JPH08116915A - 3-alkyl-1,2,4-trithiolanes - Google Patents

Abstract

PURPOSE: To obtain a new 3-alkyl-1,2,4-trithiolane useful as a spice compound, having fragrance and flavor characteristics contributing to a spice vegetable irritating feeling characteristic to Welsh onion, onion or garlic and a dressed flesh feeling in cooking meat. CONSTITUTION: This compound is shown by the formula (R is ethyl, propyl or isopropyl) such as 3-ethyl-1,2,4-trithiolane. The compound of the formula is obtained by reacting a 1-chloroalkylsulphenyl chloride with sodium sulfide in methylene chloride and DMF.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has aroma and flavor characteristics that contribute to the flavor and vegetable stimulating sensation characteristic of leeks, onions, garlic, etc., and the sensation of cooked meat when meat is cooked, and is useful as a flavor compound. The following formula (Formula 1) not described in the document

[0002]

Embedded image

3-alkyl-1, represented by the formula: wherein R represents an ethyl group, a propyl group or an isopropyl group,
It relates to 2,4-trithiolanes.

More specifically, the present invention relates to the above formula (Formula 1).
3-ethyl-1,2,4-trithiolane [R is an ethyl group, hereinafter referred to as a compound of formula (Chemical formula 1)], 3-propyl-1,2,4-trithiolane
R is a propyl group, hereinafter referred to as a compound of the formula (Formula 1) -2] and 3-isopropyl-1,2,4-trithiolane
[Wherein R is an isopropyl group, hereinafter referred to as a compound of the formula (Formula 1) -3].

[0005]

2. Description of the Related Art The present inventors have paid attention to the fact that a compound having a plurality of sulfur atoms in a 5-membered ring or 6-membered ring has a unique and persistent aroma-flavor characteristic and has been studied conventionally. I went. As a result, 3-alkyl-1, which has not been described in the conventional literature, has three sulfur atoms in the 5-membered ring,
It has been found that 2,4-trithiolanes have aroma and flavor stimulating characteristics such as scallions, onions, garlic, etc., which are characteristic of vegetables, as well as cooked meat when meat is cooked, and the compound was added. It was discovered that the fragrance composition has an excellent effect in imparting an aroma of cooked meat preparations to foods, livestock feeds and the like.

[0006]

In recent years, the taste of consumers or livestock animals has diversified, and accordingly, foods, feeds for livestock, etc. having various aroma and flavor characteristics having various characteristics have been manufactured. In response to these diversification, conventionally known perfume compounds alone cannot meet the demand for foods having various aroma and flavor characteristics and livestock feed perfume, and a new type of unique unprecedented type. There is a strong demand for the development of blended fragrance materials.

The novel compound of the above formula (Formula 1) of the present invention was found to be extremely useful as a perfume compound having a unique aroma-flavor characteristic which can solve the above-mentioned problems. completed. That is, the present invention has the following formula (Formula 1)

Embedded image (In the formula, R represents an ethyl group, a propyl group, or an isopropyl group) and is a 3-alkyl-1,2,4-trithiolane. Accordingly, it is an object of the present invention to provide compounds of formula (Chemical Formula 1) not described in the prior art that are useful in imparting cooked meat aroma and flavor. Also,
Another object of the present invention is to prepare a compound of the formula (Chemical formula 1) having aroma and flavor characteristics that contribute to a flavored vegetable stimulating sensation characteristic of leeks, onions, garlic and the like and a cooked meat sensation when meat is cooked. The present invention provides a novel flavor composition such as a cooked meat product.

[0008]

According to the present invention, the compound of the above formula (Formula 1) is obtained by subjecting an alkyl disulfide to a cleavage / halogenation reaction with sulfuryl chloride to form 1-chloroalkylsulfenyl chlorides. After that, the formed product can be easily synthesized by reacting it with sodium sulfide and methylene chloride in a dimethylformamide solvent. The details will be described below.

Alkyl disulfides as a starting material are inexpensive and easily available on the market. The reaction temperature and reaction time of the reaction for synthesizing 1-chloroalkylsulfenyl chlorides from the above alkyl disulfides are not particularly limited, and may be, for example, about -2.
Conditions of about 1 to 20 hours at a temperature in the range of about 0 ° C to 50 ° C can be adopted. The amount of sulfuryl chloride used may be, for example, in the range of about 2.0 mol to 10.0 mol with respect to 1 mol of the alkyl disulfide. Specific examples of 1-chloroalkylsulfenyl chlorides thus obtained include 1-chloropropylsulfenyl chloride, 1-chlorobutylsulfenyl chloride and 1-chloroisobutylsulfenyl chloride. Chloride can be used in the next reaction in the form of either a crude product or a purified product.

The 3-alkyl-1,2,4-trithiolanes of the present invention can be synthesized by reacting 1-chloroalkylsulfenyl chlorides with sodium sulfide and methylene chloride in dimethylformamide. The reaction temperature and reaction time in the above reaction are not particularly limited, and for example, conditions of about 2 to 20 hours at a temperature in the range of about 0 ° C to 50 ° C can be adopted.
The amount of sodium sulfide used is, for example, 2.0 mol to 1 mol of 1-chloroalkylsulfenyl chlorides.
The amount of methylene chloride used may be, for example, about 2.0 mol to 10.0 mol per 1 mol of 1-chloroalkylsulfenyl chlorides. It can be illustrated. Further, the amount of dimethylformamide used is, for example, 2.0 parts by weight to 10 parts by weight with respect to 1 part by weight of 1-chloroalkylsulfenyl chlorides.
About 0 parts by weight is used.

After the completion of the reaction, a conventional purification means such as extraction, washing, drying, distillation and the like is appropriately adopted to obtain the 3-alkyl-1, of the formula (Formula 1) in high yield and high purity. 2,4
-Trithiolanes can be synthesized. Formula (Formula 1)
Specific examples of the compound include 3-ethyl-1,2,4-trithiolane [compound of formula (formula 1) -1], 3-propyl-1,2,4-trithiolane [formula (formula 1) -2 Compound] and 3-isopropyl-1,2,4-trithiolane
[Compound of Formula (Formula 1) -3] can be mentioned.

The compound of the formula (Chemical formula 1) -1 included in the compound of the formula (Chemical formula 1) of the present invention is for cooked meat accompanied by a fresh flavored vegetable stimulating sensation characteristic of raw onions, garlic and the like. And the compound of formula (Formula 1) -2 is a flavored vegetable stimulating sensation that is characteristic of leeks, onions and the like, and the aroma and flavor properties of vegetables and meat soup, and the formula (Formula 1) -3 The compound possesses the aroma-flavored vegetable stimulating sensation that is characteristic of leeks and onions, and the aroma-flavor characteristic with vegetable and meat sauteiness, and can be used by adding it to various flavor compositions. The compounding amount of the compound of the above formula (Formula 1) varies depending on its purpose or the type of the fragrance composition, but is generally about 0.0001 to about 3.0 wt% relative to the total amount of the fragrance composition. A range of about% can be exemplified.

Thus, according to the present invention, by adding the compound of the above-mentioned formula (Formula 1) as an active ingredient, a novel flavor composition imparting an aroma and flavor characteristic similar to cooked meat accompanied by flavor and vegetables stimulating feeling. And foods characterized by containing the compound of formula (Chemical formula 1) as an aroma and flavor component using the composition, and containing a compound of the formula (Chemical formula 1) as an aroma and flavor component. It is possible to provide livestock feed and the like.

For example, cooked meat such as curries, stews, hamburgers, processed vegetable products; Japanese-style soups, Western-style soups, soups such as attached soups for ramen, unique to various snack foods, etc. It is possible to provide food products to which an appropriate amount capable of imparting various aroma and flavor is added.
Further, it is possible to provide feeds in which an appropriate amount capable of imparting the unique aroma is added to feeds for various pets and livestock.

The embodiments of the present invention will be described more specifically with reference to the following examples.

[0016]

【Example】

Example 1: Synthesis of 1-chloropropylsulfenyl chloride. A 300 ml reaction flask is charged with 96 g (0.64 mol) of propyl disulfide and cooled to -10 ° C. 216 g (1.60 mol) of sulfuryl chloride is added dropwise thereto at -10 ° C to 0 ° C over 3 hours. The reaction solution is gradually brought to room temperature and further stirred for 15 hours for reaction. After the reaction,
After distilling off excess sulfuryl chloride under reduced pressure of about 100 mmHg, 160 g of 1-chloropropylsulfenyl chloride (yield 86
%)Obtained. Boiling point: 60 to 65 ° C / 30 mmHg.

Example 2: Synthesis of 1-chlorobutylsulfenyl chloride. Using 89 g (0.50 mol) of butyl disulfide,
Synthesis was performed by the same method as in Example 1 to obtain 140 g of 1-chlorobutylsulfenyl chloride (yield 88%). Boiling point: 68 to 75 ° C / 30 mmHg.

Example 3: Synthesis of 1-chloroisobutylsulfenyl chloride. 89 g (0.50 mol) of isobutyl disulfide were synthesized in the same manner as in Example 1, and 135 g of 1-chloroisobutylsulfenyl chloride (yield 85%).
Obtained. Boiling point: 66 to 71 ° C./30 mmHg.

Example 4: Synthesis of 3-ethyl-1,2,4-trithiolane [compound of formula (Formula 1) -1]. A 2-liter reaction flask was charged with 350 g (1.46 mol) of sodium sulfide nonahydrate, 650 g of methylene chloride and 500 g of dimethylformamide, and 1-chloropropylsulfenyl chloride 106 was stirred at room temperature.
g (0.73 mol) is added over 30 minutes, and the mixture is further reacted at room temperature for 10 hours.

After the reaction was completed, the reaction product was added to 500 g of water and the layers were separated, and the aqueous layer was extracted with hexane (500 ml × 2 times).
And wash it with saline (300 ml x
(3 times), dried over anhydrous magnesium sulfate, the solvent was recovered, and the residue was purified by distillation to obtain 81 g (yield 73%) of the compound of the formula (Formula 1) -1. Boiling point: 80 to 82 ° C./1 mmHg.

Example 5: Synthesis of 3-propyl-1,2,4-trithiolane [compound of formula (1) -2]. 1-chlorobutylsulfenyl chloride 79.5g
(0.5 mol) was synthesized by the same method as in Example 4,
62 g of the compound of the formula (Formula 1) -2 of the present invention (yield 75
%)Obtained. Boiling point: 88 to 91 ° C / 1 mmHg.

Example 6: 3-Isopropyl-1,2,4
-Synthesis of trithiolane [compound of formula (Formula 1) -3]. 19.5 g of 1-chloroisobutylsulfenyl chloride
(0.50 mol) was used and synthesized in the same manner as in Example 4 to obtain 64 g of the compound of the formula (Formula 1) -3 (yield 77
%)Obtained. Boiling point: 87-89 ° C / 1 mmHg.

[0023]

INDUSTRIAL APPLICABILITY According to the present invention, a 3-alkyl-1,2,4-trithiolane represented by a novel formula (Formula 1) can be provided. The formula compound has aroma and flavor characteristics that contribute to a flavored vegetable stimulating sensation that is characteristic of leeks, onions, garlic, and the like and a cooked meat sensation when meat is cooked, and is a flavor used for foods, livestock feed, and the like. It is useful as a formulation material for the composition.

Claims (1)

[Claims] 1. The following formula (Formula 1): (In the formula, R represents an ethyl group, a propyl group, or an isopropyl group), 3-alkyl-1,2,4-trithiolanes.