JPH0338320B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the use of 4-alkylthio-2-methylfurans. More specifically, the present invention is based on the following formula (1) However, in the formula, R represents an alkyl group or an alkenyl group, and the present invention relates to a persistent aroma and flavor imparting or modulating agent characterized by containing a 4-alkylthio-2-methylfuran represented by the following as an active ingredient. The present inventors have conducted research on various sulfur-containing compounds. As a result, the 4-alkylthio-2-methylfurans represented by the above formula (1) are compounds that have excellent meat-like, spice-like, and onion-like aromas and flavors, and have excellent persistence. It was discovered that it is an extremely useful and unique component as a component for imparting or modulating persistent aroma and flavor to foods and beverages (including luxury goods) and other foods. Furthermore, the compound of formula (1) has excellent sustainability and exhibits remarkable properties as a long-lasting aroma and flavor imparting or modulating agent, and is useful in a wide range of fields such as food and beverages, cosmetics, and health/hygiene/pharmaceuticals. It has been discovered that it is effective as an excellent long-lasting aroma and flavor imparting or flavor modulating agent. Another object of the present invention is to provide a persistent aroma and flavor imparting or modulating agent characterized by containing the compound of formula (1) as an active ingredient. The above objects as well as many other objects and advantages of the present invention will become more apparent from the following description. The compound of the formula (1) of the present invention is, for example, the compound of the following formula (6) However, in the formula, R ₁ represents an alkyl group, 2-methyl-2,5-dimethoxy-
When 2,5-dihydrofuran is brought into contact with water, the following formula (5) 4-oxo-2-pentenal represented by the formula (5) is formed, and the compound of formula (5) is reacted with alcohol to form the following formula (4). However, in the formula, R ₂ represents an alkyl group, to form a 4-oxo-2-pentenal dialkyl acetal represented by the following formula (4) and the following formula (3) RSH (3) However, in the formula, R represents an alkyl group or an alkenyl group, and the alkane or alkene thiol represented by is reacted in the presence of a base to form the following formula (2). However, in the formula, R is an alkyl group or an alkenyl group,
R ₂ represents an alkyl group, to form a 4-oxo-3-alkylthio-pentanal dialkyl acetal represented by the following, and then contact the compound of formula (2) with an acid catalyst to form a 4-oxo-3-alkylthio-pentanal dialkyl acetal of the formula (1).
The compound can be industrially produced easily and inexpensively. The compound of formula (6) is a known compound, and
For example, it can be easily synthesized by the method described in Experimental Chemistry Course, page 21, 260. A production example of the compound of formula (1) of the present invention can be shown as follows in a process diagram. In the formula, R, R ₁ and R ₂ have the same meanings as described above. The compound of formula (6) of the present invention can be easily synthesized, for example, by a known method in which a methanol solution of 2-methylfuran is brought into contact with sodium acetate and bromine. The compound of formula (1) of the present invention can be synthesized, for example, using the compound of formula (6) that can be obtained as described above as a starting material. The compound of formula (5) of the present invention can be easily synthesized by contacting the compound of formula (6) with water.
There are no particular restrictions on the amount of water used in this reaction and it can be selected arbitrarily, but for example, approximately
An example is a range of about 0.2 to 20 times the weight. The compound of formula (5) can be easily synthesized by carrying out the reaction at a temperature of about 0° to about 50°C for about 1 to about 12 hours, for example. When carrying out the reaction, it is preferable to carry out the reaction while removing by-product methanol from the reaction system. The compound of formula (4) of the present invention can be easily synthesized, for example, by contacting the compound of formula (5), which can be obtained as described above, with an alcohol. The amount of alcohol used in the reaction is, for example, about 2 to about 10 times the amount of the compound of formula (5) by mole. The reaction temperature is
For example, the temperature may range from about 0° to about 70°C, and the reaction time may range from about 1 to about 12 hours. After the reaction,
For example, the compound of formula (4) can be easily synthesized by employing purification means such as distillation means. To synthesize the compound of formula (2) of the present invention, the compound of formula (4) obtained above is combined with the compound of formula (3) R.
It can be synthesized by contacting with an alkane or alkene thiol represented by SH. Examples of the base catalyst used in the reaction include pyridine, piperidine, lithium hydroxide, caustic soda, caustic potassium, sodium hydride, sodium amide, sodium methylate, and the like. The amount of these base catalysts to be used can be selected as appropriate, and for example, about 0.1 to about 10% by weight based on the compound of formula (4) can be exemplified. Examples of organic solvents used in the reaction include dichloromethane, chloroform, carbon tetrachloride, pentane, hexane, toluene, xylene,
Examples include ether and tetrahydrofuran. There is no particular restriction on the amount used, but the amount used may be, for example, about 1 to about 50 times the weight of the compound of formula (4) above. The reaction temperature and reaction time of the above reaction can be selected as appropriate, depending on the type of catalyst and solvent used, but for example, the reaction temperature
Examples include a reaction temperature of about 100° C. and a reaction time of about 0.5 to about 10 hours. or,
Specific examples of the alkyl group R in the compound of formula (3) used in the reaction include methyl, ethyl, propyl, butyl, pertyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec- Butyl, t-butyl, 1
- _C1 to _C10 alkyl groups such as methylbutyl, 2-methylbutyl, isopentyl, etc.;
Furthermore, specific examples of the alkenyl group for R include allyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 3-methyl-2-butenyl, 3-methyl-
Preferred examples include C3 to _C5 alkenyl such as ₃ -butenyl. The amount of these compounds of formula (3) to be used is, for example, about 0.5 to
An example of the amount used is about 5 times the mole. The compound of formula (1) of the present invention can be easily synthesized by contacting the compound of formula (2) obtained as described above with an acid catalyst in the presence or absence of an organic solvent. . Examples of the alkyl group or alkenyl group for R in the compound of formula (1) include those mentioned above for the compound of formula (3). Examples of acid catalysts used in the reaction include inorganic or organic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, p-toluenesulfonic acid, formic acid, and trifluoroacetic acid. The amount of these acid catalysts to be used can be selected as appropriate, for example, from about 0.1 to about 10% by weight based on the compound of formula (2). Examples of organic solvents used in the reaction include dichloromethane, chloroform, carbon tetrachloride, pentane, hexane, benzene, toluene,
Examples include ether and tetrahydrofuran. There is no particular restriction on the amount used, but for example, about 0.5 to about 10
An example of the amount used is approximately twice the weight. The reaction temperature and reaction time of the above reaction can be appropriately selected depending on the type of acid catalyst and organic solvent used, but for example, the reaction temperature is about 0° to about 110°C, and the reaction temperature is about 0.5 to about 100°C. An example of a reaction time is about 5 hours. After the reaction is completed, the compound of formula (1) can be easily produced in a good yield by employing purification means such as distillation. For example, examples of the alkyl group or alkenyl group of R in the compound of formula (1) of the present invention that can be produced as described above include R of the compound of formula (3) above.
The same groups as mentioned above can be exemplified. As representative examples of these compounds of formula (1) of the present invention, the following compounds can be exemplified. (a) 4-Methylthio-2-methylfuran (b) 4-ethylthio-2-methylfuran (c) 4-propylthio-2-methylfuran (d) 4-butylthio-2-methylfuran (e) 4-pentylthio -2-Methylfuran (f) 4-hexylthio-2-methylfuran (g) 4-octylthio-2-methylfuran (h) 4-decylthio-2-methylfuran (i) 4-(2-methylpropylthio) -2-Methylfuran (j) 4-(1-methylbutylthio)-2-methylfuran (k) 4-allylthio-2-methylfuran (l) 4-(2-butenylthio)-2-methylfuran (m ) 4-(3-butenylthio)-2-methylfuran(n) 4-(1-methyl-2-propenylthio)-
2-Methylfuran(o) 4-(3-methyl-3-butenylthio)-2
-Methylfuran(p) 4-(3-methyl-2-butenylthio)-2
-Methylfuran The boiling points of the above exemplary compounds are shown below. (a) 52° to 54°C/25mmHg (b) 77° to 79°C/24mmHg (c) 85° to 86°C/20mmHg (d) 99° to 100°C/20mmHg (e) 110° to 112°C/20mmHg (f) 126° to 128°C/20mmHg (g) 112° to 115°C/5mmHg (h) 122° to 123°C/4mmHg (i) 90° to 92°C/20mmHg (j) 97° to 98°C/20mmHg (k) 76° to 77°C/20mmHg (l) 88° to 90°C/20mmHg (m) 89° to 91°C/20mmHg (n) 88° to 90°C/20mmHg (o) 94° to 95°C/10mmHg (p) 96° to 97°C/12mmHg The compound of formula (1) of the present invention has an onion-like, spice-like, and meat-like aroma and flavor, and has excellent sustainability, so it can be used as a persistent aroma and flavor imparting or modulating agent. It is useful as Due to its unique aroma and flavor and excellent persistence, the persistent aroma and flavor imparting or modulating agent is suitable for use in foods and beverages (including luxury goods), soaps, etc.
It can demonstrate excellent effects in a wide range of applications, including detergents, cosmetics, health, hygiene, pharmaceuticals, and more. Therefore, by utilizing the persistent aroma and flavor imparting or modulating agent of the present invention, food and beverages characterized by containing the formula (1) 4-alkylthio-2-methylfuran as an aroma and flavor component; (1) Soaps, detergents, cosmetics that contain the compound as a fragrance ingredient; health, hygiene, pharmaceuticals, etc. can be provided. For example, juices, fruit alcoholic drinks, milk drinks; lactic acid bacteria drinks; drinks such as carbonated drinks; cold medicines such as ice creams and ice candy;
Japanese and Western sweets; Jams; Bread; Favorites such as chewing gum, coffee, cocoa, and tea;
It is possible to provide a variety of food and drink products, instant beverages, instant foods, and the like containing the present invention in an appropriate amount that imparts the unique aroma and flavor. In addition, for example, cosmetics containing shampoos, hair rinses, hair creams, pomades, other cosmetic bases for hair, cosmetic soaps and other makeup/facial cleansing bases in an appropriate amount to impart the unique fragrance are provided. can. Furthermore, its unique scent can be used in various health and hygiene products such as laundry detergents, disinfectant detergents, deodorant cleaning products, and other health and hygiene products; and various health and hygiene materials such as toothpaste, tissue paper, and toilet paper, as well as pharmaceutical products. Appropriate amounts that can impart flavor can be blended or applied to provide health, hygiene, and medicine. Examples of several embodiments of the present invention will be shown below. Example 1 (Reference Example) Production of 4-oxo-2-butenal 170 g of 2-methyl-2,5-dimethoxy-2,5-dihydrofuran and 680 ml of pure water were charged into a reaction flask, and the mixture was heated at room temperature under reduced pressure using an aspirator. Time reacts. The reaction solution was salted out, extracted with ether, and after distilling off the ether, it was distilled under reduced pressure to 72° to 75°C/20mm.
Fraction with Hg 4-oxo-2-butenal 60
g (yield 57%). Example 2 (Reference example) Production of 4-oxo-2-pentenal dimethyl acetal Add 20 g of 4-oxo-2-pentenal to 50 ml of methanol, react at room temperature for 1 hour, collect methanol after reaction, and reduce pressure Distilled to a boiling point of 52°~
22 g of fraction 4-oxo-2-pentenal dimethyl acetal with 55°C/20 mmHg (75% yield)
I got it. Example 3 (Reference Example) Production of 4-oxo-3-methylthio-pentanal dimethyl acetal 8 g of methanethiol was added to a mixed solution of 50 ml of ether, 20 g of 4-oxo-2-pentenal dimethyl acetal, and 2 g of piperidine at room temperature. Add by bubbling for a while, and after reacting for another 2 hours, wash with water.
After recovering the ether, it is distilled under reduced pressure to 65°~
24 g of fraction 4-oxo-3-methylthio-pentanal dimethyl acetal with 67°C/10 mmHg
(yield 90%). Example 4 (Reference Example) Production of 4-methylthio-2-methylfuran 5% aqueous hydrochloric acid solution was added over 30 minutes to a solution of 19 g of 4-oxo-3-methylthio-pentanal dimethyl acetal and 25 ml of dichloromethane, and the mixture was stirred at room temperature for 3 hours. After the reaction, the dichloromethane layer was washed with an aqueous soda ash solution, the dichloromethane was collected, and then distilled under reduced pressure to obtain 10 g of 4-methylthio-2-methylfuran (yield: 80%) having a temperature of 74° to 77°C/30 mmHg. Obtained. Example 5 (Reference Example) Table 1 shows the experimental results of various 4-alkylthio-2-methylfurans according to the methods of Examples 3 and 4.

[Table] Refran Example 6 The following components (parts by weight) were mixed as a meat-like flavor composition. Dimethyl sulfide 10% ethanol solution 8 2,5-dimethyl-4-hydroxy-3(2H)-
Furanone 10% ethanol solution 50 Furfuryl mercaptan 0.1% ethanol solution 3 2,4-decadienal 3 γ-octalactone 2 γ-decalactone 2 Methional 5 Diacetyl 10% ethanol solution 20 Dipropyl disulfide 10 4-Methyl-5-( β-Hydroxyethyl)thiazole 25 Ethanol 872 Total 1000 By adding 1 to 5 g of 4-methylthio-2-methylfuran to 1000 g of the above composition, a new flavor that is excellent as an aroma and flavor component of meat and has excellent persistence is created. was gotten. Similar results were obtained for 4-ethyl-thio-2-methylfuran, 4-butylthio-2-methylfuran, 4-hexylthio-
It was obtained by using 2-methylfuran, 4-decylthio-2-methylfuran, 4-(2-methylpropylthio)-2-methylfuran, and 4-allylthio-2-methylfuran, respectively. Example 7 A fragrance composition for shampoo was produced by mixing each component (parts by weight). Linalool 5 Absolute Diasmine 2 β-Phenylethyl Alcohol 15 Rhodinol 15 Absolute Rose 1 Hydroxycitronellol 30 Indole 10% Benzyl Benzoate Solution 2 Stilac Oil 3 Hexylcinnamic Aldehyde 15 Cyclamenaldehyde 4 Sandalwood Oil 5 Phenylacetaldehyde 10 % 3 100 By adding 0.1-0.5 g of 4-methylthio-2-methylfuran to 98 g of the above composition, a new composition with fresh lily of the valley-like character and long-lasting properties was obtained. Similar results were obtained for 4-ethylthio-2-methylfuran, 4-butylthio-2-methylfuran, 4-ethylthio-2-methylfuran, and 4-ethylthio-2-methylfuran.
It was obtained by using pentylthio-2-methylfuran and 4-octylthio-2-methylfuran, respectively. Example 8 The following components (parts by weight) were mixed as a chicken-like flavor composition. Hexanal 7 Trans-2-decenal 2 2,4-decadienal 46 Linalool 2 Terpineol 3 1-octen-3-ol 3 Maltol 10% ethanol solution 10 Diacetyl 1% ethanol solution 5 Acetoin 1% ethanol solution 5 Ethanol 917 Total 1000 Above composition By adding 10 g to 20 g of a 1% ethanol solution of 4-methylthio-2-methylfuran to 1000 g of the product, a new flavor composition which was excellent as a chicken aroma and flavor component and had excellent persistence was obtained. Similar results were obtained for 4-butylthio-2-methylfuran, 4-propylthio-methylfuran, 4-pentylthio-2-methylfuran, 4-decylthio-methylfuran, 4-octylthio-2-methylfuran, 4-hexylthio- Methylfuran, 4-
They were obtained by using ethylthio-2-methylfuran, respectively.

Claims (1)

[Claims] 1 The following formula (1) However, in the formula, R represents an alkyl group or an alkenyl group. A persistent aroma and flavor imparting or modulating agent characterized by containing 4-alkylthio-2-methylfurans as an active ingredient.