0139] Example 13: Evaluation of the pungency enhancement of ginger-flavored dressing Invention Product 2 was added at 10 ppm to a commercially available ginger-flavored dressing to prepare Invention Product 17. Five well-trained panelists tasted Invention Product 17 using the commercially available ginger-flavored dressing as a control, and evaluated its spiciness. All five panelists confirmed that Invention Product 17 had an enhanced spiciness compared to the control, and evaluated that the ginger spiciness was enhanced and the flavor was richer.

[0140] Example 14: Evaluation of enhanced spiciness of paste toothpaste Present invention product 2 was added at 5 ppm to a commercially available paste toothpaste to prepare present invention product 18. Five well-trained panelists tasted present invention product 18 using the commercially available paste toothpaste as a control, and evaluated its pungency. All five panelists confirmed that present invention product 18 had an enhanced pungency compared to the control, and evaluated that the pungency of the menthol in the paste toothpaste in particular was enhanced.

Claims

1. A flavor improver comprising a compound represented by the following formula (1) as an active ingredient: 【Chemistry 1】 [The wavy line in formula (1) indicates that cis and trans isomers may be contained in any ratio. n is an integer of 1 to 9.]

2. The flavor improver according to claim 1 , which is a pungency enhancer.

3. A flavor composition comprising the flavor improver according to claim 1.

4. A pungent composition comprising the flavor improver according to claim 2.

5. A consumer product containing the flavor improver of claim 1 or 2.

6. A consumer product containing the flavor composition according to claim 3 and / or the pungent composition according to claim 4.

7. A method for improving the flavor of consumer goods, comprising blending the flavor improver of claim 1 into the consumer goods.

8. A method for enhancing the pungency of a product containing a pungent component, comprising blending the flavor improver according to claim 2 into the product.

9. A compound represented by the following formula (2): 【Chemistry 2】 [The wavy line in formula (2) indicates that the (Z) and (E) isomers may be contained in any ratio. n is an integer of 2 to 9.]

Images