JP2024034938A - Citral deterioration flavor suppression composition - Google Patents

Abstract

The present invention provides a composition that is effective in suppressing citral deterioration flavor. [Solution] One or more compounds selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one are used as active ingredients. A citral deterioration flavor suppressing composition comprising: Preferably, it contains at least 8-methyl-4-methylenenon-7-en-2-one. Alternatively, preferably the unpleasant flavor is due to p-cresol and/or p-methylacetophenone. [Selection diagram] None

Description

FIELD OF THE INVENTION The present invention relates to compositions for suppressing citral deterioration flavor.

Consumers' demands for aroma and taste (herein referred to as flavor) for various consumer goods such as food and beverages and cosmetics are becoming increasingly sophisticated, and multiple technologies have been proposed to suppress unpleasant flavors. has been done.

Citral is known as the aromatic component of citrus fruits such as lemon and ginger, but the structure of citral changes (also called deterioration) due to light, heat, changes over time, etc., producing p-cresol and p-methylacetophenone. There is a problem in that unpleasant flavors (also referred to as deterioration odor) are generated by these products, and methods to suppress flavor deterioration (herein also referred to as citral deterioration flavor) due to the generation of unpleasant flavors have been studied. It's here.

As a method of suppressing the deterioration flavor caused by citral, for example, a technique that focuses on the above-mentioned p-cresol and p-methylacetophenone is to use oxypeucedanin hydrate and/or Byakangelicin. By adding a flavor deterioration inhibitor characterized by the following to citral-containing flavors and food/beverage products, production of p-methylacetophenone from citral can be suppressed to prevent flavor deterioration (Patent Document 1), and ethyl pill ate, methyl jasmonate, methyl dihydro jasmonate, diethyl malonate, methyl beta naphthyl ketone, maltol isobutyrate, menthol, lauric acid, acetoin, cinnamyl acetate, benzyl acetate, and alpha-terpineol. Masking the unpleasant odors of p-cresol and p-methylacetophenone produced by deterioration of citral with a deterioration odor masking agent for citral or citral-containing products, characterized by containing one or more of ) has been proposed.

Japanese Patent Application Publication No. 2010-99025 Patent No. 6517010

However, the conventionally used materials for suppressing the deterioration flavor of citral have not been able to sufficiently suppress the deterioration flavor of citral, and the discovery of more useful materials has been a challenge. Therefore, an object of the present invention is to provide a composition useful for suppressing the deterioration flavor of citral.

The present inventors conducted intensive research in view of the above problems and found that 8-methyl-4-methylenenon-7-en-2-one and 4, Deterioration caused by citral in a composition containing one or more selected from the group consisting of 8-dimethylnona-3,7-diene-2-one (4,8-dimethylnona-3,7-diene-2-one) It was discovered that this method is useful for suppressing flavor, leading to the present invention.

Thus, a brief overview of typical inventions disclosed in this application is as follows.
[1] Contains as an active ingredient one or more selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one; Citral deterioration flavor suppressing composition.
[2] The citral deterioration flavor suppressing composition according to [1], which contains at least 8-methyl-4-methylenenon-7-en-2-one as the active ingredient.
[3] The citral-degraded flavor according to [1], which contains 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one as the active ingredients. Inhibitory composition.
[4] The citral deterioration flavor suppressing composition according to any one of [1] to [3], wherein the deterioration flavor is due to p-cresol and/or p-methylacetophenone.
[5] Citral containing one or more active ingredients selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one A method for suppressing citral deterioration flavor, comprising incorporating a deterioration flavor suppression composition into a citral-containing article.
[6] For the citral-containing article, the active ingredient is added at a concentration of 1 ppt to 100 ppm based on the total mass of the citral-containing article (8-methyl-4-methylenenon-7-en-2-one and 4,8- The method for suppressing citral deterioration flavor according to [5], wherein when both dimethylnona-3,7-dien-2-one are contained, the total concentration thereof is obtained.
[7] The method for suppressing citral deterioration flavor according to [6], wherein the concentration is 1 ppb to 500 ppb.
[8] A citral-containing article containing the citral deterioration flavor suppressing composition according to any one of [1] to [3].
[9] The citral-containing article according to [8], wherein the citral-containing article is a fragrance composition, a food/beverage product, a cosmetic product, or a health and hygiene product.

According to the present invention, it is possible to provide a composition that is effective in suppressing the deterioration flavor of citral.

Hereinafter, the present invention will be explained in more detail by giving specific examples. In this specification, "~" means a range including the lower limit and upper limit, and concentration (ppt, ppb, ppm, etc.) and % represent mass concentration and mass %, respectively, unless otherwise specified. Unless otherwise specified, the concentration is based on the total mass, that is, the final concentration.

[Citral deterioration flavor suppression composition]
The citral (also referred to as 3,7-dimethyl-2,6-octadienal) deterioration flavor suppressing composition (herein sometimes simply referred to as the present deterioration flavor suppressing composition) according to one embodiment of the present invention is , 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one (herein, one or more compounds selected from the group consisting of The former is the active ingredient 1 or the active ingredient 1, the latter is the active ingredient 2 or the active ingredient 2, and either or both of these may be collectively referred to as the active ingredient. (herein sometimes referred to as a citral-containing article), it is possible to suppress the citral-degraded flavor of the article.

In the present specification, when the present deterioration flavor suppressing composition is contained in a citral-containing article, it means adding the present active ingredient to a citral-containing article to obtain a citral-containing article containing the present active ingredient, and the present active ingredient and citral. Adding a composition containing citral to an article that does not contain citral to obtain a citral-containing article containing the active ingredient, or adding a composition containing the active ingredient and citral to an article containing citral. obtaining a citral-containing article containing the active ingredient. By containing the active ingredient, the citral-containing article suppresses the deterioration flavor of citral.

As used herein, "adding" includes at least one of simply adding to a certain object by spraying, dropping, etc., and mixing with a certain object.

In this specification, "flavor" typically means a sense that includes smell and taste, and "degraded flavor" refers to a flavor that is unpleasant or foreign due to changes (deterioration) in citral. Specific examples include flavors derived from p-cresol and/or p-methylacetophenone (which may be referred to herein as degraded flavor compounds), which are compounds resulting from the degradation of citral. All of these compounds have low detection thresholds; p-cresol has an animal-like, drug-like, phenol-like, and smoky odor, and p-methylacetophenone has a fruity, strawberry-like, and almond-like odor. Therefore, if even a trace amount of these scents occurs in a citral-containing article, these scents may be felt as unpleasant and may be recognized as a citral-degraded flavor. Note that articles that are not eaten (typical examples include perfume compositions and cosmetics) may be described as aroma (i.e., olfactory sensation), which is one aspect of flavor.

As used herein, "deterioration flavor suppression" means that the deterioration flavor felt from a citral-containing article is weaker or is not substantially felt compared to when the citral-containing article does not contain the deterioration flavor suppressing composition. Including putting into a state. As shown in the Examples below, when the citral-containing article containing the Deterioration Flavor Inhibition Composition is abused, the Deterioration Flavor and Flavor Inhibition Composition exhibits a weaker or substantially lower deterioration flavor than when the Deterioration Flavor Inhibition Composition does not contain the Deterioration Flavor Inhibition Composition. Therefore, it can be said that the occurrence of deterioration flavor in citral-containing products can be suppressed. As shown in yet another example, the flavor of a compound (preferably p-cresol and/or p-methylacetophenone) resulting from a structural change (also referred to as deterioration) of citral contained in a citral-containing article is suppressed to suppress the deterioration flavor. It can also be made weaker or substantially unnoticeable than when no composition is added. Therefore, "suppressing degraded flavor" includes both suppressing the occurrence of degraded flavor in citral-containing articles and suppressing the intensity of degraded flavor that has already occurred.

The unpleasant flavor composition of the present invention can also be used as a deterioration flavor suppressing composition that can be flavored. That is, as shown in the Examples below, it is possible not only to suppress the flavor caused by citral deterioration but also to impart a citrus-like flavor that is impaired by citral deterioration. It may also have the effect of imparting both flavor and flavor.

The composition for suppressing degraded flavor may be used in combination with any known material that suppresses the production of degraded flavor compounds (for example, p-cresol and/or p-methylacetophenone) due to deterioration of citral; The effect of suppressing the degraded flavor (that is, the degraded flavor of citral) caused by degraded flavor compounds that are generated due to the generation of the material not being fully suppressed can be obtained.

Containing one or more compounds selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one means 8- Embodiment comprising both methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one, 8-methyl-4-methylenenon-7-en-2-one 4,8-dimethylnon-3,7-dien-2-one and not 8-methyl-4-methylenenon-7-en-2-one. - Dien-2-one may be included. From the viewpoint of a higher deterioration flavor suppressing effect, the present deterioration flavor suppressing composition preferably contains at least 8-methyl-4-methylenenon-7-en-2-one, that is, 8-methyl-4-methylenenona -7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one, or 8-methyl-4-methylenenon-7-en-2-one and 4,8 - does not contain dimethylnona-3,7-dien-2-one.

By citral-containing article is meant any article that contains citral and as a result can develop a citral-derived degraded flavor due to light, heat, aging, etc. The occurrence of a degraded flavor derived from citral is a state in which the flavor derived from p-cresol and/or p-methylacetophenone, which are degraded flavor compounds, is felt, and in citral-containing products, p-cresol detects the flavor. Includes conditions above the threshold and/or where p-methylacetophenone occurs at a concentration above its detection threshold. Specific examples include, but are not limited to, cases where 1 ppb or more of p-cresol and/or 1 ppb or more of p-methylacetophenone are produced. The citral-containing article may consist essentially of citral and its solvent or carrier.

The means for obtaining the active ingredient is not particularly limited, but for 8-methyl-4-methylenenon-7-en-2-one (active ingredient 1), for example, <reaction route A>, <reaction route A>, Route B> can be obtained by two methods.

<Reaction route A>
The double bond of gellanic acid or gellanic acid ester (formula (2)) is isomerized to the exo side using lithium diisopropylamide (LDA) or the like to produce a compound represented by formula (3). Thereafter, the compound represented by formula (3) is converted into morpholinamide (formula (4)). This morpholinamide (formula (4)) is methylated and purified by distillation to obtain the target product, 8-methyl-4-methylenenon-7-en-2-one (formula (1)).
<Reaction route B>
Gellanic acid or gellanic acid ester (formula (2)) is converted to morpholinamide (formula (6)). Thereafter, the double bond of this morpholinamide (formula (6)) is isomerized to the exo side to convert it into morpholinamide represented by formula (4). This morpholinamide (formula (4)) is methylated and purified by distillation to obtain the target product, 8-methyl-4-methylenenon-7-en-2-one (formula (1)).

The method of methylation is not particularly limited, but it is preferably carried out using a Grignard reagent.

The active ingredient 1 obtained by the above synthesis method may be further purified using means such as column chromatography or vacuum distillation, if necessary.

The present active ingredient 1 has a citrus-like aroma, and can be used as an active ingredient of the present deterioration flavor suppressing composition as well as imparting a citrus-like flavor as a substitute for citral.

Among the active ingredients of the present invention, 4,8-dimethylnona-3,7-dien-2-one (active ingredient 2 of the present invention) can be obtained by a known synthesis method, or a commercially available product can be used. 4,8-dimethylnona-3,7-dien-2-one is known as a stable compound that exhibits a citrus-like aroma (for example, Japanese Patent Publication No. 2003-517052), and 4,8-dimethylnona-3,7-diene. -2-one exists in the E form and the Z form, and in the present invention, either the E form, the Z form, or a mixture thereof in any proportion can be used as the active ingredient. In the present specification, unless otherwise specified, the E form, the Z form, and mixtures thereof in arbitrary proportions are collectively referred to as 4,8-dimethylnona-3,7-dien-2-one or the present active ingredient 2. Commercial products of 4,8-dimethylnona-3,7-dien-2-one are usually a mixture of E-form and Z-form, and when obtained by typical synthetic methods (for example, JP-A No. 2001-181670 and JP-A No. 2012 -158647) is also usually a mixture of the E-form and the Z-form, so preferably 4,8-dimethylnon-3,7-dien-2-one is a mixture of the E-form and the Z-form. Although the ratio is arbitrary, the E form is usually present in the mixture predominantly (approximately 60 to 90% or more of the mixture is the E form), so it is preferably within the range of 5:5 to 9:1, more preferably. is 6:4 to 8:2, and a preferred example is 8:2.

The present active ingredient 2 also has a citrus-like aroma like the present active ingredient 1, and in addition to being used as an active ingredient of the present deterioration flavor suppressing composition, it can also be used as a substitute for citral to impart a citrus-like flavor. However, since it has a floral aroma in addition to a citrus-like aroma, it may also have a floral flavor.

Examples of the present deterioration flavor suppressing composition include various additives containing the present active ingredient that can be added to various consumer goods such as food and beverages, cosmetics, and health and hygiene products. More specific examples include fragrance compositions containing the active ingredient, various animal and plant extracts, fermented products, enzyme-treated products, or heat-treated products of various animal and plant materials that can be added to various consumer goods. Examples of the form include water-soluble or oil-soluble solvent solutions, emulsified preparations, powder preparations, and other solid preparations (solid fat, etc.), but the present invention is not limited to the above examples.

In addition to the active ingredient, the deterioration flavor suppressing composition contains any other components (specific examples will be described later), such as a solvent, a dispersion medium, a flavor imparting ingredient other than the active ingredient, and auxiliary ingredients such as an antioxidant ingredient. However, it may consist essentially only of the active ingredient. If the Deterioration Flavor Suppressing Composition contains ingredients other than the Active Ingredients, the concentration of the Active Ingredient in the Deterioration Flavor Suppression Composition is arbitrarily determined depending on the subject to which the Deterioration Flavor Suppression Composition is added and the aroma characteristics. can.

As an example of the concentration of the Active Ingredient in the Degraded Flavor Suppressing Composition, if the Deteriorated Flavor Suppressing Composition substantially contains only the Active Ingredient, or only the Active Ingredient and its solvent (specific examples are described below): , a range of 10 ppb to 100%, and a preferable example is a range of 10 ppm to 99%. In this specification, the concentration of the active ingredient means any of the following unless otherwise specified.
(A) Containing either 8-methyl-4-methylenenon-7-en-2-one or 4,8-dimethylnon-3,7-dien-2-one alone as the active ingredient is either effective. Concentration of ingredients (B) If both 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one are included, the total concentration of these The Degraded Flavor As an example of the concentration of the active ingredient in the suppressing composition, especially when the deteriorating flavor suppressing composition contains components (details will be described later) in addition to the active ingredient and its solvent, the composition to which the deteriorating flavor suppressing composition is added is The concentration can be arbitrarily determined depending on the taste and aroma characteristics, and may be set to an appropriate concentration so that it can be added to consumer products at a concentration that exhibits the effect of suppressing deterioration flavor. For example, the amount may be in the range of 100 ppt to 10%, preferably 1 ppb to 10%, more preferably 100 ppb to 10% of the unpleasant flavor improving composition. More specifically, the lower limit is 100ppt, 1ppb, 10ppb, 100ppb, 1ppm, 10ppm, 100ppm, 0.1%, 1%, and the upper limit is 10%, 1%, 0.1%, 100ppm. , 10 ppm, 1 ppm, 100 ppb, 10 ppb, and 1 ppb, and any combination of these lower and upper limits can be used, but the range is not limited thereto.

That is, when the present deterioration flavor suppressing composition contains 8-methyl-4-methylenenon-7-en-2-one or 4,8-dimethylnon-3,7-dien-2-one alone as the present active ingredient. 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7 -dien-2-one, the total concentration ranges from 100 ppt to 10%, preferably from 1 ppb to 10%, and more preferably from 100 ppb to 10%.

Although it depends on the formulation of the deterioration flavor suppressing composition, if the concentration of the active ingredient in the deterioration flavor suppressing composition is 100 ppt to 10%, the flavor derived from the active ingredient can be consumed without being excessively prominent. It becomes easier to obtain the effect of suppressing deterioration flavor on goods. However, depending on the deterioration flavor suppressing composition, the flavor and other conditions to which it is added, the active ingredient may be contained in a concentration outside the range of 100 ppt to 10%.

In the Deterioration Flavor Suppressing Composition, specific examples of other ingredients that may be further included in addition to the Active Ingredient and its solvent include various flavor compounds, flavor compositions, pigments, vitamins, functional substances, and fish meat extract. meat extracts, animal and plant extracts, animal and plant oils, yeast extracts, animal and plant proteins, animal and plant protein decomposition products, starch, dextrin, sugars, amino acids, nucleic acids, organic acids, solvents, emulsifiers, specific gravity adjusters, Examples include antioxidants. For example, "Patent Office Bulletin, Collection of Well-Known and Commonly Used Techniques (Fragrances) Part II Food Flavors, Published January 14, 2000," "Survey on the Use of Food Flavor Compounds in Japan" (FY2000 Health Science Research Report, Japan Fragrance Industry Association, published March 2001) and "Synthetic Fragrances Chemistry and Product Knowledge" (published in a new and enlarged edition on December 20, 2016, edited by the Synthetic Fragrances Editorial Committee, published by Kagaku Kogyo Nippo). Examples include natural essential oils, natural fragrances, and synthetic fragrances.

Examples of flavor compounds include various compounds that contribute to the flavor of various animal and plant materials containing citral; examples of such animal and plant materials include lemon, orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, Various citrus fruits such as Hassaku, Iyokan, Yuzu, Shikuwasa, and Kumquat; Ginger; Various soft fruits such as grape; Various tropical fruits such as guava and feijoa; Various spices or herbs such as olive; Pistachio; Quince; Marjoram, and thyme. ; Examples include various teas such as green tea, black tea, and oolong tea.

Specific examples of compounds include hydrocarbons such as ocimene, limonene, α-phellandrene, terpinene, 3-carene, bisabolene, β-pinene, and valencene; 3-heptanol, 1-undecanol, 2-undecanol, 1- Dodecanol, prenol, 10-undecen-1-ol, dihydrolinalool, tetrahydromugol, myrcenol, dihydromyrcenol, tetrahydromyrcenol, ocimenol, terpineol, 3-thyanol, benzyl alcohol, β-phenylethyl alcohol, α- Alcohols such as phenylethyl alcohol, linalool, cis-3-hexenol; acetaldehyde, n-hexanal, n-heptanal, n-octanal, n-nonanal, 2-methyloctanal, 3,5,5-trimethylhexanal, decanal , undecanal, 2-methyldecanal, dodecanal, tridecanal, tetradecanal, trans-2-hexenal, trans-4-decenal, cis-4-decenal, trans-2-decenal, 10-undecenal, trans-2 -Undecenal, trans-2-dodecenal, 3-dodecenal, trans-2-tridecenal, 2,4-hexadienal, 2,4-decadienal, 2,4-dodecadienal, 5,9-dimethyl-4,8-decadienal , dimethyloctanal, α-methylenecitronellal, citronellyloxyacetaldehyde, myrtenal, neral, α- or β-cinensal, mylacaldehyde, phenylacetaldehyde, octanal dimethyl acetal, nonanal dimethyl acetal, decanal dimethyl acetal, Aldehydes such as decanal diethyl acetal, 2-methylundecanal dimethyl acetal, citral dimethyl acetal, citral diethylacetal, citral propylene glycol acetal; 3-heptanone, 3-octanone, 2-nonanone, 2-undecanone, 2-tridecanone, Ketones such as methylheptenone, dimethyloctenone, geranylacetone, 2,3,5-trimethyl-4-cyclohexenyl-1-methylketone, neron, nootkatone, dihydronootkatone, acetophenone; propyl formate, octyl formate, linalyl formate, formic acid Citronellyl, geranyl formate, neryl formate, terpinyl formate, ethyl acetate, isopropyl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate, octyl acetate, nonyl acetate, decyl acetate, dodecyl acetate, dimethylundecadienyl acetate, acetic acid Ocymenyl, myrcenyl acetate, dihydromyrcenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, tetrahydromugol acetate, lavandulil acetate, nerolidol acetate, dihydrocuminyl acetate, terpinyl acetate, citryl acetate, nopyl acetate, acetic acid Dihydroterpinyl, 2,4-dimethyl-3-cyclohexenylmethyl acetate, mirardyl acetate, beticol acetate, decenyl propionate, linalyl propionate, geranyl propionate, neryl propionate, terpinyl propionate, tricyclodecyl propionate styralyl propionate, octyl butyrate, neryl butyrate, cinnamyl butyrate, isopropyl isobutyrate, octyl isobutyrate, linalyl isobutyrate, neryl isobutyrate, linalyl isovalerate, terpinyl isovalerate, phenylethyl isovalerate, 2-methyl 2-Methylpentyl valerate, methyl 3-hydroxyhexanoate, ethyl 3-hydroxyhexanoate, methyl octoate, octyl octoate, linalyl octoate, methyl nonanoate, methyl undecylenate, linalyl benzoate, methyl cinnamate, angelica Esters such as isoprenyl acid, methyl gellanate, and triethyl citrate; Phenols such as thymol, carvacrol, and β-naphthol isobutyl ether; Lactones such as γ-undecalactone and δ-dodecalactone; Acetic acid, propionic acid, Acids such as butyric acid, valeric acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, 2-decenoic acid, gellanic acid; methyl anthranilate, ethyl anthranilate, methyl N-methylanthranilate, N-2'-methylpentyl Methyl lideneanthranilate, ligantral, dodecanenitrile, 2-tridecenenitrile, geranylnitrile, citronellylnitrile, 3,7-dimethyl-2,6-nonadienonitrile, indole, 5-methyl-3-heptanone oxime, Nitrogen-containing and sulfur-containing compounds such as thiogeraniol, limonenethiol, p-menthyl-8-thiol; furfuryl alcohol, furfural, rose oxide, linalool oxide, mentofuran, theaspiran, 4,7-dihydro-2-isopentyl- Examples include known synthetic fragrance compounds such as furan ether compounds such as 2-methyl-1,3-dioxepine, and preparations prepared by mixing any combination of these compounds.

[Method for producing the deterioration flavor suppressing composition]
One aspect of the present invention provides a method for producing a deterioration flavor suppressing composition, which includes adding the active ingredient of the present invention to any composition that can be added to various consumer products. As another aspect of the present invention, by adding the present deterioration flavor suppressing composition to another flavor imparting composition, the flavor imparting composition to be added can also be manufactured as another present deterioration flavor suppressing composition. . Examples of compositions that can be added to various consumer goods include one or more selected from solvents, antioxidants, pigments, and other additives that can be added to foods, drinks, cosmetics, and health and hygiene products. Examples include compositions containing the same.

The deterioration flavor suppressing composition produced in this manner can be used in the production of various consumer goods as an additive composition for various consumer goods such as food and drink products, cosmetics, and health and hygiene products.

Moreover, the present deterioration flavor suppressing composition may be used as an emulsion preparation, a powder preparation, or other solid preparation (solid fat, etc.).

There are no particular restrictions on the type of solvent used. Examples of water-soluble solvents include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, ethylene glycol, propylene glycol, dipropylene glycol, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, and the like. I can give an example. Among these, ethanol or propylene glycol is particularly preferred when used in food and drink products. Oil-soluble solvents include vegetable oils, animal oils, 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 tripropionine), Herkolin, various essential oils, and triethyl. Examples include citrate.

In order to make the subject deterioration flavor suppressing composition into an emulsified formulation, the subject active ingredient or a composition containing the subject active ingredient is diluted with appropriate vegetable oil and fat, and if necessary, a specific gravity adjuster (sucrose acetate isobutyric acid ester, etc.), an oil-soluble antioxidant, and then emulsified with a water-soluble solvent and an emulsifier. The emulsification method is not particularly limited, and various types of emulsifiers conventionally used in foods and drinks, such as fatty acid monoglyceride, fatty acid diglyceride, fatty acid triglyceride, propylene glycol fatty acid ester, sucrose fatty acid ester, polyglycerin. Emulsifiers such as fatty acid ester, lecithin, modified starch, sorbitan fatty acid ester, Quillaya extract, gum arabic, gum tragacanth, guar gum, gum Karaya, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, casein, Quillaya saponin, sodium caseinate, etc. An emulsion with excellent stability can be obtained by emulsification treatment using a homomixer, colloid mill, rotating disk homogenizer, high-pressure homogenizer, etc. The amount of these emulsifiers used is not strictly limited and can be varied over a wide range depending on the type of emulsifier used, but is usually about 0.01 to about 1 part by mass of the active ingredient. A range of 100 parts by weight, preferably from about 0.1 to about 50 parts by weight, is suitable. In order to stabilize the emulsification, the aqueous solvent solution may contain, in addition to water, polyhydric alcohols such as glycerin, propylene glycol, sorbitol, maltitol, sucrose, glucose, trehalose, sugar solution, and reduced starch syrup. One type or a mixture of two or more types can be added.

Moreover, the emulsion thus obtained can be made into a powder formulation by drying, if desired. Upon powdering, saccharides such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, reduced starch syrup, etc. may be added as necessary. The amounts used can be appropriately selected depending on the desired properties of the powder formulation.

[Method for suppressing deterioration flavor of citral-containing products]
In one aspect of the invention, one or more active agents selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one A method for inhibiting citral degraded flavor is provided, the method comprising incorporating a citral degraded flavor inhibiting composition comprising the following ingredients into a citral-containing article.

The present inventors have confirmed that when the concentration of the active ingredient contained in the citral-containing article is in the range of 1 ppt to 100 ppm, the effect of suppressing the degraded flavor caused by the degraded flavor compound in the citral-containing article is exerted. The concentration of the active ingredient is not limited to these concentrations, and can be adjusted depending on the concentration of the degraded flavor compound and the desired degree of suppressive effect. For example, the lower limit is 1 ppt, 10ppt, 100ppt, 1ppb, 10ppb, 100ppb, 500ppb, 1ppm, 5ppm, 10ppm, 50ppm, upper limit of 100ppm, 50ppm, 10ppm, 5ppm, 1ppm, 500ppb, 100ppb, 10ppb, 1ppb, 100 Either ppt or 10ppt may be within the range of any combination of these lower and upper limits, and examples of preferred ranges include 1 ppb to 500 ppb.

That is, when a citral-containing article contains 8-methyl-4-methylenenon-7-en-2-one or 4,8-dimethylnon-3,7-dien-2-one alone as the active ingredient, the amount is 1 ppt. ~100 ppm, preferably 1 ppb to 500 ppb concentration range containing both 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one For example, the total concentration ranges from 1 ppt to 100 ppm, preferably from 1 ppb to 500 ppb.

Typical examples of citral-containing products include consumer products such as food and beverages, cosmetics, health and hygiene products, and various additives used in the production of consumer products. Examples include compositions for imparting flavor, and more specifically flavor compositions and essential oils.

When the citral-containing article is a consumer product, the timing of adding the deterioration flavor suppressing composition to various products is arbitrary, and the deterioration flavor suppressing composition itself can be added to various products such as food and beverages, cosmetics, health and hygiene products, etc. or one or more other flavoring compositions (e.g., water-soluble flavoring compositions, emulsified flavoring compositions, arbitrary flavoring compounds, natural essential oils (e.g., Flavor compounds listed in Publications, Collection of Commonly Known and Commonly Used Techniques (Fragrances) Part II Food Flavors," "Survey on the Use of Food Flavor Compounds in Japan," and "Synthetic Flavors Chemistry and Product Knowledge." (one or more types) may be added to various consumer products.

Citral-containing products to which the present deterioration flavor suppressing composition can be added are not particularly limited as long as they contain citral, and may have any flavor (especially in the case of food and drink products, also referred to as flavor), but Examples include various citrus flavors such as lemon, orange, grapefruit, lime, mandarin, tangerine, kabosu, sudachi, hassaku, iyokan, yuzu, shikwasa, kumquat; strawberry, blueberry, raspberry, apple, cherry, plum, apricot, peach. Various fruit flavors such as , pineapple, banana, melon, mango, papaya, kiwi, pear, grape (grape, muscat, kyoho, etc.), lychee, passion fruit; milk flavor such as milk, yogurt, butter, custard, etc. Vanilla flavor; Various tea flavors such as green tea, matcha, roasted tea, black tea, oolong tea, barley tea, corn tea, buckwheat tea, Pu'er tea, herbal tea; Coffee flavor; Cola flavor; Cacao flavor; Cocoa flavor; Various flavors such as spearmint and peppermint. Mint flavor: cinnamon, chamomile, cardamom, caraway, cumin, cloves, pepper, coriander, Japanese pepper, perilla, ginger, star anise, thyme, chili pepper, nutmeg, basil, marjoram, rosemary, laurel, wasabi, Japanese pepper, garlic. Various spice or herb flavors such as (garlic); Various nut flavors such as almonds, cashew nuts, and walnuts; Various alcoholic flavors such as wine, brandy, whisky, rum, gin, liqueur, sake, shochu, and beer; Carrot, Various vegetable flavors such as tomatoes, cucumbers, onions, corn (maize), potatoes, etc.; Various legume flavors such as soybeans, peas, and chickpeas; Various meat flavors such as chicken, pork, beef, mutton, and horse meat; seafood flavors; Articles having one or more of the following flavors: soup stock (bouillon) flavor of vegetables, meat, seafood, etc.; consommé flavor; caramel flavor; barley flavor such as barley, wheat; vinegar flavor such as rice vinegar, black vinegar, apple vinegar, etc. can be mentioned.

In the present invention, the flavor of the citral-containing article may be an article that makes you feel only one type of flavor mentioned above, or an article that makes you feel two or more types of flavor, such as banana, peach, and apple flavor among fruit flavors. Examples include products that give a feeling of multiple fruit flavors (so-called mixed fruit flavor flavoring compositions, foods and drinks, cosmetics, etc.), and products that give a feeling of citrus flavors such as lemon and milk flavors (such as citrus-flavored lactic acid bacteria drinks). Examples include, but are not limited to, products that give a sense of mint flavor, citrus flavor, and cola flavor (such as mint or lemon flavored cola drinks). In the case of an article that gives the impression of two or more types of flavors, it must have one or more types of various flavors such as citrus fruits, ginger, fruits, and herbs, as well as milk flavor, cola flavor, and fruit flavor, which are flavors that can be preferably used in combination with these flavors. is preferred.

In particular, citral-containing articles for which the present deterioration flavor suppressing composition can be suitably used include articles containing animal and plant materials that contain a relatively large amount of citral, and specific examples of such animal and plant materials include the above-mentioned lemon, Various citrus fruits such as orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, hassaku, iyokan, yuzu, shikkuwasa, kumquat; ginger; various soft fruits such as grape; various tropical fruits such as guava and feijoa; olive; Various spices or herbs such as pistachio; quince; marjoram and thyme; various teas such as green tea, black tea, and oolong tea; examples of citral-containing products include animal and plant materials that contain relatively large amounts of citral; Examples include, but are not limited to, various beverages containing seeds or more.

Specific examples of food and drink include rice crackers, arare, okoshi, rice cakes, manju, rou, bean paste, yokan, water yolk, nishikidama, jelly, castella, hard candy, biscuits, crackers, potato chips, cookies, pies, Confectionery or confectionery materials such as pudding, ice cream, ice cream, ice milk, butter cream, custard cream, cream puffs, waffles, sponge cake, donuts, chocolate, chewing gum, caramel, candies, peanut paste or other pastes, whipped cream, etc. Bread, udon, ramen, Chinese noodles, sushi, gomoku rice, fried rice, pilaf, gyoza skin, shumai skin, okonomiyaki, takoyaki, etc.; noodles, rice, and other grains; rice bran pickles, pickled plums, fukujinzuke, Pickles such as Bettara-zuke, Senmaizuke, Rakkyo, Miso-zuke, Takuan-zuke, and the base of these pickles; Fish such as mackerel, sardines, saury, salmon, tuna, bonito, whale, flounder, sand eel, sweetfish, Japanese common squid , squid such as spear squid, crested squid, and firefly squid; octopus such as common octopus and common octopus; shrimp such as kuruma prawn, botan prawn, spiny lobster, and black tiger; crabs such as red king crab, snow crab, blue crab, and king crab; clams and clams. Seafood such as scallops, oysters, mussels and other shellfish; Livestock such as chicken, pork, beef, mutton and horse meat; Canned food, boiled fish, tsukudani, surimi, seafood paste products (chikuwa, kamaboko, fried kamaboko, crab legs) kamaboko, etc.), fries, tempura, curry, stew, beef stew, hayashi rice sauce, meat sauce, mapo tofu, hamburger steak, gyoza, kamameshi base, soups (corn soup, tomato soup, consommé soup, etc.), meatballs, braised meat , canned meat, boiled vegetables, Chikuzenni, oden, hot pot dishes, take-out side dishes, noodles such as ramen, soba, udon, and somen, and processed foods using animal and plant materials such as soups and vegetable soups; table salt; Seasoned salt, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hishio, furikake, ochazuke base, margarine, mayonnaise, dressing, vinegar, sambai vinegar, powdered sushi vinegar, Chinese base, tempura soup, mentsuyu (kelp soup or bonito stock) ), sauces (chuno sauce, tomato sauce, etc.), ketchup, yakiniku sauce, curry roux, stew base, soup base, dashi base (kelp stock or bonito stock, etc.), compound seasonings, new mirin, tang Seasonings such as fried flour, mixed flour such as takoyaki flour, and animal or vegetable stock-flavored foods and drinks containing these seasonings; Dairy products such as cheese, yogurt, butter, and fresh cream; Apples, Fruit drinks made from the juice, pulp, grains, peel, etc. of grapes, mangoes, peaches, citrus fruits (grapefruit, oranges, lemons, etc.); tomatoes, green peppers, celery, cucurbits, bitter gourd, carrots, potatoes, asparagus, bracken Foods and beverages containing vegetables, such as vegetables such as Zenmai, vegetable drinks containing these vegetables, and vegetable soups; including coffee, cocoa, green tea, black tea, oolong tea, soft drinks, carbonated drinks, cola drinks, lactic acid bacteria drinks, and milk. Beverages (milk tea, cafe au lait, etc.), beverages containing fruit or fruit juice (fruit tea such as lemon tea, orange tea, etc.); Beverages containing herbal medicines and herbs; Cola drinks, sports drinks, honey drinks, vitamin supplement drinks, Functional drinks such as mineral supplement drinks, energy drinks, and nourishing drinks; Non-alcoholic beverages such as alcohol-flavored drinks with various alcoholic flavors (beer flavor, plum wine flavor, chuhai flavor, etc.) (non-alcoholic beer, non-alcoholic chuhai, etc.) wine, shochu, awamori, sake, beer, chuhai, cocktail drinks, low-malt beer, fruit liquor, condiments, beer-flavored beverages (also called beer-flavored beverages), including so-called "third beer", and other brewed liquors ( (foaming), liqueurs (foaming), and alcoholic beverages containing these.

Specific examples of cosmetics and health and hygiene products include perfumes such as eau de cologne, eau de toilette, eau de parfum, and parfum; hair care products such as shampoo, conditioner, and hair styling products (hair cream, pomade, etc.); foundation, lipstick, lip balm, Cosmetics such as lip glosses, lotions, cosmetic emulsions, cosmetic creams, cosmetic gels, serums, packs, etc. Various preparations for suppressing scalp odor (scalp care agents, etc.), various types for suppressing body odor Deodorant products such as formulations (antiperspirant sprays, deodorant sheets, deodorant creams, deodorant sticks, etc.), formulations for suppressing bad breath (mouthwashes, toothpastes, masks with halitosis prevention effects, etc.); inorganic salt-based, refreshing types , carbon dioxide-based, skin care-based, enzyme-based, herbal medicine-based bath additives; tanning cosmetics such as suntan products and sunscreen products; facial cleansers such as face soap and face cream, body soap and body soap, and laundry. Health and hygiene detergents such as soap, laundry detergent, disinfectant detergent, deodorant detergent, fabric softener, kitchen detergent, and cleaning detergent; Health and hygiene materials such as tissue paper and toilet paper; Spaces such as indoors and cars Examples include deodorants for suppressing various unpleasant odors such as odors and excrement odors; air fresheners such as room fragrances; and the like.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the present invention is not limited to these.

[Example 1] Synthesis of the active ingredient 8-methyl-4-methylenenon-7-en-2-one One of the active ingredients, 8-methyl-4-methylenenon-7-en-2-one (the active ingredient) Active ingredient 1) was synthesized through the following steps of Examples 1-1 to 1-3 (synthesis route A above). In addition, in the reaction formula, when an isomer other than the exo form is produced, the position of the double bond of the isomer other than the exo form is shown by a broken line.
<Example 1-1: Conversion of gellanic acid to exo-isogellanic acid>

Tetrahydrofuran (THF, 2.0 L) was placed in a 5L 4-diameter flask, cooled on ice under a nitrogen atmosphere, and sodium hydride (60%, 84.0 g, 2.10 mol) was added, followed by gellanic acid (337 g, 2.0 mol). .00 mol) was added dropwise over 40 minutes. After stirring at the same temperature for 30 minutes, lithium diisopropylamide (LDA, 2.0 mol/L tetrahydrofuran solution, 1.15 L, 2.30 mol) was added dropwise over 75 minutes. After 1 hour and 20 minutes at the same temperature, the reaction was stopped by pouring into dilute hydrochloric acid, and the layers were separated. The obtained organic layer and an extract obtained by extracting the separated aqueous layer with toluene were combined and washed three times with saturated brine. From the obtained organic layer, the solvent was distilled off under reduced pressure, and the crude product (411 g) was subjected to vacuum distillation, and 280 g ( 1.67 mol, yield 83.4%, exo body 67.4%) was obtained.
<Example 1-2: Conversion of exo-isogellanic acid to exo-isogellanic acid amide>

Pyridine (136 g, 1.71 mol) and toluene (920 mL) were placed in a 3L 4-diameter flask, cooled on ice under a nitrogen atmosphere, and the exo-isogellanic acid obtained in Example 1-1 (262 g, 1.56 mol) was added. ) was added. Subsequently, pivaloyl chloride (207 g, 1.71 mol) was added, and after the temperature was raised to room temperature, the temperature was returned to ice cooling for 1.5 hours, and morpholine (305 g, 3.50 mol) was added. The reaction was completed after 1 hour at the same temperature, and the reaction solution was poured into dilute hydrochloric acid. After layer separation, the obtained organic layer and the extract obtained by extracting the separated aqueous layer with toluene were combined and washed sequentially with 20% brine, 20% sodium carbonate aqueous solution, and 20% brine. The solvent was distilled off from the organic layer under reduced pressure to obtain a crude product (394 g) of exo-isogellanic acid morpholinamide (compound represented by the above formula (4)).
<Example 1-3: Conversion from exo-isogellanic acid amide to the present active ingredient 1>

A 3L 4-diameter flask was charged with the raw material crude exo-isogellanic acid morpholinamide (394 g) obtained in Example 1-2 and anhydrous tetrahydrofuran (1.0 L), cooled on ice under a nitrogen atmosphere, and methyl chloride was added. Magnesium (3.0 mol/L tetrahydrofuran solution, 624 mL, 1.87 mol) was added dropwise over 50 minutes. The reaction was completed after 4.5 hours at the same temperature, and the reaction solution was poured into 20% ammonium chloride water. After layer separation, the obtained organic layer and an extract obtained by extracting the separated aqueous layer with ethyl acetate were combined and washed with dilute hydrochloric acid. The obtained organic layer was washed twice with 5% aqueous sodium bicarbonate and then with 20% brine, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by precision distillation under reduced pressure to obtain 90 g of 8-methyl-4-methylenenon-7-en-2-one (purity: 95.5%). This was used as one of the active ingredients in the following examples.
<<Physical properties of 8-methyl-4-methylenenon-7-en-2-one synthesized in Example 1>>
^1H -NMR (400MHz, CDCl ₃ ): δ1.60 (s, 3H), 1.68 (s, 3H), 2.03-2.12 (m, 4H), 2.16 (s, 3H) , 3.12 (s, 2H), 4.88 (s, 1H), 4.97 (s, 1H), 5.08 (m, 1H).
^13C -NMR (100MHz, _CDCl3 ): δ17.7, 25.7, 26.0, 29.1, 36.0, 51.8, 114.1, 123.5, 132.0, 142.9 , 207.2.
MS (EI, 70eV) m/z: 43 (58), 69 (100), 81 (19), 108 (49), 123 (39), 151 (5), 166 (4).
A 1% ethanol solution of the obtained 8-methyl-4-methylenenon-7-en-2-one was prepared, and five well-trained panelists with more than 10 years of experience were asked to smell it and comment on the perceived aroma. When asked, all five people answered Mr. Citrus.

[Example 2] Production example of the present deterioration flavor suppressing composition An ethanol solution of any concentration of 8-methyl-4-methylenenon-7-en-2-one obtained in Example 1 was prepared, and a solution of the composition according to the present invention was prepared. A composition for suppressing the deterioration flavor of a citral-containing article according to the embodiment was obtained (Product 1-1 of the present invention). The aroma of product 1-1 of the present invention, which was a 1% ethanol solution, was citrus-like. In addition, commercially available 4,8-dimethylnona-3,7-dien-2-one (mixture of E form and Z form, E form: Z form = 8:2) was prepared, and an ethanol solution of any concentration was added. A composition for suppressing deterioration flavor of a citral-containing article according to one embodiment of the present invention was obtained (Product 1-2 of the present invention). The aroma of product 1-2 of the present invention, which was a 1% ethanol solution, was citrus-like with a slight rose-like nuance. These were used in the following examples as one aspect of the present deterioration flavor suppressing composition.

[Example 3] Confirmation of deterioration flavor suppression effect 1 (deterioration odor suppression test due to abuse of citral-containing articles)
A blended fragrance composition with a lemon-like fragrance (hereinafter referred to as basic lemon fragrance) having the formulation shown in Table 1 below was prepared. The amount of citral in the base lemon flavor was approximately 0.25%.

In addition, a sugar acid solution was prepared by dissolving citric acid and granulated sugar in water (Bx 3.0°, pH 2.7, acidity 0.2% asC.A).

Then, a basic lemon flavor was added to the sugar acid solution at a concentration of 0.1% by mass (about 2.5 ppm as citral concentration) to prepare a lemon flavored solution. This was called the basic lemon flavored drink and was used as a control product 2. Control product 2 is one embodiment of a citral-containing article.

Next, the present invention product 1-1 or the present invention product 1-2 is added to the control product 2 so that the active ingredient in the control product 2 has a concentration shown in Table 2 below, to obtain an embodiment of the present invention. Such citral-containing articles were obtained (products of the present invention 2-1 to 2-14).

Then, an abuse test was conducted in which the control product 2 and the products 2-1 to 2-14 of the present invention were placed in a transparent container and allowed to stand for one week in a constant temperature bath at 50° C. shielded from light. In addition, in the control product 2 after abuse, about 25 ppb of p-cresol and about 25 ppb of p-methylacetophenone were produced.

Twelve well-trained panelists with over 10 years of experience evaluated the degraded flavor of products 2-1 to 2-14 of the present invention after abuse compared to control product 2 after abuse, based on the following criteria. Ta. "Degraded flavor is similar to control product 2" = 1 point is a degraded flavor equivalent to the degraded flavor felt from control product 2 (flavor including p-cresol-like flavor and p-methylacetophenone-like flavor) A score of 4, "almost no deterioration flavor is felt," was defined as a deterioration flavor equivalent to Control Product 2 immediately after preparation, which had not been abused.
(Criteria) Regarding the degraded flavor compared to the control product: “You can hardly feel the degraded flavor” = 4 points “You can feel the degraded flavor, but it is clearly weaker than the control product” = 3 points “The degraded flavor is slightly weaker than the control product” ” = 2 points “Degraded flavor is similar to the control product” = 1 point Table 2 shows the average evaluation scores of the 12 panelists.

As shown in Table 2, it was confirmed that when the present deterioration flavor suppressing composition (invention product 1-1 or 1-2) was added to a citral-containing article, the generation of unpleasant flavor in the article could be suppressed. In addition, all 12 panelists agreed that when the present invention product 1-1 (active ingredient 1: 8-methyl-4-methylenenon-7-en-2-one) was added, the present invention products 2-3 and 2-3 and 2-5, when inventive product 1-2 (active ingredient 2: 4,8-dimethylnona-3,7-dien-2-one) is added, inventive product 2-10 and 2-11, Respondents answered that the suppression of deterioration flavor and the flavor imparted by the active ingredient itself had a good balance, resulting in a pleasant lemon flavor.

In the case of the present invention product 1-1 (active ingredient 1: 8-methyl-4-methylenenon-7-en-2-one), if it exceeds 1 ppm, the present invention product 1-2 (active ingredient 2: 4, In the case of 8-dimethylnona-3,7-dien-2-one), when it exceeds 500 ppb, the flavor of the active ingredient itself is imparted while deterioration flavor is suppressed, and the slightly floral citrus-like flavor is emphasized. was. In this way, when it is desired to clearly impart a citrus-like flavor, it can be added at a concentration above a certain level.

In addition, a composition was obtained by adding the present invention product 1-1 or the present invention product 1-2 obtained in Example 2 to the basic lemon flavor containing citral shown in Table 1 of Example 3, and the composition was can also be used as the present deterioration flavor suppressing composition containing the present active ingredient, and the same effects as in Example 3 can be obtained.

[Example 4] Confirmation of deterioration flavor suppression effect 2 (deterioration odor suppression test due to abuse of citral-containing articles)
As one embodiment of a citral-containing article, a commercially available juice containing lemon juice (5% fruit juice, hereinafter referred to as basic lemon juice) was prepared. Hereafter, it is called basic lemon juice.

On the other hand, the product 1-1 of the present invention was blended with the basic lemon flavor prepared in Example 3 so that the concentration of the active ingredient 1 was 0.01% by mass to create the citral-degraded flavor according to one embodiment of the present invention. An inhibitory composition was obtained (invention product 3-1). In addition, the product 1-2 of the present invention was blended with the basic lemon flavor prepared in Example 3 so that the concentration of the active ingredient 2 was 0.01% by mass to suppress the citral deterioration flavor according to one aspect of the present invention. A composition was obtained (invention product 3-2).

Next, the present invention product 3-1 was added to the basic lemon juice at a concentration of 0.1% by mass to obtain a lemon beverage according to one aspect of the present invention (present invention product 3-3, the present active ingredient 1). concentration 100 ppb). In addition, the present invention product 3-2 was added to the basic lemon juice at a concentration of 0.1% by mass to obtain a lemon beverage according to one aspect of the present invention (the present invention product 3-4, the present active ingredient 1 concentration 100 ppb).

On the other hand, a control lemon beverage was obtained by adding a basic lemon flavor to the basic lemon juice to a concentration of 0.1% by mass, and designated as control product 3-1.

Then, an abuse test was conducted on products 3-3 and 3-4 of the present invention and control product 3-1. The abuse test was carried out in the same manner as in Example 3, in which each of the present invention products 3-3, 3-4 and the control product 3-1 was placed in a transparent container and allowed to stand for one week in a constant temperature bath at 50°C shielded from light. We conducted a test. Next, five well-trained panelists with more than 10 years of experience evaluated the flavor of the invention products 3-3 and 3-4 after abuse compared to the flavor of control product 3-1 after abuse. . As a result, the foreign degraded flavor, which was felt in the control product 3-1, such as p-cresol-like drug-like flavor and p-methylacetophenone-like fruity flavor, was not felt in the present invention product 3-3. All five panelists answered that, with Invention Product 3-4, two panelists answered that they could not feel it, and three panelists answered that they could feel it very slightly, but it was significantly suppressed.

[Example 5] Confirmation of deterioration flavor suppression effect 3 (deterioration flavor suppression effect of deterioration flavor compound)
Add commercially available carbonated water to a concentration of 100 ppb of p-cresol, 100 ppb of p-methylacetophenone, or 100 ppb each of p-cresol and p-methylacetophenone (total concentration 200 ppb), which are typical examples of degraded flavor compounds. Control product 4-1 contains 100 ppb of p-cresol, Control product 4-2 contains 100 ppb of p-methylacetophenone, and 100 ppb each of p-cresol and p-methylacetophenone. was designated as Control Product 4-3 (all of which are embodiments of citral-containing products, in which a degraded flavor was generated).

On the other hand, an ethanol solution of any concentration of 8-methyl-4-methylenenon-7-en-2-one prepared in Example 2 (invention product 1-1), and 4,8-dimethylnon-3,7 An ethanol solution of -dien-2-one at an arbitrary concentration (invention product 1-2) was prepared.

Then, control products 4-1 to 4-3 were added to the present invention product 1-1 (the active ingredient 1:8-methyl-4-methylenenonan-7-en-2-one) or the present invention product 1-2 (the present active ingredient). Active ingredient 2: 4,8-dimethylnona-3,7-dien-2-one) was added as shown in Table 3 below to obtain beverages according to one embodiment of the present invention (products of the present invention 4-1 to 4). -18).

Then, sensory evaluation regarding suppression of deterioration flavor of products 4-1 to 4-18 of the present invention was conducted. In the sensory evaluation, 12 well-trained panelists with over 10 years of experience evaluated the p-cresol-like flavor and/or p-methylacetophenone-like flavor of the products of the present invention compared to control products 4-1 to 4-3. People were given points using the following criteria.
(Criteria) Regarding the p-cresol-like flavor and/or p-methylacetophenone-like flavor compared to the control product, “almost not perceptible” = 4 points “Feelable but clearly weaker than the control product” = 3 points “Control "Slightly weaker than the control product" = 2 points "Same as the control product" = 1 point Table 3 shows the average evaluation scores of the 12 panelists.

As shown in Table 3, it was confirmed that the active ingredient of the present invention can suppress deterioration flavor at a concentration in the range of at least 1 ppt to 1 ppm. Furthermore, as can be seen from the evaluation scores, it was confirmed that the present active ingredient 1 exhibited a higher suppressive effect than the present active ingredient 2.

[Example 6] Confirmation of deterioration flavor suppression effect 4 (deterioration flavor suppression effect of deterioration flavor compound)
The basic lemon-like flavor composition prepared in Example 3 was added to carbonated water at a concentration of 0.1% by mass to obtain a basic lemon-flavored beverage. To this, as representative examples of degraded flavor compounds, 100 ppb of p-cresol, 100 ppb of p-methylacetophenone, or 100 ppb each of p-cresol and p-methylacetophenone (total concentration 200 ppb) were added. , Control product 5-1 contains 100 ppb of p-cresol, Control product 5-2 contains 100 ppb of p-methylacetophenone, and Control product 5-3 contains 100 ppb of p-cresol and p-methylacetophenone. (Both are embodiments of citral-containing articles.)

On the other hand, an ethanol solution of any concentration of 8-methyl-4-methylenenon-7-en-2-one prepared in Example 2 (invention product 1-1), and 4,8-dimethylnon-3,7 An ethanol solution of -dien-2-one at an arbitrary concentration (invention product 1-2) was prepared.

Then, control products 5-1 to 5-3 were added to the present invention product 1-1 (active ingredient 1: 8-methyl-4-methylenenon-7-en-2-one) or the present invention 1- as shown in Table 4 below. 2 (active ingredient 2: 4,8-dimethylnona-3,7-dien-2-one) to obtain lemon flavored beverages according to one embodiment of the present invention (products of the present invention 5-1 to 5- 30).

In addition, as a comparative example, geranyl acetate, which is known to contribute to a citrus-like aroma, was added to each of Control Products 5-1 to 5-3 at a concentration of 1 ppb, and a lemon flavored drink of a comparative product was added. (Comparative Product 5-1, Comparative Product 5-2 and Comparative Product 5-3).

Then, a sensory evaluation was conducted regarding suppression of deterioration flavor of the products of the present invention 5-1 to 5-30 and comparative products 5-1 to 5-3. In the sensory evaluation, the p-cresol-like flavor and/or p-methylacetophenone-like flavor of the present invention product and the comparative product compared to the lemon flavored drinks of Control Products 5-1 to 5-3 were evaluated based on the experience of 10 years or more. Twelve well-trained panelists were asked to make comments and give scores based on the following criteria.
(Criteria) Regarding the p-cresol-like flavor and/or p-methylacetophenone-like flavor compared to the control product, “almost not perceptible” = 4 points “Feelable but clearly weaker than the control product” = 3 points “Control "Slightly weaker than the control product" = 2 points "Same as the control product" = 1 point Table 4 shows the average scores and representative comments of the 12 panelists.

As shown in Table 4, it was confirmed that the deterioration flavor suppression composition of the present invention can suppress the deterioration flavor of citral-containing articles.
[Example 7] Confirmation of deterioration flavor suppression effect 5: Deterioration flavor suppression effect on deterioration components In Example 6, the concentration of p-cresol, p-methylacetophenone, which is a deterioration flavor compound, and their total concentration were determined as shown in Table 5 below. Well-trained panelists with more than 10 years of experience were treated in the same manner as in Example 6, except that the concentration of the active ingredient was changed to 1 ppm, which gives a very strong sense of degraded flavor, and the concentration of the active ingredient was changed as shown in Table 5 below. Sensory evaluation by 12 people confirmed the effect of the present deterioration flavor suppressing composition on suppressing citral deterioration flavor.

As a result, it was confirmed that even at a high concentration of the degraded flavor compound, that is, 1 ppm, where the degraded flavor is strongly perceived, the degraded flavor suppressing composition of the present invention effectively suppresses the degraded flavor.
[Example 8] Effect of combination of two types of active ingredients The active ingredients 8-methyl-4-methylenenon-7-en-2-one (active ingredient 1) and 4,8-dimethylnon-3,7- The effect of suppressing deterioration flavor when used in combination with dien-2-one (active ingredient 2) was confirmed.

First, a commercially available body fragrance product with a citrus and floral scent (also referred to as floral citrus or citrus floral) was prepared. Thereto, p-cresol was added to a concentration of 100 ppb and p-methylacetophenone was added to a concentration of 100 ppb to obtain a control lemon-like cosmetic product (control product 7-1).

Then, as shown in Table 6 below, two types of the present invention product 1-1 (ethanol solution of the present active ingredient 1) and the present invention product 1-2 (ethanol solution of the present active ingredient 2) were added. Lemon-like cosmetics according to the embodiments were obtained (products of the present invention 7-1 to 7-3).

Then, sensory evaluation regarding suppression of deterioration flavor of the products 7-1 to 7-3 of the present invention was conducted. In the sensory evaluation, five well-trained panelists with over 10 years of experience were asked to comment on the aroma of the product of the present invention compared to the control product 7-1. Table 6 shows typical comments.

As shown in Table 6, the degraded flavor is effectively suppressed in all of the products of the present invention, and from this, it can be seen that not only when the present active ingredient 1 and the present active ingredient 2 are used alone, but also when the present active ingredient 1 and the present active ingredient 2 are used alone. It was confirmed that the degraded flavor was effectively suppressed even when 2 was used in any ratio.

It was also confirmed that the comments differed depending on the ratio of the present active ingredients 1 and 2, and that the ratio could be arbitrarily determined according to the desired suppressive effect based on the effect characteristics of each of the present active ingredients.
[Example 9] Ratio example of E form and Z form of active ingredient 2 4,8-dimethylnona-3,7-dien-2-one prepared in Example 2 (active ingredient 2, E form: Z form) = approximately 8:2) ethanol solution (product of the present invention 1-2) was prepared. Another example of 4,8-dimethylnona-3,7-dien-2-one (active ingredient 2) is a mixture of E form and Z form, where the ratio of E form and Z form is about 7: An ethanol solution of about 3 (present invention product 8-1) and an ethanol solution of about 9:1 (present invention product 8-2) were prepared.

On the other hand, commercially available lemon juice contains 100 ppb of p-cresol, 100 ppb of p-methylacetophenone, or 100 ppb each of p-cresol and p-methylacetophenone (total concentration 200 ppb), which are typical examples of degraded flavor compounds. Control product 8-1 contains 100 ppb of p-cresol, Control product 8-2 contains 100 ppb of p-methylacetophenone, and 100 ppb of p-cresol and p-methylacetophenone each. The control product 8-3 was defined as control product 8-3.

As shown in Table 7 below, in addition to the control products 8-1 to 8-3, the present invention product 1-2 (E body: Z body = approximately 8:2), the present invention product 8-1 (E body: Z body) = about 7:3) and the product of the present invention 8-2 (E form: Z form = about 9:1), respectively, were added so that the concentration of each active ingredient was 1 ppb. Beverages according to the embodiments were obtained (products of the present invention 8-3 to 8-11).

Then, sensory evaluation regarding suppression of deterioration flavor of the products 8-3 to 8-11 of the present invention was conducted. In the sensory evaluation, the p-cresol-like flavor and/or p-methylacetophenone-like flavor of the product of the present invention compared with each of the control products 8-1 to 8-3 was evaluated by well-trained experts with more than 10 years of experience. It was evaluated by five panelists.

As a result, all panelists agreed that the present invention products 8-3 to 8-5, the present invention products 8-6 to 8-8, and the present invention products 8-9 to 8- No. 11 commented that there was no difference in the deterioration flavor suppressing effect and that it was the same, and it was confirmed that the deterioration flavor suppressing effect was achieved regardless of the ratio of E-form and Z-form.

Claims (9)

Citral-degraded flavor containing as an active ingredient one or more selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one Inhibitory composition. The citral-degraded flavor suppressing composition according to claim 1, comprising at least 8-methyl-4-methylenenon-7-en-2-one as the active ingredient. The citral deterioration flavor suppressing composition according to claim 1, comprising 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one as the active ingredients. . The citral deterioration flavor suppressing composition according to any one of claims 1 to 3, wherein the deterioration flavor is due to p-cresol and/or p-methylacetophenone. Citral deterioration flavor suppression containing one or more active ingredients selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3,7-dien-2-one A method for suppressing citral deterioration flavor, comprising incorporating a composition into a citral-containing article. For the citral-containing article, the active ingredient is added at a concentration of 1 ppt to 100 ppm (8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnon-3) based on the total weight of the citral-containing article. , 7-dien-2-one, the method for suppressing citral deterioration flavor according to claim 5, wherein the total concentration of both citral and 7-dien-2-one is contained. The method for suppressing citral deterioration flavor according to claim 6, wherein the concentration is 1 ppb to 500 ppb. A citral-containing article comprising the citral deterioration flavor suppressing composition according to any one of claims 1 to 3. The citral-containing article according to claim 8, wherein the citral-containing article is a fragrance composition, a food/beverage product, a cosmetic product, or a health and hygiene product.