JP2021014423A - Acetoxy fatty acid ethyl esters and flavoring compositions - Google Patents

Abstract

To provide: novel flavoring compositions that allow food and drink and the like to be provided with or increased in milk flavor; flavoring compositions containing the compounds as active ingredients; and methods of producing the compounds.SOLUTION: The present invention provides: acetoxy fatty acid ethyl esters represented by the general formula (1) in the figure, where n represents 1 or 2 and R represents a C4-9 alkyl group, and specifically, R is a C7-9 alkyl group if n is 1, whereas R is a C4-6 alkyl group if n is 2; flavoring compositions containing one or more compounds selected from the group of compounds; and methods of producing the compounds.SELECTED DRAWING: None

Description

The present invention relates to novel acetoxy fatty acid ethyl esters that are useful as fragrance compounds.

In recent years, with the diversification of foods and drinks, the demand for characteristic flavors has increased, and various flavor compounds have been demanded. In addition, with the tightness of dairy ingredients, this demand is particularly increasing in dairy flavors.

Various flavors have been proposed for the purpose of meeting this demand, one containing 3-methylnonane-2,4-dione (Patent Document 1), and a specific diglyceride composed of a relatively long-chain fatty acid in a specific ratio. A mixture containing a blended diglyceride (Patent Document 2) and an alkyl 5-acyloxydecanoate (excluding methyl 5-acetoxydecanoate and ethyl 5-acetoxydecanoate) added to a fragrance composition (Patent). Document 3), those to which ethyl 5-formyloxyalkate is added (Patent Document 4), those to which alkyl 5-[(1-alkoxy) ethoxy] alkanoate is used as an active ingredient (Patent Document 5), (E)- 6-octenal added (Patent Document 6), 2,4,7-tridecatrienal added (Patent Document 7), 7-dodecenoic acid, 8-dodecenoic acid, 9-dodecenoic acid or 10-dodecene Examples thereof include those to which an acid is added (Patent Document 8). However, these were not always satisfactory in terms of flavor. Further, Patent Document 3, Patent Document 4 and Patent Document 5 are proposals relating to a ring-opening product of a lactone, and although there is a description regarding a ring-opening product of a δ-lactone having 8 to 12 carbon atoms, the present invention relates to ethyl 5-acetoxidedecanoate. There was no suggestion. Furthermore, there was no proposal for a ring-opened lactone having 13 or more carbon atoms or ε-lactone.

Japanese Unexamined Patent Publication No. 2003-052330 Japanese Unexamined Patent Publication No. 2013-153738 Japanese Unexamined Patent Publication No. 2013-173708 Japanese Unexamined Patent Publication No. 2014-031331 JP-A-2015-131573 JP-A-2018-0000022 Japanese Unexamined Patent Publication No. 2018-057310 JP-A-2019-065212

An object of the present invention is a novel flavor compound that can impart or enhance milky flavor to foods and drinks and can be used for general purposes as a flavor material, a method for producing the compound, and the compound as an active ingredient. The purpose is to provide a fragrance composition to be contained.

The present inventors synthesized a plurality of lactone ring-opening compounds and diligently studied their aromas, and found that a novel acetoxy fatty acid ethyl ester, which is a lactone ring-opening product having a specific carbon number, is useful as a fragrance compound. Heading The present invention has been completed.

That is, the present invention is as follows.
[1] General formula (1)

(N in the formula represents 1 or 2, R represents an alkyl group having 4 to 9 carbon atoms.)
An acetoxy fatty acid ethyl ester represented by, in which R is an alkyl group having 7 to 9 carbon atoms when n is 1, and R is an alkyl group having 4 to 6 carbon atoms when n is 2 in the formula.
[2] The above-described in [1], wherein when n in the formula is 1, R is an alkyl group having 7 or 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 or 6 carbon atoms. Acetoxy fatty acid ethyl ester.
[3] A fragrance composition containing one or more compounds selected from the acetoxy fatty acid ethyl ester according to the above [1] or [2].
[4] General formula (2)

(N in the formula represents 1 or 2, R represents an alkyl group having 4 to 9 carbon atoms.)
When n in the formula is 1, R is an alkyl group having 7 to 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 to 6 carbon atoms, δ-lactone or ε. -The general formula (3) is obtained by transesterification of the lactone with ethanol using an acid catalyst.

(N in the formula represents 1 or 2, R represents an alkyl group having 4 to 9 carbon atoms.)
When n in the formula is 1, R is an alkyl group having 7 to 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 to 6 carbon atoms. The acetoxy fatty acid ethyl according to [1] or [2], which comprises the step of obtaining the acetoxy fatty acid ethyl ester according to [1] or [2] by acylating the hydroxy fatty acid ethyl with anhydrous acetic acid. Method for producing ester.

The acetoxy fatty acid ethyl ester of the present invention can be used as a fragrance compound for purposes such as aroma modulation and taste enhancement. In addition, the acetoxy fatty acid ethyl ester can be easily produced by the production method of the present invention.

The acetoxy fatty acid ethyl ester of the present invention has the general formula (1).

(N in the formula represents 1 or 2, R represents an alkyl group having 4 to 9 carbon atoms.)
When n in the formula is 1, R is an alkyl group having 7 to 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 to 6 carbon atoms. Is.

The method for synthesizing these acetoxy fatty acid ethyl esters is not limited, but for example, they can be synthesized by the following methods.

First, it is represented by the general formula (2). When n in the formula is 1, R is an alkyl group having 7 to 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 to 6 carbon atoms. The hydroxy fatty acid ethyl represented by the general formula (3) is obtained by a transesterification reaction with ethanol using an acid catalyst using the above lactones as a substrate.

The lactones used in this reaction can be synthesized by a known method, or commercially available products can also be used.

The amount of ethanol used in this reaction is arbitrary as long as it is equal to or greater than the amount of lactones that are substrates, but since the transesterification reaction is a reversible reaction, the equilibrium is large so that it is biased toward the target product. An excess amount is preferably used, preferably 5 to 15 equivalents relative to the substrate lactones.

Any acid catalyst used in this reaction may be used as long as it can be used for the transesterification reaction, and p-toluenesulfonic acid monohydrate is a preferred example. The amount of the acid catalyst used is arbitrary as long as it is a catalyst amount, but is preferably 0.01 to 0.03 equivalent with respect to the lactones as substrates.

The reaction temperature may be arbitrarily determined depending on the lactones used and the acid catalyst, but is preferably between 20 and 40 ° C. The reaction time may be determined while monitoring the progress of the reaction by thin layer chromatography, gas chromatography or the like, but the reaction is preferably carried out for 3 to 4 hours.

Next, the acyl fatty acid ethyl ester of the present invention represented by the general formula (1) is obtained by acylating the hydroxy fatty acid ethyl represented by the general formula (3) obtained in the above reaction with acetic anhydride.

As the hydroxy fatty acid ethyl used in this reaction, the crude product obtained in the above reaction can be purified and used, but the crude product may be used as it is.

As the acylating agent used in this reaction, any carboxylic acid anhydride or carboxylic acid halide that can be used for acylation may be used, and acetic anhydride is a preferable example. The amount of the acylating agent used is arbitrary as long as it is equivalent or more with respect to the lactones as substrates, but it is preferable to use an excess amount with respect to ethyl hydroxy fatty acid, preferably in the range of 2 to 3 equivalents.

Pyridine can be used as a solvent in this reaction. The amount of pyridine used can be reduced, and in that case, in order to suppress the intermolecular reaction between the hydroxy fatty acid ethyls as substrates, it is preferable to use a solvent inactive for the substrate and the acylating agent in combination, as a preferable example. Toluene can be mentioned.

The reaction temperature may be arbitrarily determined depending on the hydroxy fatty acid ethyl used and the acylating agent, but it is preferably carried out at room temperature. The reaction time may be determined while monitoring the progress of the reaction by thin layer chromatography, gas chromatography, or the like, but it is preferable to carry out the reaction overnight.

The acetoxy fatty acid ethyl ester of the present invention obtained as described above may be purified by means such as column chromatography and vacuum distillation, if necessary.

The acetoxy fatty acid ethyl ester of the present invention can be used alone or in combination of two or more, or can be combined with other commonly used fragrance materials to form a fragrance composition. The blending amount of the compound of the present invention when used as a fragrance composition may be arbitrarily determined in consideration of the purpose of blending, the type of fragrance composition, etc., but is preferably 10 ppm to 10%, more preferably 100 ppm. A range of ~ 1% is good. Further, a composition may be prepared by adding other additives commonly used as ingredients other than fragrances as long as the aroma or flavor is not adversely affected. Furthermore, it is possible to apply a formulation technique generally applied to fragrances, and it is also possible to prepare a desired form depending on the situation such as powdering and encapsulation.

The acetoxy fatty acid ethyl ester of the present invention can be widely used as a fragrance compound. In addition, by adding it to foods and drinks, it is possible to impart a milk flavor having a thickness and a long-lasting milk fat feeling from middle to last when eating and drinking. Furthermore, it is possible to enhance the sweetness, saltiness, and umami of foods and drinks, and to bring a smooth feeling and a soft and good melting feeling in the oral cavity, and these aromas, tastes, and textures are imparted or enhanced in a well-balanced manner. Therefore, the enhancement of richness is also recognized.

[Example 1] Synthesis of ethyl 5-acetoxide decanoate Under a nitrogen atmosphere, in a test tube, δ-dodecalactone (3.0 g, 15 mmol), ethanol (7.0 g), p-toluenesulfonic acid monohydrate ( 0.05 g (0.26 mmol) was charged, and the mixture was stirred at 30 ° C. for 4 hours. Water (13 ml) was added, the mixture was extracted with ethyl acetate (10 mL), and the obtained ethyl acetate layer was washed twice with water (10 mL). By concentrating under reduced pressure, ethyl 5-hydroxydodecanoate (3.8 g) was obtained as a colorless oily crude product.

Under a nitrogen atmosphere, the above-mentioned ethyl 5-hydroxydodecanoate (3.8 g, 15 mmol), toluene (10.0 g), pyridine (1.2 g), acetic anhydride (3.2 g, 31 mmol) were placed in a test tube. And stir overnight at room temperature. Water (15.3 g) was added, the mixture was extracted with toluene (10 mL), and the obtained toluene layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (15 mL) and water (15 mL x 2 times). The residue (4.7 g) obtained by concentration under reduced pressure was distilled and purified with a silica gel chromatogram to obtain ethyl 5-acetoxidedecanoate (3.1 g, 11 mmol) as a colorless oil. The yield from δ-dodecalactone was 72%.

The physical characteristics of the obtained ethyl 5-acetoxide decanoate were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δppm 0.88 (t, 3H, J = 6.9 Hz), 1.22-1.31 (m, 13H), 1.53-1.67 (m, 6H), 2.04 (s, 3H) 2.30 (t, 2H, J = 7.3Hz), 4.13 (q, 2H, J = 7.2Hz), 4.87 (quin, 1H, J) = 6.0Hz)
¹³ C-NMR (400 MHz, CDCl ₃ ): δppm 13.99, 14.15, 20.63, 21.15, 22.55, 25.20, 29.09, 29.10, 29.37, 31. 69, 33.31, 33.92, 60.19, 73.70, 170.78, 173.28

[Example 2] Synthesis of ethyl 5-acetoxytetradecanoate Under a nitrogen atmosphere, in a test tube, δ-tetradecalactone (1.5 g, 6.6 mmol), ethanol (3.0 g), p-toluenesulfonic acid monohydrate. A Japanese product (0.02 g, 0.11 mmol) was charged and stirred at 30 ° C. for 3 hours. Water (12 ml) was added, the mixture was extracted with toluene (10 mL), and the resulting toluene layer was washed twice with water (10 mL). By concentrating under reduced pressure, ethyl 5-hydroxytetradecanoate (1.8 g) was obtained as a colorless oily crude product.

Under a nitrogen atmosphere, in a test tube, the ethyl 5-hydroxytetradecanoate (1.8 g, 6.6 mmol) obtained above, toluene (10.0 g), pyridine (0.2 g), acetic anhydride (2.0 g, 19.6 mmol) was charged, and the mixture was stirred overnight at room temperature. Water (10 ml) was added, the mixture was extracted with toluene (10 mL), and the obtained toluene layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (10 mL) and water (10 mL × 2 times). The residue (1.9 g) obtained by concentration under reduced pressure was distilled and purified with a silica gel chromatogram to obtain ethyl 5-acetoxytetradecanoate (0.7 g, 2.2 mmol) as a colorless oil. .. The yield from δ-tetradecalactone was 33%.

The physical characteristics of the obtained ethyl 5-acetoxytetradecanoate were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δppm 0.88 (t, 3H, J = 6.4 Hz), 1.23-1.27 (m, 17H), 1.52-1.67 (m, 6H), 2.04 (s, 3H) 2.30 (t, 2H, J = 7.3Hz), 4.13 (q, 2H, J = 7.5Hz), 4.87 (quin, 1H, J) = 5.9Hz)
¹³ C-NMR (400 MHz, CDCl ₃ ): δppm 14.02, 14.16, 20.63, 21.16, 22.60, 25.21, 29.21, 29.42, 29.43, 29. 44, 31.81, 33.31, 33.92, 33.94, 60.19, 73.70, 170.78, 173.28

[Example 3] Synthesis of ethyl 6-acetoxydecanoate Under a nitrogen atmosphere, ε-decalactone (1.9 g, 11 mmol), ethanol (4.0 g), p-toluenesulfonic acid monohydrate (0) were placed in a test tube. .03 g, 0.16 mmol) was charged and stirred at 30 ° C. for 4 hours. Water (10 ml) was added, the mixture was extracted with toluene (10 mL), and the resulting toluene layer was washed twice with water (10 mL). By concentrating under reduced pressure, ethyl 6-hydroxydecanoate (2.8 g) was obtained as a colorless oily crude product.

Ethyl 6-hydroxydecanoate (2.8 g, 11 mmol), toluene (10.0 g), pyridine (1.0 g), acetic anhydride (2.4 g, 24 mmol) obtained above in a test tube under a nitrogen atmosphere. Was charged and stirred overnight at room temperature. Water (12.2 g) was added, the mixture was extracted with toluene (10 mL), and the obtained toluene layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (14 mL) and water (13 mL x 3 times). The residue (2.9 g) obtained by concentration under reduced pressure was distilled and purified with a silica gel chromatogram to obtain ethyl 6-acetoxydecanoate (2.6 g, 10 mmol) as a colorless oil. The yield from ε-decalactone was 88%.

The physical characteristics of the obtained ethyl 6-acetoxydecanoate were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δppm 0.89 (t, 3H, J = 6.9 Hz), 1.22-1.38 (m, 9H), 1.49-1.67 (m, 6H), 2.04 (s, 3H), 2.29 (t, 2H, J = 7.4Hz), 4.12 (q, 2H, J = 7.0Hz), 4.86 (quin, 1H, J = 6.2Hz)
¹³ C-NMR (400 MHz, CDCl ₃ ): δppm 13.90, 14.16, 21.17, 22.512.47, 24.79, 27.39, 33.68, 33.71, 34. 12,60.13,74.00,170.82,173.49

[Example 4] Synthesis of ethyl 6-acetoxide decanoate Under a nitrogen atmosphere, in a test tube, ε-dodecalactone (2.0 g, 10 mmol), ethanol (6.0 g), p-toluenesulfonic acid monohydrate ( 0.05 g (0.26 mmol) was charged, and the mixture was stirred at 30 ° C. for 4 hours. Water (10 ml) was added, the mixture was extracted with ethyl acetate (10 mL), and the obtained ethyl acetate layer was washed twice with water (10 mL). By concentrating under reduced pressure, ethyl 6-hydroxydodecanoate (3.1 g) was obtained as a colorless oily crude product.

Under a nitrogen atmosphere, the above-mentioned ethyl 6-hydroxydodecanoate (3.1 g, 10 mmol), toluene (8.0 g), pyridine (0.8 g), acetic anhydride (2.3 g, 23 mmol) were placed in a test tube. Was charged and stirred overnight at room temperature. Water (15.8 g) was added, the mixture was extracted with toluene (10 mL), and the obtained toluene layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (15 mL) and water (15 mL x 2 times). The residue (2.7 g) obtained by concentration under reduced pressure was distilled and purified with a silica gel chromatogram to obtain ethyl 6-acetoxidedecanoate (2.3 g, 8 mmol) as a colorless oil. The yield from ε-dodecalactone was 81%.

The physical characteristics of the obtained ethyl 6-acetoxide decanoate were as follows.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δppm 0.88 (t, 3H, J = 6.9 Hz), 1.23-1.38 (m, 13H), 1.50-1.67 (m, 6H), 2.03 (s, 3H) 2.29 (t, 2H, J = 7.4Hz), 4.12 (q, 2H, J = 7.2Hz), 4.86 (quin, 1H, J) = 6.3Hz)
¹³ C-NMR (400 MHz, CDCl ₃ ): δppm 13.86, 14.05, 21.02, 22.40, 24.66, 24.69, 25.08, 29.00, 31.56, 33. 60, 33.93, 34.00, 59.99, 73.87, 170.64, 173.32

[Example 5] Evaluation of aroma of acetoxy fatty acid ethyl ester of the present invention The aroma of the compounds of the present invention obtained in Examples 1 to 4 was evaluated by four well-trained panelists. The aroma evaluation was carried out by preparing each compound in a sample bottle and using the aroma at the mouth of the bottle and the odor paper impregnated with the compound. Table 1 shows the average aroma evaluation of the four subjects.

[Example 6] Evaluation of coffee milk to which the compound of the present invention was added 0.1% of the compound of the present invention shown in Table 1 dissolved in ethanol at a concentration of 0.1% was added to commercially available coffee milk. A sensory evaluation was performed. The sensory evaluation was performed by four well-trained panelists on a 7-point scale shown in Table 2. The results are shown in Table 3. As a result of the sensory evaluation, it was confirmed that all the compounds of the present invention had the effect of imparting a milky flavor having a thickness and a long-lasting milky fat feeling from the middle to the last. In addition, enhancement of sweetness was also observed. In addition, it provided a smooth, soft and good melting sensation in the oral cavity, and the throat was smooth. By imparting or enhancing these aromas, tastes, and textures in a well-balanced manner, enhancement of richness was also observed.

[Example 7] Evaluation of cookie to which butter flavor containing the compound of the present invention was added The butter flavor shown in Table 4 to which 1% of the compound of the present invention shown in Table 1 was added was added to the cookie dough shown in Table 5. 0.1% of the cookie dough was blended, and the cookie dough was placed in an oven preheated to 150 ° C. at the bottom and 180 ° C. at the top and baked for 7 minutes to prepare a cookie, which was subjected to sensory evaluation in the same manner as in Example 6. The results are shown in Table 6. As a result of the sensory evaluation, it was confirmed that all the compounds of the present invention had the effect of imparting a milky flavor having a thickness and a long-lasting milky fat feeling from the middle to the last. As a result, the prominent lactone flavor was suppressed, resulting in a harmonious butter flavor. In addition, enhancement of sweetness, saltiness, and umami was also observed. In addition, it provided a smooth, soft and good melting sensation in the oral cavity, and the throat was smooth. By imparting or enhancing these aromas, tastes, and textures in a well-balanced manner, enhancement of richness was also observed.

Claims (4)

General formula (1)

(N in the formula represents 1 or 2, R represents an alkyl group having 4 to 9 carbon atoms.)
An acetoxy fatty acid ethyl ester represented by, in which R is an alkyl group having 7 to 9 carbon atoms when n is 1, and R is an alkyl group having 4 to 6 carbon atoms when n is 2 in the formula. The ethyl acetoxy fatty acid according to claim 1, wherein when n in the formula is 1, R is an alkyl group having 7 or 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 or 6 carbon atoms. ester. A fragrance composition containing one or more compounds selected from the acetoxy fatty acid ethyl ester according to claim 1 or 2. General formula (2)

(N in the formula represents 1 or 2, R represents an alkyl group having 4 to 9 carbon atoms.)
When n in the formula is 1, R is an alkyl group having 7 to 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 to 6 carbon atoms, δ-lactone or ε. -The general formula (3) is obtained by transesterification of the lactone with ethanol using an acid catalyst.

(N in the formula represents 1 or 2, R represents an alkyl group having 4 to 9 carbon atoms.)
When n in the formula is 1, R is an alkyl group having 7 to 9 carbon atoms, and when n in the formula is 2, R is an alkyl group having 4 to 6 carbon atoms. The method for producing an acetoxy fatty acid ethyl ester according to claim 1 or 2, which comprises the step of obtaining the acetoxy fatty acid ethyl ester according to claim 1 or 2 by acylating the hydroxy fatty acid ethyl with anhydrous acetic acid. ..