JP5158463B2 - 3,7-dimethyl-5-octenoic acid and its derivatives, and a perfume composition containing them. - Google Patents

Description

The present invention relates to 3,7-dimethyl-5-octenoic acid and esters thereof, and perfume compositions, foods and drinks, and cosmetics containing these compounds.

（Ｒ^３は水素原子またはエチル基を示す）で表される（３Ｒ）−３，７−ジメチル−５Ｅ−オクテン酸およびそのエチルエステルは、昆虫に対する生理活性物質をＬ−メントールから合成する過程の中間体として報告されている（非特許文献１）が、これらの化合物の香気に関する報告はされてない。 Chemical formula (3)

^{(R 3} is a hydrogen atom or an ethyl group) represented by (3R)-3,7-dimethyl -5E- octene acid and its ethyl ester is, the process of synthesizing a physiologically active substance against insects from L- menthol Although reported as an intermediate (Non-Patent Document 1), there is no report on the aroma of these compounds.

（波線はＺ−配置またはＥ−配置を示し、Ｚ−配置の場合、Ｒ^１は水素原子、或は炭素数１〜５のアルキル基またはアルケニル基を示し、Ｅ−配置の場合、Ｒ^１は、炭素数１、３、４または５のアルキル基またはアルケニル基を示す）で表される３，７−ジメチル−５−オクテン酸および同誘導体は、天然界に存在するとの報告も、有機合成により製造したとの報告もされてない。 Chemical formula (1)

(The wavy line indicates the Z-configuration or the E-configuration. In the Z-configuration, R ¹ represents a hydrogen atom, or an alkyl or alkenyl group having 1 to 5 carbon atoms. In the E-configuration, R ¹ represents 3-7-dimethyl-5-octenoic acid and its derivatives represented by C1, C3, C4 or C5) are also reported by organic synthesis There are no reports of production.

（波線はＺ−配置またはＥ−配置を示し、Ｒ^２は水素原子、或は炭素数１〜５のアルキル基またはアルケニル基を示す）で表される３，７−ジメチル−５−オクテン酸および同誘導体を含有する香料組成物、或はこれらを含有する飲食品や香粧品は報告されてない。 Further, the compounds represented by the chemical formula (3) and the chemical formula (1), that is, the chemical formula (2)

(The wavy line indicates Z-configuration or E-configuration, R ² represents a hydrogen atom, or an alkyl group or alkenyl group having 1 to 5 carbon atoms) and 7,7-dimethyl-5-octenoic acid represented by A fragrance composition containing the derivative, or a food or beverage containing the derivative has not been reported.

Prior art documents relating to the invention of the present application include the following.
Bulletin de l'Academie Polonides des Sciences, Series des Sciences Chimices, 25, 529-40 (1977) Synthesis, 767-768 (1976).

Since the palatability required for foods and beverages and cosmetics has been diversified, fragrance compositions having various characteristic fragrance characteristics are required, and in particular, fragrance compositions having unprecedented fragrance characteristics. Is required.

  In view of the above, the present inventor has conducted extensive studies on carboxylic acids and ester compounds thereof, and as a result, 3,7-dimethyl-5E-octenoic acid, 3,7-dimethyl-5Z-octenoic acid, and these The present inventors have found that a lower alkyl or alkynyl ester compound has a characteristic aroma characteristic with an unprecedented fragrance, and thus completed the present invention.

  3,7-dimethyl-5Z-octenoic acid has a heavy fatty acid odor with a somewhat mint-like nuance, and isopropyl 3,7-dimethyl-5-octenoate (mixture of geometric isomers) is a diffusible apple, pair-like The green scent and fruit scent of methyl 3,7-dimethyl-5-octenoate (mixture of geometric isomers) have a fragrance characteristic of having a sharp and metallic pair-like green scent and fruit scent, both of which have Has a characteristic aroma characteristic with no fragrance. Moreover, the fragrance | flavor composition containing these also has characteristic fragrance | flavor and can be used as a useful preparation raw material in a fragrance | flavor composition.

Each symbol used in this specification will be described below. R ¹ and R ² represent a hydrogen atom or an alkyl group or alkenyl group having 1 to 5 carbon atoms. The alkyl group or alkenyl group having 1 to 5 carbon atoms may be linear, branched or cyclic. However, when the wavy line of the compound (1) has an E configuration, R ¹ excludes a hydrogen atom and an ethyl group from the above description.

Examples of R ¹ and R ² include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and n-pentyl. Group, isopentyl group, secondary pentyl group, tertiary pentyl group, 2-methylbutyl group, vinyl group, allyl group, crotonyl group, methallyl group, isopropenyl group, butenyl group, prenyl group, cyclopropyl group, cyclopentyl group Preferred examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group.

に示す方法で合成することができる。 The compound represented by the chemical formula (1) or chemical formula (2) used in the present invention is, for example, the following process diagram.

It can be synthesized by the method shown in

  That is, in Step-1, 3,7-dimethyl-, starting from δ-oxocarboxylic acid ester (Formula 3 in the process diagram) by Wittig reaction or Horner-Wadsworth-Emmons reaction (hereinafter also referred to as HWE reaction). 5-Octenoic acid ester (formula 2 in the process diagram) is obtained. Subsequently, in step-2, the desired 3,7-dimethyl-5-octenoic acid (formula 1 in the process diagram) is obtained by a hydrolysis reaction.

  The δ-oxocarboxylic acid ester represented by Formula 3 in the process diagram can be synthesized by a conventionally known method. For example, a method is known in which a monoacid chloride that can be easily prepared from 3-methylglutaric acid monoester is used to efficiently convert it to a δ-oxocarboxylic acid ester by improved Rosenmund reduction (Non-patent Document 2). .

  In addition, for example, a δ-oxocarboxylic acid ester can also be obtained by directly reducing 3-methylglutaric acid monoester or diester.

  In Step-1, the reaction reagent used for the Wittig reaction includes, for example, isobutyltrialkylphosphorane, more preferably isobutyltriphenylphosphorane. Examples of the phosphorane precursor include isobutyltrialkylphosphonium halide, and more preferably isobutyltriphenylphosphonium halide. Iodide, bromide, and chloride are suitable as the halide.

  The amount of isobutyltrialkylphosphonium halide added may be in the range of 0.5 to 3.0 mol, preferably 0, per 1 mol of δ-oxocarboxylic acid ester represented by formula 3 in the process diagram. The added amount is from 8 to 2.0 mol.

  In Step-1, when the HWE reaction is carried out instead of the Wittig reaction, examples of the reaction reagent to be used include dialkylisobutylphosphonate. Examples of the dialkyl moiety include dimethyl, diethyl, diisobutyl and the like.

  Either the Wittig reaction or the HWE reaction requires a base. Examples of the base used here include alkylmetals such as butyllithium, metalamides such as lithium diisopropylamide (LDA), and gymsil. An anion etc. can be mentioned, The addition amount can mention the range of 0.7-1.5 mol with respect to 1 mol of isobutyl trialkyl phosphonium halides or dialkyl isobutyl phosphonate, 0.8-1.3 A molar addition amount is preferred.

  Examples of the solvent used in the reaction include ethers such as diethyl ether and tetrahydrofuran (THF), and sulfoxides such as dimethyl sulfoxide (DMSO).

  About reaction temperature, the range of -100 degreeC-100 degreeC can be mentioned, for example, More preferably, it can adjust suitably according to the difference of the reaction reagent to be used in the range of -80 degreeC-80 degreeC.

  The reaction time can be, for example, in the range of 10 minutes to 24 hours, but more preferably in the range of 30 minutes to 10 hours, and can be appropriately adjusted according to the result of reaction tracking by TLC (thin layer chromatography) or the like. .

  In step-2, the alkali method is the most efficient for the hydrolysis. Examples of the reaction reagent used include caustic alkalis such as sodium hydroxide and potassium hydroxide, and carbonates such as potassium carbonate and cesium carbonate. The amount of addition may be in the range of 0.7 to 3.0 moles with respect to 1 mole of the carboxylic acid ester represented by Formula 2 in the process diagram, but the addition amount of 0.8 to 2.0 moles. An amount is preferred.

  Moreover, it is preferable to use the aqueous solution of the said reaction reagent as embodiment of reaction, The density | concentration is the range of 5%-50% (weight%), and can be suitably adjusted according to the difference in a reaction reagent.

  As the solvent used in the reaction, for example, alcohols such as methanol and ethanol, ethers such as diethyl ether and THF, sulfoxides such as DMSO, amides such as N, N-dimethylformamide, and the like that are easily soluble in water are preferable. .

  About reaction temperature, the range of 0 to 150 degreeC can be mentioned, for example, More preferably, it can adjust suitably according to the difference of the reaction reagent to be used in the range of 10 to 100 degreeC.

The reaction time can be, for example, in the range of 30 minutes to 10 hours, but more preferably in the range of 1 hour to 5 hours, and can be appropriately adjusted according to the result of reaction tracking by TLC or the like.

  In all steps, the inert gas used as necessary includes nitrogen and argon.

  In all steps, methods used for isolation and purification include, for example, fractionation by atmospheric or vacuum distillation, normal phase or reverse phase chromatography, gas chromatography (hereinafter also referred to as GC) or high performance liquid chromatography (hereinafter also referred to as HPLC). Examples include chromatography, recrystallization, and the like, and each operation can be used appropriately or in combination depending on the purpose.

  Further, the compound represented by the chemical formula (1) or (2) can be extracted from a natural product and obtained by an isolation operation.

That is, among the compounds represented by the chemical formula (2), a compound in which R ² is hydrogen, that is, 3,7-dimethyl-5E-octenoic acid or 3,7-dimethyl-5Z-octenoic acid is an essential oil of Mentha avensis, It can also be obtained by extraction or isolation from a fraction containing essential oil-derived components produced in the natural menthol production process.

  As the method, for example, Mentha arvensis essential oil is extracted into an aqueous layer using an alkali such as a saturated aqueous sodium bicarbonate solution as an acidic component as a salt, and then the aqueous layer is made acidic by adding an acid such as dilute hydrochloric acid to perform solvent extraction. By evaporating the resulting organic layer, a concentrate of acidic components is obtained. From the concentrate, 3,7-dimethyl-5E-octenoic acid or 3,7-dimethyl-5Z-octenoic acid can be isolated by distillation or column chromatography.

  The compounds obtained by the above organic chemical synthesis or extraction / isolation from natural products have a unique aroma. Furthermore, not only the fragrance itself, but also a known fragrance composition may contain one or more of the compounds of the present invention and used in combination.

  The fragrance composition of the present invention comprises one or two of 3,7-dimethyl-5E-octenoic acid, 3,7-dimethyl-5Z-octenoic acid, or a mixture thereof, or a lower alkyl or alkenyl ester of these acids. It contains the above.

  In general, the content ranges from about 0.001 to about 20% by weight, preferably from about 0.01% to about 10% by weight of the total weight of the fragrance composition, but is not limited thereto. Alternatively, the content may be changed according to the type of the target fragrance composition.

  Further, the ratio of 3,7-dimethyl-5E-octenoic acid to 3,7-dimethyl-5Z-octenoic acid is not particularly limited, and any ratio of the compound of the present invention can be used. Dimethyl-5E-octenoic acid or 3,7-dimethyl-5Z-octenoic acid can be used alone.

  When preparing a fragrance composition using the compound of the present invention, the fragrance compound used together is not particularly limited. For example, various hydrocarbons represented by limonene and pinene; various aldehydes such as octanal, decanal and citral; various ketones such as maltol, damasenone and methylheptenone; various alcohols such as L-menthol, octanol, linalool and phenylethyl alcohol Various ethers and oxides such as methylphenyl ethyl ether, linalool oxide and 1,4-cineole; various esters such as ethyl butyrate, geranyl acetate and hexyl acetate; various lactones such as γ-decalactone, coumarin and jasmine lactone Various hetero compounds such as indole, phenylacetonitrile, limonenethiol; peppermint oil, jasmine absolute, cedarwood oil, orisco Various natural flavors materials such as cleats; but like not limited thereto.

  There are no particular restrictions on the solvent used, and examples include ethanol, glycerin, triacetin, triethyl citrate, water, dipropylene glycol (DPG), benzyl benzoate (BB), and the like.

  By using the fragrance composition of the present invention in the following foods and beverages and cosmetics, it is possible to impart a characteristic fragrance or fragrance flavor property to the product, thereby satisfying consumer needs and providing a characteristic product. Can be created.

  Examples of foods and beverages include alcoholic beverages, citrus beverages, fruit beverages, milk beverages, various beverages such as tea and coffee beverages, various cold confections such as ice cream, sherbet, and ice candy, tobacco, and gum Foods such as candy, candy, pudding, jelly, instant foods such as soups and instant noodles, snacks represented by potato chips, and animal and plant extracts. Examples of cosmetics include perfumes such as parfum and eau de toilette, shampoos, rinses, treatments, soaps, toothpastes, mouthwashes, body shampoos, and other toiletry products, incense sticks, candles, pastes, etc. Fragrances, hair dyes, bleaches, hair tonics and other hair products, foundations, lotions, lipstick and other cosmetics, indoor and in-car fragrances, dishwashing detergents, Various detergents such as laundry detergents and softeners are included.

It is preferable to use the compound represented by the chemical formula (2) for gum, candy, and toothpaste. In particular, among the compounds represented by the chemical formula (2), the compound in which R ² is a hydrogen atom is also a component contained in mint oil, and it is particularly preferable to use it for gum, candy, and toothpaste. The compound represented by the chemical formula (2) may be either one obtained by organic synthesis or one extracted from a natural product.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this.

Synthesis of isopropyl 3,7-dimethyl-5-octenoate

  To a suspension of 19.2 g (48.0 mmol) of isobutyltriphenylphosphonium bromide and 80 mL of cyclopentylmethyl ether (hereinafter also referred to as CPME) at 0 ° C. with stirring, 16.0 mL of a 2.62 M n-butyllithium hexane solution. (48.0 mmol) was added dropwise. After completion of dropping, the temperature was raised to room temperature in 3 hours to prepare a Wittig reagent.

  To a solution of isopropyl 3-methyl-5-oxopentanoate 7.3 g (40 mmol) and CPME 40 mL, the CPME solution of Wittig reagent prepared previously was added dropwise at -20 ° C. After raising the temperature to 0 ° C. over 2 hours, 100 mL of n-hexane was added and the precipitated triphenylphosphine oxide was filtered off. A saturated aqueous ammonium chloride solution was added to the filtrate for liquid separation, and the aqueous layer was extracted again with 40 mL of n-hexane.

  The combined organic layers were washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 7.9 g of a yellow oily substance. This was purified using a silica gel column chromatograph (hereinafter also referred to as SCC) to obtain 6.6 g of a transparent liquid substance (yield 77.1%).

  As a result of GC measurement, it was confirmed to be isopropyl 3,7-dimethyl-5-octenoate (mixture of geometric isomers) having a purity of 98.1% and E: Z = 17: 83.

  0.2 g of isopropyl 3,7-dimethyl-5-octenoate (mixture of geometric isomers) obtained by the above operation was separated and purified by reverse phase HPLC, and 5 mg of isopropyl 3,7-dimethyl-5E-octenoate was obtained. 40 mg of isopropyl 3,7-dimethyl-5Z-octenoate was obtained.

  The spectral data of isopropyl 3,7-dimethyl-5E-octenoate are shown.

EI-MS (m / z, relative intensity) 212 (M ⁺ , 2), 169 (12), 153 (38), 152 (52), 110 (100), 109 (49), 95 (82), 81 (17), 69 (75), 55 (34), 43 (34), 41 (40)
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.91 (3H, d), 0.96 (3H, d), 1.24 (3H, d), 1.90-2.10 (4H, m), 2.25 (1H, m), 2.30 (1H, dd), 5.01 (1H, m), 5.20-5.45 (2H, m)
¹³ C-NMR (100 MHz, CDCl ₃ , δ ppm): 19.6, 21.8, 21.9, 22.6, 22.7, 30.5, 30.9, 39.6, 40.8, 67 .4,124.3,140.1,172.9

The spectral data of isopropyl 3,7-dimethyl-5Z-octenoate are shown.
EI-MS (m / z, relative intensity) 212 (M ⁺ , 2), 169 (12), 153 (38), 152 (52), 110 (100), 109 (49), 95 (82), 81 (17), 69 (75), 55 (34), 43 (34), 41 (40)
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.94 (6H, d), 0.95 (3H, d), 1.23 (3H, d), 1.94-2.10 (4H, m), 2.29 (1H, dd), 2.56 (1H, m), 5.01 (1H, m), 5.15-5.30 (2H, m)
¹³ C-NMR (100 MHz, CDCl ₃ , δ ppm): 19.5, 21.8, 21.9, 23.1, 23.1, 26.4, 30.9, 34.1, 41.6, 67 .3, 124.7, 139.1, 172.8

Synthesis of methyl 3,7-dimethyl-5-octenoate

  1 g (4.7 mmol) of isopropyl 3,7-dimethyl-5-octenoate (E: Z = 17: 83), 30 ml of methanol and 0.2 g (0.1 mmol) of a methanol solution containing 28% sodium methoxide were placed in a flask. The reaction was completed by stirring for 3 hours in a 50 ° C. hot water bath. The mixture was allowed to cool to room temperature, and the reaction mixture was poured into an ice-cooled diluted hydrochloric acid aqueous solution and extracted twice with 20 mL of ethyl acetate. The combined organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.8 g of a yellow oily crude. This was purified using SCC to obtain 0.6 g of a transparent liquid substance (yield 69.4%).

  When measured by GC, it was confirmed to be methyl 3,7-dimethyl-5-octenoate having a purity of 98.1% and E: Z = 17: 83.

The spectral data of methyl 3,7-dimethyl-5Z-octenoate are shown.
EI-MS (m / z, relative intensity) 184 (M ⁺ , 1), 153 (15), 152 (38), 110 (66), 95 (100), 69 (31), 55 (29), 41 (25)
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.93 (6H, d), 0.95 (3H, d), 1.90-2.15 (4H, m), 2.34 (1H, dd), 2.55 (1H, m), 5.15-5.30 (2H, m)
¹³ C-NMR (100 MHz, CDCl ₃ , δ ppm): 19.7, 23.0, 23.1, 26.4, 30.8, 34.2, 41.0, 51.4, 124.6, 139 .2,173.7

Synthesis of 3,7-dimethyl-5Z-octenoic acid

  In Example 1, 0.1 ml of methanol and 0.1 ml of 10% aqueous sodium hydroxide solution were added to 20 mg (0.094 mmol) of isopropyl 3,7-dimethyl-5Z-octenoate purified by HPLC, and a warm bath at 50 ° C. For 1 hour to complete the reaction. The mixture was allowed to cool to room temperature, ice water was added, and the mixture was extracted with 10 mL of hexane. The aqueous layer was adjusted to pH 3 with diluted hydrochloric acid, and extracted with 20 mL of ethyl acetate. The ethyl acetate layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 12 mg of a yellow oily substance.

  The obtained yellow oily substance was purified by SCC to obtain 10 mg of the title compound having a GC purity of 99% (yield 62.6%). The spectrum data of this carboxylic acid is shown below.

Spectral data of 3,7-dimethyl-5Z-octenoic acid

GC-MS (Retention Index (RI), DB-WAX): 2147
EI-MS (m / z, relative intensity) 170 (M ⁺ , 3), 152 (20), 110 (63), 95 (100), 69 (46), 55 (52), 41 (38)
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.93 (6H, d), 0.98 (3H, d), 1.96-2.18 (4H, m), 2.40 (1H, dd), 2.56 (1H, m), 5.17-5.32 (2H, m)
¹³ C-NMR (100 MHz, CDCl ₃ , δ ppm): 19.6, 23.1, 23.1, 26.5, 30.6, 34.1, 41.7, 124.5, 139.4, 178 .5

From the Mentha arvensis essential oil, the residue part 700g which arose in the L-menthol refinement | purification process was attached | subjected to vacuum distillation, and 250 g of fractions with a distillation temperature of 170 degreeC were obtained at 3 mmHg. This fraction was fractionated into 11 by SCC using a solvent in which the composition ratio of hexane and ethyl acetate was changed.
Among the above fractions, 55 g of the fraction eluted with a mixed solvent of 3% ethyl acetate and 97% hexane was dissolved in diethyl ether, and the acidic component was extracted with a 10% aqueous sodium carbonate solution. The aqueous layer was adjusted to pH 3 with dilute hydrochloric acid and extracted with ethyl acetate. After washing, drying and concentration under reduced pressure, 0.6 g of an oily substance having a strong acid odor was obtained.

  This was methyl esterified with diazomethane and then fractionated by reverse phase ODS column chromatography. Finally, fractionation by GC equipped with an Apiezon column was performed to obtain 5 mg of the desired methyl 3,7-dimethyl-5-octenoate.

When the obtained methyl 3,7-dimethyl-5-octenoate was analyzed by GC-MS, it was a geometric isomer mixture of E: Z = 81: 19 (total ion ratio of GC-MS).

Spectral data of methyl 3,7-dimethyl-5E-octenoate EI-MS (m / z, relative intensity) 184 (M ⁺ , 1), 153 (15), 152 (38), 110 (66), 95 (100 ), 69 (31), 55 (29), 41 (25)
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.92 (3H, d), 0.96 (6H, d), 1.89-2.15 (4H, m), 2.25 (1H, m), 2.33 (1H, dd), 5.25-5.45 (2H, m)
¹³ C-NMR (100 MHz, CDCl ₃ , δ ppm): 19.6, 22.6, 22.6, 30.6, 31.1, 39.7, 40.9, 51.4, 124.4, 140 .1, 173.8

  A small amount of aqueous sodium hydroxide and methanol were added to 1 mg of this methyl ester, and alkaline hydrolysis was carried out in the same manner as in Example 3 to obtain a carboxylic acid. As a result of GC-MS analysis, two peaks showing the same mass pattern appeared, and it was confirmed that the smaller content was 3,7-dimethyl-5Z-octenoic acid shown in Example 3.

Spectral data of 3,7-dimethyl-5E-octenoic acid GC-MS (RI, DB-WAX): 2128
EI-MS (m / z, relative intensity) 170 (M ⁺ , 3), 152 (20), 110 (63), 95 (100), 69 (46), 55 (52), 41 (38)

3,7-Dimethyl-5Z-octenoic acid GC-MS (RI, DB-WAX): 2147
EI-MS (m / z, relative intensity) 170 (M ⁺ , 3), 152 (20), 110 (63), 95 (100), 69 (46), 55 (52), 41 (38)

Analysis of 3,7-dimethyl-5-octenoic acid contained in natural mint oil distillation distillate

  104 g of the mint oil distillation final stage produced in the natural L-menthol production process was dissolved in hexane, and the acidic component was extracted with saturated multistory water. It processed like Example 4 and obtained 0.1 g of acid components. As a result of GC-MS analysis, it was confirmed by comparison with Example 4 that 3,7-dimethyl-5E-octenoic acid and 3,7-dimethyl-5Z-octenoic acid were present, and GC-MS These E / Z ratios were E: Z = 77: 23.

  As a result of evaluating the aroma of 3,7-dimethyl-5Z-octenoic acid synthesized in Example 3 by three skilled panelists, it was expressed as a heavy fatty acid odor with a somewhat mint-like nuance.

  The odor of isopropyl 3,7-dimethyl-5-octenoate (mixture of geometrical isomers) synthesized in Example 1 with a purity of 98.1% and E: Z = 17: 83 was evaluated by three skilled panelists. As a result, it was expressed as diffusible apple, pair-like green incense and fruit incense.

  Methyl 3,7-dimethyl-5-octenoate (mixture of geometric isomers) of purity 98.1% and E: Z = 17: 83 synthesized in Example 2 was evaluated for its aroma by three skilled panelists. The result was a sharp, metallic pair-like green and fruit incense.

  The fragrance composition shown in Formula 1 below was prepared and subjected to sensory evaluation by three skilled panelists. As a result, the comparative example gave a sense of volume while maintaining the refreshing mint feeling at the top. It was done.

Formula 1
Component name Example Comparative example ----------------------------
Peppermint oil 61.9 62.0
Menthol 30.0 30.0
Eucalyptus oil 5.0 5.0
Citrus oil 3.0 3.0
Compound synthesized in Example 3 0.1 Not added ----------------------------
Total 100.0 100.0

  The fragrance composition shown in Formula 2 below was prepared and subjected to sensory evaluation by three skilled panelists. As a result, the example showed a natural apple flesh-like green fragrance with respect to the comparative example. .

Formula 2
Component name Example Comparative example ----------------------------
Ethanol 526.7 527.7
Purified water 400.0 400.0
Isoamyl acetate 15.0 15.0
Ethyl butyrate 12.0 12.0
Ethyl acetate 8.0 8.0
Hexanol 6.0 6.0
Isoamyl isovalerate 6.0 6.0
Trans-2-hexanal 5.0 5.0
Hexanal 5.0 5.0
2-Methylbutyric acid 4.0 4.0
Acetaldehyde diethyl acetal 4.0 4.0
Propionic acid 3.0 3.0
Butyl formate 2.0 2.0
Ethyl isovarate 2.0 2.0
Hexanal 0.2 0.2
Damasenon 0.1 0.1
Mixture of geometric isomers synthesized in Example 1 0.1 No addition ----------------------------
Total 100.0 100.0

  The fragrance composition shown in Formula 3 below was prepared and subjected to sensory evaluation by three skilled panelists. As a result, the example was enhanced with a natural pair of fresh and green top notes. .

Formula 3
Component name Example Comparative example ----------------------------
Ethanol 557.5 560.0
Purified water 400.0 400.0
Hexyl acetate 15.0 15.0
Ethyl acetate 10.0 10.0
Cis-3-hexenol 6.0 6.0
Isoamyl acetate 5.0 5.0
Hexyl butyrate 2.0 2.0
2-Methylbutyric acid 1.0 1.0
Cis-3-hexenyl acetate 0.7 0.7
α-Damascon 0.2 0.2
1-Hexanal 0.1 0.1
Mixture of geometric isomers synthesized in Example 2 2.5 No addition ----------------------------
Total 100.0 100.0

By using the compound of the present invention, a fragrance composition having a characteristic aroma characteristic can be obtained, and by using these in a food or drink or cosmetic, a characteristic food or drink or cosmetic can be obtained.

Claims (5)

Chemical formula (1)

(The wavy line indicates the Z-configuration or the E-configuration. In the Z-configuration, R ¹ represents a hydrogen atom, or an alkyl or alkenyl group having 1 to 5 carbon atoms. In the E-configuration, R ¹ represents 3,7-dimethyl-5-octenoic acid or an ester compound thereof represented by a C1, C3, C4 alkyl group or an alkenyl group. Chemical formula (2)

(The wavy line indicates the Z- arrangement or E- configuration, ^{R 2} is a hydrogen atom, or an alkyl or alkenyl group having 1 to 5 carbon atoms) is 3,7-dimethyl-5-octene acid or represented by A fragrance composition containing an ester compound. A food or drink containing the compound according to claim 1 or the fragrance composition according to claim 2. A cosmetic comprising the compound according to claim 1 or the fragrance composition according to claim 2. Use of the compound according to claim 1 as a fragrance.