JPS60149592A - 2-alkyl-thiazolidino(3,4-b)thiazolidine and its use - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula (R is 2-5C alkyl). EXAMPLE:2-Ethyl-thiazolidino-[3,4-b]thiazolidine. USE:An imparter or modifier for durable fragrance and flavor. Having fragrance like natural, improved roasted Welsh onion, garlic, Lentinus edodes, meat, green, etc. PREPARATION:For example, cysteamine hydrochloride is brought into contact with 2,5-dihydroxy-1,4-dithian in the presence of an alkali and ammonium acetate to give 2-mercaptomethylthiazolidine, which is brought into contact with an alkylaldehyde shown by the formula R1-CHO (R1 is 1-5C alkyl with the proviso that it is well-known compound when R is methyl group).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 2-
This invention relates to alkyl-thiasirisino[3,4=b]thiazolidines, their production methods, and further their uses.

More specifically, the present invention provides 2-alkyl-thiasilidino[3゜4-b
] Regarding thiazolidines. Furthermore, the present invention provides 2-alkyl-thiasiridino[3゜4-b
] The present invention also relates to a persistent aroma and flavor imparting or modulating agent characterized by containing thiazolidines as an active ingredient, and also relates to a method for producing these.

Traditionally, mild and rich natural-looking kaashi,
Moreover, there is a demand for something with excellent durability. For this reason, various known fragrance materials are combined appropriately and/or by changing their blending amounts to create a formulation that has as much naturalness as possible. At present, there are few fragrance compound materials that can impart freshness and sustainability, and in particular, there is a shortage of materials that can be easily and inexpensively obtained.

Therefore, it is difficult in practice to formulate satisfactory perfume compositions.

In view of the above circumstances, the present inventors have been conducting research on the development of a fragrance substance that exhibits a mild and rich natural tone and has excellent sustainability.

As a result, the 2-alkyl-thiasilidino[3,4-b]thiazolidines of the formula (2) compound met the above requirements and were found to be mild and rich in natural flavor, such as roasted onions, garlic, shiitake mushrooms, and meat. , green, spice, and vegetable-like aromas, and blends well with various synthetic fragrances, natural fragrances, natural essential oils, citrus oils, synthetic essential oils, etc., and has a long-lasting aroma that provides or modulates the fragrance. 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 fields such as food and drink (including luxury goods), cosmetics, health care, hygiene products, and pharmaceuticals. Furthermore, it was found that among the compounds of formula (2), the compound of formula (]) is a novel compound that has not been previously described in any literature.

In the above formula (2) compound of the present invention, 2-methyl-thiasilidino[3゜4-b]thiazoline, in which R is a methyl group, is a known compound found in Maillard reaction products. . That is, 2-methyl-thiasilidino [
3,4-b]thiazolidine, for example, Flavor
'8] 3rd Weurman Symposium
Proceedings of the Inter-n
ational conference, Munic
h Apri128-30.1981,, SHIGE
MATSU VA-RIATION OF THE M
It is a known substance described in the literature under the title AILARD REACTION. According to this document, 2-methyl-thiacyridino[3,4-b)thiazolidine is described as a compound found in the Maillard reaction production of gelcol and cysteine and having a tamitic, gravy-like flavor. There is.

However, the document describes that the compound blends well with various synthetic fragrances, natural fragrances, natural essential oils, citrus oils, synthetic essential oils, etc., and provides a novel long-lasting aroma that is mild, rich, and has excellent persistence. No mention is made of any findings that might suggest that it is useful as a modulator.

Therefore, an object of the present invention is to provide a new type of persistent aroma and flavor imparting or modulating agent containing as an active ingredient a compound of formula (2) below, which includes the new compound of formula (1) above and the known compound above. be.

Another object of the present invention is to obtain the compound of the formula (1) and the compound of the formula (2).
) An object of the present invention is to provide a manufacturing method that can advantageously produce the compound.

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

The formula (2) below includes the novel compound of the formula (0) of the present invention.
) In the formula, R1 is 2-alkyl-thiasilidino [3゜4-b
] Thiazolidines, for example, the following formula (6)% formula% (6
) Cysteamine hydrochloride represented by 2,5 represented by the following formula (5) in the presence of an alkali and ammonium acetate.
-9hydroxy-1,4-dithiane to form 2-mercaptomethylthiacilidine represented by the following formula (4), and then the lower formula (3) % formula % (3) where, R2 represents an alkyl group of Cr''Cs, and can be easily synthesized by contacting with an argylaldehyde represented by the following formula.The process diagram of the above reaction of the present invention is shown below.

(6)　05) R.

In the above embodiment, 2-mercaptomethyltiapridine of the above formula (4) is prepared by, for example, converting the above formula (6) cysteamine hydrochloride into the above formula (5) 2,5-dihydroxy- The sister compound can be easily synthesized by reacting with 1,4-dithiane at a temperature range of about 10° to about 100° C. for about 3 to about 8 hours.

In the above reaction, the amount of the compound of formula (5) used is:
For example, a range of about 0.1 to about 0.5 mol can be exemplified with respect to the compound of formula (6). Also, A Ba(O
H)z, etc. can be used, and these alkalis can be used in an amount of, for example, about 1.0 to about 2.0 mol based on the compound of formula (6). The amount of ammonium acetate to be used may be selected appropriately, for example, about 5
A range of about 0 to about 150% by weight can be mentioned.

The above reaction is preferably carried out in an organic solvent, and specific examples of the organic solvent include methanol, ethanol,
Examples include solvents such as inpropyl alcohol and DMF. There are many specific restrictions on the amount of these organic solvents to be used, but for example, about 100 to about 1000 to the compound of formula (6)! It can be used within a certain amount. After the completion of the reaction, the compound of formula (4) may be isolated, but it is usually possible to proceed to the next -1:1 reaction.

In the present invention, the 2-alkyl-thiazolidino[3,4-b]thiazolidines of formula (2) can be synthesized, for example, by the reaction completion system without isolating the compound of formula (4) that can be synthesized as described above. For example, when the formula (3) alkanal is added to the formula (4) compound contained in the reaction completion system, about 2
It can be easily formed by reacting at a temperature of about 0°C to about 100°C for about 1 to about 10 hours.

Examples of the alkanal of formula (3) include acetaldehyde, propionaldehyde, invaleraldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, and hexanal. The amount of these alkanals to be used may be, for example, about 1 to about 0 mol, based on the compound of formula (4). After completion of the reaction, the reaction mixture is washed with water in a conventional manner, extracted with ether, for example, and distilled under reduced pressure after distilling off the ether to easily obtain the compound of formula (2).

Specific examples of the compound of formula (2) that can be obtained as described above, as well as its aroma and flavor characteristics and boiling point, are shown below.

Strong roasted green onions, sweet garlic, and shiitake mushrooms.

Strong shiitake mushrooms with a green feel, cabbage-like sweetness.

Roast green onion-like with a slight green and citrus feel, slightly meat-like.

Shiitake mushrooms and roasted green onions with a slight coffee and green feel.

Garlic-like and shiitake-like with a slightly ripe tomato taste.

Tomato-like, green onion-like, and shiitake-like with a slight green feel.

2-alkyl-thiasilidino[3,
4-b) Thiazolidines have been discovered to be useful as persistent aroma flavoring or flavoring agents. The compound of formula (2) has roasted onion-like, garlic-like, meat-like, green-like, citrus-like, spice-like, shiitake-like, and cabbage-like aromas and flavors, and has excellent persistence. In particular, it has excellent persistence and unique aroma as a flavor imparting or modulating agent for various foods and beverages, cosmetics, health care, sanitary products, pharmaceuticals, etc.

2-alkyl-thiasilidino (3,
4-b) Thiazolidines have been discovered to be useful as persistent aroma and flavoring agents. The formula (2
) The compound is a new compound that has a caramel-like aroma as its main tone and exhibits green, fruit, fat, camphor, and spice tones, and has excellent sustainability, and is particularly useful in various foods and drinks. It has excellent persistence and unique aroma as a flavor imparting or modulating agent for cosmetics, health care, hygiene, pharmaceuticals, etc.

2-alkyl-thiasilidino[3,
4-b] Thiazolidines harmonize well with various synthetic fragrances, natural fragrances, natural essential oils, synthetic essential oils, citrus oils, etc., and have the formula (
2) Novel fragrance compositions can be prepared using the compound.

Specifically, when the compound of formula (2) is blended into synthetic essential oils such as bergamot oil, lemon oil, geranium oil, lavender oil, and mandarin oil, the aroma and flavor that natural essential oils have is mild and rich. It is possible to impart a long-lasting improvement effect to synthetic essential oils. 1. It is also good for citrus essential oils such as orange, lime, lemon, grapefruit, etc. @natural essential oils such as chive lavender oil, vetiver oil, cedarwood oil, citronella oil, geranium oil, lavandin oil, sandal oil, etc. It is possible to prepare a novel perfume composition that harmonizes and emphasizes the characteristics of its essential oils, has a mellow, rich, natural appearance, and, in addition, has excellent long-lasting properties. Further, for example, strawberry, lemon, orange, grapefruit, apple, pineapple, prepared from various synthetic fragrances, natural fragrances, natural essential oils, citrus oils, etc.
When blended with flavor compositions such as banana, melon, etc., it is possible to prepare a mild, rich, natural-looking fragrance composition with an emphasis on sustainability. 2 of the above formula (2)
The amount of -alkyl-thiacyridino[3,4-b]thiazolidines to be blended varies depending on the purpose and the aroma and flavor composition to be blended, but is generally about 0,
An example of the range is 01 to about 30% by weight.

Thus, according to the invention, 2-alkyl- of formula (2)
It is possible to provide a long-lasting fragrance-imparting reinforcing agent containing thiacyridino[3,4-b]thiazolidines as an active ingredient, and by using a nucleating agent, 2% formula% of formula (2): ] lysine is added to the fragrance. Foods and beverages characterized by containing and as a flavor component, 2-alkyl-thiasilidino [ of formula (2)]
3,4-b] Cosmetics characterized by containing thiazolidines as a fragrance ingredient, formula (2) % Formula %:] Health/hygiene/cosmetics characterized by containing azolines as a fragrance ingredient Pharmaceuticals, etc. can be provided.

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, luxury goods such as tea; soups such as Japanese-style soups and Western-style soups; flavor seasonings, various instant drinks and foods, various snack foods, etc. in appropriate amounts to impart unique aromas and aromas. It is possible to provide food and drinks containing the following. 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, toilet detergents, anti-blue detergents, deodorizing detergents, room air fresheners, and various health and hygiene detergents: toothpaste, tissues, toilet paper, etc. Materials: We can provide health, hygiene, and pharmaceuticals that have been blended or applied with appropriate amounts to impart unique flavor to health, hygiene, and pharmaceuticals, such as flavorings and flavoring agents to make medicines easier to take.

EXAMPLES Below, several embodiments of production and usage examples of the compound of formula (1) of the present invention will be explained in more detail with reference to Examples.

Example 1 (1) 2-Methyl-thiacirisino[3,4-b,:]
Synthesis of Tithiazosine Dissolve 7.9 g of KOH in 100 ml of methanol, then dissolve 22.5 g (0.2 mol) of cysteamine hydrochloride at room temperature.
After that, 23 g of ammonium acetate was added and stirred for 30 minutes. Next, 2,5-dihydroxy-1°4-dithiane 1
5.2. ! 9 (0.1 mol) and the reaction mixture was reduced to 60
Stirred at 70°C for 5 hours. After cooling, 44.0 g (1.0 mol) of acetaldehyde was added dropwise at room temperature over 20 minutes.
After stirring for an hour, the mixture was reacted for 2 hours under reflux. After cooling, the reaction mixture was poured into 200 g of water, extracted with 200 g of ether, the ether layer was washed with a saturated aqueous sodium bicarbonate solution, the anhydride was dried with acid soda, the ether was distilled off, and the residue was distilled under reduced pressure. 97-b (yield 46.5 cm) was obtained.

Example 2 In place of acetaldehyde in Example 1, the following (2
The following compounds (2) to (7) were obtained in the following yields according to the method of Example J, except that the alkyl aldehydes corresponding to each of the compounds (2) to (7) were used.

Silicino[3°4-b]-thiazolidine (3) 2-probylucci 52.0 112-114/
3azolidino[3°4-b]-thiazolidine (4) 2-isopropyl 53.0 110-1]
]2/3-thiasirisino 3.4-bl-thiazolidine (5) 2-butyl-thia 59.5 120-122/
3° lysino[3°4-b]-thiazolidine (6) 2-isobutyl-65,0118-120/3-thiasilicino[3,4-bl-thiazolidine (7) 2-pentylucci 67.0 122-124/
3azolidino[3°4-b]-thiazolidine Example 3 The following components (parts by weight) were mixed as an aromatic flavor component for pineapple.

Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acetate 100 Isoamyl valerate 55 Isobutyric acid 70 Invaleric acid 30 Allyl caproate 35 Ethyl caproate 20 Isoamyl alcohol 35 Diethyl malonate 30 Citral 15 Linalool 5 Maltol 20 Total 1000 The above composition 1000 .9 to 2-methyl-thiasilidino[
:3.4-b:] By adding 65 g of thiazolidine, a very good new composition was obtained with excellent persistence as a pineapple aroma and flavor component. Similar results were obtained with 2-propyl-thiacyridino[3,4-b,)
lthiazolidine, 2-isobutyl-thiasiridino [3,
4-b] Thiazolidine, 2-pentyl-thiasiridino [
3,4-b:]Also obtained using tithiazosin,
Each one had a slightly different nuance, but all had a strong sense of freshness.

Example 4 The following components (parts by weight) were mixed as a chicken-like flavor button product.

Hexanal 7 Trans-2-Decenal 2 2.4-Decagenal 46 Linalool 2 Terpineol 3 ]-Octen-3-ol 3 Maltoyl 10% ethanol solution i10 Diacetyl 1% ethanol solution 5 Acetoin 1% ethanol solution 5 Ethanol 917 Total 000 The above composition 1000F was added with 2-ethyl-thiacyridino (3
,4-b) 10g of 10% ethanol solution of thiazolidine
By adding .about.20 g, a novel flavor composition was obtained which was very superior to the aroma and flavor components of chicken and had excellent persistence.

Similar results were obtained for 2-butyl-thiasilidino[3,4-b]
Thiazolidine, 2-propyl-thiasiridino [3,4-
b) Thiazolidine, 2-isopropyl-thiasiridino [
It was also obtained using 3,4-b)-thiazolidine. However, these had an accentuated body with a somewhat burnt odor.

Example 5 Each of the following components (parts by weight) as a nut flavor composition
were mixed.

Isobutyraldehyde 2 Diacetyl 0.6 Acetylmethylcarbinol 15 Furfural 11 Benzaldehyde 3 γ-octalactone 4 Vanillin 55 2-Methyl-thiasiridino[3,4-b)thiazolidine 5 The above flavor base may be mixed with an appropriate solvent such as propylene glycol, ethanol, etc. With a solvent of
．． Add approximately 05 to 1 weight factor. 2- of the above amount
The addition of methyl-thiasilidino[3°4-b]thiazolidine showed excellent persistence, emphasizing the rich, nutty aroma. The results for the same eel were 2-isobutyl-thiasiridino[3゜4-b]thiazolidine, 2-inguropyruthiazolidino[3,4-blthiazolidine, 2-ethyl-
It was also obtained by using thiacyridino[3,4-b]thiazolidine. However, these cases showed excellent persistence with a somewhat emphasized sweetness.

Example 6 The following ingredients (
(parts by weight) and mix.

Ethyl acetate 150 Ethyl gropionate 150 Ethyl imbutyrate 300 Isoamyl acetate 50 Isoamyl propionate 30 Isoamyl butyrate 20 Methyl cinnamate 30 Ethyl benzoate ] 0 Ethyl acetyl acetate 80 Ethyl acetate 50 Benzaldehyde 5 Isobutyric acid 20 Cis-3-hexenol 20 linalool 10 cis-3-hexenyl acetate 20 caproic acid 30 γ-undecalactone 5 maltol 10 vanillin 8 α-ionone 2 000 2-methyl-thiacyridino [3
, 4-b] By adding 3 g of thiazolidine, a novel arene composition having strawberry aroma and flavor components with very fresh taste and excellent long-lasting properties was obtained. Similar results were obtained with 2-ethyl-thiacyridino[3,4-b:)
Thiazolidine, 2-propyl-thiasiridino [3,4-
b) obtained by using thiazolidine, respectively.

Example 7 A fragrance composition for shampoo was produced by mixing the following components (parts by weight).

Linalool 5 Abunryut Jasmine 2 β-Phenylethyl Alcohol 5 0 Synol 15 Hydroxycitronellol 30 Abunryut Rose 1 Indole 10 benzyl benzoate solution 2 Staylac oil 3 Hexylcinnamic aldehyde 15 Cyclamenaldehyde 4 Sandalwood oil 5 Phenyl acetate 2-butyl-thiacyridino[3,
4-b] By adding 3 g of thiazolidine, a new composition with lily of the valley-like odor characteristics and long-lasting properties was obtained. Similar results were obtained with 2-ethyl-thiacyridino[3
, 4-b) Thiasiridino, 2-butyl-thiasiridino [
3,4-1)] also obtained with tithiazosin.

(1 other person)

Claims (1)

[Claims] 1. 2-alkyl-thiasiridino[3,4-b] represented by the following formula (1), where R represents a group selected from the group of C2 to C6 alkyl groups;
, :lthiazolidines. 2. The following formula (2), where RI represents a group selected from the group of alkyl groups of CI""Cs.
] A persistent aroma and flavor imparting or modulating agent characterized by containing a thiazolidine as an active ingredient.