JPS6150960A - Methylthioacetic ester and its use - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is 2-4C alkyl). EXAMPLE:1 Methyl methylthioacetate. USE:A fragrance and flavor imparter and a modifier. Mild and with body, showing fresh natural tone and having improved durability. Useful for food and drink, cosmetic, drugs for health and hygiene, etc. PREPARATION:A monochloroacetic ester shown by the formula II (R' is 1-4C alkyl) is reacted with a compound shown by the formula III in the presence of preferably a base (e.g., triethylbenzylammonium chloride) in an organic solvent at 0-80 deg.C for 1-8hr, to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a methylthioacetate, which has not been described in any prior art literature, and a long-lasting aromatic flavor with excellent persistence that is hitherto unknown and which includes the new ester compound and has a methylthioacetate as an active ingredient. The present invention also relates to an imparting or modulating agent and a method for producing these methylthioacetic esters.

More specifically, the present invention is based on the following formula (1) % formula % (1) where R is C! It relates to a novel methylthioacetate represented by -C4 alkyl group.

The present invention also uses methylthioacetate represented by the following formula (1)' \s/ゝ\C00R-... (1)' where R' represents a Ct-C* alkyl group as an active ingredient. It also relates to a persistent aroma and flavor imparting or modulating agent.

Furthermore, the present invention provides monochloroacetic acid ester represented by the following formula (3) % formula % (3) where R' represents a Cs-04 alkyl group, preferably in the presence of a base, into the following formula ( 2) The method for producing the above formula (1)' methylthioacetate, which is characterized by contacting with a compound represented by the formula (%), has been conventionally used as a flavoring agent for various food and drink flavors or fragrances for cosmetics. The composition is required to be mild, full-bodied, have a fresh, natural appearance, and be long-lasting. For this reason, various known fragrance materials are combined as appropriate and in varying amounts to create a formulation that has as much naturalness as possible. Traditionally, there has been a desire for fragrance compound materials that are mild, full-bodied, fresh, natural, and have the ability to impart sustainability, but there are few materials with such performance, and they are particularly easy to obtain. At present, there is a shortage of materials that can be obtained at low cost and have the above-mentioned properties.

Conventionally, among the methylthioacetic esters represented by the formula (1)', methylthioacetate in which R' is a C1 argyl group has been described in the known literature @ elv, Chim.

Actao. There is no disclosure regarding its synthesis method. Naturally, therefore, no mention is made of either the usefulness of the compound as a perfume substance or its persistence. As mentioned above, the present inventors have been conducting research on the development of a fragrance substance that is mild, full-bodied, exhibits a fresh, natural tone, and has excellent long-lasting performance.

As a result, we succeeded in synthesizing the above-mentioned compound of formula (1)', which includes the above-mentioned known compound methyl methylthioacetate and the new methylthioacetate represented by the above-mentioned formula (1), and these compounds have the above-mentioned excellent performance. I discovered that.

According to the research conducted by the present inventors, methylthioacetate represented by the above formula (1)' has the following properties at relatively low concentrations:
It exhibits a mild, full-bodied, and fresh natural flavor with grass-like, fruit-like, and vegetable-like aromas, and in a relatively high concentration state, it has a mild, full-bodied aroma and aroma with an excellent fresh, natural flavor. A substance useful for flavoring applications that exhibits a bran pickle-like aroma and flavor and has excellent persistence, such as:
Mushroom-like, tomato-like, cheese-like, fruit-like, cabbage-like,
It exhibits excellent properties for imparting aromas and flavors such as baked nuts, onions, garlic, meat, and grass, and has excellent sustainability, making it suitable for use in food and drink as a long-lasting aroma and flavor imparting or modulating agent. goods (including luxury goods), cosmetics, health and
It has been discovered that it can be used as a long-lasting aroma and flavor imparting or modulating agent that is useful in a wide range of applications such as hygiene and pharmaceuticals.

According to the research of the present inventors, the compound of formula (1) can be easily and industrially advantageously produced in a high yield by the desalting reaction of the compound of formula (3) and the compound of formula (2). It turned out that it can be synthesized at low cost.

Therefore, an object of the present invention is to provide a novel methylthioacetate represented by the formula (1).

Another object of the present invention is to provide a new type of long-lasting aroma and flavor imparting or modulating agent containing as an active ingredient the compound of formula (1), including the compound of formula (1).

Still another object of the present invention is to provide a method for producing the compound of formula (1)'.

The above and many other objects and advantages of the present invention will become more apparent from the following description.

The formula (1)-active ingredient of the present invention is, for example, the formula (3) below.
Desalting is carried out by contacting a monochloroacetic acid ester represented by % formula % (3 in which R- represents a C1-C4 alkyl group) with formula (2) CH38Na, preferably in the presence of a base. It can be produced easily, in high yield, and at low cost by reaction.

A process diagram of the method for producing the compound of formula (1)' according to the above embodiment can be shown as follows.

Base CI CH! COOR-+ CH38N a-1 (
3) (2> CHs 5CHz C0OR- The details of synthesizing the compound of formula (1)' according to the above embodiment are illustrated below. The compound of formula (3) is a compound easily available on the market, and the compound of formula (3) ) Specific examples of R' in the compound include C1-C4 alkyl groups such as methyl, ethyl, propyl, butyl and the like.

The reaction between the compound of formula (3) and the compound of formula (2) is carried out in an organic solvent, preferably in the presence of a base, as necessary.
This can be easily carried out by bringing the compound and the compound of formula (2) into contact. The amount of the compound of formula (2) to be used can be selected as appropriate, but for example, the amount of the compound of formula (3) is about 1 to 1.
An example of the amount used is about 10 times the amount by mole. The compound of formula (2) is usually used in the form of an aqueous solution.

Examples of the base used in the reaction include quaternary ammonium salts such as 1-ethylbenzylammonium chloride, tetrabutylammonium chloride, and tributylbenzylammonium chloride. The amount of these bases to be used can be selected as appropriate, for example, in a range of about 0.1 to about 50% by weight based on the compound of formula (3). Furthermore, examples of organic solvents used in the reaction include polar solvents such as methanol, ethanol, propyl alcohol, and butyl alcohol, and nonpolar solvents such as toluene and hexane diethyl ether. The amount of these solvents to be used can be selected as appropriate.
) can be used in an amount of, for example, about 1 to about 10 times the weight of the compound. The reaction temperature and reaction time can be selected as appropriate, depending on the type of base used and the organic solution process, but for example, conditions for about 1 to about 8 hours in the range of about 10°C to 80°C are used. Then, the above formula (1)
'Compounds can be easily synthesized.

The boiling point and aroma and flavor characteristics of the compounds included in the formula (1)' methylthioacetic esters synthesized as described above are shown below.

The above formula (1)' compound imparts, for example, mushroom-like, tomato-like, strawberry-like, melon-like, fruit-like, cabbage-like, onion-like, garlic-like, meat-like, baked nut-like, grass-like aroma and flavor. It also has a mild, full-bodied, fresh, and natural appearance, and is particularly effective as an aromatic or flavor component for various foods and beverages, cosmetics, and health/hygiene/pharmaceuticals. It has a unique aroma and flavor.

More specifically, the methylthioacetic acid ester of formula (1)- may be used, for example, with bergamot oil, lemon oil, geranium oil,
When blended with synthetic essential oils such as lavender oil and mandarin oil, it is possible to prepare a mild, rich, fresh, and persistent aroma and flavor imparting or modulating agent that natural essential oils originally possess. It also harmonizes well with citrus essential oils such as orange, lime, lemon, grapefruit, etc., and can emphasize the characteristics of the essential oil, providing a fresh, supple, and long-lasting aroma with a more natural feel. Modulators can be prepared. Furthermore, for example, when blended with a full-bodied fruit such as strawberry, lemon, orange, grapefruit, apple, pineapple, melon, etc., it imparts a mild, full-bodied, natural-like aroma and a long-lasting aroma. A modulator can be obtained. Furthermore, for example, single florals such as rose, jasmine, lilac, osmanthus, carnation, and muguet, combined floral bouquets of these, and modern florals with green notes, spicy notes, or aldehyde notes added to these. When incorporated into fragrance compositions such as bouquets or oriental bouquets,
It is possible to obtain an aroma imparting or modulating agent that has a mild, fresh, natural floral aroma and is highly persistent. Furthermore, when blended with natural meat extracts, seafood extracts, and flavor compositions thereof, a long-lasting aroma and flavor imparting or modulating agent that emphasizes the mild, rich, and natural flavor inherent in the above extracts is prepared. can.

The amount of the methylthioacetic acid ester represented by the formula (1) varies depending on the purpose and the aroma/flavor imparting or modulating agent, but for example, it is generally about o, oo of the total amount.
An example range is from about oi to about 20% by weight.

Thus, according to the present invention, methylthioacetic esters of formula (1)' can be prepared by using a persistent aroma imparting, modulating or enhancing agent comprising methylthioacetic esters of formula (1)' as an active ingredient. Foods and beverages characterized by containing as a flavor component, cosmetics characterized by containing a methylthioacetate of formula (1)- as a fragrance component, and methylthioacetate of formula (1)'. It is possible to provide health products, 147 raw materials, pharmaceuticals, etc., which are characterized by containing the aromatic flavor component.

For example, beverages such as fruit juice drinks, fruit alcoholic beverages, milk drinks, and carbonated drinks; frozen desserts such as ice cream, sherbet, and popsicles; Japanese and Western sweets, jams, chewing gums, breads, and coffee. , cocoa, black tea, UZ favorites such as tea; soups such as Japanese-style soups and Western-style soups; flavor seasonings, various instant drinks and foods, various snack foods, etc., suitable for imparting their unique aroma and flavor. It is possible to provide food and drinks with a blended amount. For example, an appropriate amount that can impart a unique aroma to shampoos, hair creams, pomades, and other hair cosmetic bases; as well as lipsticks, lipsticks, and other cosmetic bases and cosmetic detergent bases. We can provide cosmetics containing the following. Furthermore, laundry detergents, disinfectant detergents, armor detergents, and various other health and hygiene detergents; various health and hygiene materials such as toothpaste, tissues, and toilet paper; making it easier to take medicines; It is possible to provide health, hygiene, and pharmaceutical products such as flavoring and flavoring agents that are blended or applied in an appropriate amount to impart a unique flavor.

EXAMPLES Below, examples will be given to explain in more detail how to prepare and utilize the compound of formula (1) according to the present invention.

Example 1 Synthesis of methyl methylthioacetate (A> Me 0f-1700 (J) was charged into a reaction vessel, and metallic sodium 23 (J (1,0 mole>) was charged.

Next, 48 g (1
, 0 mole). 5. Triethylbenzylammonium chloride was added to this reaction solution. Add Oa. Under water cooling, 15°C to 20°C, i, ohrr” methyl monochloroacetate 130.2 g (1,211018>2.0 at room temperature
Stir for hr. The reaction solution is filtered and methanol is recovered under reduced pressure.

90 o of crude methyl methylthioacetate was obtained.

This was purified by distillation under reduced pressure to obtain the target compound 81Q. Yield: 67% bp, 65° C./21 mm)-1 g Example 2 The results of compound examples synthesized by the same method as Example 1 are shown in Table 1 below.

Kimi 1 f f's: 1 Da Fuki Fuki★Flow Side 3 The following components (by weight) were mixed as an aroma and flavor composition for plums.

Amyl butyrate 20 Benzaldehyde 115 Butylfomate 10 Cyto Nerol
1j ethyl butyrate
50 ・Ethyl valerate 15 Isoamyl propionate 10 γ-nonalactone 5 Orange essential oil 15 “2-phenyl-1-propyl 100 Dibutyrate γ-undecalactone ゛ 3 Vanillin 10-Nitinol
586-total 1000
- By adding 1 g of methyl methylthioacetate to 1000 g of the above composition, a new composition with excellent persistence as a plum aroma and flavor component was obtained. Similar results were obtained for ethyl itylthioacetate,
Although propyl methylthioacetate and butyl methylthioacetate were also used, new compositions with slightly different nuances were obtained.

Example 4 The following components (weight) as an apple aroma composition
were mixed.

1 Tyl acetate 50 L Tyl propionate 20 L Tyl butyrate 30 1 Tyl isovaler 1-60 Isoamyl acetate 301 Tyl alcohol 150? Mill alcohol 501 methyl propionate 70 methyl butyrate
102-hexenol
io.

2-hexenyl acetate 180 isobutyric acid 40 vanillin 20 hexyl butyrate 10 ethyl alcohol
180 Total 1000 By adding 20 of propyl methylthioacetate to 1000 g of the above composition, an extremely excellent fresh charcoal composition having a long-lasting apple aroma and flavor component was obtained. Similar results were obtained using methyl methylthioacetate, propyl methylthioacetate, butyl methylthioacetate-1-. However, these new compositions had even more pronounced apple-like aroma and flavor.

Example 5 The following components (circled) were mixed as an aroma and flavor composition for pineapple.

Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acetate 100 Isoamyl valerate 55 Isoacetic acid
10 iso old grass IS! 30 Allyl caproate 35 Ethyl caproate 20 Ethyl caprylate 15 Ethyl caprate 20 Isoamyl alcohol 35 Diethyl malonate
30 citral
15 linalool
5 maltol 20
Total: 1000 By adding 5 g of methyl methylthioacetate to 1000 g of the above composition, a new composition with excellent persistence as a pineapple aroma and flavor component was obtained. Similar results were obtained using ethyl methylthioacetate, propyl methylthioacetate, and butyl methylthioacetate. Propyl methylthioacetate and butyl methylthioacetate had an emphasized sweetness.

Example 6 The following components (surrounded) were mixed as an aroma and flavor composition for apricots.

Allyl cyclohexyl cabbenzaldehyde 11,5 amyl acetate 7.5 amyl butyrate 7.5 amyl formate 10.0 amyl valerate 15.0 cinnamic aldehyde 0.5 ethyl acetate 14.5 ethyl butyrate 4.5 Ethylhexanoate io. .

Ethyl acetate 50.0 Geranium o,sα-
Ionone 9,5 isoamyl phenyl acetate 0.1 benzyl acetate 9.5 lemon oil
5.0 orange oil
10.5 Propyl cinnamate 0,2 γ-undecalactone 213.0 Neroli oil
18,5 vanillin
85.0 ethanol
527.0 Total 1000.0 By adding 5 g of propyl methylthioacetate to 1000 g of the above composition, a new composition with excellent persistence as an apricot aroma and flavor component was obtained.

Similar results were obtained using methyl methylthioacetate and ethyl methylthioacetate. Example 7 Composition for Soap A fragrance composition of Nibouketaibu was prepared by mixing 10 parts by weight of each of the following components.

Bergamot Synthetic 4゜Linalyl Acetate 3゜Geranium
5゜β-ionone
100 lavender
2゜Geraniol
110 heliotropin
8゜Benzyl acetate-1”
60 phenylethyl alcohol 18
° Citronellol 5 ° Cedar oil 100 Turbinyl acetate 135 Amyl salicylate 45 Total 1000 1 to 5 g of methylthioacetate was mixed with 1000 g of the above composition to produce a fragrance composition.

This product and a composition to which methyl methylthioacetate 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 the compound was added had a strong bouquet-like aroma and exhibited excellent persistence compared to the soap to which the compound was not added.

Similar results were obtained using ethyl methylthioacetate, propyl methylthioacetate, and butyl methylthioacetate.

Example 8 The following ingredients (
parts by weight) were mixed.

Ethyl acetate 150 Ethyl propionate 150 Ethyl iso7 tyrate 300 Isoamyl(reacetate) 50 Isoamyl propionate 30 Isoamyl butyrate 20 Methyl cinnamate 30 Ethyl benzoate
10 ethyl acetylacetate
80 ethyl lactate
50 benzaldehyde
5 isodairyu 1! l!
20 linalool
10 cis-3-hexenol 20 cis-3-hexenyl acetate 20 caproic acid 3゜γ-undecalactone 5 maltol
1゜Vanillin
8α-ionone
2 Total: 1000 By adding 1 to 5 g of methyl methylthioacetate to 1000 g of the above composition, a new flavor composition with excellent strawberry aroma and flavor components and excellent persistence was obtained.

Similar results were obtained using ethyl methylthioacetate, but with a sweeter character.

Example 15 The following components (parts by weight) were mixed as a meat-like aroma/flavor composition.

Beefextract 600 Vegetable protein hydrolyzate 100 Maltol 2β-methylthiopropanal 10 (1% ethanol solution) Onion extract 50 Bork extract 300 Monosodium glutamate 50 Nucleic acid seasoning
2 By adding methyl methylthioacetate 109 to the above composition 1009, a novel aroma composition with excellent meat-like aroma and flavor components was obtained. Similar results were obtained using ethyl methylthioacetate, propyl methylthioacetate, and butylmethylthioacetate, respectively.

Example 6 Commercially available vegetable protein hydrolyzate 15g commercially available powder io g salt so g monosodium glutamate 20 (]Nucleic acid seasoning 1g dextrin 5g dried onion powder 1g strained
2 g Methyl methylthio acetate 2 g The instant Chinese noodle powder soup prepared according to the formulation shown in the above recipe resulted in a very pleasant powder soup with a harmonious garlic-like flavor.

Similar results were obtained when propyl methylthioacetate was used instead of methyl methylthioacetate.

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Claims (1)

[Claims] 1. A methylthioacetate ester represented by the following formula (1) ▲ Numerical formulas, chemical formulas, tables, etc.▼... (1) In the formula, R represents a C_2 to C_4 alkyl group. 2. The following formula (1)' ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1)' However, in the formula, R' represents a C_1 to C_4 alkyl group, and contains methylthioacetate as an active ingredient. A persistent aroma and flavor imparting or modulating agent.