Perfume composition

Abstract

To provide a perfume compound with different characteristics to deliver fragrances such as naturalness, authenticity or luxury, and to ensure prolonged perfume persistence.SOLUTION: Epidihydrokaranone represented by the following formula (1) and / or (2) is used as a perfume compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel epidihydrocalanone-containing fragrance composition, which can impart a sweet feeling, a natural feeling, an authentic feeling, and a luxurious feeling, and to a fragrance composition containing epidihydrocalanone and dihydrocalanone. [Background technology]

[0002] The market is flooded with scented products, and there is a demand for differentiation of products through scent. In particular, for food, beverages, and cosmetics, which have a wide variety of scents, there is a demand for a harmonious scent that meets requirements such as fragrance quality that matches the product image, fragrance tone, fragrance strength, and persistence (aftertaste and lingering scent). Therefore, in order to create fragrance compositions based on new needs, fragrance companies are constantly searching for fragrance compounds with new fragrance tones and qualities, and making efforts to meet customer demands. Thanks to the tireless efforts of fragrance companies, a great number of synthetic and natural fragrances have been discovered to date. However, the demands for a natural feel, a luxurious feel, and an authentic feel for foods, beverages, and cosmetics are becoming higher, and there is still a demand for fragrance compounds that can satisfy these high demands. For example, if there were a fragrance composition that could impart a natural feel and a luxurious feel (fragrance quality) to the aroma (fragrance note) of black tea or the aroma (fragrance note) of roses, it would be an effective means for producing authentic black tea beverages and luxurious fabric softeners, and the value of the black tea beverages and fabric softeners could be improved with that aroma.

[0003] 2. Description of the Related Art Adding a sweet sensation is an effective means for imparting a natural, luxurious, and authentic feel to foods, beverages, fragrances, and cosmetics. For example, Patent Document 1 describes that the use of perhydro-3,6-dimethyl-3a,7a-epoxybenzo[b]furan-2(3H)-one can emphasize the sweet, milky or sweet fragrance of foods and beverages such as vanilla ice cream and starch syrup, or cosmetics such as shampoo, thereby enhancing the natural feel. Furthermore, Patent Document 2 describes that cis- and / or trans-2-pentylcyclopropane-1-carboxylic acid imparts a fermented sweetness and aged flavor that only natural flavors have to spearmint-like, peppermint-like, dairy product-like (butter-like, milk-like, cheese-like, etc.) flavors, chocolate-like, tropical fruit-like, citrus-like flavors, and other food flavors, and also envelops and balances the entire flavor, enhancing the natural feel.

[0004] Furthermore, it is desired that a fragrance composition not only has a good fragrance quality and tone, but also that the fragrance lasts for a long time. In order to increase the persistence of fragrance, methods of adjusting the volatility of fragrance have been considered. For example, capsule fragrances (Patent Document 3, etc.) that suppress the volatilization of fragrance by encapsulating the fragrance and a technology for sustained release of fragrance by polymers (Patent Document 4, etc.) have been developed. However, when using a fragrance composition that uses auxiliary agents such as capsules or polymers, or when adjusting the amount of fragrance to increase the remaining amount of fragrance, the fragrance may last too long or the scent may be stronger than necessary, causing discomfort. In this way, attention has been focused in recent years on optimizing the duration and intensity of a fragrance, that is, the property of having a fragrance that lasts for a long time and gradually disappears at a concentration that is not unpleasant to anyone and that can be perceived as natural.

[0005] In particular, for fragrance compounds used in foods and beverages (e.g., tea, coffee, beer, etc.) and cosmetics (e.g., perfume, shampoo, fabric softener, etc.) that are expected to have a natural feel, a luxurious feel, and a lingering aftertaste (a luxurious aroma that lasts for a while, leaving you feeling its elegance and flavor), There is a high demand for the persistence of these scents.

[0006] If there was an aroma imparting agent that could give a lingering aroma to foods, beverages, and cosmetics without altering their fragrance, it would be possible to improve the value of the product without changing the existing fragrance. Therefore, technological development of auxiliary agents that do not have their own fragrance has progressed. However, with fragrance compounds that use auxiliary agents, it is difficult to achieve both a natural fragrance that fades away over time and a pleasant fragrance intensity. Therefore, there is a search for fragrance compounds that take advantage of the characteristic of fragrance compounds that gradually lose their scent due to their own volatility, do not alter the fragrance notes of other fragrances, and have the property of being highly long-lasting.

[0007] It is widely known in the art of fragrance compounds that even small changes in the chemical structure of a fragrance compound can result in significant changes in the sensory properties, e.g., odor and taste, or incompatibility with other fragrance compositions. Furthermore, even fragrance compounds that differ only in their three-dimensional structures may exhibit different sensory characteristics with different aroma features and aroma intensities (Patent Document 5). In other words, in the technical field of fragrance compounds, the sensory characteristics of a fragrance compound cannot be accurately predicted based only on its chemical structure, three-dimensional structure, or affinity with a specific olfactory receptor. In order to search for fragrance compounds that impart a sweet sensation to foods, beverages, and cosmetics to improve their natural, luxurious, and authentic feel and that also have long-lasting aromas, it is necessary to carry out sensory evaluations of many fragrance compounds at various concentrations, which requires an enormous amount of time and effort, and therefore few such fragrance compounds have been found. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2019-182766 A [Patent Document 2] Japanese Patent Application Publication No. 10-165132 [Patent Document 3] JP 2004-99743 A [Patent Document 4] Special Publication No. 2009-518492 [Patent Document 5] JP 2012-17274 A [Patent Document 6] JP 2004-189643 A [Patent Document 7] Patent Publication No. 2022-68828 [Non-patent literature]

[0009] [Non-Patent Document 1] J. Org. Chem.,1984, 49, 5282-5283 [Non-Patent Document 2] J. Am. Chem. Soc., 1986, 108, 7791-7800 [Non-Patent Document 3] J. Chem. Soc. Perkin Trans. 1, 1992, 387-396 [Non-Patent Document 4] Helvetica Chimica Acta,1988, 71, 977-980 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention relates to a fragrance compound, which was discovered after extensive trial and error within the above-mentioned technical common knowledge in the technical field of fragrance compounds, and which has different properties of imparting a fragrance with a natural feel, authentic feel, and luxurious feel, and also imparting long-lasting fragrance properties. An object of the present invention is to provide a compound that can be used to impart flavor to various products such as flavor compositions, foods and beverages, and cosmetics. [Means for solving the problem]

[0011] As a result of intensive research, the present inventors have found that a compound represented by the following formula (1) and / or the following formula (2) (epidhydrocalanone), which has not been known to be used as a fragrance, has long-lasting and voluminous properties. The inventors discovered that this compound has a sweet, mellow flavor that goes well with a variety of fragrances, and that the use of this compound can solve the above problems, and thus filed the present application. [ka]

[0012] In other words, the present application provides a fragrance imparting agent based on the fact that epidihydrocalanone can impart a natural feel and a sense of luxury to fragrance compositions, foods and beverages, and cosmetic products, while at the same time improving the persistence of their fragrances (lasting fragrance and lingering aftertaste). Although epidihydrocalanone itself is reported in the above-mentioned Non-Patent Documents 1 to 4 and Patent Document 6, there is no description of its fragrance, and it was not known that epidihydrocalanone was useful as a fragrance.

[0013] Specifically, the present invention is as follows. [1] A fragrance imparting agent comprising epidihydrocalanone represented by the following formula (1) and / or formula (2) as an active ingredient: [ka] [2] A fragrance composition comprising the fragrance imparting agent of [1]. [3] A method for imparting fragrance, comprising using epidihydrocalanone represented by the above formula (1) and / or formula (2) as a fragrance component. [4] A fragrance lingering enhancer comprising epidihydrocalanone represented by the above formula (1) and / or formula (2) as an active ingredient. [5] A method for improving fragrance lingering, comprising using epidihydrocalanone represented by the above formula (1) and / or formula (2) as a fragrance lingering improving component. [6] A method for producing a food or beverage, comprising adding epidihydrocalanone represented by the above formula (1) and / or formula (2). [7] A method for producing a cosmetic product, comprising adding epidihydrocalanone represented by the above formula (1) and / or formula (2). [8] A fragrance imparting agent comprising, as an active ingredient, a mixture containing epidihydrocalanone represented by the above formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4). [ka] A fragrance composition comprising the fragrance imparting agent according to [9][8].

[10] A method for using a mixture containing epidihydrocalanone represented by the above formula (1) and / or formula (2) and dihydrocalanone represented by the above formula (3) and / or formula (4) as a fragrance component.

[11] A method for perfumery, comprising using a mixture of epidihydrocalanone represented by the above formula (1) and / or formula (2) and dihydrocalanone represented by the above formula (3) and / or formula (4) in a ratio of 1:99 to 80:20 as a perfumery component.

[12] A method for imparting lingering properties to a fragrance compound, comprising adding a mixture containing epidihydrocalanone represented by the above formula (1) and / or formula (2) and dihydrocalanone represented by the above formula (3) and / or formula (4) to the fragrance compound.

[13] A method for imparting a lingering aftertaste to a fragrance compound, comprising adding to the fragrance compound a mixture of epidihydrocalanone represented by the above formula (1) and / or formula (2) and dihydrocalanone represented by the above formula (3) and / or formula (4) in a ratio of 1:99 to 80:20.

[14] A method for producing a food or beverage, comprising adding a mixture containing epidihydrocalanone represented by the above formula (1) and / or formula (2) and dihydrocalanone represented by the above formula (3) and / or formula (4).

[15] A method for producing a cosmetic product, comprising adding a mixture containing epidihydrocalanone represented by the above formula (1) and / or formula (2) and dihydrocalanone represented by the above formula (3) and / or formula (4). Effect of the Invention

[0014] The present invention can impart a sweet feeling, a natural feeling, a luxurious feeling, an authentic feeling, and the like to foods, beverages, and fragrances and cosmetics, and can also impart a lingering fragrance. Furthermore, by using it in combination with dihydrocalanone (Patent Document 7), which is known to have a fragrance lingering effect, a new effect of a lingering fragrance can be imparted. The lingering aroma is "the memorable, deep emotion or taste that one gets from the aroma of authenticity or luxury that lingers for some time." DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The epidihydrocalanone used in the present invention is a compound having the structure of the following formula (1) or formula (2). [ka] Epidihydrocalanone can be produced by known methods described in Non-Patent Documents 1-4. For example, as described in Patent Document 6, [ka] By the process described above, it is possible to produce a mixture containing dihydrocalanone as described in Patent Document 7, and epidihydrocalanone can be obtained in the form of a racemate by separating it from dihydrocalanone by the method described in Non-Patent Document 2.

[0016] When a racemic mixture of epidihydrocalanone is obtained, it is possible to separate it into its optical isomers by known methods. Alternatively, optically active epidihydrocalanone can be obtained by using optically active cis-2-hydroxycyclohexanecarboxylic acid as a starting material and by the method described in Non-Patent Document 4. However, for the purpose of the present invention, it can be used in the form of a racemate.

[0017] Dihydrocalanone is a compound having the structure of the following formula (3) and / or formula (4), and is a diastereomer of epidihydrocalanone. [ka]

[0018] The aroma imparting agent of the present invention can also be used in foods, beverages, and cosmetics.

[0019] Food and beverages include foods, beverages, spices, seasonings, medicines, and other items that can be consumed. say. Examples of these foods and beverages include sports drinks, carbonated drinks, nutritional drinks, fruit juice drinks, coffee drinks with milk, black tea, and other beverages; dairy drinks such as processed milk and soy milk; thick liquid foods for nutritional supplementation; ice creams such as lacto ice cream; bread and confectioneries such as bread, biscuits, candy, and jelly; processed dairy and meat foods such as yogurt and ham; seasonings such as white sauce, miso, sauces, sauces, and dressings; processed oil and fat foods such as margarine, fat spreads, and shortening; powdered foods such as powdered drinks and powdered soups; health foods in capsule, tablet, powder, granule, etc., tofu, noodles, and the like; there is no particular restriction on the scope of these foods and beverages, and they refer to all kinds of foods and beverages.

[0020] Additionally, the term "cosmetics" refers to perfumes, air fresheners, makeup products, toiletry products, skin care products, hair care products, and household products, as described below. "Perfume" refers to eau de toilette, eau de parfum, eau de cologne, etc., and comes in bottle, roll, and spray types depending on the purpose. "Fragrance" includes aqueous liquid fragrances, oil-based liquid fragrances, aqueous gel fragrances, oil-based gel fragrances, fragrance sprays, fragrance aerosols, impregnated fragrances, incense, fragrance deodorants, deodorant sprays, deodorant aerosols, and the like. "Makeup products" are used for the aesthetic purpose of making the face look beautiful, for the protective purpose of protecting the skin, and for the purpose of bringing enjoyment and satisfaction. Examples include makeup cosmetics such as foundation, lipstick, lip balm, blusher, eyeliner, mascara, eye shadow, eyebrow pencil, eyebrow pencil, powder face powder, solid face powder, nail enamel, nail polish, nail polish remover, etc. "Toiletries" include body care products such as soap, hand soap, bath salts, body shampoo, and lip balm, sunscreen, antiperspirant deodorants, shaving products (razors, shaving razors, shaving foam, etc.), toothpaste, mouthwash, dental floss, denture cleaner and other oral care products, wet tissues, disposable diapers, and sanitary products. "Skin care products" have functions such as removing sweat and dirt, tightening the skin, maintaining proper nutrients and moisture, supporting normal skin condition, and protecting the skin from ultraviolet rays. Products include washing cream, vanishing cream, facial wash cream, cleansing cream, cold cream, sunscreen cream, milk lotion, toner, pack, makeup remover, aftershave lotion, talcum powder, lip balm, hand cream, antiperspirant, and face care (facial cleanser, makeup remover, cleansing oil, blotting paper, etc.). "Hair care products" are products used for cleaning and protecting hair and scalp, as well as styling hair, and include shampoos, rinses, conditioners, tonics that improve blood circulation in the scalp, hair oils, pomades, balms, hair liquids, setting lotions, hair gels, hair sprays, hair foams, hair wax and other hair styling products, hair dyes such as hair color, hair manicure, bleach and gray hair dye, hair transformation products such as perms and curling agents, hair treatments and other hair growth products, etc. "Household products" include clothing products such as detergents and fabric softeners used in ordinary households, housing and furniture products such as cleaners and wax, kitchen products such as bleach and food waste deodorizers, and daily miscellaneous products such as office glue and paints. Examples of such products include liquid laundry detergent, powder laundry detergent, solid laundry soap, laundry fabric softener, laundry bleach, kitchen detergent, dish dryer detergent, bath cleaner, glass cleaner, mold remover, drain cleaner, fumigation agent, mosquito coils, insecticide, insect repellent, and toilet cleaner.

[0021] There is no limit to the amount of the fragrance imparting agent of the present invention used, and it can be used as long as it produces the desired effect. It is desirable to use the fragrance imparting agent of the present invention so that epidihydrocaranone is present at 100 ppb to 10,000 ppm in the fragrance composition. A more preferable concentration is m, and a more preferable concentration is 500 ppb to 500 ppm.

[0022] The fragrance imparting agent of the present invention can be used in combination with various fragrance compositions. There is no particular limitation on the range of fragrance of the fragrance composition to be used in combination, but the optimal desired effect can be obtained by combining it with a rose-type fragrance having a leafy nuance, a floral-type fragrance, black tea, coffee, beer, or vanilla.

[0023] The fragrance imparting agent of the present invention can be used alone in fragrance compositions, foods, beverages, and cosmetics to impart a natural, luxurious, and authentic feel to the fragrance, and can also improve the lingering scent of the fragrance.The fragrance imparting agent of the present invention can be used together with dihydrocalanone in fragrance compositions, foods, beverages, and cosmetics to improve the lingering scent of the fragrance.

[0024] The blending ratio of epidihydrocalanone to dihydrocalanone is not particularly limited as long as the desired effect is achieved, but is suitably in the range of 1:99 to 80:20, preferably 1:99 to 70:30, more preferably 1:99 to 50:50, particularly preferably 1:99 to 30:70, and even more preferably 5:95 to 30:70.

[0025] In the present invention, lingering fragrance means that the initial fragrance lasts for a long time without any change in fragrance tone, or the quality of lasting, and lingering aftertaste means the effect of feeling the atmosphere and flavor for a while due to the lingering of a luxurious fragrance. Next, the present invention will be explained in more detail by showing Test Examples and Examples, but the present invention is not limited to these Test Examples and Examples. EXAMPLES

[0026] [Test Example 1] Epidihydrocalanone was prepared in the following manner.

[0027] [Production of 2,3-dimethylcyclohexanone] Commercially available 2,3-dimethylcyclohexanol (Tokyo Chemical Industry Co., Ltd.) (69 g) was dissolved in acetic acid (270 g), and sodium hypochlorite aqueous solution (495 g) was added dropwise in an ice bath. After the reaction was completed, neutralization, decomposition of excess sodium hypochlorite, solvent extraction, drying, solvent distillation, and distillation were performed to obtain 65 g of 2,3-dimethylcyclohexanone (boiling point: 80°C / 2000 Pa).

[0028] [Production of 4a,5-dimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one] 2,3-Dimethylcyclohexanone (29g), dichloromethane (580g), and methyl vinyl ketone (32g) were mixed and cooled to -55℃, and then methanesulfonic acid (44g) was added dropwise, gradually warmed, and reacted overnight. After the reaction was completed, neutralization, solvent extraction, drying, solvent distillation, and column purification (silica gel, ethyl acetate:hexane = 1:4) were performed, and 11g of 4a,5-dimethyl-4,4a,5,6,7,8-hexahydronaphthalene-2(3H)-one (boiling point: 96-99℃ / 180Pa) was obtained by distillation.

[0029] [Preparation of a mixture of epidihydrocalanone and dihydrocalanone] After cooling the lithium diisopropylamide solution (2M, 78mL) to -70°C, a solution of 4a,5-dimethyl-4,4a,5,6,7,8-hexahydronaphthalene-2(3H)-one (11g) in tetrahydrofuran (60mL) was added dropwise at -65 to -50°C. Then, a solution of zinc chloride in 2-methyltetrahydrofuran (2M, 48mL) was added dropwise at -40 to -30°C. Furthermore, a solution of acetone (5g) in tetrahydrofuran (36mL) was added dropwise at the same temperature, and the temperature was gradually raised to 0°C to react. After the reaction was completed, the mixture was quenched by adding an ammonium chloride solution, and then the mixture was extracted with a solvent, dried, and the solvent was distilled off to obtain a crude product of 3-(2-hydroxypropan-2-yl)-4a,5-dimethyl-4,4a,5,6,7,8-hexahydronaphthalene-2(3H)-one (15.4g). To the crude product, heptane (300 g) and p-toluenesulfonic acid monohydrate (0.3 g) were added, and the mixture was heated and reacted for 2 hours using a Dean-Stark apparatus. After the reaction was completed, the mixture was cooled, neutralized, washed with water, dried, and the solvent was removed by distillation. The residue was purified by column (silica gel, ethyl acetate:hexane = 1:12) and then distilled to obtain 8 g of a mixture of epidihydrocaranone and dihydrocaranone (boiling point: 105-118 °C / 180 Pa).

[0030] [Separation and purification of epidihydrocalanone] The mixture of epidihydrocalanone and dihydrocalanone was subjected to column chromatography (silica gel, ethyl acetate:hexane=1:9) to obtain epidihydrocalanone. (Boiling point: 120°C / 65Pa) The epidihydrocalanone obtained was identified by NMR spectroscopy. Hereinafter, the racemic form of epidihydrocalanone produced in Test Example 1 will be referred to as epidihydrocalanone.

[0031] 13 C NMR(100MHz,CDCl3,δppm) 16.3,20.7,22.1,22.5,24.0,28.6,31.0,38.6,39.4,42.0,128.1,128.8,142.1,167.3,192.0 1H NMR(400MHz, CDCl3, δppm) 0.93(d,3H),1.16(d,3H),1.39-1.47(m,1H),1.61-1.68(m,2H),1.73-1.79(m,1H),1.81(d,3H),1. 87-1.97(m,1H),2.07(d,3H),2.17-2.24(m,1H),2.28-2.38(m,2H),2.49-2.56(d,1H),5.79(d,1H)

[0032] [Test Example 2] (Effect of adding to black tea beverages) Epidihydrocalanone was added to commercially available bottled black tea beverages to the concentrations shown in Table 1 to prepare the black tea beverages of Test Examples 2-1 to 2-5. The resulting black tea beverages of Test Examples 2-1 to 2-5 were then evaluated by 10 expert panelists who had undergone training in advance. The sensory evaluation was performed by having expert panelists comment on the aroma when comparing Test Examples 2-1 to 2-5 with a black tea beverage without added epidihydrocalanone as Comparative Example 1, and by averaging the scores given by the expert panelists for the tea leaf feel according to the following evaluation criteria.

[0033] <Evaluation criteria for tea leaf texture> Significantly increased compared to Comparative Example 1: 4 Significant increase compared to Comparative Example 1: 3 There was a certain increase compared to Comparative Example 1: 2 Slightly increased compared to Comparative Example 1: 1 Equivalent to Comparative Example 1: 0

[0034] [Table 1]

[0035] At a concentration of 0.1 ppb to 20 ppm in the black tea beverage, it is possible to impart the tea leaf texture and sweet odor characteristic of black tea, thereby increasing the richness of the flavor of the black tea beverage. To increase the depth of flavor of the black tea beverage, it is preferable to use epidihydrocalanone so that the concentration in the black tea beverage is 0.1 ppb to 10 ppm.Moreover, by setting the concentration to 0.1 ppb to 5 ppm, more preferably 0.5 ppb to 5 ppm, and even more preferably 50 ppb to 5 ppm, better results can be obtained.

[0036] [Test Example 3] (Effect of adding to rose-type fragrance) As shown in Table 2, rose-type fragrance compositions (manufactured by Ogawa Fragrance Co., Ltd.) containing different concentrations of epidihydrocalanone were prepared and evaluated by 10 expert panelists who had undergone prior training. The sensory evaluation was performed on the fragrance compositions prepared according to the formula of Comparative Example 2. Fragrance compositions containing different concentrations of epidihydrocalanone (Test Examples 3-1 to 3-6), and a fragrance composition containing β-damascone, which exhibits a floral, sweet, rose-like fragrance (Comparative Example 3), were applied to scent strips, and expert panelists were asked to comment on the fragrance of each composition. The sweetness of the fragrance was also evaluated by averaging the scores given by the expert panelists according to the following evaluation criteria.

[0037] <Sweetness evaluation criteria> Significantly increased compared to Comparative Example 2: 4 Significant increase compared to Comparative Example 2: 3 There was a certain increase compared to Comparative Example 2: Slightly increased compared to Comparative Example 2: 1 Equivalent to Comparative Example 2: 0

[0038] [Table 2]

[0039] [Table 3]

[0040] By blending epidihydrocalanone with a rose-type fragrance, it is possible to impart a sweet feeling to the fragrance, and to impart a sense of luxury to the rose scent. β-Damascone used in Comparative Example 3 is a fragrance often used in rose-type fragrances, but the results of this test example show that by using the fragrance composition of the present invention in a rose fragrance, a unique fragrance tone is imparted that cannot be obtained with a rose fragrance that uses β-Damascone. In order to impart a sweet feeling to the rose fragrance and a luxurious feel to the rose scent, it is preferable to use epidihydrocalanone in the rose fragrance at a concentration of 100 ppb to 10,000 ppm.Moreover, by setting the concentration to preferably 100 ppb to 1,000 ppm, more preferably 100 ppb to 100 ppm, particularly preferably 500 ppb to 50 ppm, and even more preferably 1 ppm to 20 ppm, better results can be obtained.

[0041] [Test Example 4] (Evaluation of the lingering fragrance of epidihydrocalanone) Epidihydrocalanone was mixed at the concentration shown in Table 5 into a floral type fragrance composition (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the recipe shown in Table 4. 5 μL of each mixture was dropped onto a filter paper with a diameter of 1 cm, and left to stand for 12 hours at room temperature (25°C). The lingering fragrance after that was evaluated by 10 pre-trained expert panelists, who commented on the results and averaged the scores they gave according to the following evaluation criteria.

[0042] [Table 4]

[0043] [Table 5]

[0044] <Evaluation criteria for lingering fragrance> The residual fragrance was significantly improved compared to Comparative Example 4: The residual fragrance was significantly improved compared to Comparative Example 4: 3 The residual fragrance has increased to some extent compared to Comparative Example 4: 2 Slightly increased lingering fragrance compared to Comparative Example 4: 1 The residual fragrance is the same as that of Comparative Example 4: 0

[0045] [Table 6]

[0046] In aromatic products such as perfumes, makeup products, skin care products, hair care products, toiletry products, household products, air fresheners, etc., the long-lasting fragrance (fragrance lingering) is an important factor in providing consumer satisfaction, a refreshing feeling, and an uplifting feeling, and in increasing the commercial value. Therefore, there is a demand for the development of a fragrance composition for cosmetic products that can improve the fragrance lingering of aromatic products. By blending epidihydrocalanone into a floral type fragrance, it is possible to impart a lingering fragrance to the fragrance. The concentration of epidihydrocalanone in the floral type fragrance is suitable to be 100ppb to 10000ppm. And, by setting the concentration to preferably 100ppb to 1000ppm, more preferably 1ppm to 1000ppm, particularly preferably 5ppm to 500ppm, and even more preferably 50ppm to 500ppm, better results can be obtained.

[0047] [Test Example 5] (Effect of adding a mixture of epidihydrocalanone and dihydrocalanone to rose-type fragrance) A rose-type fragrance composition (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the formula shown in Table 7 was mixed with a mixture of dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.) and epidihydrocalanone in different mixing ratios to give a total concentration of 1000 ppm, and the mixture was evaluated by 10 expert panelists who had undergone prior training. The sensory evaluation was performed for the fragrance composition of Comparative Example 5. Different concentration ratios of dihydrocalanone and epidihydrocalanone were added to scent strips as shown in Table 8 (Test Examples 5-1 to 5-6, Comparative Example 6). Expert panelists were asked to comment on the scent of each, and the sweetness was evaluated by averaging the scores given by the expert panelists according to the following evaluation criteria.

[0048] <Sweetness evaluation criteria> Significantly increased compared to Comparative Example 5: 4 Significant increase compared to Comparative Example 5: 3 There was a certain increase compared to Comparative Example 5: 2 Slightly increased compared to Comparative Example 5: 1 Equivalent to Comparative Example 5: 0

[0049] [Table 7]

[0050] [Table 8]

[0051] [Table 9]

[0052] Dihydrocalanone is known to have a woody and smoky aroma (Patent Document 7 It was confirmed that by mixing such dihydrocalanone with the epidihydrocalanone of the present invention, which has a sweet feeling, it is possible to impart a fresh, gorgeous, and luxurious feeling with a white floral nuance that cannot be obtained with dihydrocalanone alone. The blending ratio of epidihydrocalanone:dihydrocalanone is suitably in the range of 1:99 to 80:20, preferably 1:99 to 70:30, more preferably 1:99 to 50:50, particularly preferably 1:99 to 30:70, and especially preferably 5:95 to 30:70.

[0053] [Test Example 6] (Evaluation of the lingering fragrance and aftertaste of a mixture of epidihydrocalanone and dihydrocalanone) A floral type fragrance composition (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the formula shown in Table 4 was mixed with a mixture of dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.) and epidihydrocalanone in different mixing ratios so that the total concentration was 1000 ppm as shown in Table 10, and the mixture was evaluated by 10 expert panelists who had been trained in advance. Specifically, for the fragrance composition of Comparative Example 7, 5 μL of each mixture in the mixing ratios in Table 10 was dropped onto a filter paper with a diameter of 1 cm, and the mixtures were left to stand for 12 hours at room temperature of 25° C., after which the lingering fragrance and lingering aftertaste were evaluated by having 10 expert panelists who had been trained in advance comment on them and averaging the scores they assigned according to the evaluation criteria below.

[0054] [Table 10]

[0055] <Evaluation criteria for lingering fragrance> Significantly increased compared to Comparative Example 7: 4 Significant increase compared to Comparative Example 7: 3 Some increase compared to Comparative Example 7: 2 Slightly increased compared to Comparative Example 7: 1 Equivalent to Comparative Example 7: 0 <Evaluation criteria for aftertaste> Significantly increased compared to Comparative Example 7: 4 Significant increase compared to Comparative Example 7: 3 Some increase compared to Comparative Example 7: 2 Slightly increased compared to Comparative Example 7: 1 Equivalent to Comparative Example 7: 0

[0056] [Table 11]

[0057] Dihydrocalanone is also known to have a strong lingering fragrance. It has been confirmed that by mixing such dihydrocalanone with the epidihydrocalanone of the present invention, it is possible to impart a lingering aftertaste that has both a lingering fragrance and a gorgeous, luxurious feel. In particular, it was revealed that the coexistence of dihydrocalanone and epidihydrocalanone enhances not only the lingering fragrance but also the aftertaste. The blending ratio of epidihydrocalanone:dihydrocalanone is suitably in the range of 1:99 to 80:20, preferably 1:99 to 70:30, more preferably 1:99 to 50:50, particularly preferably 1:99 to 30:70, and especially preferably 5:95 to 30:70.

[0058] [Example 1] Application of epidihydrocalanone and mixtures to fragrances According to the recipe in Table 12, methylparaben, the floral fragrances prepared in Test Examples 4-4 and 6-2, polyoxyethylene (POE) hydrogenated castor oil, ethanol, and water were mixed in that order to prepare a spray-type air freshener. The spray-type air freshener of Example 1 maintained its floral fragrance even several hours after spraying, and showed a more favorable lingering scent than ordinary spray air fresheners. In addition, the luxurious scent spread throughout the air, allowing the user to feel a lingering aftertaste.

[0059] [Table 12]

[0060] Example 2: Application of epidihydrocalanone and mixtures in skin care products According to the formulation in Table 13, 1,3-butylene glycol, glycerin, and methyl paraoxybenzoate were dissolved in ethanol and mixed with water to prepare a lotion base. To the lotion base, PEG-20 sorbitan cocoate and the floral-type fragrances prepared in Test Examples 4-4 and 6-2, which had been uniformly mixed in advance, were added to prepare lotions. The lotion of Example 2 maintained a floral fragrance even several hours after application, and showed a pleasant lingering fragrance comparable to that of perfume. In addition, the luxurious fragrance, like that of perfume, could be felt for a long time, resulting in a lingering aftertaste.

[0061] [Table 13]

[0062] Example 3: Application of epidihydrocalanone and mixtures in hair care products According to the recipe in Table 14, the aqueous base was weighed into a beaker and mixed uniformly while heating at 85°C, and then an activator such as sodium cocoyl glutamate was added while stirring and dissolved uniformly, and 1% citric acid water and water were added and mixed uniformly. Finally, the floral type fragrances prepared in Test Examples 4-4 and 6-2 were added to the obtained mixture to prepare shampoos. The shampoo of Example 3 maintained a floral-type fragrance and the scent lasted longer after washing than with a regular shampoo, demonstrating a favorable lingering fragrance.

[0063] [Table 14]

[0064] Example 4: Application of epidihydrocalanone and mixtures in household products According to the formulation in Table 15, phase A was weighed into a beaker and mixed uniformly while heating at 80°C, and then phase B, which had been mixed uniformly at 80°C, was added and stirred with a homomixer. Finally, the floral perfumes prepared in Test Examples 4-4 and 6-2 were added to the resulting mixture to prepare fabric softeners. The fabric softener of Example 4 maintained a floral fragrance even after two days of washing, demonstrating favorable lingering fragrance. Furthermore, the lingering fragrance had a luxurious feel to it, allowing one to feel a lingering aftertaste.

[0065] [Table 15]

[0066] [Example 5] Application of epidihydrocalanone to beer beverages A beer flavoring was prepared according to the recipe in Table 16. 1 g of epidihydrocalanone and a mixture of 0.3 g of epidihydrocalanone and 0.7 g of dihydrocalanone were mixed with this beer flavoring, and each was added to a commercially available beer-flavored alcoholic beverage (ingredients: malt, hops, barley, corn, starch, spirits, alcohol content: 6%) so that the concentration was 0.1%. A commercially available beer-flavored alcoholic beverage containing 1 ppm of epidihydrocalanone had a more authentic beer feel than one without epidihydrocalanone. Also, a commercially available beer-flavored alcoholic beverage containing a mixture of 0.3 ppm of epidihydrocalanone and 0.7 ppm of dihydrocalanone had a rich, gorgeous aroma and a mellow flavor with a lingering aftertaste.

[0067] [Table 16]

[0068] [Example 6] Application of epidihydrocalanone to coffee drinks Commercially available coffee beans (with an L value of 20, which indicates the degree of roasting) were ground, and the ground coffee beans were dripped with 10 times the amount of hot water to obtain a coffee extract. The obtained coffee extract was diluted with water to a solid content of 1.2%, and then sodium bicarbonate was added to adjust the pH to 6.3. The mixture was filled into a container and retorted at 121°C for 10 minutes to produce a black coffee beverage. A coffee flavor was prepared according to the recipe in Table 17. 0.1 g of epidihydrocalanone and a mixture of 0.03 g of epidihydrocalanone and 0.07 g of dihydrocalanone were added to this coffee flavor, and each was added to the black coffee beverage at 0.1%. A black coffee beverage containing 1 ppm of epidihydrocalanone had an improved sense of authentic coffee flavor, while a black coffee beverage containing 0.3 ppm of epidihydrocalanone and 0.7 ppm of dihydrocalanone had a deep aroma, a sense of authentic coffee flavor, and a lingering aftertaste.

[0069] [Table 17]

[0070] [Example 7] Application of epidihydrocalanone to vanilla ice cream Vanilla flavor was prepared according to the recipe in Table 18. 1g of epidihydrocalanone, 0.3g of epidihydrocalanone, and 0.7g of dihydrocalanone were mixed with this vanilla flavor. Each vanilla flavor was added to a commercially available vanilla ice cream kneaded with a spatula so that the concentration was 0.1%, and each was poured into a plastic pudding cup and frozen. After freezing, a sensory evaluation was performed. Adding 1 ppm of epidihydrocalanone increased the sweetness and volume of the vanilla ice cream, improving its authenticity. In addition, by combining 0.3 ppm of epidihydrocalanone and 0.7 ppm of dihydrocalanone, the sweetness and aroma of vanilla were sustained, allowing for a lingering vanilla aftertaste.

[0071] [Table 18]

[0072] [Example 8] Application of epidihydrocalanone to fruit juice drinks A peach flavor was prepared according to the recipe in Table 19. 1 g of epidihydrocalanone, 0.3 g of epidihydrocalanone, and 0.7 g of dihydrocalanone were mixed with this peach flavor. According to the recipe below, each peach flavor was added to a concentration of 0.1% to prepare a fruit juice beverage, which was then sterilized at 95°C. The fruit juice drink containing 1 ppm of epidihydrocalanone had an improved sense of authenticity of peach, while the fruit juice drink containing 0.3 ppm of epidihydrocalanone and 0.7 ppm of dihydrocalanone had a natural and authentic aroma and a lingering aftertaste. (Prescription) (g) Fructose glucose syrup 50 Peach juice straight 5.0 Vitamin C 0.5 Adjust the pH to 3.5 with citric acid and make up to 1000g with water.

[0073] [Table 19] [Industrial Applicability]

[0074] The epidihydrocalanone according to the present invention has a long-lasting, characteristically sweet fragrance, and when used in combination with various fragrance compositions, it imparts a voluminous, authentic, sweet fragrance that also has lingering fragrance properties, and therefore can be used as a fragrance component for foods, beverages, and cosmetics, either alone or in combination with other components.

Claims

1. A fragrance imparting agent comprising epidihydrocalanone represented by the following formula (1) and / or formula (2) as an active ingredient: [Formula 1]

2. A fragrance composition comprising the fragrance imparting agent according to claim 1.

3. A method for imparting fragrance, comprising using epidihydrocalanone represented by the following formula (1) and / or formula (2) as a fragrance component. [Case 2]

4. A fragrance lingering enhancer comprising epidihydrocalanone represented by the following formula (1) and / or formula (2) as an active ingredient: [C3]

5. A method for improving fragrance lingering, comprising using epidihydrocalanone represented by the following formula (1) and / or formula (2) as a fragrance lingering improving component. [C4]

6. A method for producing a food or beverage, comprising adding epidihydrocalanone represented by the following formula (1) and / or formula (2): [C5]

7. A method for producing a cosmetic product, comprising adding epidihydrocalanone represented by the following formula (1) and / or formula (2): [C6]

8. A fragrance imparting agent comprising, as an active ingredient, a mixture containing epidihydrocalanone represented by the following formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4). [C7]

9. A fragrance composition comprising the fragrance imparting agent according to claim 8.

10. A method for using a mixture containing epidihydrocalanone represented by the following formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4) as a fragrance component. [C8]

11. A method for perfumery comprising using a mixture of epidihydrocalanone represented by the following formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4) in a ratio of 1:99 to 80:20 as a perfumery component. [C9]

12. A method for imparting a lingering aftertaste to a fragrance compound, comprising adding a mixture containing epidihydrocalanone represented by the following formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4) to the fragrance compound. [C10]

13. A method for imparting a lingering aftertaste to a fragrance compound, comprising adding to the fragrance compound a mixture of epidihydrocalanone represented by the following formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4) in a ratio of 1:99 to 80:

20. [C11]

14. A method for producing a food or beverage, comprising adding a mixture containing epidihydrocalanone represented by the following formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4). [C12]

15. A method for producing a cosmetic product, comprising adding a mixture containing epidihydrocalanone represented by the following formula (1) and / or formula (2) and dihydrocalanone represented by the following formula (3) and / or formula (4). [C13]

Images