JPS6159712B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the use of β-methylthioacrylic acid esters, which have not been previously described in any known literature, in perfumery applications. More specifically, the present invention is a β-methylthioacrylate ester represented by the following formula (1) CH ₃ SCH=CHCOOR (1) where R represents a C ₂ to _{C 10} alkyl group or a benzyl group. The present invention relates to a long-lasting aroma and flavor imparting or modulating agent characterized by containing as an active ingredient. Hitherto, the proposal of JP-A-52-151121 regarding β-sulfenyl acrylic acid and its derivatives represented by a wide range of general formulas that can include the compound of formula (1) above has been known. However, this proposal requires the above formula
Specific compounds that can be included in (1) are not exemplified at all, and of course, no examples are given. Furthermore, this proposal states that its wide range of general formula compounds have surfactant properties and antibacterial effects, and can be used as cleaning agents, disinfectants, disinfectants, etc., but what are these agents? There is no mention or suggestion of perfume applications requiring different effects. The present inventors have continued to study the aroma and flavor components of plums and grapes (Kyoho), but until now, the aroma and flavor components of plums, grapes (Kyoho), and quince were completely unknown, and there was no prior literature. Ethyl β-methylthioacrylate (Grape Kyoho, plum), butyl β-methylthioacrylate (quince, plum), isobutyl β-methylthioacrylate (quince), β-methylthioacrylate corresponding to the above formula (1) described We succeeded in extracting and separating isoamyl (quince) from natural plums, grapes (Kyoho), and quince as key flavors of plums, grapes (Kyoho), and quince, and these can be easily synthesized. I discovered that. Furthermore, as a result of continuing research related to the above compounds, we found that alkyl and aryl derivatives of β-methylthioacrylic acid corresponding to the above formula (1), which have not been previously described in literature, have plum and grape-like aromas and flavors. discovered that these compounds exist, and succeeded in synthesizing these compounds. Furthermore, the novel compound included in the above formula (1) is a compound that deserves attention as an excellent persistent aroma, persistent flavor imparting agent, or persistent aroma or persistent flavor modifier, and is a compound that is noteworthy as an excellent persistent aroma or persistent flavor modifier. It has been discovered that it is useful as an excellent long-lasting aroma and flavor imparting or flavor modulating agent in a wide range of fields of application such as soaps, detergents, cosmetics, health, hygiene, and pharmaceuticals. Therefore, an object of the present invention is to provide a novel formula (1) β-
An object of the present invention is to provide a persistent aroma and flavor imparting or modulating agent containing methylthioacrylic acids as an active ingredient. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The following formula (1) of the present invention CH ₃ SCH=CHCOOR (1) However, in the formula, R has the same meaning as above, β-methylthioacrylic acid esters represented by the following exist in two geometric isomerisms, cis and trans forms. can. Examples of R in the compound included in the above formula (1) include ethyl, n-propyl, iso
-Propyl, n-butyl, iso-butyl, tert-butyl, sec-butyl, n-pentyl, iso-pentyl, neopentyl, 1-methylbutyl, 1,2-
Examples include C2 _{- C10} alkyl and _C7 aryl groups such as dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 2-ethylhexyl, benzyl and the like. Specific examples of these new compounds include (b) cis-,
Ethyl trans-β-methylthioacrylate, (c)
cis-, trans-β-methylthioacrylate propyl, (d) cis-, trans-β-methylthioacrylate butyl, (e) cis-, trans-β-methylthioacrylate isobutyl, (f) cis-, trans-β-methylthioacrylate. Isoamyl acid, (g)β
-2-ethylhexyl methylthioacrylate, (h)
Examples include benzyl cis-, trans-β-methylthioacrylate. The physicochemical properties of the above-mentioned exemplified compounds are as follows. n ²⁰ _D boiling point (b) 1.5419 70-73℃/2mmHg (c) 1.5129 74-81℃/2mmHg (d) 1.5088 98-102℃/2mmHg (e) 1.5062 85-90℃/3mmHg (f) 1.5029 91 〜94℃／1mmHg (g) 1.4962 115〜123℃／1mmHg (h) 1.5829 131〜132℃／0.5mmHg The β-methylthioacrylic acid ester of the formula (1) of the present invention is, for example, shown in the following formula. In this way, it can be easily manufactured. (R = C ₂ - C ₁₀ alkyl group or benzyl group) The known compound propiolisuccinic acid ester of the above formula () can be prepared by, for example, as shown in the above formula, propiolisuccinic acid of the easily available formula () in the presence of an acid catalyst. It can be easily obtained in good yield by contacting with alcohol, or by an azeotropic method in which water is distilled out of the reaction system in an azeotropic inert organic solvent with water. I can do it. As the acid catalyst used for the above esterification reaction,
Examples include sulfuric acid, phosphoric acid, hydrochloric acid, and p-toluenesulfonic acid. The amount used is
For example, the amount used is about 0.1 to about 10% by weight, more preferably about 0.2 to about 5% by weight, based on propiolic acid. When the esterification reaction is carried out in an azeotropic inert organic solvent, examples of the inert organic solvent include benzene, toluene, xylene, and isopropylbenzene. There is no particular restriction on the amount of these solvents to be used, and a desired amount suitable for the reaction operation can be appropriately selected and used, but it is preferably about 0.5 to about 10 times the weight of propiolic acid, and more preferably An example of the amount used is about 1 to about 5 times the weight. In addition, in the above esterification reaction, the above formula ()
The amount of alcohol to be used is, for example, about 1 to about 10 mol, preferably about 1.2 to about 5 mol, per 1 mol of the compound of formula (). The reaction temperature and reaction time can be changed as appropriate depending on the type and amount of the alcohol, catalyst, and solvent used. The reaction product is poured into water, the target product is extracted with an appropriate solvent as necessary, the extracted solvent layer is neutralized, washed with water, the solvent is removed, and the formula () is obtained by distillation, for example.
compound can be obtained. The novel compound β-methylthioacrylic acid ester of the above formula (1) is preferably prepared by adding the known compound propiolic acid ester of the above formula () to an inert organic solvent, optionally in the presence of a reaction accelerator, as shown in the above formula. It can be easily obtained in good yield by contacting it with methyl mercaptan of the above formula () in medium or in the absence of a solvent. The reaction can also be carried out under light irradiation if desired.
Further, if desired, the compound of formula (1) may be obtained by contacting the propiolic acid of the formula () with the methyl mercaptan of the formula () and esterifying it. In the above addition reaction, the amount of the formula () methyl mercaptan to be used is, for example, about 1 to about 10
The amount is about twice the molar amount, preferably about 1 to about 5 times the molar amount. The reaction can be carried out by gradually blowing the required amount of methyl mercaptan into the propiolic acid ester, or by blowing it all at once, and the operation can be changed as necessary. The above addition reaction is preferably carried out in the presence of a nonpolar solvent. Examples of such solvents include hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, benzene, and the like. These solvents can be used alone or in combination. There are no particular restrictions on the amount of solvent to be used, and the desired amount suitable for the reaction operation can be appropriately selected and used. , more preferably about 0.5~
It is about 5 times the weight. Further, in the above addition reaction, general radical initiators can be used, and specific examples thereof include isobutylnitrile, 2,2-azobisisobutylnitrile, azobishexanecarbonyl, and tetramethylculam disulfide. I can give an example. The amount of these reaction accelerators used may range, for example, from about 0.1 to about 20% by weight, more preferably from about 0.5 to about 10% by weight, based on the propiolic acid ester. The reaction temperature is, for example, about 5° to about 100°C, more preferably about 10° to about 50°C.
The reaction time can also be appropriately selected, and can be changed as appropriate depending on the reaction accelerator used, the type and amount of the solvent, the reaction temperature, etc. The reaction product is poured into water, the target product is extracted with an appropriate solvent as necessary, and the extracted solvent layer is, for example, neutralized, washed with water, the solvent is removed, and, for example, by distillation, to obtain the formula (1).
compound can be obtained. Furthermore, in the embodiment in which methyl mercaptan is added to the propiolisic acid and then esterified, the above reaction conditions can be appropriately employed. It has been discovered that the compound β-methylthioacrylic acid esters of formula (1) of the present invention are extremely useful as persistent aroma and flavor imparting or modulating agents. These compounds have excellent persistence and unique flavors as fruity, especially plum and grape key flavors or similar aromas or flavor components. Thus, according to the present invention, there can be provided a persistent aroma and flavor imparting or modulating agent characterized by containing the β-methylthioacrylic acid ester of formula (1) as an active ingredient. Furthermore, by utilizing this persistent aroma and flavor imparting or modulating agent, food and beverages characterized by containing β-methylthioacrylic acid esters as an aromatic flavor component; β-methylthioacrylic acid esters as an aromatic component; Soaps, detergents, cosmetics characterized by containing; β
- Health and hygiene products characterized by containing methylthioacrylic acid esters as aromatic and flavoring ingredients,
Pharmaceuticals, etc. can be provided. For example, drinks such as juices, fruit alcoholic beverages, milk drinks, lactic acid bacteria drinks, carbonated drinks; frozen desserts such as ice creams and ice candy;
Gives its unique aroma and flavor to various foods, including Japanese and Western sweets; jams; breads; chewing gum, coffee, cocoa, black tea, and other favorite foods; and various instant beverages and foods. Foods and beverages can be provided in appropriate amounts. For example, cosmetics containing shampoos, hair rinses, hair creams, pomades, and other hair cosmetic bases; cosmetic soaps and other cosmetic detergent bases in an appropriate amount to impart the unique fragrance. can be provided. Furthermore, its unique properties can be applied to laundry detergents, disinfectant detergents, deodorizing cleaning agents, and other health and hygiene detergents; and to various health and hygiene materials such as toothpaste, tissue paper, and toilet paper, as well as pharmaceuticals. It is possible to provide health, hygiene, and pharmaceutical products that are blended or applied in an appropriate amount to impart aroma and flavor. Examples of several embodiments of the present invention will be shown below. Reference Example 1 Synthesis of ethyl propiolisuclate: - 235 g (5 mol) of ethanol, 70 g (1 mol) of propiolic acid, and 7 g of concentrated sulfuric acid were placed in a reaction vessel, and the reaction was carried out with stirring at a temperature of 15 to 60°C for 10 hours. After the reaction was completed, the reaction solution was poured into saturated brine, extracted with methylene chloride, and the solvent layer was washed with water.
The mixture was washed with an aqueous sodium bicarbonate solution, the solvent was removed, and the mixture was distilled to obtain ethyl propiolysate. This product has a boiling point of 40° to 43°C/25 mmHg and a theoretical yield of 89.8%.
It was hot. Reference Example 2 Synthesis of butyl propiolic acid: - In a reaction vessel, 35 g (0.5 mol) of propiolic acid,
Butyl alcohol 56g (0.75 mol), benzene 100
1 g of p-toluenesulfonic acid were added, and the reaction was carried out by stirring under reflux for 6 hours. The end point of the reaction was defined as the point at which the theoretical amount of water was distilled off. After the reaction is complete,
The reaction solution was poured into saturated brine, extracted with benzene, the solvent layer was neutralized with a saturated aqueous sodium bicarbonate solution, washed with water to remove the solvent, and distilled to a boiling point of 88° to 92°C/80 mm.
58.72 g of butyl propiolysate containing Hg was obtained. Theoretical yield: 93.2% Reference Example 3 Synthesis of propyl propiolisuccinate: - In Reference Example 2, propyl alcohol was used instead of butanol, and the same procedure as in Reference Example 2 was carried out to obtain the corresponding propyl propiolysuccinate. This product had a boiling point of 52°-57°C/20 mmHg and a theoretical yield of 88.7%. Reference Example 4 Synthesis of isobutyl propiolitsucate: - The same procedure as in Reference Example 2 was carried out except that isobutyl alcohol was used instead of butyl alcohol to obtain 57 g of the corresponding isobutyl propiolysinate. This item has a boiling point of 58° to 62°C/25mm
The yield was 91% of theory. Reference Example 5 Synthesis of isoamyl propiolitsucate: - The same procedure as in Reference Example 2 was carried out except that isoamyl alcohol was used instead of butyl alcohol to obtain the corresponding isoamyl propiolitsucate. This item has a boiling point of 59° to 63°C/11mmHg
The theoretical yield was 99.5%. Reference example 6 Synthesis of 2-ethylhexyl propiolic acid:
- In Reference Example 2, 2-ethylhexyl alcohol was used instead of butyl alcohol, and the same procedure as in Reference Example 2 was carried out to obtain 173 g of the corresponding 2-ethylhexyl propiolysate. This product had a boiling point of 86°-92°/3 mmHg and a theoretical yield of 95%. Reference Example 7 Synthesis of benzyl propiolitsucate: - In Reference Example 2, benzyl alcohol was used instead of butyl alcohol, and the same procedure as in Reference Example 2 was carried out to synthesize the corresponding benzyl propiolitsucate.
I got 140g. This item has a boiling point of 105° to 110°C/3mm
It contained Hg, and the theoretical yield was 87.5%. Reference Example 8 Synthesis of ethyl β-methylthioacrylate: - Charge 98 g (1 mole) of ethyl propiolysate, 50 g of hexane, and 1 g of isobutyronitrile into a reaction vessel, and add 96 g (2 moles) of methyl mercaptan to the reaction vessel for 10 to 20 minutes. The mixture was stirred at ℃ and the reaction was carried out for 10 hours. The reactant was poured into a 5% aqueous soda ash solution, extracted with ether, and after removing the ether, distilled under reduced pressure to obtain the corresponding ethyl β-methylthioacrylate (structure confirmed by IR, MS, and NMR).
Obtained 108g of. The boiling point of this substance is 70° to 73°C/2
mmHg and theoretical yield of 74%. Reference Example 9 Synthesis of propyl β-methylthioacrylate: - Synthesis of propyl β-methylthioacrylate in the same manner as in Reference Example 8, using propyl propionate instead of ethyl propiolyscate, to synthesize the corresponding propyl β-methylthioacrylate (structure (confirmed by IR, MS and NMR) was obtained. The boiling point of this product was 74°-81°C/2 mmHg, and the theoretical yield was 76%. Reference Example 10 According to the method of Reference Example 8, various β-
Methylthioacrylic acid ester was obtained. The results are shown in Table-1.

[Table] Example 1 The following components (parts by weight) were mixed as a grape-like aroma composition. Amyl isovalerate 8 Cinnamyl alcohol 5 Cinnamyl propionate 6 Citral 1 Ethyl acetate 62 Ethyl benzoate 3 Ethyl butyrate 15 Ethyl caproate 3 Ethyl enanthate 17 Hydroxycitronellal 4 Methyl anthranilate 132 Methyl salicylate 13 Ter Pinylacetate 10 Tolylaldehyde 3 Propylene glycol 718 total 1000 By adding 1 g of ethyl β-methylthioacrylate to 1000 g of the above composition, a new long-lasting aroma composition with excellent grape aroma and flavor components was created. Obtained. Similar results were obtained when propyl β-methylthioacrylate, butyl β-methylthioacrylate, isobutyl β-methylthioacrylate, and isoamyl β-methylthioacrylate were used instead of ethyl β-methylthioacrylate.
were obtained by using, respectively. Example 2 The following components (parts by weight) were mixed as an apple-like aroma composition. Ethyl acetate 290 Ethyl butyrate 70 Isoamyl acetate 100 Isoamyl propionate 50 Asoamyl alcohol 50 Propyl alcohol 30 Isoamyl butyrate 70 Trans-2-hexenal 20 Ethyl caproate 10 Hexyl acetate 20 Diethyl malonate 50 Isoamyl isovalerate 30 Butyl Acetate 150 Butiric acid 15 Caproitic acid 10 Citronellyl butyrate 15 Geranyl acetate 5 Cis-3-hexenol 15 1000 By adding 0.8 g of ethyl β-methylthioacrylate to 100 g of the above composition, apple aroma and flavor components can be obtained. A new long-lasting composition with excellent properties was obtained. Similar results were obtained by using butyl β-methylthioacrylate, isobutyl β-methylthioacrylate and isoamyl β-methylthioacrylate in place of ethyl β-methylthioacrylate, respectively. Example 3 The following components (parts by weight) were mixed as a meat-like aroma/flavor composition. Beef extract 600 Vegetable protein hydrolyzate 100 Maltol 2 β-methylthiopropanal 10 (1% ethanol solution) Onion extract 50 Pork extract 300 Monosodium glutamate 50 Nucleic acid seasoning 2 1114 Add 100 g of the above composition to β-methylthioacryl By adding 4 g of butyl acid (1% ethanol solution), a new long-lasting aroma composition with excellent meat-like aroma and flavor components was obtained. Similar results were obtained for isobutyl β-methylthioacrylate, β
-obtained by using isoamyl methylthioacrylate and benzyl β-methylthioacrylate, respectively. Example 4 Composition for Soap A novel floral fragrance composition was prepared by mixing the following components (parts by weight). Bergamot oil 20 Ylang-ylang oil 5 Linalool 25 Benzyl acetate 5 Benzyl alcohol 32 Terpineol 15 Paracresyl acetate 1 Cinnamic alcohol 5 Eugenol 4 Heliotropin 4 Absolute diasmin 2 total 118 Add β-methylthioacryl to 99.5 g of the above composition A fragrance composition was prepared by mixing 0.5 g of ethyl acid. This product and a composition to which ethyl β-methylthioacrylate was not added were added to an unscented soap paste at a ratio of 1% by weight and molded to produce soap. The soap to which ethyl β-methylthioacrylate was added had a strong fresh floral aroma and excellent longevity compared to the soap without ethyl β-methylthioacrylate. Similar results were obtained for butyl β-methylthioacrylate, isobutyl β-methylthioacrylate,
It was also obtained by using propyl methylthioacrylate, isoamyl β-methylthioacrylate and benzyl β-methylthioacrylate, respectively. Comparative Test Example 1 For each of the compound (1) ethyl β-methylthioacrylate included in the present invention and the known methyl (X) β-methylthioacrylate (compound described in JP-A-52-151121), ethyl alcohol Make a 10% solution and use scented paper 6 mm wide and 120 mm long (1.
Using a dropper, apply 1 drop of ethyl alcohol solution to each of the above compounds (1) and (2) at 10 mm and 20 mm from the tip of the seed (approximately 0.0025
g) was added dropwise. The scent strength (residual scent) of scented paper scented in this way was compared and examined over time. The strength of the aroma (residual scent) was evaluated by a sensory test, and was scored four times by six sensory testers, and the presence or absence of a significant difference was analyzed. Among the samples of compounds (1) and (X),
The sample numbers of those judged to have strong aromas (lingering scent) are shown in Table 2 below. From the sensory test results shown in Table 2, it can be seen that compound (1) ethyl β-methylthioacrylate has significantly longer persistence than the known substance (X). In particular, in the sensory test results after 14 days, all the sensory testers judged that Compound (1) had a higher sustainability than (X).

[Table] Comparative Test Example 2 Apple-like fragrance composition 100 prepared in Example 2
g to 1.5 g of the invention product β-methyl ethyl acrylate (1)
A new flavor composition (A) with enhanced apple-like aroma was prepared by adding g. Similarly, 100 g of apple-like aroma and flavor composition prepared in Example 2 was added with methyl β-methylacrylate (X), a known substance.
An apple-like aroma flavor composition (B) was prepared by adding 1.5 g. For each of the above apple-like aroma and flavor compositions (A) and (B), scented paper with a width of 6 mm and a length of 20 mm (1 piece of
Using a dropper, one drop (approximately 0.004 g) was dropped at 10 mm and 20 mm from the tip of the seed. The strength of the apple-like aroma (lingering scent) of the scented paper scented in this way was compared and examined over time. The strength of the aroma (residual scent) was evaluated by a sensory test, repeated four times by six sensory testers, and the presence or absence of a significant difference was analyzed. Among them, the sample numbers of those judged to have a strong apple-like aroma (lingering aroma) are shown in Table 3 below. From the sensory test results shown in Table 3, composition (A) did not show a significant difference in the strength of the apple-like aroma (residual aroma) for the first 7 days compared to composition (B). However, in the sensory test results after 14 days, all the sensory testers agreed that composition (A) had significantly higher persistence (strength of apple-like aroma) than composition (B). It was determined that there was.

[Table] Comparative Test Example 3 99.5 g of the floral aroma composition prepared in Example 4 was mixed with 1 g of ethyl β-methylthioacrylate of the present invention to create a new composition (A) with enhanced floral aroma. was prepared. Similarly, 99.5 g of the flower-like aroma composition prepared in Example 4 was mixed with 1 g of the known substance methyl β-methylthioacrylate to prepare a flower-like aroma composition (B). Each of the flower-like fragrance compositions (A) and (B) prepared above was scented at a ratio of 1% by weight to an unscented soap paste to prepare a molded soap.
For each of the soaps prepared in this way, the strength of the floral aroma (lingering scent) was compared over time. The strength of the aroma (residual scent) was evaluated by sensory testing four times by six sensory testers, and the presence or absence of a significant difference was analyzed. Among the samples of compositions (A) and (B),
Sample No. which was determined to have a strong flower-like aroma (lingering scent).
are shown in Table 4 below. From the sensory test results shown in Table 4, it can be seen that composition (A) has significantly longer durability than composition (B). In particular, in the sensory test results after 14 days, all the sensory testers judged that Composition (A) had a longer lasting floral aroma than Composition (B).

【table】

Claims (1)

[Claims] 1 A β-methylthioacrylate ester represented by the following formula (1) CH ₃ SCH=CHCOOR (1) where R represents a C ₂ to _{C 10} alkyl group or a benzyl group 1. A persistent aroma and flavor imparting or modulating agent characterized by containing as an active ingredient.