JP7326243B2 - Lactone compound having cyclopropane skeleton - Google Patents

Description

TECHNICAL FIELD The present invention relates to a lactone compound having a cyclopropane skeleton and a flavor imparting composition containing the lactone compound.

In recent years, consumer demands for foods, beverages, and cosmetics have become sophisticated and diversified, and in particular, attention has been focused on fragrance, and the characteristics of fragrance have become an important factor in the appeal of products. For example, there is an increasing demand for compounds capable of imparting characteristic flavors such as long-lasting flavor and natural flavor to the aroma and taste of the product when blended into the product.

For example, in lactones to which the compound according to the present invention belongs, a fragrance composition containing 4-(4-methyl-3-pentenyl)-2(5H)-furanone as an active ingredient is used to improve citrus or floral flavor. (Patent Document 1), and a method of enhancing sweetness by 3-hydroxy-4,5-dimethyl-2(5H)-furanone (Patent Document 2).

Among compounds having a cyclopropane structure like the compound according to the present invention, cis-2-hexylcyclopropaneacetic acid is used for imparting flavor to various citrus fruits (Patent Document 3), 1-methyl-2 -(1-Phenylethyl)cyclopropylmethanol and other aromatic compounds having side chains with a cyclopropane structure have aromas such as citrus and floral, and these compounds are used to create muguet and marine fragrances. It has been proposed to impart a floral scent, marine, and ozone feeling to each of them (Patent Document 4).

However, there are continuing expectations for the development of new compounds that impart better flavor to various articles such as foods, beverages, cosmetics, and the like, making it possible to differentiate them from the flavors of existing products.

JP 2017-025182 A JP-A-4-8264 JP 2019-68756 A WO2014/142025

An object of the present invention is to provide a new compound useful for imparting flavor to articles.

The present inventors diligently searched for an unknown compound that is effective in imparting flavor, and found that a lactone compound having a cyclopropane skeleton, which was not known for exhibiting fragrance or imparting flavor, was useful for imparting flavor. I found something.

Thus, the present invention provides the following.
[1] A lactone compound having a cyclopropane skeleton, represented by the following formula (1).

［式中、ｎは０～３の整数を表し、破線は、そのいずれか１箇所がシクロプロパン骨格であり、シクロプロパン骨格以外の０～１箇所が炭素－炭素間二重結合であり、その他の箇所は単結合であることを表す。］
［２］ ［１］に記載のラクトン化合物を含む香味付与組成物。
［３］ ［２］に記載の香味付与組成物を含む消費財。
［４］ ［２］に記載の香味付与組成物を消費財に配合することを含む、消費財の香味付与方法。
［５］ ［２］に記載の香味付与組成物を他の香味付与組成物に配合することを含む、香味付与組成物の香味付与方法。

[Wherein, n represents an integer of 0 to 3, any one of the dashed lines is a cyclopropane skeleton, 0 to 1 positions other than the cyclopropane skeleton are carbon-carbon double bonds, and other indicates that it is a single bond. ]
[2] A flavoring composition containing the lactone compound of [1].
[3] A consumer product comprising the flavoring composition of [2].
[4] A method for imparting flavor to consumer goods, comprising blending the flavor imparting composition of [2] into consumer goods.
[5] A method for imparting flavor to a flavor-imparting composition, comprising blending the flavor-imparting composition according to [2] with another flavor-imparting composition.

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

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with specific examples. In the present specification, "-" means a range including the lower and upper limits, and concentrations (ppt, ppb, ppm, etc.) and % represent mass concentration and mass%, respectively, unless otherwise specified.

(Lactone compound having a cyclopropane skeleton represented by formula (1))
All of the lactone compounds having a cyclopropane skeleton represented by formula (1) (also referred to herein as the lactone compound of formula (1)) are novel compounds that have not been described in the prior art. It was a group of compounds that had not been known at all either to have a scent or to be used for imparting flavor to various articles such as consumer goods. .

［式中、ｎは０～３の整数を表し、破線は、そのいずれか１箇所がシクロプロパン骨格であり、シクロプロパン骨格以外の０～１箇所が炭素－炭素間二重結合であり、その他の箇所は単結合であることを表す。］
好ましくは、ｎは１～３の整数であり、より好ましくは１または２であり、さらに好ましくは１である。好ましくは、破線において、シクロプロパン骨格が１箇所であり、１箇所が炭素－炭素間二重結合であり、その他の箇所が単結合である。さらに好ましくは、シクロプロパン骨格がラクトン環の側鎖（以下、単に側鎖ともいう）に１箇所であり炭素－炭素間二重結合がラクトン環に１箇所であり、その他の箇所が単結合であるか、シクロプロパン骨格がラクトン環に１箇所であり炭素－炭素間二重結合が側鎖に１箇所であり、その他の箇所が単結合である。例えば、好ましい態様として、ｎは１であり、シクロプロパン骨格が側鎖に１箇所であり炭素－炭素間二重結合がラクトン環に１箇所であり、その他の箇所が単結合であるか、シクロプロパン骨格がラクトン環に１箇所であり炭素－炭素間二重結合が側鎖に１箇所であり、その他の箇所が単結合である態様が例示できる。また、好ましくは、側鎖はラクトン環の４位に結合している。

[Wherein, n represents an integer of 0 to 3, any one of the dashed lines is a cyclopropane skeleton, 0 to 1 positions other than the cyclopropane skeleton are carbon-carbon double bonds, and other indicates that it is a single bond. ]
Preferably n is an integer from 1 to 3, more preferably 1 or 2, more preferably 1. Preferably, the dashed line has one cyclopropane skeleton, one carbon-carbon double bond, and other single bonds. More preferably, the cyclopropane skeleton is at one site on the side chain of the lactone ring (hereinafter also simply referred to as a side chain), the carbon-carbon double bond is at one site on the lactone ring, and the other sites are single bonds. Alternatively, the cyclopropane skeleton is at one position on the lactone ring, the carbon-carbon double bond is at one position on the side chain, and the other positions are single bonds. For example, in a preferred embodiment, n is 1, the cyclopropane skeleton has one position in the side chain, the carbon-carbon double bond is one position in the lactone ring, and the other positions are single bonds or cyclo An embodiment can be exemplified in which the propane skeleton has one position in the lactone ring, one carbon-carbon double bond in the side chain, and single bonds in the other positions. Also preferably, the side chain is attached to the 4-position of the lactone ring.

Preferred specific examples of the lactone compound of formula (1) include the following compounds of formula (1-1), compounds of formula (1-2), and compounds of formula (1-3). Not limited.

(Production example of lactone compound of formula (1))
Although the means for obtaining the lactone compound of formula (1) is not particularly limited, it can be obtained, for example, by the following method.

(Synthesis example 1)
The lactone compound of formula (1) can be obtained by directly cyclopropanating a lactone compound having a double bond. A lactone compound having a double bond may be either one synthesized according to a general method or a commercially available product.

A lactone compound having a double bond can be synthesized, for example, according to the method described in Reaction Route 1 below. In reaction route 1, R is an alkyl or alkenyl group.

In the above reaction process, propargyl alcohol A (in formula A, PG represents a protecting group) in which the hydroxyl group is protected is used as a raw material, and is ethoxycarbonylated using an arbitrary base and ethyl chloroformate to produce an unsaturated compound having a triple bond. Ester B. A Grignard reagent is added to the unsaturated ester B thus obtained in the presence of a copper reagent to effect a Z-selective conjugate addition reaction to obtain an unsaturated ester C having a double bond. When the obtained unsaturated ester C is deprotected, it proceeds to cyclization and the target lactone compound can be obtained. A general production method for each step will be described below, but the present invention is not limited thereto. The hydroxyl group-protected propargyl alcohol A used as a starting material for the above reaction may be either one synthesized according to a general method or a commercially available product. Examples of protective groups include acetal protective groups such as ethoxyethyl (EE) and tetrahydropyranyl (THP) groups, and silyl protective groups such as t-butyldimethylsilyl (TBS). EE groups are preferred. Although the base used in the ethoxycarbonylation reaction is not particularly limited, n-butyllithium is preferred. Grignard reagents used in conjugate addition reactions can be prepared from the corresponding alkyl halides and magnesium. The alkyl halide may be either one synthesized according to a general method or a commercially available product. The copper reagent to be used includes a copper bromide dimethylsulfide complex, copper bromide, copper iodide and the like, and a copper bromide dimethylsulfide complex is preferred. Deprotection conditions may be appropriately selected depending on the type of protecting group used. An acetal protecting group such as an EE group is generally deprotected by acid hydrolysis, but is not particularly limited. Examples of the acid used for acid hydrolysis include hydrochloric acid and sulfuric acid, with hydrochloric acid being preferred. As the deprotection progresses, it progresses to cyclization and is converted into the desired product.

Reaction pathway 1 is a reaction pathway in which the lactone ring has a side chain at the 4-position. Biotechnolo. Biochem. , 66(1), pp. 135-140 (2002), and in the case of a lactone compound having a side chain at the 5-position of the lactone ring, Biosci. Biotechnolo. Biochem. , 84(8), pp. 1560-1569 (2020).

Reaction route 2 and reaction route 3 will be described below as examples of the cyclopropanation method of a lactone compound, but the cyclopropanation method is not limited to these.

Cyclopropanation methods include Simmons-Smith reaction, Corey-Tchaikovsky reaction, and methods using metal carbenoids prepared from diazo compounds. is preferred, and the Corey-Tchaikovsky reaction is preferred for cyclopropanation of electron-deficient conjugated double bonds such as α,β-unsaturated carbonyl compounds. A metal and diiodomethane are used in the Simmons-Smith reaction, and an alloy of zinc and copper is generally used, but samarium or the like can also be used. In the Corey-Tchaikovsky reaction, trimethylsulfoxonium iodide is treated with a base to convert it to the ylide, and the resulting ylide can be cyclopropanated by reacting it with an α,β-unsaturated carbonyl compound. Examples of the base used for forming the ylide include t-butoxypotassium, sodium bis(trimethylsilyl)amide, sodium hydride and the like, with t-butoxypotassium being preferred. By appropriately selecting the conditions, the double bond at the desired position can be selectively cyclopropanated.

(Synthesis example 2)
As shown in reaction pathways 4 and 5, lactone precursors F and I having double bonds are cyclopropanated, and then lactonized to lactone compounds having a cyclopropane skeleton (in reaction pathway 4, the formula ( 1-1) and compounds of formula (1-2), and in Reaction Scheme 5, compounds of formulas (1-3) and (1-4)).

Lactone precursors F and I having a double bond used as starting materials for the above reaction were synthesized according to a general method (for example, J.Agric.Food.Chem.2019, 67, pp.7410-7415 described method) or a commercially available product. Protective groups (PG) for lactone precursors include acetal protective groups such as ethoxyethyl (EE) and tetrahydropyranyl (THP) groups, and silyl protective groups such as t-butyldimethylsilyl (TBS). EE group is preferred. Examples of R in the lactone precursor include a methyl group, an ethyl group, a propyl group, and an isopropyl group, with the ethyl group being preferred. When the lactone precursor is cyclopropanated by the method described above and the resulting lactone precursor having a cyclopropane skeleton is deprotected, it proceeds to cyclization and is converted into the desired product. Deprotection conditions may be appropriately selected depending on the type of protecting group used. An acetal protecting group such as an EE group is generally deprotected by acid hydrolysis, but is not particularly limited. Examples of the acid used for acid hydrolysis include hydrochloric acid and sulfuric acid, with hydrochloric acid being preferred.

Each lactone compound of formula (1) has an oily (oil-like), waxy (wax-like), lactone-like (feeling including sweetness, creaminess, etc. felt from a lactone compound), herbal , terpenic-like (including slightly petroleum-like sensations that can be exhibited by hydrocarbon-based fragrance compounds and waxy sensations from citrus peels), citrus-like (e.g., lemon-like), citronella-like (plant (e.g., green, citrus-like, etc.). The composition is not particularly limited, but consumer goods such as flavor-imparting compositions (details will be described later), food and drink, cosmetics, and medical hygiene products can be exemplified.

As used herein, flavor means one or more senses that may be altered by smell, typically including smell and/or taste. As used herein, the term "adding flavor" includes newly adding or enhancing the flavor, and for example, the flavor may be improved as a result of the addition. Furthermore, as a result of imparting flavor, sensations other than olfactory and/or gustatory sensations, such as cold sensation, warm sensation, texture (such as throat, hardness, viscosity, etc., also referred to as texture), stimulating sensation such as carbonic acid and hotness. , etc., may be enhanced, suppressed, or improved. Moreover, in this specification, the flavor of food and drink may be called flavor.

(Flavor imparting composition of the present invention)
The flavor-imparting composition of the present invention contains a predetermined amount of one or more lactone compounds of formula (1), and is blended into various articles to impart flavor to the articles (the definition of flavor-imparting is as described above). It is something that can be done. Examples of the flavor-imparting composition of the present invention include compositions capable of imparting aromas to various articles, ie so-called fragrances; various extracts capable of imparting aromas and/or tastes to various articles; and imparting aromas and/or tastes to various foods and drinks. Other food additives that can be used; additives that can impart aroma and/or taste to various cosmetics and medical and sanitary products; but not limited to these.

The flavor-imparting composition of the present invention may contain optional ingredients in addition to the lactone compound of formula (1), but may consist essentially of the lactone compound of formula (1). When the flavor-imparting composition of the present invention also contains components other than the lactone compound of formula (1), the concentration of the lactone compound of formula (1) in the flavor-imparting composition is determined by the target of blending of the flavor-imparting composition and the aroma characteristics. can be arbitrarily determined according to

Examples of such concentrations are in the range of 0.01 ppm to 10%, preferably 0.1 ppm to 1%, based on the total weight of the flavoring composition. More specifically, the lower limit is 0.01 ppm, 0.1 ppm, 1 ppm, 10 ppm, 100 ppm, 1000 ppm, or 1%, and the upper limit is 10%, 1%, 1000 ppm, 100 ppm, 10 ppm, 1 ppm, 0 Any combination of these lower and upper limits may be in the range, but is not limited thereto, as anywhere from .1 ppm. Although it depends on the formulation and flavor of the flavor-imparting composition, if the concentration of the lactone compound of formula (1) in the flavor-imparting composition is less than 0.01 ppm, the blending effect may be felt to be low. , If it exceeds 10%, the scent derived from the lactone compound of formula (1) is strong, and it may be felt that the fragrance and / or flavor properties of the flavor imparting composition to be blended are unfavorably altered. The lactone compound of formula (1) may be blended at a concentration below the lower limit or above the upper limit depending on the flavor of the flavor imparting composition.

In addition to the lactone compound of formula (1), the flavor-imparting composition of the present invention may further contain other optional compounds or components, such as various types of flavoring compounds or flavoring compositions, oil-soluble dyes, , vitamins, functional substances, fish extracts, livestock meat extracts, plant extracts, yeast extracts, animal and plant proteins, animal and plant protein decomposition products, starch, dextrin, sugars, amino acids, nucleic acids, organic acids, solvents etc. can be exemplified. For example, "Patent Office Gazette, Collection of Well-known and Commonly Used Techniques (Fragrance) Part II Food Flavors, Issued on January 14, 2000", "Survey on the Usage of Food Flavoring Compounds in Japan" (2000 Welfare Science Research Report, Japan Perfumery Industry Association, published March 2001) and "Synthetic Perfume Chemistry and Product Knowledge" (published December 20, 2016, enlarged new edition, edited by the Synthetic Perfume Editorial Committee, The Chemical Daily) natural essential oils, natural fragrances, synthetic fragrances, and the like.

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; - undecatriene and the like.

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

Aldehyde compounds include saturated or unsaturated aldehydes such as acetaldehyde, hexanal, octanal, decanal, (E)-2-hexenal, and 2,4-octadienal, citronellal, hydroxycitronellal, citral, myrtenal, perillaldehyde, and the like. aromatic aldehydes such as terpenealdehyde, benzaldehyde, cinnamaldehyde, amylcinnamaldehyde, vanillin, ethylvanillin, heliotropine, and p-tolylaldehyde.

Ketone compounds include saturated or unsaturated ketones such as 2-heptanone, 2-undecanone, 1-octen-3-one, acetoin, diacetyl, 2,3-pentanedione, maltol, ethyl maltol, cyclotene, 2,5- diketones and hydroxyketones such as dimethyl-4-hydroxy-3(2H)-furanone, terpene ketones such as carvone, menthone, nootkatone, ketones derived from terpene degradation products such as α-ionone, β-ionone, β-damascenone, Aromatic ketones such as raspberry ketones are included.

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

Ester compounds include ethyl acetate, isoamyl acetate, ethyl butyrate, ethyl isobutyrate, isoamyl butyrate, ethyl 2-methylbutyrate, ethyl 3-methylbutyrate, 2-methylbutyl isobutyrate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate. , ethyl caproate, isoamyl isovalerate, ethyl nonanoate, etc. Terpene alcohol esters, such as linalyl acetate, geranyl acetate, lavandulil acetate, terpenyl acetate, benzyl acetate, benzyl butyrate, methyl salicylate, benzyl salicylate, cinnamon aromatic esters such as methyl acid, cinnamyl propionate, ethyl benzoate, cinnamyl isovalerate, and ethyl 3-methyl-2-phenylglycidate;

The lactone compounds include saturated or unsaturated lactones such as γ-decen-decenate, γ-dodecalactone, δ-decen-decenate, δ-dodecalactone, 7-decen-4-olide, 2-decene-5-olide.

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

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

Sulfur-containing compounds include methanethiol, dimethylsulfide, dimethyldisulfide, allyl isothiocyanate, 3-methyl-2-butene-1-thiol, 3-methyl-2-butanethiol, 3-methyl-1-butanethiol, 2 -methyl-1-butanethiol, and furfuryl mercaptan.

Natural essential oils include sweet orange, bitter orange, petitgrain, lemon, bergamot, mandarin, neroli, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, hyacinth, lilac, geranium, jasmine, ylang ylang. , anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, labdanum.

Various animal and plant extracts include herb or spice extracts, coffee, green tea, black tea, or oolong tea extracts, milk or processed milk products, and various enzymatic decomposition products thereof such as lipase and/or protease.

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

Examples of the form of the flavor-imparting composition of the present invention include a solution obtained by dissolving the lactone compound of formula (1) and other components in a water-soluble or oil-soluble solvent, an emulsified formulation, a powder formulation, and other solid formulations (such as solid fats). is preferred.

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

Moreover, in order to prepare an emulsified preparation, the lactone compound of formula (1) can be emulsified with a water-soluble solvent and an emulsifier. The method for emulsifying the lactone compound of formula (1) is not particularly limited, and various types of emulsifiers conventionally used in food and drink, such as fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, and propylene glycol fatty acid esters. , sucrose fatty acid ester, polyglycerol fatty acid ester, lecithin, modified starch, sorbitan fatty acid ester, quillaya extract, gum arabic, tragacanth gum, guar gum, karaya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, casein quillaya saponin A highly stable emulsion can be obtained by emulsifying with an emulsifier such as sodium caseinate using a homomixer, a colloid mill, a rotating disc type homogenizer, a high pressure homogenizer, or the like. The amount of these emulsifiers to be used is not strictly limited, and can vary over a wide range depending on the type of emulsifier used. 0.01 to about 100 parts by weight, preferably about 0.1 to about 50 parts by weight. In order to stabilize the emulsification, such a water-soluble solvent liquid contains, 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 blended.

Moreover, the emulsion thus obtained can be made into a powder formulation by drying if desired. At the time of pulverization, saccharides such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, reduced starch syrup, etc., can be added as appropriate. The amount of these agents to be used can be appropriately selected according to the desired properties of the powder formulation.

The flavoring compositions of the present invention may, if desired, further contain ingredients commonly used in flavoring compositions. For example, solvents such as water and ethanol, and perfume retention such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hacoline, medium chain fatty acid triglyceride, medium chain fatty acid diglyceride, etc. agent.

(Use for various articles)
The flavor imparting composition containing the lactone compound of formula (1) of the present invention can be used by blending it in various articles. Flavoring various articles produces flavored articles. Therefore, in the present invention, the method for imparting flavor to various articles can also be said to be a method for producing an article to which flavor is imparted. Here, the various articles to be blended in the present invention may be those in the process of being manufactured by producers, or those that have been put on the market and can be used by consumers. For example, by blending the flavor-imparting composition of the present invention into various consumer goods such as food and drink, cosmetics, and hygiene products, flavor-imparted consumer goods can be produced. may be performed by the producer during the manufacture of the consumer good or by the consumer for the consumer good placed on the market. Further, by blending the flavor-imparting composition of the present invention with another flavor-imparting composition to further impart flavor, a new flavor-imparting composition imparted with flavor may be produced. The imparting composition can also be used in the manufacture of various articles as the flavor imparting composition of the present invention. For example, the flavor-imparting composition containing the lactone compound of formula (1) can be blended into various consumer goods such as food and drink, cosmetics, medical hygiene products, or various articles such as other flavor-imparting compositions. Alternatively, one or more water-soluble flavors, emulsified flavor-imparting compositions, arbitrary flavoring compounds, natural essential oils (for example, the above-mentioned "Patent Office Gazette, Collection of Well-known and Commonly Used Techniques (Fragrance), Part II Foods Fragrance”, “Survey on the actual use of food flavoring compounds in Japan”, and “Synthetic flavoring compounds described in Chemistry and Product Knowledge”). .

There are no particular restrictions on the food or drink in which the flavor imparting composition containing the lactone compound of formula (1) of the present invention can be blended, but examples include lemon, orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, hassaku, and iyokan. , Yuzu, Shikuwasa, Kumquat, etc. Strawberry, Blueberry, Raspberry, Apple, Cherry, Plum, Apricot, Peach, Pineapple, Banana, Melon, Mango, Papaya, Kiwi, Pear, Grape, Muscat, Kyoho Grape, etc. Fruit flavor; milk flavor such as milk, yogurt, butter; vanilla flavor; various tea flavors such as green tea, matcha, roasted tea, black tea, oolong tea, pu-erh tea, herbal tea; coffee flavor; cola flavor; cacao flavor; cocoa flavor; spearmint flavor , various mint flavors such as peppermint; cinnamon, chamomile, cardamom, caraway, cumin, cloves, pepper, coriander, Japanese pepper, perilla, ginger, star anise, thyme, capsicum, nutmeg, basil, marjoram, rosemary, laurel, Various spice or herb flavors such as wasabi and Japanese pepper; various nut flavors such as almonds, cashew nuts, and walnuts; alcoholic beverage (alcohol) flavors such as wine, brandy, whiskey, rum, gin, liqueur, sake, shochu, and beer; vegetable flavor such as tomato and cucumber; That is, it may be a food or drink that makes you feel only one of the above flavors, or it may be a food or drink that makes you feel two or more flavors, and the plurality of flavors may be the same or different. Examples of fruit flavors include those that make you feel multiple fruit flavors such as banana, peach and apple flavors (so-called mixed fruit flavors), and examples of the latter include those that make you feel citrus flavors such as lemon and milk flavors (citrus Flavored lactic acid bacteria beverages, etc.), and those with mint, citrus, and cola flavors (mint or lemon flavored cola beverages, etc.), the lactone compound of formula (1) or a flavor composition containing it It may be any flavor that can be flavored by Examples of flavors that can be suitably used include various fruit flavors typified by citrus; beer flavor; various tea flavors typified by black tea and green tea; milk flavor; Various spice or herbal flavors can include, but are not limited to.

More specific examples of food and drink include senbei, arare rice crackers, rice cakes, rice cakes, steamed buns, uiro, red bean paste, yokan, mizu yokan, kingyoku, jelly, castella, hard candy, biscuits, crackers, potato chips, cookies, Confectionery such as pie, pudding, butter cream, custard cream, cream puff, waffle, sponge cake, donut, chocolate, chewing gum, caramel, candy, paste such as peanut paste; bread, udon, ramen, Chinese noodles, sushi, Gomoku rice, fried rice, pilaf, gyoza skin, shumai skin, okonomiyaki, takoyaki, and other breads, noodles, rice, and other grains; , and their bases for pickles; , octopus such as common octopus and octopus, prawns such as tiger prawns, botan prawns, spiny lobsters and black tigers, crabs such as king crabs, snow crabs, blue crabs and kegani, shellfish such as clams, clams, scallops, oysters and mussels, etc. Seafood; canned fish, boiled fish, tsukudani, surimi, fish paste products (chikuwa, kamaboko, fried kamaboko, crab leg kamaboko, etc.), fried foods, tempura, and other processed seafood foods; chicken, pork, beef, mutton, Meat such as horse meat; curry, stew, beef stew, hayashi rice sauce, meat sauce, mapo tofu, hamburger steak, dumplings, kamameshi mix, soups (corn soup, tomato soup, consommé soup, etc.), meatballs, boiled cubes, meat Processed foods and drinks using livestock meat such as canned foods; table salt, seasoning salt, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hishio, furikake, ochazuke mix, margarine, mayonnaise, dressing, vinegar, sanbaizu, powder Sushi vinegar, Chinese ingredients, tempura sauce, mentsuyu (kelp or bonito stock, etc.), sauces (chuno sauce, tomato sauce, etc.), ketchup, grilled meat sauce, curry roux, stew ingredients, soup ingredients, dashi ingredients (kelp) Dashi or bonito stock), seasonings such as compound seasonings, new mirin, mixed powder such as fried chicken powder and takoyaki powder, animal or plant-based dashi-flavored foods and drinks to which these seasonings are added; Dairy products such as cheese, yogurt, and butter; Boiled vegetables, Chikuzen-ni, oden, hot pot, and other dishes; Fruit juice drinks, juice-containing soft drinks, fruit pulp drinks and fruit drinks containing fruits; vegetables such as tomatoes, green peppers, celery, gourds, bitter melons, carrots, potatoes, asparagus, bracken, and fern, and vegetables containing these vegetables Vegetable-containing beverages such as system drinks and vegetable soups; Coffee, cocoa, green tea, black tea, oolong tea, soft drinks, cola drinks, lactic acid beverages and other beverages; Beverages containing herbal medicines and herbs; Cola drinks, fruit juice drinks, milk Beverages, beer-flavored beverages (also called beer-flavored beverages) including non-alcoholic beer and so-called "third beer", sports drinks, honey beverages, vitamin supplement beverages, mineral supplement beverages, nutritional drinks, nutritional drinks, lactic acid beverages, etc. Functional beverages; Non-alcoholic beverages such as alcohol-flavored beverages with various alcoholic beverages (beer flavor, plum wine flavor, chuhai flavor, etc.); wine, shochu, awamori, sake, beer, chuhai, cocktail drinks, low-malt beer, fruits Sake, spiced sake, so-called "third beer" and other fermented liquors (sparkling) or liqueurs (sparkling), or alcoholic beverages containing these;

There are no particular restrictions on cosmetics or medical hygiene products in which the flavor-imparting composition containing the lactone compound of formula (1) of the present invention can be blended, but examples include perfumes such as eau de cologne, eau de toilette, eau de parfum, and parfum; shampoos and conditioners. , hair care products such as hair care products (hair cream, pomade, etc.); cosmetics such as foundation, lipstick, lip balm, lip gloss, lotion, cosmetic milky lotion, cosmetic cream, cosmetic gel, serum, pack agent; Deodorant products such as antiperspirant sprays, deodorant sheets, deodorant creams, and deodorant sticks; bath agents such as inorganic salt-based, refreshing, carbon dioxide-based, skin care, enzyme-based, and crude drug-based products; sunscreen products such as suntan products and sunscreen products. Cosmetics; Face cleansers such as face soaps and cleansing creams, body soaps and body soaps, laundry soaps, laundry detergents, disinfectant detergents, deodorant detergents, fabric softeners, kitchen detergents, cleaning detergents and other health care products sanitary detergents; health and hygiene materials such as toothpaste, tissue paper, and toilet paper; aromatic deodorants for rooms, cars, etc., and aromatic products such as room fragrances; Usable fragrance tone is not particularly limited, and may be any fragrance tone that can be improved by the lactone compound of formula (1) or the flavor-imparting composition containing the same, such as citrus tone and floral tone. , fruity tone, green tone and the like.

In the present invention, the concentration of the lactone compound of formula (1) in various consumer goods such as food and drink, cosmetics, medical hygiene products, and other flavor-imparting compositions blended with the flavor-imparting composition of the present invention can be arbitrarily determined according to the flavor of the article, the degree of desired effect, and the like.

As an example of the concentration, in the case of other flavor-imparting compositions, the concentrations described in the above section "Flavor-imparting composition of the present invention" can be adopted.

As an example of the concentration, in the case of food and drink, the concentration of the lactone compound of formula (1) is in the range of 10 ppt to 10 ppm with respect to the total weight of the food and drink. More specifically, the lower limit is 10ppt, 100ppt, 1ppb, 10ppb, 100ppb, or 1ppm, and the upper limit is 10ppm, 1ppm, 100ppb, 10ppb, 1ppb, or 100ppt. Including, but not limited to, any combination of ranges. Examples of preferred concentrations include 100ppt to 100ppb, 100ppt to 1ppm, 1ppb to 100ppb, 1ppb to 1ppm, 10ppb to 100ppb, and 10ppb to 10ppb as the concentration of the lactone compound of formula (1) of the present invention with respect to the total weight of food and drink. It can be selected from 1 ppm depending on the flavor characteristics of the food or drink, but is not limited thereto. Although it depends on the type and flavor of the food and drink, if the concentration of the lactone compound of formula (1) in the food and drink is less than 10 ppt, the effect of improving the flavor may be felt to be low. In some cases, it is felt that the aroma of the compound itself is prominent and the flavor of the food and drink to be blended is unfavorably altered.

In the case of cosmetics, the concentration of the lactone compound of formula (1) of the present invention is in the range of 10 ppt to 10% with respect to the total weight of the cosmetics. More specifically, the lower limit is 10ppt, 100ppt, 1ppb, 10ppb, 100ppb, 1ppm, 10ppm, 100ppm, 1000ppm, or 1%, and the upper limit is 10%, 1%, 1000ppm, 100ppm, 10ppm, 1ppm, Any of 100 ppb, 10 ppb, 1 ppb, 100 ppt includes, but is not limited to, any combination of these lower and upper limits. Examples of preferred concentrations include the concentration of the lactone compound of the formula (1) of the present invention with respect to the total weight of the cosmetic, from each range of 1 ppm to 1000 ppm, 10 ppm to 1000 ppm, 10 ppm to 1%, and 100 ppm to 1%. , can be selected according to the fragrance characteristics of cosmetics, but is not limited to these. Although it depends on the type and fragrance of the cosmetic product, if the concentration of the lactone compound of the formula (1) of the present invention in the cosmetic product is less than 10 ppt, the effect of improving the fragrance is low or there is no change. If it exceeds 10%, it may be felt that the fragrance of the cosmetics to be blended is unfavorably altered.

The lactone compound of the formula (1) of the present invention can impart a good aroma or taste to various products, and can, for example, enhance the thickness and aftertaste of the middle to last taste. As a specific example of the effect, for example, by blending an effective amount of the lactone compound of the formula (1) of the present invention into articles such as food and drink and cosmetics, animal and plant materials used in food and drink and cosmetics and the like At least one of the natural feeling, freshness, fruit juice, freshness, depth of taste, richness, oiliness, etc. is enhanced to create a core flavor that maintains a good balance ( Also called lingering). In the present specification, the depth of taste includes the sensation of enhanced overall strength of aroma and taste in a well-balanced manner.

As a specific example, if it is a fruit flavor, it can impart a feeling of fruit juice, a feeling of peel (bitterness, astringency, waxyness, etc.), a thickness of taste, a richness, etc. In particular, it can enhance the feeling of juice and peel of citrus fruits. It can give a natural feeling and a fresh feeling. If it is a tea flavor, it can impart a feeling of tea leaves, a gorgeous aroma peculiar to black tea, and a lingering flavor. If it is a cocoa flavor, richness and depth of taste can be imparted. If it is a chocolate flavor, richness and depth of taste can be imparted. If it is a milky flavor, it can impart richness, depth of taste, and a feeling of milk fat. If it is a beer flavor, it can impart a good aftertaste (aftertaste) unique to beer. The herb flavor can impart freshness, richness, depth of taste, etc., and in particular impart herbal flavor such as lemongrass or rosemary, or impart fresh flavor like freshly grated ginger. can be done. If it is an alcohol, it can impart depth of taste, and can impart a sense of satisfaction that makes it feel satisfying to drink. If it is a floral tone, it is possible to impart a natural feeling and a lingering scent. However, the flavor imparting effect of the lactone compound of formula (1) of the present invention is not limited to these.

Furthermore, the flavor-imparting composition of the present invention has bitterness, astringency, harshness (collectively referred to as astringent taste), off-flavours such as protein odors, and irritation caused by alcohol (typically It can also be used to mask an unpleasant taste such as a hot or burning sensation in the mouth or throat when eating alcohol-containing food or drink, which is called a burning sensation or burning sensation. That is, the flavor-imparting composition of the present invention is blended in foods and drinks that may cause problems such as an astringent taste, protein odor, etc., and unpleasant tastes and odors, and excessive stimulation of alcohol. By imparting richness and/or thickness of taste, it can be used to mask protruding offensive taste and offensive odor and unpleasant taste. Examples of such foods and beverages include foods and beverages containing a high amount of protein. More specifically, protein beverages, concentrated liquid diets, various highly nutritious foods such as highly nutritious beverages, and substitutes using vegetable proteins. Meat (also called vegetable meat), etc., and other examples include, but are not limited to, beverages with a relatively high alcohol concentration and flavored alcoholic beverages that are easy to feel the stimulation of alcohol. . In order to obtain the masking effect, the concentration of the lactone compound of formula (1) in the food or drink can be adjusted. For example, in the concentration range of 10 ppt to 10 ppm described above, by blending in food and drink at a slightly higher concentration, it is possible to sufficiently impart richness and thickness of taste, etc., and sufficiently obtain a masking effect. Examples of the concentration range in which the masking effect is likely to be obtained include a lower limit of 0.1 ppb, 1 ppb, 10 ppb, 100 ppb, 200 ppb, 500 ppb, 1 ppm, and 5 ppm, and an upper limit of 1 ppm, 500 ppb, 200 ppb, 100 ppb, 10 ppb, and 1 ppb. , the concentration range may be any combination of these, specifically, 0.1 ppb to 100 ppb or 1 ppb to 200 ppb can be exemplified, but not limited to these, the desired degree of masking effect and the blending target may be determined according to the flavor of the food and drink.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. In addition, this invention is not limited to these.

[Example 1]
As examples of the lactone compound of formula (1), compounds of the following formulas (1-1) to (1-3) were synthesized. Hereinafter, room temperature means a temperature within the range of about 20°C to about 30°C.

Example 1 (1): Synthesis of compound (5-(4-methyl-3-pentenyl)-3-oxabicyclo[3.1.0]hexan-2-one) of formula (1-1) First, J . Agric. Food. Chem. 2019, 67, pp. 7410-7415 to synthesize ethyl (Z)-3-[(1-ethoxyethoxy)methyl]-7-methylocta-2,6-dienoate (compound α below), followed by the reaction pathway below. was synthesized.

(Step 1) Put trimethylsulfoxonium iodide (2.32 g, 10.5 mmol) and dehydrated dimethyl sulfoxide (DMSO) (20 mL) into a 100 mL two-necked flask, and t-butoxypotassium (KOtBu) (1. 14 g, 10.2 mmol) was added and stirred at room temperature for 30 minutes under an argon atmosphere to prepare the ylide.

Compound A (2.00 g, 7.03 mmol) and dehydrated dimethylsulfoxide (10 mL) were placed in a 200 mL three-necked flask and stirred under an argon atmosphere. The above-prepared ylide was added dropwise over 30 minutes, followed by stirring at room temperature for 6 hours. 20% aqueous ammonium chloride was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was washed twice with 20% brine, dried over magnesium sulfate, and concentrated under reduced pressure to obtain crude product β (1.85 g).

(Step 2) Crude purified product β (1.85 g), tetrahydrofuran (THF) (15 mL) and 1 M hydrochloric acid (15.0 mL, 15.0 mmol) were placed in a 100 mL eggplant flask and stirred for 30 minutes under an argon atmosphere. A saturated sodium bicarbonate aqueous solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a crude product (1.37 g). The resulting crude product was purified by flash silica gel column chromatography (SiO ₂ : 30 g, hexane:ethyl acetate = 13:1), and further purified by Kugelrohr (oven setting: ~230°C/0.27 kPa). 229 mg (18% yield over two steps) of the compound of formula (1-1) was obtained as a colorless oil. This product was designated as Product 1 of the present invention.

The physical properties of the obtained compound of formula (1-1) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.01 (m, 1H), 1.22 (dd, J = 5.2, 9.2 Hz, 1H), 1.54 (m, 1H), 1. 62 (s, 3H), 1.69 (d, J = 1.2Hz, 3H), 1.78-1.88 (m, 2H), 2.08 (q, J = 7.2Hz, 2H), 4.15 (dd, J=0.8, 9.2 Hz, 1 H), 4.20 (dd, J=1.2, 9.2 Hz, 1 H), 5.08 (m, 1 H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 17.6, 18.1, 22.9, 25.6, 25.6, 29.7, 31.7, 72.7, 122.8, 132.9 , 176.5.
IR (total reflection measurement): 2967, 2913, 2855, 1769, 1451, 1361, 1174, 1013, 955, 936, 883, 812 cm ^-1 .
DART-TOFMS: m/z calcd. for _C11H17O2 [M+H] ⁺ 181.1223, found _{181.1226 .}

Example 1(2): Synthesis of compound (4-[2-(2,2-dimethylcyclopropyl)ethyl]furan-2(5H)-one) of formula (1-2) Agric. Food. Chem. 2019, 67, pp. 7410-7415, 4-(4-methyl-3-pentenyl)-2(5H)-furanone (compound γ below) was synthesized according to the following reaction route.

Compound γ (1.00 g, 6.02 mmol), dehydrated diethyl ether (Et ₂ O) (20 mL), and zinc-copper alloy (Zn-Cu, 3.92 g, 60.1 mmol) were placed in a 100 mL three-necked flask, Stir under an argon atmosphere. Diiodomethane (CH ₂ I ₂ ) (15.94 g, 59.5 mmol) was added thereto under gentle reflux over 2 hours, and then heated under reflux for 3 hours.

After cooling the reaction mixture to room temperature, 1M hydrochloric acid was added and the mixture was extracted with diethyl ether. The organic layer was washed with 1M hydrochloric acid and saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate and concentrated under reduced pressure to obtain a crude product (4.79 g). The resulting crude product was purified by flash silica gel column chromatography (SiO ₂ : 50 g, hexane:ethyl acetate = 13:1 → 10:1), and further purified by Kugelrohr (oven temperature: ~ 240 ° C./0.27 kPa ) to obtain 797 mg of the compound of formula (1-2) as a pale yellow oil (yield of all steps: 73%). This product was designated as Product 2 of the present invention.

The physical properties of the obtained compound of formula (1-2) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ-0.05 (t, J=4.4 Hz, 1 H), 0.43-0.54 (m, 2 H), 1.04 (s, 3 H), 1.05 (s, 3H), 1.54 (dq, J=14.4, 7.2Hz, 1H), 1.66 (dq, J=14.4, 7.2Hz, 1H), 2.49 (t, J=7.2 Hz, 2 H), 4.75 (d, J=1.6 Hz, 2 H), 5.85 (quin, J=1.6 Hz, 1 H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 15.7, 19.7, 19.8, 23.8, 27.3, 27.6, 29.0, 73.1, 115.3, 170.5 , 174.1.
IR (total reflection measurement): 2939, 2925, 2889, 2865, 1778, 1743, 1636, 1451, 1169, 1142, 1129, 1026, 885, 849 cm ^-1 .
DART-TOFMS: m/z calcd. for _C11H17O2 [M+H] ⁺ 181.1223, found _{181.1228 .}

Example 1 (3): Synthesis of compound (5-(4-methyl-3-pentenyl)-2-oxabicyclo[3.1.0]hexan-3-one) of formula (1-3) First, J . Agric. Food. Chem. 2019, 67, pp. 7410-7415, followed by synthesis of ethyl (Z)-3-[(1-ethoxyethoxy)methyl]-7-methylocta-2,6-dienoate (Compound α) according to the following reaction scheme. performed the synthesis.

(Step 1) Diisopropylamine (DIPA) (1.60 mL, 11.4 mmol) and dehydrated tetrahydrofuran (THF, 15 mL) were placed in a 100 mL three-necked flask under an argon atmosphere and stirred at -78°C. n-Butyllithium (n-BuLi) (1.59 M hexane solution, 7.00 mL, 11.1 mmol) was added thereto over 35 minutes at the same temperature, and then stirred at -5°C for 45 minutes. The reaction mixture was cooled to −78° C. again, a solution of compound A (2.00 g, 7.03 mmol) in dehydrated tetrahydrofuran (4 mL) was added dropwise over 10 minutes, and the mixture was stirred at the same temperature for 1 hour. Then, ethanol (3 mL) was added to the reaction solution at −60° C. or lower, and after raising the temperature, 20% aqueous ammonium chloride was added. The product was extracted with diethyl ether, and the resulting organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a crude product (2.00 g). The resulting crude product was purified by flash silica gel column chromatography (SiO ₂ : 60 g, hexane:ethyl acetate = 50:1→30:1) to give 1.89 g of compound δ as a colorless oil (yield in step 1). yield 95%, 7:3 diastereomeric mixture).

(Step 2) Compound δ (1.00 g, 3.52 mmol), dehydrated diethyl ether (Et ₂ O) (10 mL), and zinc-copper alloy (259 mg, 3.97 mmol) were placed in a 100 mL three-necked flask and placed in an argon atmosphere. Stirred down. Diiodomethane (CH ₂ I ₂ ) (0.32 mL, 3.97 mmol) was added thereto over 20 minutes while gently refluxing, followed by heating under reflux for 22 hours. After the reaction solution was cooled to room temperature, it was passed through silica gel (SiO ₂ : 10 g, diethyl ether) to remove insoluble matter. The distillate was washed successively with water and saturated brine, dried over magnesium sulfate and concentrated under reduced pressure to obtain a crude product (1.01 g). The resulting crude product was purified by flash silica gel column chromatography (SiO ₂ : 50 g, hexane:ethyl acetate=40:1). The purified product was dissolved in diethyl ether, washed successively with 1M hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine, dried over magnesium sulfate, concentrated under reduced pressure, and subjected to flash silica gel column chromatography (SiO ₂ : 20 g, hexane:ethyl acetate = 35:1) and further purification on Kugelrohr (oven settings: ~210°C/0.13 kPa) to give 71.5 mg of the compound of formula (1-3) as a colorless oil (yield of step 2: 11 %)Obtained. This product was designated as Product 3 of the present invention.

The physical properties of the obtained compound of formula (1-3) were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.66 (d, J = 7.2 Hz, 1 H), 0.86 (m, 1 H), 1.39 (dt, J = 14.4, 7.2 Hz , 1H), 1.62 (s, 3H), 1.69 (m, 1H), 1.69 (s, 3H), 2.09 (q, J = 7.2Hz, 2H), 2.57 ( d, J = 18.8Hz, 1H), 2.72 (dd, J = 1.6, 18.8Hz, 1H), 4.07 (d, J = 4.4Hz, 1H), 5.09 (m , 1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 17.6, 20.4, 21.9, 25.7, 25.7, 34.4, 37.1, 61.3, 123.0, 132.6 , 176.9.
IR (total reflection measurement): 2967, 2916, 2855, 1777, 1442, 1414, 1377, 1295, 1145, 1101, 1065, 999, 984, 895, 862, 818, 768, 732, ^{556 cm -1} .
DART-TOFMS: m/z calcd. for _C11H17O2 [M+H] ⁺ 181.1223, found _{181.1222 .}

[Example 2] Aroma characteristics of the synthesized lactone compound of formula (1) Each lactone compound of formula (1) obtained in Examples 1 (1) to (3) (that is, formula (1-2) and compounds of formula (1-3)) were evaluated for aroma. In the odor evaluation, five well-trained panelists with more than 10 years of experience smelled and commented on the odors they sensed. )-furanone (Japanese Patent Laid-Open No. 2017-025182) was used as a control product, and comments were also made on the aroma intensity compared with the control product. Representative comments are shown in Table 1 below.

As shown in Table 1, the compounds of formulas (1-1), (1-2) and (1-3), which are lactone compounds of formula (1) of the present invention (Invention Products 1 to 3), Each had a characteristic scent. The same lactone compound, the control product (4-(4-methyl-3-pentenyl)-2(5H)-furanone), also has properties that are not present, and each lactone compound of formula (1) of the present invention is a control product. It can be said that it is possible to impart a flavor different from that of the product compound. In addition, each lactone compound of the formula (1) of the present invention has a stronger aroma intensity than the compound of the control product, and it can be said that even a trace amount of the lactone compound provides an aroma-imparting effect and is economical.

[Example 3] Effect of blending in fruity flavor composition A lemon-like basic blended flavor composition was prepared according to the general formulation in Table 2 below.

To the obtained basic blended fragrance composition, each lactone compound of formula (1) obtained in Examples 1 (1) to (3) was added to a concentration of 0.1 relative to the total mass of the basic blended fragrance composition. % to obtain the flavor imparting compositions of the present invention (Inventive Products 4 to 6). Then, seven well-trained panelists with 10 years or more of experience were asked to evaluate the aroma of the flavor-imparting composition of the present invention, using the above-mentioned basic blended flavor composition as a control. As a result, all seven panelists said that the flavor-imparting composition of the present invention remarkably enhanced the waxy feeling and oily feeling of citrus peel, the freshness of freshly squeezed lemon fruit, and the lingering aroma. I answered.

[Example 4] Effect of blending in fruit-flavored food and drink As shown in Table 3 below, the fruit-flavored beverage of the present invention was prepared by blending so that it was 0.1 ppb, 0.1 ppm or 1 ppm with respect to the total lemonade mass. The natural feeling of the fruit-flavored beverage of the present invention was sensory evaluated using a commercially available packaged lemonade as a control. Specifically, 10 well-trained panelists with 10 years or more of experience were asked about the natural feeling compared to the control product. = 2 points, and "no change" = 1 point. Here, the term "natural feeling" means that some flavor reminiscent of lemon fruit as a raw material is enhanced, and a natural flavor as if more lemon was used. Table 3 below shows the average scores and typical comments of the 10 panelists.

As shown in Table 3, it was confirmed that each lactone compound of formula (1) exerts a characteristic flavor-imparting effect typified by fruit skin feeling and richness. In addition, it was confirmed that the flavor-imparting effect can be obtained at least within the concentration range of 0.1 ppb to 1 ppm in food and drink, and as a result, the natural feeling can be enhanced.

[Example 5] Effect of blending in tea beverages In a commercially available unsweetened black tea, each lactone compound of formula (1) obtained in Examples 1 (1) to (3) was added to the concentration of unsweetened black tea total weight to 100 ppb to obtain the milk-flavored beverage of the present invention. Then, sensory evaluation was performed by 10 well-trained panelists with 10 years or more of experience regarding the flavor of the tea beverage of the present invention compared with the control product, using a commercially available sugar-free black tea as a control product. Specifically, the 10 panelists were asked about the desirability compared to the control product: “greatly improved” = 4 points, “improved” = 3 points, “slightly improved” = 2 points, “no change = 1 point, and commented on the flavor. Here, liking means feeling that it is delicious and makes you want to drink it next time. Table 4 below shows the average scores and typical comments of the 10 panelists.

As shown in Table 4, each of the lactone compounds of formula (1) was confirmed to have a characteristic flavor-imparting effect typified by the rich flavor of tea leaves and the gorgeous aroma of black tea. was done. In addition, it was confirmed that the flavor imparting effect can be obtained at least within the concentration range of 0.1 ppb to 1 ppm in food and drink.

[Example 6] Effect of blending in beer-flavored beverages In a commercially available non-alcoholic beer, each lactone compound of the formula (1) obtained in Examples 1 (1) to (3) was added to the concentration of the total non-alcoholic beer. Non-alcoholic beer beverages of the present invention (Products 25 to 27 of the present invention) were obtained by blending so as to be 50 ppb relative to the mass. Then, using a commercially available non-alcoholic beer as a control product, the flavor of the beer-flavored beverage of the present invention compared with the control product was subjected to a sensory evaluation by five well-trained panelists with 10 years or more of experience. As a result, all five panelists found that the beer-flavored beverages of the present invention had enhanced richness and depth of taste compared to the control product, the aftertaste of the flavor lasted longer, and the feeling of satisfaction after drinking increased. , responded that the flavor became more favorable. Among them, the product 26 of the present invention blended with the compound of formula (1-2) and the product 27 of the present invention blended with the compound of formula (1-3) have an enhanced citrus-like flavor reminiscent of hops and have a particularly favorable flavor. answered that it had become

[Example 7] Effect of blending in chocolate-flavored food and drink Each lactone compound of formula (1) obtained in Examples 1 (1) to (3) was added to a commercially available chocolate drink (with milk) at a concentration of The chocolate-flavored beverages of the present invention (Products 28 to 30 of the present invention) were obtained by blending at a concentration of 100 ppb with respect to the total weight of the chocolate drink. Then, using a commercially available chocolate drink as a control product, sensory evaluation was performed by five well-trained panelists with more than 10 years of experience on the flavor of the chocolate-flavored beverage of the present invention compared to the control product, and what kind of flavor was enhanced. I was asked to answer whether or not it was done. As a result, all five panelists found that all of the chocolate-flavored beverages of the present invention had an overall enhanced chocolate flavor, a richer taste, and a more favorable flavor than the control commercial chocolate drink. I answered that I did. Among them, the product 28 of the present invention blended with the compound of formula (1-1) and the product 29 of the present invention blended with the compound of formula (1-2) are particularly enhanced in the richness of fats and oils reminiscent of cacao fat and milk fat. They answered that they had a favorable flavor.

[Example 8] Effect of blending on cocoa flavor To commercially available milk cocoa, each lactone compound of formula (1) obtained in Examples 1 (1) to (3) was added at a concentration of The cocoa-flavored beverages of the present invention (Products 31 to 33 of the present invention) were obtained by blending to a concentration of 50 ppb. Then, using commercially available milk cocoa as a control product, the flavor of the cocoa-flavored beverage of the present invention compared to the control product was subjected to a sensory evaluation by five well-trained panelists with 10 years or more of experience. I was asked to answer whether or not it was done. As a result, all five panelists found that all of the cocoa-flavored beverages of the present invention had a more favorable flavor with an overall enhanced cocoa fragrant flavor and an increased depth of taste compared to the commercial milk of the control product. I answered that I did. Among them, the product 31 of the present invention blended with the compound of formula (1-1) and the product 32 of the present invention blended with the compound of formula (1-2) have enhanced richness of milk reminiscent of milk fat and have a particularly favorable flavor. I answered that I did.

[Example 9] Blending effect on various spice flavors Commercially available ginger-flavored paste, lemongrass-flavored paste, and rosemary-flavored paste were added to each of the formulas (1) obtained in Examples 1 (1) to (3). A lactone compound is blended so that its concentration is 100 ppb with respect to the total mass of each paste, and the spice-flavored paste of the present invention (ginger-flavored paste ... present invention products 34 to 36, lemongrass-flavored paste ... present invention product 37 to 39, rosemary-flavored pastes 40 to 42) of the present invention were obtained. Then, using a commercially available paste of each flavor as a control product, the flavor of the paste of each flavor of the present invention compared to the control product was subjected to a sensory evaluation by four well-trained panelists with more than 15 years of experience. Respondents were asked whether the flavor was enhanced.

As a result, with regard to the ginger-flavored paste, all four panelists answered that the richness of the oil, the thickness of the taste, and the aftertaste of the products 34 to 36 of the present invention were all enhanced and had a favorable flavor. The product 36 of the present invention, in which the compound of 3) was blended, was answered to have a particularly favorable flavor with enhanced freshly grated ginger-like stimulating sensation.

Regarding the lemongrass-flavored paste, all four panelists answered that the richness of the oil, the thickness of the taste, and the lingering finish of the products 37 to 39 of the present invention were all enhanced, resulting in a favorable flavor. The product 38 of the present invention, in which the compound of (1) was blended, enhanced the refreshing green and citrus-like flavor peculiar to lemongrass, resulting in a particularly favorable flavor.

Regarding the rosemary-flavored paste, all four panelists answered that the richness of the oil, the thickness of the taste, and the aftertaste of the products 40 to 42 of the present invention were enhanced. The product 41 of the present invention, which contains the above, enhanced the refreshing flavor peculiar to rosemary, resulting in a particularly favorable flavor.

[Example 10] Effect of blending in protein beverage In a commercially available protein beverage, each lactone compound of formula (1) obtained in Examples 1 (1) to (3) was added at a concentration of The protein beverages of the present invention (Products 43 to 45 of the present invention) were obtained by blending to a concentration of 200 ppb. Then, using a commercially available protein drink as a control, four well-trained panelists with 10 years or more of experience were asked to answer changes in the flavor of the protein drink of the present invention compared to the control. As a result, all four panelists found that all the protein drinks of the present invention had a richer taste than the control product, the commercially available protein drink, and reduced the unique bitterness and astringency felt in high-concentration proteins. , The so-called protein odor was weakened, and the overall feeling of satisfaction after drinking increased.

[Example 11] Effect of blending in jasmine-like fragrance composition A jasmine-like basic blended fragrance composition was prepared according to the general formulation shown in Table 5 below.

Each of the lactone compounds of the formula (1) of the present invention obtained in Examples 1 (1) to (3) was added to the obtained jasmine-like basic blended perfume composition so that the concentration was 1 ppm. Thus, flavoring compositions of the present invention (Inventive Products 46 to 48) were prepared. Then, using the jasmine-like basic blended fragrance composition as a control, the fragrance of the flavor-imparting composition of the present invention was subjected to sensory evaluation by four well-trained panelists with 10 years or more of experience. I asked him to answer about Taka. As a result, all four panelists found that all the flavor imparting compositions of the present invention had a higher intensity of floral fragrance and a longer lingering aftertaste compared to the basic blended fragrance composition of the control product. In addition, the present invention product 46, which contains the compound of formula (1-1), has enhanced sweetness, which is one of the characteristics of jasmine, and the present invention product 47, which contains the compound of formula (1-2). They answered that the product 48 of the present invention containing the compound of formula (1-3) also enhanced the somewhat green sensation reminiscent of flower petals.

As described above, it was confirmed that each lactone compound of formula (1) exerts an excellent flavor-imparting effect in various flavors and is useful for imparting flavor to articles.

Claims (5)

A lactone compound having a cyclopropane skeleton, represented by the following formula (1-1), (1-2) or (1-3) .

A flavoring composition comprising the lactone compound of claim 1 . A consumer product comprising the flavoring composition of claim 2 . A method of flavoring a consumer product comprising incorporating the flavoring composition of claim 2 into the consumer product. 3. A method for imparting flavor to a flavor imparting composition, comprising blending the flavor imparting composition according to claim 2 to another flavor imparting composition.