Fragrance composition

Abstract

The purpose of the present invention is to provide a fragrance composition which is capable of enhancing citrus-like aroma and flavor. The present invention relates to a fragrance composition which contains (5E)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate.

Description

fragrance composition

[0001] The present invention relates to compounds and fragrance compositions useful as blended fragrance ingredients and the like.

[0002] In recent years, as consumer preferences have become more diverse, there has been a strong demand for flavors that have a fruity or natural flavor, or that are differentiated from others, in flavors used in foods, beverages, etc. However, it is sometimes difficult to meet these demands with combinations of conventional flavor raw materials, and there is a strong demand for new flavor materials.

[0003] The present invention aims to provide novel compounds having a fragrance useful as a compound fragrance ingredient, etc., and fragrance compositions containing said compounds. The present inventors synthesized various compounds and examined their fragrances, and found that compounds having a terminal aldehyde group and an ester structure have an excellent fragrance. Specifically, the present invention relates to the following [1] to [6]. [1] A compound represented by the following formula (1): (In formula (1), R represents an alkyl group having 1 to 4 carbon atoms, and the wavy line represents cis or trans, or a mixture of cis and trans.) [2] The compound according to [1] above, wherein R is a methyl group. [3] A flavor composition containing the compound according to [1] or [2] above. [4] The flavor composition according to [3] above, which is for use in food or drink. [5] A food or drink, oral composition, tobacco product, or consumer product, which contains the compound according to [1] or [2] above, or the flavor composition according to [3] or [4]. [6] A method for producing a food or drink, oral composition, tobacco product, or consumer product, which comprises adding the compound according to [1] or [2] above, or the flavor composition according to [3] or [4]. According to the present invention, there can be provided a novel compound having an aroma useful as a compound flavor ingredient, etc., and a flavor composition containing said compound.

[0004] The present invention will be described in detail below. (5E)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl carboxylate (hereinafter also referred to as the compound of the present invention) in the present invention, for example, in the case of an acetate ester, exists as two isomers represented by the following (1a) and (1b). Either one may be used alone or as a mixture thereof, but compound (1a) is preferred. In addition, there are two enantiomers represented by the following formulas (1c) and (1d), which may be used alone or as a mixture.

[0005] Compounds (1a) and (1b) of the present invention can be prepared, for example, by the following process. Geranyl acetone is reacted with NaBH4 to reduce the ketone, and then acetylated with acetyl chloride to form geranyl acetate. Subsequently, allyl chloride is synthesized by chlorination with calcium hypochlorite, and after introduction of a hydroxyl group accompanied by rearrangement with formate, allyl alcohol is synthesized with triethylamine. This is oxidized with manganese dioxide to obtain a mixture of compounds (1a) and (1b). The above process is summarized in the following scheme. (In the scheme, the wavy line represents cis or trans, or a mixture of cis and trans.) Compound (1a) and compound (1b) of the present invention thus obtained can be purified by distillation, various types of chromatography, etc.

[0006] The compound of the present invention has an excellent aroma and can be used alone or in combination with other ingredients as a flavoring ingredient for foods and beverages, oral compositions, tobacco products, etc. The flavor composition and the compound of the present invention can be added directly to foods and beverages in trace amounts to impart or enhance aroma and flavor, or can be mixed with other ingredients to impart or enhance aroma and flavor to foods and beverages. Examples of other flavor ingredients that can be mixed include various synthetic flavors, natural flavors, natural essential oils, plant extracts, etc., such as the natural essential oils, natural flavors, and synthetic flavors described in "Japan Patent Office Publication, Collection of Well-Known and Commonly Used Techniques (Fragrances) Part II Food Flavors, pp. 88-131, published January 14, 2000." The concentration of the compound of the present invention in the flavor composition of the present invention varies depending on the other flavor components to be mixed, and cannot be generalized, but it can usually be in the range of 0.00001 to 10,000 ppm, preferably 0.0001 to 1,000 ppm, and more preferably 0.001 to 100 ppm, based on the weight of the flavor composition. When the compound of the present invention is added to a food or beverage to enhance its aroma or flavor, it can be in the range of 0.00001 to 10,000 ppb, preferably 0.0001 to 1,000 ppb, and more preferably 0.001 to 100 ppb, based on the weight of the food or beverage.

[0007] The fragrance composition of the present invention containing the compound of the present invention may contain, as necessary, commonly used solvents such as water and ethanol; and fixatives such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, Hercolin, triacetin, medium-chain fatty acid triglycerides, and medium-chain fatty acid diglycerides.

[0008] The flavor and aroma of foods and beverages can be enhanced by adding a flavor composition containing the compound of the present invention or the compound itself. Specific examples of foods and beverages whose flavor and aroma can be enhanced by adding the flavor and aroma composition of the present invention or the compound of the present invention include beverages such as carbonated drinks, soft drinks, fruit juice drinks, fruit liquors, dairy drinks, lactic acid bacteria drinks, health supplements, soy milk, and tea drinks; desserts such as ice cream, ice milk, lacto ice cream, frozen desserts, yogurt, pudding, jelly, and dairy desserts; confectioneries such as caramel, candy, tablet candy, crackers, biscuits, cookies, pies, chocolates, snacks, chewing gum, steamed buns, and sweet bean paste; soups such as Japanese soup, Western soup, and Chinese soup; breads; jams; flavor seasonings; various instant drinks; and various instant foods. The amount of flavor composition added to food or drink varies depending on the type and form of the product, but it is usually 0.1% by weight of the food or drink, preferably in the concentration range of 0.001 to 5%.

[0009] Oral compositions that can be scented or flavored with the flavor composition of the present invention or the compound of the present invention include, for example, dentifrices, mouthwashes, mouth lozenges, chewing gums, etc. The amount of the flavor composition added to the oral composition varies depending on the type and form of the product, but can usually be preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the oral composition.

[0010] Tobacco products that can be scented or flavored with the flavor composition or compound of the present invention include cigarettes, electronic cigarettes, etc. The amount of the flavor composition added to a tobacco product varies depending on the type and form of the product, but can be, for example, preferably 0.00001 to 90% by mass, more preferably 0.0001 to 50% by mass, based on the total mass of the tobacco leaf portion.

[0011] Specific examples of consumer products include fragrance products such as perfume, eau de parfum, eau de toilette, and eau de cologne; basic cosmetics such as facial cleansing cream, cleansing cream, emulsion, lotion, and serum; finishing cosmetics such as lipstick, lip balm, eyeliner, mascara, eye shadow, eyebrow pencil, eye pack, nail enamel, and enamel remover; hair cosmetics such as pomade, brilantine, setting lotion, hair stick, hair solid, hair oil, hair treatment, hair cream, hair tonic, hair liquid, hair spray, bandolin, hair tonic, and hair dye; sunscreen cosmetics such as tanning products and sunscreen products; medicated cosmetics such as antiperspirants, aftershave lotions and gels, permanent wave agents, medicated soaps, medicated shampoos, and medicated skin cosmetics; hair care products such as shampoos, rinses, rinse-in shampoos, conditioners, treatments, and hair packs; Soaps such as toilet soap, bath soap, perfumed soap, transparent soap, synthetic soap, etc.; body cleansers such as body soap, body shampoo, hand soap, face cream, etc.; bath additives such as bath salts (bath salts, bath tablets, bath liquid, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jellies, bath cubes, etc.; detergents such as heavy-duty laundry detergents, light-duty laundry detergents, liquid detergents, laundry soaps, compact detergents, powdered soaps, etc.; fabric softeners such as softeners and furniture care products; cleaning agents such as cleansers, house cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mold removers, drain cleaners, etc.; kitchen detergents such as kitchen soap, synthetic kitchen soap, and dish detergent; bleaches such as oxidation bleaches (chlorine bleaches, oxygen bleaches, etc.), reduction bleaches (sulfur bleaches, etc.), and optical bleaches; aerosols such as spray types and powder sprays; Examples include deodorizers and air fresheners in solid, gel, and liquid types (water-based and oil-based), daily necessities and miscellaneous items such as tissue paper and toilet paper, quasi-drugs such as liquid bath additives, mouthwash, and repellents (mist spray type, water-based liquid type), and pharmaceuticals such as medicated cosmetics and medicated lotions.The compound of the present invention can be added to a consumer product in a concentration range of 0.00001 to 10,000 ppb, preferably 0.0001 to 1,000 ppb, more preferably 0.001 to 100 ppb, based on the weight of the consumer product.

[0012] Furthermore, all geometric isomers of the compound of the present invention are useful as fragrance components, and any isomer or mixture of isomers can be used in the fragrance composition of the present invention.

[0013] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0014] [Measurement Instruments] The analytical instruments used in the examples are as follows: NMR measurement device: AVANCEIII 500 (BRUKER BIO SPIN K.K.: manufactured by Bruker Biospin) Gas chromatograph mass spectrometer: GCMS-QP2010 (manufactured by Shimadzu Corporation) Gas chromatograph-Orbitrap mass spectrometer: TRACE1310 (GC) + Exactive GC (mass spectrometer) (manufactured by Thermo Fisher Scientific) High-performance liquid chromatograph pump: LC-20A (manufactured by Shimadzu Corporation) Detector: SPD-M20A (manufactured by GL Sciences) Separation column: YMC-TriartC18 ExRS (manufactured by YMC Corporation)

[0015] (Example 1) Synthesis of Compound (1a) and Compound (1b) (1) Synthesis of (E)-6,10-dimethylundeca-5,9-dien-2-ol A solution of (E)-6,10-dimethylundeca-5,9-dien-2-one (58.30 g, 0.3 mol) in methanol (250 mL) was cooled to 0°C, sodium borohydride (11.35 g, 0.3 mol) was added, and the mixture was reacted for 2 hours. Diethyl ether and water were then added, and the organic layer was separated. The separated organic layer was purified by distillation to obtain 45.14 g of (E)-6,10-dimethylundeca-5,9-dien-2-ol (yield: 76.6%, GC purity: 92.6%).

[0016] (2) Synthesis of (E)-6,10-dimethylundeca-5,9-dien-2-yl acetate To a toluene (200 mL) solution of (E)-6,10-dimethylundeca-5,9-dien-2-ol (45.14 g, 0.23 mol) obtained in (1) above, acetyl chloride (19.85 g, 0.25 mol) and pyridine (22.2 mL, 0.28 mol) were added, and the mixture was allowed to react at room temperature for 2 hours. Water was added to the reaction solution, and the organic layer was separated. The separated organic layer was purified by distillation to obtain 49.05 g of (E)-6,10-dimethylundeca-5,9-dien-2-yl acetate (yield: 89.5%, GC purity: 93.1%).

[0017] (3) Synthesis of (E)-9-chloro-6,10-dimethylundeca-5,10-dien-2-yl acetate To a solution of (E)-6,10-dimethylundeca-5,9-dien-2-yl acetate (11.92 g, 0.05 mol) obtained in (2) above in ethyl acetate (120 mL) was added a solution of calcium hypochlorite (3.57 g, 0.025 mol), tetrabutylammonium bromide (298 mg), and acetic acid (3.30 g, 0.055 mol) in water (15 mL), and the mixture was allowed to react at 0°C for 2 hours. Water was added to this reaction solution, and the organic layer was separated. The separated organic layer was concentrated to obtain 15.47 g of crude (E)-9-chloro-6,10-dimethylundeca-5,10-dien-2-yl acetate.

[0018] (4) Synthesis of (5E)-11-formyloxy-6,10-dimethylundeca-5,9-dien-2-yl acetate To a solution of the mixture (7.91 g, 0.03 mol) of (E)-9-chloro-6,10-dimethylundeca-5,10-dien-2-yl acetate and 5-chloro-10-methyl-6-methyleneundec-9-en-2-yl acetate obtained in (3) above in N,N-dimethylformamide (100 mL), tetrabutylammonium iodide (10.71 g, 0.03 mol) and potassium formate (12.20 g, 0.15 mol) were added, and the mixture was reacted at 80°C for 2 hours. A 5% aqueous solution of lithium chloride (200 mL) and hexane were added to the reaction solution, and the organic layer was separated. The separated organic layer was concentrated to obtain crude (5E)-11-formyloxy-6,10-dimethylundeca-5,9-dien-2-yl acetate. At this time, 42% of (Z)-6-formylmethyl-10-methylundeca-5,9-dien-2-yl acetate was produced as a by-product. Purification using silica gel column chromatography (hexane:ethyl acetate=30:1) afforded 2.93 g of (5E)-11-formyloxy-6,10-dimethylundeca-5,9-dien-2-yl acetate (yield: 39.7%, GC purity: 52.7%).

[0019] (5) Synthesis of (5E)-11-hydroxy-6,10-dimethylundeca-5,9-dien-2-yl acetate To a solution of (5E)-11-formyloxy-6,10-dimethylundeca-5,9-dien-2-yl acetate (2.93 g, 0.01 mol) obtained in (4) in methanol (50 mL) was added triethylamine (1.44 mL, 0.01 mol), and the mixture was heated under reflux for 2 hours to obtain 1.56 g of (5E)-11-hydroxy-6,10-dimethylundeca-5,9-dien-2-yl acetate (yield: 59.1%, GC purity: 90.1%).

[0020] (6) Synthesis of (5E,9E)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate and (5E,9Z)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate Manganese dioxide (5.33 g, 0.06 mol) was added to a hexane (50 mL) solution of (5E)-11-hydroxy-6,10-dimethylundeca-5,9-dien-2-yl acetate (1.56 g, 0.006 mol) obtained in (5), and the reaction mixture was allowed to react at room temperature for 8 hours. The reaction mixture was purified using silica gel column chromatography (hexane:ethyl acetate=30:1) to obtain 0.6 g of a mixture of (5E,9E)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate (1a) and (5E,9Z)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate (1b) (yield 38.7%, GC purity 90.4%, 9Z / 9E=68 / 32). The synthesized mixture was purified by HPLC (eluent: water:acetonitrile=36:64 (volume ratio)) to obtain (5E,9E)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate (1a) (purity 100%) and (5E,9Z)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate (1b) (purity 100%).

[0021] Physical Data for (5E,9E)-6,10-Dimethyl-11-oxoundeca-5,9-dien-2-yl Acetate H NMR (500 MHz, CDCl) δ: 9.39 (s, 1H), 6.46 (t, J = 7.33 Hz, 1H), 5.15 (t, J = 7.16 Hz, 1H), 4.88 (m, 1H), 2.46 (q, J = 7.33 Hz, 2H), 2.17 (t, J = 7.33 Hz, 2H), 2.03 (s, 3H), 2.03 (m, 2H), 1.48-1.68 (m, 2H), 1.75 (s, 3H), 1.62 (s, 3H), 1.21 (d, J = 6.25 Hz, 3H) NMR (125MHz, CDCl3) δ: 195.31, 170.72, 154.26, 139.42, 134.20, 124.71, 70.46, 37.96, 35.80, 27.32, 23.88, 21.36, 19.97, 15.80, 9.21 HRMS (CI+): calcd C15H25O3 ([M+H]+) 253.1798; found, 253.1799

[0022] Physical Data for (5E,9Z)-6,10-Dimethyl-11-oxoundeca-5,9-dien-2-yl Acetate H NMR (500 MHz, CDCl) δ: 10.12 (s, 1H), 6.48 (t, J = 7.51 Hz, 1H), 5.13 (t, J = 7.15 Hz, 1H), 4.88 (m, 1H), 2.66 (q, J = 7.51 Hz, 2H), 2.15 (t, J = 7.51 Hz, 2H), 2.03 (s, 3H), 2.03 (m, 2H), 1.48-1.68 (m, 2H), 1.77 (s, 3H), 1.60 (s, 3H), 1.21 (d, J = 6.25 Hz, 3H) NMR (125MHz, CDCl3) δ: 191.13, 170.72, 149.00, 136.16, 133.90, 125.07, 70.47, 39.32, 35.77, 25.08, 23.87, 21.35, 19.96, 15.85, 9.20 HRMS (CI+): calcd C15H25O3 ([M+H]+) 253.1798; found, 253.1797

[0023] Example 2: Grapefruit food flavor composition A grapefruit food flavor composition (A) was prepared according to the following formulation using the compound of the present invention produced by the method described in Example 1. The mixture in Example 1 refers to a mixture of (5E,9E)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate and (5E,9Z)-6,10-dimethyl-11-oxoundeca-5,9-dien-2-yl acetate (the same applies to the following examples).

[0024] Comparative Example 1 As Comparative Example 1, a grapefruit food flavor composition (B) was prepared according to the following formulation.

[0025] Comparative Experiment 1: The grapefruit food flavor compositions (A) and (B) obtained in Example 2 and Comparative Example 1 were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (A) of Example 2 was far superior to flavor composition (B) of Comparative Example 1, imparting a juicy, voluminous feel reminiscent of citrus fruits and a sandbag-like granular feel. The same results were obtained when the 5E,9E isomer or the 5E,9Z isomer was used alone.

[0026] Example 3 Addition to Commercially Available Grapefruit Juice Drink The 5E,9E isomer, 5E,9Z isomer, or a mixture thereof obtained in Example 1 was added at 0.1 ppb to a commercially available grapefruit juice drink, and a sensory test was conducted by six expert panelists. All panelists pointed out that the addition of the 5E,9E isomer, 5E,9Z isomer, or a mixture thereof imparts a rich, juicy feel and a natural fruity taste, making the drink far superior.

[0027] Example 4 Grapefruit Food Flavor Composition A grapefruit food flavor composition (C) was prepared according to the following formulation.

[0028] Comparative Example 2 As Comparative Example 2, a grapefruit food flavor composition (D) was prepared according to the following formulation.

[0029] Comparative Experiment 2: The grapefruit food flavor compositions (C) and (D) obtained in Example 4 and Comparative Example 2 were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (C) of Example 4 was far superior to flavor composition (D) of Comparative Example 2, imparting a juicy, voluminous feel reminiscent of citrus fruits and a sandbag-like granular feel. The same results were obtained when the 5E,9E isomer or the 5E,9Z isomer was used alone.

[0030] Example 5: Orange food flavor composition An orange food flavor composition (E) was prepared according to the following formulation.

[0031] Comparative Example 3 As Comparative Example 3, an orange food flavor composition (F) was prepared according to the following formulation.

[0032] Comparative Experiment 3: The orange food flavor compositions (E) and (F) obtained in Example 5 and Comparative Example 3 were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (E) of Example 5 had a more natural peel feeling and a more voluminous citrus fruit feeling than flavor composition (F) of Comparative Example 3, and was far superior. The same results were obtained when the 5E,9E isomer or the 5E,9Z isomer was used alone.

[0033] Example 6 Addition to Commercially Available Orange Juice Drink The 5E,9E isomer, 5E,9Z isomer, or a mixture thereof obtained in Example 1 was added to a commercially available orange juice drink at a concentration of 0.1 ppb, and a sensory test was conducted by six expert panelists. All panelists pointed out that the addition of the 5E,9E isomer, 5E,9Z isomer, or a mixture thereof enhanced the natural peel and fruit flavor, resulting in a significantly superior taste.

[0034] Example 7: Orange food flavor composition An orange food flavor composition (G) was prepared according to the following formulation.

[0035] Comparative Example 4 As Comparative Example 4, an orange food flavor composition (H) was prepared according to the following formulation.

[0036] Comparative Experiment 4 The orange food flavor compositions (G) and (H) obtained in Example 7 and Comparative Example 4 were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (G) of Example 7 imparted a more natural peel feeling and fruity feeling than flavor composition (H) of Comparative Example 4, and was far superior. The same results were obtained when the 5E,9E isomer or the 5E,9Z isomer was used alone.

[0037] (Example 8) Lemon food flavor composition Lemon food flavor composition (I) was prepared according to the following formulation.

[0038] Comparative Example 5 As Comparative Example 5, a lemon food flavor composition (J) was prepared according to the following formulation.

[0039] Comparative Experiment 5: The lemon food flavor compositions (I) and (J) obtained in Example 8 and Comparative Example 5 were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (I) of Example 8 had a more natural peel feeling and a more voluminous citrus fruit feeling than flavor composition (J) of Comparative Example 5, and was far superior. The same results were obtained when the 5E,9E isomer or the 5E,9Z isomer was used alone.

[0040] (Example 9) Addition to a commercially available lemon juice drink The 5E,9E isomer, 5E,9Z isomer, or a mixture thereof obtained in Example 1 was added at 0.1 ppb to a commercially available lemon juice drink, and a sensory test was conducted by six expert panelists. All panelists pointed out that the addition of the 5E,9E isomer, 5E,9Z isomer, or a mixture thereof enhanced the natural peel and fruity flavor, making the drink significantly superior.

[0041] (Example 10) Lemon food flavor composition Lemon food flavor composition (K) was prepared according to the following formulation.

[0042] Comparative Example 6 As Comparative Example 6, a lemon food flavor composition (L) was prepared according to the following formulation.

[0043] Comparative Experiment 6: The lemon food flavor compositions (K) and (L) obtained in Example 10 and Comparative Example 6 were each added to water at a concentration of 0.1%, and a sensory test was conducted by six expert panelists. All panelists pointed out that flavor composition (K) of Example 10 imparted a more natural peeling and fruity flavor than flavor composition (L) of Comparative Example 6, and was far superior. The same was true when the 5E,9E isomer or the 5E,9Z isomer was used alone.

Claims

1. A compound represented by the following formula (1): (In formula (1), R represents an alkyl group having 1 to 4 carbon atoms, and the wavy line represents cis or trans, or a mixture of cis and trans.) 2. The compound according to claim 1, wherein R is a methyl group.

3. A fragrance composition containing the compound according to claim 1 or 2.

4. The flavor composition according to claim 3, which is for use in food and beverages.

5. A food or drink, an oral composition, a tobacco product, or a consumer product comprising the compound according to claim 1 or 2, or the flavor composition according to claim 3 or 4.

6. A method for producing a food or beverage, an oral composition, a tobacco product, or a consumer product, comprising adding a compound according to claim 1 or 2, or a flavor composition according to claim 3 or 4.

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