JP5500661B2 - Novel ethyl 5-formyloxyalkanoate and perfume composition containing the compound - Google Patents

Description

  The present invention relates to a novel ethyl 5-formyloxyalkanoate useful as a fragrance compound and a novel fragrance composition containing the compound as an active ingredient.

  In recent years, with the diversification of consumer preferences, development of various products that meet consumer needs is desired. In particular, this trend is strong in the food and beverage industry, and there is a strong demand for the development of a variety of food and drink that matches the taste of consumers. In response to these demands, the flavor (food fragrance) compounds that have been proposed in the past have not been able to adequately respond to the fragrance that is one of the raw materials for foods and drinks. Development of flavor compounds possessing excellent durability is an urgent issue.

  In particular, there are many requests for the purpose of imparting and enhancing flavors and flavors such as milk, fat, and cream to foods and drinks, etc., but conventional flavor compounds alone have increased the diversifying preferences of consumers in recent years. Since it has become very difficult to meet the demand, development of flavor compounds having unprecedented unique aroma and flavor characteristics is strongly desired.

  A 5-hydroxyalkanoic acid derivative is used for the purpose of imparting an aroma and flavor such as a milky feeling, a faty feeling, and a creamy feeling to foods and drinks. For example, ethyl 5-hydroxydecanoate known as a perfume compound is a coffee flavor (Patent Document 1), a fermented milk-like flavor (Patent Document 2), a milk-based flavor (Patent Document 3), and a crustacean flavor (Patent Document 1). Document 4), the use of seafood flavors (Patent Document 5) and seaweed flavors (Patent Document 6) are disclosed. However, this compound is unstable and there is a problem that purification such as distillation is difficult. Similarly, ethyl 5-hydroxyoctanoate, known as a perfume compound, is a coffee flavor (Patent Document 1), a crustacean flavor (Patent Document 4), a seafood flavor (Patent Document 5), and a seaweed flavor. The use of a flavor (Patent Document 6) is disclosed. However, this compound is also unstable, and there is a problem that purification such as distillation is difficult. In addition, the use of a cocoa-like composition (Patent Document 7) is disclosed for ethyl 5-hydroxydodecanoate. However, this compound is also unstable, and there is a problem that purification such as distillation is difficult.

  Furthermore, methyl 5-formyl oxide decanoate is mentioned as a 5-formyl oxyalkanoic acid derivative known as a fragrance | flavor compound, and use of coffee flavor (patent document 1) is disclosed. However, this compound was not always satisfactory in terms of aroma.

JP 2006-20526 A JP 2006-124490 A JP 2005-15685 A Japanese Patent Laid-Open No. 2005-160402 JP 2005-143466 A JP 2005-143465 A JP 2006-121958 A

  An object of the present invention is to provide a novel fragrance compound capable of imparting an aroma and flavor such as a milk feeling, a fat sensation and a cream feeling to foods and drinks, and a novel fragrance composition containing the compound as an active ingredient. That is.

  As a result of intensive studies to solve the above problems, the present inventors have found that a novel 5-formyloxyalkanoic acid derivative, ethyl 5-formyloxyalkanoate, itself has a milky feeling, a faty feeling, It has unique aroma characteristics such as cream, coconut-like, coumarin-like, peach-like, fruity, butter-like, and it can be added to fragrance compositions or foods and drinks to give it an aroma and flavor such as milk, fat, and cream. Has been found to be able to be imparted or enhanced, and the present invention has been completed.

  Thus, the present invention provides the following formula (1):

[Wherein R represents an alkyl group having 3 to 7 carbon atoms. Except for ethyl 5-formyloxydecanoate]
It is intended to provide ethyl 5-formyloxyalkanoate represented by

  The present invention also provides a fragrance composition comprising ethyl 5-formyloxyalkanoate represented by the above formula (1) as an active ingredient.

  Moreover, this invention provides the food-drinks characterized by including the ethyl 5-formyloxyalkanoate as described above.

  Furthermore, this invention provides the food / beverage products characterized by including the fragrance | flavor composition as described above.

  The ethyl 5-formyloxyalkanoate of the present invention can impart or enhance unconventional aroma and flavor such as milk, fat, and cream to the perfume composition, and 5-formyloxyalkanoic acid. By adding a flavor composition containing ethyl to foods and drinks, a characteristic aroma and flavor such as milk, fat, and cream can be imparted or enhanced, and a variety that suits consumer preferences It becomes possible to provide food and drinks rich in food.

  Hereinafter, the present invention will be described in more detail.

  The ethyl 5-formyloxyalkanoate represented by the above formula (1) which is the compound of the present invention is, for example, ethyl 5-formyloxyoctanoate, ethyl 5-formyloxynonanoate, ethyl 5-formyloxyundecanoate. , Ethyl 5-formyloxide decanoate, ethyl 5-formyloxyisooctanoate, ethyl 5-formyloxyisononanoate, ethyl 5-formyloxyisodecanoate, ethyl 5-formyloxyisoundecanoate, 5-formyloxyisododecanoic acid Examples include ethyl, ethyl 5-formyloxy-7-methylnonanoate, ethyl 5-formyloxy-8-methyldecanoate, and the like. Preferably, the use of ethyl 5-formyloxyoctanoate, ethyl 5-formyloxynonanoate, ethyl 5-formyloxyundecanoate and ethyl 5-formyloxide decanoate as perfume compounds is preferred, but not limited thereto.

  The ethyl 5-formyloxyalkanoate represented by the above formula (1), which is a compound in the present invention, can be produced, for example, according to the reaction route shown below.

[Wherein R represents an alkyl group having 3 to 7 carbon atoms]

  In the first step of the above reaction, a commonly used transesterification reaction can be used. Examples thereof include a method of reacting with ethanol in the presence of a metal alkoxide and a method of reacting with ethanol in the presence of an acid catalyst.

  Moreover, the esterification reaction generally used can be used for the 2nd process of the said reaction. For example, a method of reacting with a mixed acid anhydride prepared from formic acid and another carboxylic acid, a method of performing a transesterification reaction with a formate in the presence or absence of a catalyst such as a base or an acid, an acid catalyst, Examples thereof include a method of directly reacting formic acid in the presence or absence of various condensing agents.

  Hereinafter, although a general manufacturing method is described about each process, this invention is not limited.

  The δ-lactone represented by the formula (2) used as a starting material for the above reaction may be either synthesized according to a general method or a commercially available product. Commercially available products include δ-octalactone (manufactured by Tokyo Chemical Industry Co., Ltd.), δ-nonalactone (manufactured by Sigma-Aldrich), δ-nonalactone (manufactured by Hichem), δ-undecalactone (manufactured by Sigma-Aldrich), δ -Dodecalactone (manufactured by Sigma-Aldrich), δ-dodecalactone (manufactured by Hichem) and the like can be mentioned.

  The δ-lactone represented by the formula (2) can be used as a starting material and reacted with sodium alkoxide in the presence of ethanol to produce ethyl 5-hydroxyalkanoate represented by the formula (3).

  Ethanol can be used in the range of usually 1.0 to 200.0 mol, preferably 30.0 to 80.0 mol per mol of δ-lactone. Sodium alkoxide can be used in the range of usually 0.05 to 0.5 mol, preferably 0.1 to 0.3 mol, per mol of δ-lactone. The reaction is usually carried out at a temperature in the range of 10 ° C to 50 ° C, preferably 15 ° C to 40 ° C, usually for 30 minutes to 24 hours, preferably about 30 minutes to 12 hours.

  Reacting ethyl 5-hydroxyalkanoate represented by the formula (3) with a carboxylic acid anhydride using pyridine as a solvent to produce ethyl 5-formyloxyalkanoate represented by the formula (1) Can do.

  The mixed solution of formic acid and carboxylic anhydride used for the production of ethyl 5-formyloxyalkanoate can be prepared by a known method and used for the reaction.

  Carboxylic anhydride can be used in the range of usually 1 to 10 mol, preferably 2 to 5 mol per mol of ethyl 5-hydroxyalkanoate. The dropwise addition of carboxylic acid anhydride to ethyl 5-hydroxyalkanoate is usually at a temperature in the range of 0 ° C. to 20 ° C., preferably 5 ° C. to 15 ° C., usually 10 minutes to 5 hours, preferably 30 minutes to The dripping is performed in about 2 hours.

  Ethyl 5-formyloxyalkanoate represented by the above formula (1), which is a compound of the present invention, is blended as it is in foods and beverages, cosmetics, health / hygiene / pharmaceuticals, milky feeling, fatty feeling, creamy feeling, etc. The fragrance / flavor can be imparted or enhanced, but a milk-based fragrance composition is prepared by mixing with other ingredients, and the fragrance composition is used to prepare milk for foods / drinks, cosmetics, health / hygiene / pharmaceuticals. Aromas and flavors such as feeling, fat feeling and cream feeling can be imparted or enhanced. Further, two or more ethyl 5-formyloxyalkanoates of the present invention can be mixed and used in an arbitrary ratio, and can be used by mixing with other perfume ingredients. Examples of other fragrance components that can be contained together with ethyl 5-formyloxyalkanoate in the fragrance composition include various synthetic fragrances, natural fragrances, natural essential oils, plant extracts, and the like. For example, natural essential oils, natural fragrances, and synthetic fragrances described in "Patent Office, Well-known and commonly used technology (fragrance) Part II food fragrance, P88-131, issued on January 14, 2000" can be mentioned. .

  For example, γ-caprolactone, γ-heptalactone, γ-octalactone, γ-nonalactone, γ-decalactone, 7-decen-4-olide, 3-methyl-4-decen-4-olide, 3-methyl-5- Decene-4-olide, γ-undecalactone, γ-dodecalactone, γ-tridecalactone, γ-tetradecalactone, δ-caprolactone, 2-hexene-5-olide, 2-heptene-5-olide, δ -Octalactone, 2-octene-5-olide, 4-methyl-5-octanolide, δ-nonalactone, 2-nonene-5-olide, 4-methyl-5-nonanolide, δ-decalactone, 2-decene-5 Orido, 4-methyl-5-decanolide, δ-undecalactone, 2-undecen-5-olide, 4-methyl-5-undecanolide, δ-dodecalactone 2-dodecene-5-olide, 4-methyl-5-dodecanolide, δ-tridecalactone, 2-tridecen-5-olide, 4-methyl-5-tridecanolide, δ-tetradecalactone, 2-tetradecene-5 Orido, 2-Pentadecene-5-Olide, 2-Hexadecene-5-Olide, 2-Heptadecene-5-Olide, 2-Octadecene-5-Olide, 2-Nonadecene-5-Olide, 2-Eicocene-5-Olide, Lactones such as ε-decalactone; propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, trans-2-hexenoic acid, heptanoic acid, caprylic acid, nonanoic acid, 5-hydroxynonanoic acid, capric acid, 2- Decenoic acid, 4-decenoic acid, 5-decenoic acid, 6-decenoic acid, 9-decenoic acid, 5-hydroxydecenoic acid, 5-hydroxyundeca Fatty acids such as acid, lauric acid, 5-hydroxydodecanoic acid, myristic acid, pentadecanoic acid, isopentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid; acetaldehyde, propanal, butanal, 2-butenal, hexanal, octanal, 4-heptenal, 2,4-octadienal, nonanal, 2-nonenal, 2,4-nonadienal, 2,6-nonadienal, decanal, 2,4-decadienal, undecanal, 2 , 4-Undecadienal, dodecanal, benzaldehyde, vanillin, ethyl vanillin, furfural, heliotropin diethyl acetal and other aldehydes; ethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, decyl acetate, acetic acid Dodecyl, phenethyl acetate, ethyl lactate, ethyl butyrate, ethyl 2-methylbutyrate, ethyl 3-ethylbutyrate, methyl valerate, methyl caproate, ethyl caproate, methyl heptanoate, ethyl heptanoate, ethyl caprylate, isoamyl caprylate , Heptyl caprylate, methyl nonanoate, ethyl nonanoate, methyl caprate, ethyl caprate, ethyl undecanoate, methyl laurate, ethyl laurate, ethyl myristate, ethyl palmitate, methyl salicylate, diethyl succinate, sebacic acid Diethyl, ethyl 5-hydroxyhexanoate, ethyl 5-hydroxydecanoate, ethyl 5-hydroxyundecanoate, propyl 5-hydroxydecanoate, isopropyl 5-hydroxydecanoate, 2-methylpropyl 5-hydroxyoctanoate Esters such as ethyl 5-hydroxy-9-methyldecanoate, methyl 5-acetoxydecanoate, ethyl 5-acetoxydecanoate; ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, benzyl alcohol, Alcohols such as phenylethyl alcohol and furfuryl alcohol; 2-heptanone, 2-octanone, 3-octanone, 1-octen-3-one, 2-nonanone, 3-nonanone, 8-nonen-2-one, 2- Undecanone, 2-tridecanone, acetoin, 5-hydroxy-4-octanone, diacetyl, 2,3-pentadione, 2,3-hexadione, 2,3-heptadione, acetylisovaleryl, p-methoxyacetophenone, benzopheno , Ketones such as maltol; nitrogen-containing compounds such as phenylethyl anthranilate, trimethylamine, indole, skatole, pyridine, isoquinoline, pyrazine, methylpyrazine; methanethiol, isobutyl mercaptan, 2,4-dithiapentane, dimethyl sulfide, dimethyl Disulfide, dimethyl trisulfide, dimethyl sulfoxide, dimethyl sulfone, methyl sulfonyl methane, methyl isothiocyanate, ethyl isothiocyanate, allyl isothiocyanate, 2-methyl-3-butanethiol, methional, ethyl thioacetate, methyl thiobutyrate, 3 -Butenyl isothiocyanate, 2-methylthiophene, benzothiazole, sulfuryl, acetyl lactate thiomethyl ester, propionyl lactate thiol Methyl ester, butyryl lactate thiomethyl ester, valeryl lactate thiomethyl ester, 2-methylbutyryl lactate thiomethyl ester, desilyl lactate thiomethyl ester, acetyl lactate thioethyl ester, propionyl lactate thioethyl ester, butyryl lactate thioethyl ester, valeryl lactate thiol Known perfume compounds such as sulfur-containing compounds such as ethyl ester, isocaproyl lactate thiopropyl ester; lipase degradation product of milk fat; protease degradation product of milk protein; milk, concentrated milk, powdered milk, milk whey, butter, cheese, yogurt or these Examples thereof include fractions of milk or milk processed products from the mixture.

  In the fragrance composition containing ethyl 5-formyloxyalkanoate of the present invention, a solvent such as water or ethanol, which is usually used in the fragrance composition, for example, ethylene glycol, propylene glycol, di-ethylene is used as necessary. Perfume retention agents such as propylene glycol, glycerin, hexylene glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercoline, fatty acid triglyceride, and fatty acid diglyceride can be contained.

  The ethyl 5-formyloxyalkanoate of the present invention itself has a characteristic aroma, but has a strong aroma, milk-like, coconut-like, peach-like, cream-like aroma and flavor due to changes over time. Since it produces lactone, it also has use as a precursor of δ-lactone.

  As described above, ethyl 5-formyloxyalkanoate of the present invention can be used alone or as a perfume composition containing ethyl 5-formyloxyalkanoate to prepare various products such as food and drink. It is also possible to impart or enhance the flavor or richness of the products, cosmetics, health / hygiene / pharmaceuticals utilizing the above-mentioned aroma characteristics.

  Specific examples of foods and drinks that can impart or enhance aroma and flavor such as milk feeling, fat feeling, cream feeling, etc. by the fragrance composition containing ethyl 5-formyloxyalkanoate of the present invention are not limited at all. For example, carbonated drinks such as cola drinks, carbonated drinks with fruit juice, carbonated drinks with milk; fruit juice drinks, vegetable drinks, sports drinks, honey drinks, soy milk, vitamin supplement drinks, mineral supplement drinks, nutrition drinks, Soft drinks such as nourishment drinks, lactic acid bacteria drinks, milk drinks; favorite drinks such as green tea, black tea, oolong tea, herbal tea, milk tea, coffee drinks; alcohol such as chuhai, cocktail drinks, sparkling liquor, fruit liquor, condiment Beverages; dairy products such as butter, cheese, milk, yogurt; ice cream, lacto ice, Desserts such as confectionery, yogurt, pudding, jelly, daily dessert and mixes for producing them; caramel, candy, tablet confectionery, crackers, biscuits, cookies, pies, chocolate, snacks and other confectionery For example, cake mixes such as cake mixes; general foods such as breads, soups and various instant foods.

  Specific examples of cosmetics, health / hygiene / pharmaceuticals that can impart or enhance aroma or flavor such as milk, fat or cream with the perfume composition containing ethyl 5-formyloxyalkanoate of the present invention Is not limited at all, for example, fragrance products, basic cosmetics, finish cosmetics, hair cosmetics, tanning cosmetics, medicated cosmetics, hair care products, soap, body detergent, bath preparation, detergent, softener, bleach, Examples include aerosols, deodorants and fragrances, repellents, oral compositions, and external preparations for skin.

  The amount of ethyl 5-formyloxyalkanoate of the present invention varies depending on the purpose or the type of food or drink, but for example, the range of 1 ppb to 100 ppm, preferably 10 ppb to 10 ppm, relative to the total weight of the food or drink. It can be illustrated. Within these ranges, the food / beverage product has an excellent effect of imparting or enhancing aroma and flavor such as milk, fat and cream. On the other hand, when the blending amount of ethyl 5-formyloxyalkanoate with respect to food and drink exceeds 100 ppm, the aroma and flavor characteristics as a fat-like odor peculiar to ethyl 5-formyloxyalkanoate alone are not preferable. Moreover, when the compounding quantity of 5-formyloxyalkanoic acid ethyl with respect to food-drinks is less than 1 ppb, the fragrance and flavor imparting effect peculiar to this invention are not acquired.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these.

Example 1: Synthesis of ethyl 5-hydroxyoctanoate A 500 mL four-necked flask was charged with δ-octalactone (Tokyo Kasei Co., Ltd., 14.2 g, 0.10 mol) and 99% ethanol (270.0 g). Sodium ethoxide (manufactured by Sigma-Aldrich, 21% ethanol solution, 5.5 g, 0.017 mol) is added dropwise under stirring at 25 ° C. to 30 ° C./30 minutes. After stirring overnight at room temperature, glacial acetic acid (1.0 g, 0.017 mol) is added for neutralization, and the mixture is concentrated under reduced pressure. 15% brine (100 g) was added to the resulting residue, and the mixture was extracted with ether (100 g). The resulting organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (100 g) and 15% brine (100 g). To do. By drying over anhydrous magnesium sulfate and concentration under reduced pressure, ethyl 5-hydroxyoctanoate (13.5 g) was obtained as a colorless oily crude product. Crude yield 72%.

Example 2: Synthesis of ethyl 5-formyloxyoctanoate In a 200 mL four-necked flask, the crude ethyl 5-hydroxyoctanoate obtained in Example 1 (13.5 g) and pyridine (manufactured by Junsei Co., Ltd., 54.0 g) were prepared. ) And stirring under ice water cooling, a mixed solution of acetic anhydride (18.4 g, 0.18 mol) and 98% formic acid (manufactured by Junsei Chemical Co., Ltd., 8.7 g, 0.19 mol) was added at 5 ° C. to 15 ° C. / Add dropwise in 1 hour. After stirring at room temperature for 3.5 hours, 99% ethanol (46.1 g, 1.0 mol) is added dropwise at 5 ° C. to 15 ° C./30 minutes under ice water cooling, and stirred at room temperature for 30 minutes. Pour into cold 10% hydrochloric acid (100 mL), extract with n-hexane (100 mL × 2 times), combine the organic layers obtained, cold 10% hydrochloric acid (100 g), 5% aqueous sodium carbonate solution (100 g), 15 Wash sequentially with% saline (100 g). The residue (18.0 g) obtained by drying under anhydrous magnesium sulfate and concentrating under reduced pressure was purified by distillation to obtain a colorless oily ethyl 5-formyloxyoctanoate (Product 1 of the present invention, 15.4 g). 0.071 mol) was obtained. Yield 71% from δ-octalactone.

  As a result of gas chromatographic analysis of ethyl 5-formyloxyoctanoate obtained in Example 2 above, the chemical purity of ethyl 5-formyloxyoctanoate was 96.3% (gas chromatographic conditions, column: TC −1 (30 m × 0.53 mm), temperature rising conditions: 100 ° C. to 300 ° C., 20.0 ° C./min temperature rising, carrier gas: nitrogen, linear velocity: 60 cm / sec, holding time: 5.0 min).

Physical property data of ethyl 5-formyloxyoctanoate
¹ H-NMR (400 MHz, CDCl ₃ ): δ ppm 0.89 (t, 3H, J = 7.4 Hz), 1.23 (t, 3H, J = 7.2 Hz), 1.20-1.40 ( m, 2H), 1.45-1.70 (m, 6H), 2.29 (m, 2H), 4.10 (q, 2H, J = 7.2 Hz), 5.00 (quin, 1H, J = 6.0 Hz), 8.06 (s, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ ppm 13.83, 14.22, 18.44, 20.61, 33.31, 33.91, 36.03, 60.31, 73.56, 160. 94, 173.24
MS (m / z): 187 (1), 171 (3), 125 (44), 124 (53), 99 (90), 96 (52), 88 (88), 71 (37), 55 (100 ), 43 (45), 41 (39), 29 (36)

Example 3: Synthesis of ethyl 5-hydroxynonanoate A 500 mL four-necked flask was charged with δ-nonalactone (Sigma-Aldrich, 15.6 g, 0.10 mol) and 99% ethanol (270.0 g), and cooled with ice water. Sodium ethoxide (manufactured by Sigma-Aldrich, 21% ethanol solution, 5.5 g, 0.017 mol) is added dropwise under stirring at 25 ° C. to 30 ° C./30 minutes. After stirring overnight at room temperature, glacial acetic acid (1.0 g, 0.017 mol) is added for neutralization, and the mixture is concentrated under reduced pressure. 15% brine (100 g) was added to the resulting residue, and the mixture was extracted with ether (100 g). The resulting organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (100 g) and 15% brine (100 g). To do. By drying over anhydrous magnesium sulfate and concentrating under reduced pressure, ethyl 5-hydroxynonanoate (19.8 g) was obtained as a colorless oily crude product. Crude yield 98%.

Example 4: Synthesis of ethyl 5-formyloxynonanoate In a 300 mL four-necked flask, the crude ethyl 5-hydroxynonanoate obtained in Example 3 (19.8 g) and pyridine (manufactured by Junsei Co., Ltd., 80.0 g) ) And stirring under ice-water cooling, a mixed solution of acetic anhydride (25.5 g, 0.25 mol) and 98% formic acid (manufactured by Junsei Chemical Co., Ltd., 12.0 g, 0.26 mol) was added at 5 ° C. to 15 ° C. / Add dropwise in 1 hour. After stirring overnight at room temperature, 99% ethanol (64.5 g, 1.4 mol) is added dropwise at 5 ° C. to 15 ° C./1 hour under ice water cooling, and stirred at room temperature for 30 minutes. Pour into cold 10% hydrochloric acid (100 mL), extract with n-hexane (100 mL × 2 times), combine the organic layers obtained, cold 10% hydrochloric acid (100 g), 5% aqueous sodium carbonate solution (100 g), 15 Wash sequentially with% saline (100 g). After drying over anhydrous magnesium sulfate and concentrating under reduced pressure, the residue (20.5 g) obtained by distillation was purified by distillation to give colorless oily ethyl 5-formyloxynonanoate (Inventive product 2, 15.9 g). 0.069 mol) was obtained. Yield 69% from δ-nonalactone.

  As a result of gas chromatographic analysis of ethyl 5-formyloxynonanoate obtained in Example 4 above, the chemical purity of ethyl 5-formyloxynonanoate was 94.5% (gas chromatographic conditions were as in Example 2). And holding time: 5.6 min).

Physical property data of ethyl 5-formyloxynonanoate
¹ H-NMR (400 MHz, CDCl ₃ ): δ ppm 0.87 (t, 3H, J = 7.2 Hz), 1.23 (t, 3H, J = 7.2 Hz), 1.20-1.32 ( m, 3H), 1.50-1.70 (m, 7H), 2.29 (m, 2H), 4.10 (q, 2H, J = 7.2 Hz), 4.98 (quin, 1H, J = 5.7 Hz), 8.07 (s, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ ppm 13.92, 14.22, 20.62, 22.47, 27.32, 33.30, 33.60, 33.92, 60.31, 73. 82, 160.95, 173.24
MS (m / z): 201 (1), 185 (2), 138 (54), 99 (92), 96 (75), 88 (100), 71 (35), 69 (48), 55 (68 ), 43 (39), 41 (52), 29 (39)

Example 5: Synthesis of ethyl 5-hydroxyundecanoate A 500 mL four-necked flask was charged with δ-undecalactone (manufactured by Sigma-Aldrich, 18.4 g, 0.10 mol) and 99% ethanol (270.0 g). Sodium ethoxide (manufactured by Sigma-Aldrich, 21% ethanol solution, 5.5 g, 0.017 mol) is added dropwise under conditions of 25 ° C. to 30 ° C./30 minutes with stirring under ice-water cooling. After stirring overnight at room temperature, glacial acetic acid (1.0 g, 0.017 mol) is added for neutralization, and the mixture is concentrated under reduced pressure. 15% brine (100 g) was added to the resulting residue, and the mixture was extracted with ether (100 g). The resulting organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (100 g) and 15% brine (100 g). To do. After drying over anhydrous magnesium sulfate and concentration under reduced pressure, ethyl 5-hydroxyundecanoate (19.6 g) was obtained as a colorless oily crude product. Crude yield 85%.

Example 6: Synthesis of ethyl 5-formyloxyundecanoate In a 300 mL four-necked flask, the crude ethyl 5-hydroxyundecanoate obtained in Example 5 (19.6 g) and pyridine (manufactured by Seikagaku Corporation, 80.0 g) ) And stirring under ice-water cooling, a mixed solution of acetic anhydride (25.5 g, 0.25 mol) and 98% formic acid (manufactured by Junsei Chemical Co., Ltd., 12.0 g, 0.26 mol) was added at 5 ° C. to 15 ° C. / Add dropwise in 1 hour. After stirring overnight at room temperature, 99% ethanol (64.5 g, 1.4 mol) is added dropwise at 5 ° C. to 15 ° C./1 hour under ice water cooling, and stirred at room temperature for 30 minutes. Pour into cold 10% hydrochloric acid (100 mL), extract with n-hexane (100 mL × 2 times), combine the organic layers obtained, cold 10% hydrochloric acid (100 g), 5% aqueous sodium carbonate solution (100 g), 15 Wash sequentially with% saline (100 g). The residue (20.4 g) obtained by drying under anhydrous magnesium sulfate and concentrating under reduced pressure was purified by distillation to give a colorless oily ethyl 5-formyloxyundecanoate (Product 3, 17.0 g of the present invention). 0.066 mol) was obtained. Yield 66% from δ-undecalactone.

  Further, as a result of gas chromatographic analysis of ethyl 5-formyloxyundecanoate obtained in Example 6 above, the chemical purity of ethyl 5-formyloxyundecanoate was 91.7% (gas chromatographic conditions were as in Example 2). And holding time: 6.8 min).

Physical property data of ethyl 5-formyloxyundecanoate
¹ H-NMR (400 MHz, CDCl ₃ ): δ ppm 0.85 (t, 3H, J = 7.0 Hz), 1.23 (t, 3H, J = 7.2 Hz), 1.20-1.30 ( m, 9H), 1.50-1.70 (m, 5H), 2.29 (m, 2H), 4.10 (q, 2H, J = 7.2 Hz), 4.98 (quin, 1H, J = 5.7 Hz), 8.07 (s, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δppm 14.01, 14.21, 26, 12.52, 25.13, 29.05, 31.66, 33.29, 33.91 (2C) , 60.31, 73.84, 160.94, 173.23
MS (m / z): 229 (1), 213 (1), 124 (44), 99 (80), 96 (41), 88 (100), 71 (34), 69 (38), 55 (85 ), 43 (54), 41 (55), 29 (43)

Example 7: Synthesis of ethyl 5-hydroxydodecanoate A 500 mL four-necked flask was charged with δ-dodecalactone (manufactured by Sigma-Aldrich, 19.8 g, 0.10 mol) and 99% ethanol (270.0 g), and iced. While stirring under water cooling, sodium ethoxide (Sigma-Aldrich, 21% ethanol solution, 5.5 g, 0.017 mol) is added dropwise under conditions of 25 ° C. to 30 ° C./30 minutes. After stirring overnight at room temperature, glacial acetic acid (1.0 g, 0.017 mol) is added for neutralization, and the mixture is concentrated under reduced pressure. 15% brine (100 g) was added to the resulting residue, and the mixture was extracted with ether (100 g). The resulting organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (100 g) and 15% brine (100 g). To do. By drying over anhydrous magnesium sulfate and concentration under reduced pressure, ethyl 5-hydroxydodecanoate (20.3 g) was obtained as a colorless oily crude product. Crude yield 83%.

Example 8: Synthesis of ethyl 5-formyloxide decanoate In a 300 mL four-necked flask, crude 5-hydroxyundecanoate obtained in Example 5 (20.3 g) and pyridine (manufactured by Junsei Co., Ltd., 80.0 g) were prepared. ) And stirring under ice-water cooling, a mixed solution of acetic anhydride (25.5 g, 0.25 mol) and 98% formic acid (manufactured by Junsei Chemical Co., Ltd., 12.0 g, 0.26 mol) was added at 5 ° C. to 15 ° C. / Add dropwise in 1 hour. After stirring overnight at room temperature, 99% ethanol (64.5 g, 1.4 mol) is added dropwise at 5 ° C. to 15 ° C./1 hour under ice water cooling, and stirred at room temperature for 30 minutes. Pour into cold 10% hydrochloric acid (100 mL), extract with n-hexane (100 mL × 2 times), combine the organic layers obtained, cold 10% hydrochloric acid (100 g), 5% aqueous sodium carbonate solution (100 g), 15 Wash sequentially with% saline (100 g). The residue (23.3 g) obtained by drying under anhydrous magnesium sulfate and concentrating under reduced pressure was purified by distillation to give a colorless oily ethyl 5-formyloxide decanoate (product of the present invention, 19.1 g). 0.070 mol) was obtained. Yield 70% from δ-dodecalactone.

  Further, as a result of gas chromatographic analysis of ethyl 5-formyloxide decanoate obtained in Example 8 above, the chemical purity of ethyl 5-formyloxide decanoate was 92.4% (gas chromatographic conditions were as in Example 2). And holding time: 7.4 min).

Physical property data of ethyl 5-formyloxide decanoate
¹ H-NMR (400 MHz, CDCl ₃ ): δ ppm 0.85 (t, 3H, J = 7.0 Hz), 1.23 (t, 3H, J = 7.2 Hz), 1.20-1.30 ( m, 11H), 1.45-1.72 (m, 5H), 2.29 (m, 2H), 4.10 (q, 2H, J = 7.2 Hz), 4.98 (quin, 1H, J = 5.8 Hz), 8.07 (s, 1H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ ppm 14.04, 14.21, 20.26, 2.59, 25.18, 29.12, 29.35, 31.72, 33.29, 33. 91 (2C), 60.30, 73.84, 160.94, 173.23
MS (m / z): 243 (1), 227 (2), 138 (37), 99 (76), 97 (34), 96 (52), 88 (100), 69 (43), 55 (77 ), 43 (54), 41 (55) 29 (38)

Example 9: Aroma evaluation Ethyl 5-formyloxyoctanoate (Product 1 of the present invention), Ethyl 5-formyloxynonanoate (Product 2 of the present invention), Ethyl 5-formyloxyundecanoate (Product 3 of the present invention), 5- For each 0.1% ethanol solution of ethyl formyloxide decanoate (Product 4 of the present invention), fragrance evaluation was performed by five well-trained panelists. The fragrance evaluation was performed using the 0.1% ethanol solution prepared in a 30 ml sample bottle and smelling paper impregnated with the fragrance of the bottle mouth and the solution. Table 1 shows the average aroma evaluation of five people.

Example 10: Effect of addition to a milk-like blended fragrance composition Each component (% by mass) in Table 2 was formulated as a milk-like blended fragrance composition. 2.0 g of the products 1 to 3 or 4 of the present invention were mixed with the milk-like blended fragrance composition of Table 2 (Comparative Product 1) to prepare a novel milk-like blended fragrance composition. The inventive products 5 to 8 and the comparative product 1 obtained by mixing the inventive products 1 to 3 or 4 were subjected to sensory evaluation by 10 well-trained panelists.

  As a result, all 10 panelists evaluated the products 5 to 8 of the present invention as being creamy, with a better milk feeling emphasized compared to the comparative product 1.

Example 11: Effect of addition to a butter-like blended fragrance composition Each component (mass%) in Table 3 was formulated as a butter-like blended fragrance composition. A novel butter-like blended fragrance composition was prepared by mixing 5.0 g of the present invention products 1-3 or 4 with the butter-like blended fragrance composition of Table 3 (Comparative Product 2). The inventive products 9 to 12 and the comparative product 2 in which the inventive products 1 to 3 or 4 were mixed were subjected to sensory evaluation by 10 well-trained panelists.

  As a result, all 10 panelists evaluated the products 9 to 12 of the present invention as having a better buttery feeling than the comparative product 2 and having a rich feeling unique to milk fat.

Example 12 Effect of Addition of Invention Product 1 to Milk Coffee Milk coffee (target product 1) was prepared according to the formula (% by weight) of milk coffee in Table 4.

  For milk coffee (target product 1), 10 μg of 1% solution obtained by diluting ethyl 5-formyloxyoctanoate of the product 1 of the present invention with ethanol and further diluted with water (addition concentration of the product 1 of the present invention 0.1 ppb) : Comparative product 3), 100 μg (addition concentration 1 ppb of the product 1 of the present invention: product 13 of the present invention) 1 mg (addition concentration 10 ppb of the product 1 of the present invention: 14 product of the present invention) 10 mg (addition concentration of the product 1 of the present invention 100 ppb) : Invention product 15), 100 mg (Additional concentration of Invention product 1 1 ppm: Invention product 16), 1 g (Invention product 1 addition concentration 10 ppm: Invention product 17), 10 g (Invention product 1 addition concentration) 100 ppm: Invention product 18) and 100 g (Additional concentration 1000 ppm of the invention product 1: Comparison product 4) are mixed to prepare milk coffee of comparison products 3 and 4 and invention products 13-18. did. Each milk coffee was subjected to sensory evaluation by 10 panelists who were well trained. Table 5 shows a comparative evaluation with the target product 1 to which the product 1 of the present invention is not added.

  From the results of Table 5, the inventive products 13 to 18 were given a creamy body feeling and enhanced milk aroma. In particular, the products 15 and 16 of the present invention have a rich and rich creamy body feeling, and a good milky aroma is remarkably emphasized. On the other hand, the comparative product 3 was not much different from the target product 1, and the comparative product 4 was evaluated as having lost the original flavor of milk coffee.

Example 13 Effect of Addition of Invention Product 2 to Milk Coffee 1 With respect to milk coffee (target product 1), ethyl 5-formyloxynonanoate of the product 2 was diluted with ethanol and further diluted with water. % Solution 10 μg (invention product 2 addition concentration 0.1 ppb: comparative product 5), 100 μg (invention product 2 addition concentration 1 ppb: invention product 19), 1 mg (invention product 2 addition concentration 10 ppb: book) Invention product 20), 10 mg (additional concentration of the product of the present invention 100 ppb: Invention product 21), 100 mg (additional concentration of the product of the present invention 1 ppm: invention product 22), 1 g (additional concentration of the product of the present invention 2 10 ppm: Invention product 23) 10 g (addition concentration 100 ppm of the invention product 2: invention product 24) 100 g (addition concentration 1000 ppm of the product 2 of the invention 2: comparison product 6) were mixed to give comparative products 5 and 6 and milk coffee of the present invention products 19 to 24 were prepared. Each milk coffee was subjected to sensory evaluation by 10 panelists who were well trained. Table 6 shows a comparative evaluation with the target product 1 to which the product 2 of the present invention is not added.

  From the results shown in Table 6, the inventive products 19 to 24 were given a creamy body feeling and enhanced milk aroma. In particular, the products 21 and 22 of the present invention have a rich and rich creamy body feeling, and a good milky aroma is remarkably emphasized. On the other hand, the comparative product 5 was not much different from the target product 1, and the comparative product 6 was evaluated as having lost the original aroma of milk coffee.

Example 14: Effect of Addition of Invention Product 3 to Milk Coffee 1 With respect to milk coffee (target product 1), ethyl 5-formyloxyundecanoate of the product 3 was diluted with ethanol and further diluted with water. % Solution 10 μg (invention product 3 addition concentration 0.1 ppb: comparative product 7), 100 μg (invention product 3 addition concentration 1 ppb: invention product 25), 1 mg (invention product 3 addition concentration 10 ppb: book Invention product 26) 10 mg (additional concentration 100 ppb of the product 3 of the invention: 27 product of the invention), 100 mg (addition concentration 1 ppm of the product 3 of the invention: product 28 of the invention), 1 g (addition concentration 10 ppm of the product 3 of the invention: Inventive product 29) 10 g (additional concentration 100 ppm of inventive product 3: inventive product 30) 100 g (added concentration 1000 ppm of inventive product 3: comparative product 8) were mixed to give comparative product 7 And 8, milk coffee of the product 25-30 of the present invention was prepared. Each milk coffee was subjected to sensory evaluation by 10 panelists who were well trained. Table 7 shows a comparative evaluation with the target product 1 to which the product 3 of the present invention is not added.

  From the results shown in Table 7, the inventive products 25 to 30 were given a creamy body feeling and enhanced milk aroma. In particular, the products 27 and 28 of the present invention have a rich and rich creamy body feeling, and a good milky aroma is remarkably emphasized. On the other hand, the comparative product 7 was not much different from the target product 1, and the comparative product 8 was evaluated as having lost the original aroma of milk coffee.

Example 15: Effect of Addition of Invention Product 4 to Milk Coffee 1 With respect to milk coffee (target product 1), ethyl 5-formyloxide decanoate of the product 4 was diluted with ethanol and further diluted with water. % Solution 10 μg (additional concentration 0.1 ppb of the product 4 of the invention: comparative product 9), 100 μg (addition concentration 1 ppb of the product 4 of the invention: product 31 of the invention), 1 mg (addition concentration 10% of the product 4 of the invention: book Invention product 32) 10 mg (additional concentration 100 ppb of the invention product 4: invention product 33), 100 mg (addition concentration 1 ppm of the invention product 4: invention product 34), 1 g (addition concentration 10 ppm of the invention product 4: This product 35) 10 g (additional concentration 100 ppm of the present product 4: present product 36) 100 g (additional concentration 1000 ppm of the present product 4 1000: comparative product 10) are mixed to give a comparative product 9 And 10, milk coffee of the products 31 to 36 of the present invention was prepared. Each milk coffee was subjected to sensory evaluation by 10 panelists who were well trained. Table 8 shows a comparative evaluation with the target product 1 to which the product 4 of the present invention is not added.

  From the results shown in Table 8, the products 31 to 36 of the present invention were given a creamy body feeling and enhanced milk aroma. In particular, the products 33 and 34 of the present invention have a rich and rich creamy body feeling, and a good milky aroma is remarkably emphasized. On the other hand, the comparative product 9 was not much different from the target product 1, and the comparative product 10 was evaluated that the original aroma of milk coffee was lost.

Example 16: Effect of adding milk-like formulated fragrance composition to milk tea The milk-like formulated fragrance composition obtained in Example 10 (Comparative product 1, products 5-8 of the present invention) was prepared according to the formulation in Table 9. Milk tea beverage was prepared by a conventional method. Milk tea to which Comparative Product 1 and Invention Products 5 to 8 were added was referred to as Comparison Product 11 and Invention Products 37 to 40, respectively. These milk teas were subjected to sensory evaluation by 20 well-trained panelists.

  As a result, all 20 panelists evaluated that the products 37 to 40 of the present invention had a good milk fat feeling and body feeling and the milk-like aroma was enhanced as compared with the comparative product 11.

Example 17: Effect of addition of butter-like blended fragrance composition to cookies The butter-like blended fragrance composition obtained in Example 11 (Comparative product 2, Invention products 9 to 12) was prepared according to the formulation in Table 10. Added to the cookie dough and baked cookies at 220 ° C. for 7 minutes to prepare. Cookies added with Comparative Product 2 and Invention Products 9 to 12 were referred to as Comparison Product 12 and Invention Products 41 to 44, respectively. These cookies were subjected to sensory evaluation by 20 well-trained panelists.

  As a result, all 20 panelists evaluated that the inventive products 41 to 44 are given a unique creamy milk fat feeling and the butter-rich image flavor and flavor are emphasized compared to the comparative product 12. Met.

Example 18: Effect of adding a milk-like blended fragrance composition to a milk coffee beverage The milk-like blended fragrance composition obtained in Example 10 (Comparative product 1, products 5-8 of the present invention) was prepared according to the formulation in Table 11. It was added to the milk coffee thus prepared, and 200 g cans were filled in 190 g portions, the head space was replaced with nitrogen, sealed, and heat sterilized at 121 ° C. for 20 minutes to prepare a canned milk coffee beverage. The milk coffee beverages to which Comparative Product 1 and Invention Products 5 to 8 were added were referred to as Comparison Product 13 and Invention Products 45 to 48, respectively. These milk coffee drinks were subjected to sensory evaluation by 20 well-trained panelists.

  As a result, all 20 panelists evaluated that the products 45 to 48 of the present invention had a good milk fat feeling and body feeling and the milky aroma was enhanced compared to the comparative product 13.

Claims (4)

Following formula (1)

[Wherein R represents an alkyl group having 3 to 7 carbon atoms. Except for ethyl 5-formyloxydecanoate]
An ethyl 5-formyloxyalkanoate represented by Following formula (1)

[Wherein R represents an alkyl group having 3 to 7 carbon atoms. Except for ethyl 5-formyloxydecanoate]
The fragrance | flavor composition characterized by containing the ethyl 5-formyloxy alkanoate represented by these as an active ingredient.   A food or drink comprising the compound according to claim 1.   A food or drink comprising the fragrance composition according to claim 2.