JP4476386B2 - Preparation of cyclic disulfides - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing cyclic disulfides, and more particularly, the present invention relates to 1,4-dihalogenopentan-3-one, 2,4-dihalogenopentan-3-one and 3,5-dihalogeno-2-one. 3-methyl-1,2-dithian-4-one, 3,5-dimethyl-1,2-dithiolane-4-one and 3 characterized by reacting dihalide selected from pentanone with sodium hydrosulfide It relates to a process for the preparation of cyclic disulfides selected from -acetyl-1,2-dithiolane .
[000 2 ]
[Prior art]
Cyclic disulfides are useful compounds as various synthetic raw materials, and certain cyclic disulfides have aroma such as meat-like, onion-like, shiitake-like, and are shown to be useful as fragrance compounds. (J. Agric. Food Chem., 38, 2027-2041, 1990).
[000 3 ]
As a method for producing cyclic disulfides, for example, a method of producing a cyclic disulfide by cyclizing a dibromo compound in the presence of lithium disulfide (Flavour Fragrance J., 13, 177-184, 1998), 5-hydroxy-2-pentanone is used. As a starting material, a process for producing 3-acetyl-1,2-dithiolane via four steps (J. Agric. Food Chem., 38, 2027-2041, 1990), butane-1,4-dithiol or propane- A method for producing 1,2-dithiane or 1,2-dithiolane by oxidizing 1,3-dithiol (SYNTHESIS, (11), 1587-1589, 1998), metal sulfide and halogen, sulfur dichloride or monochloride Production of cyclic polysulfide to react with sulfur The method (JP 56-164181 JP), and manufacturing method of the disulfide compound which comprises reacting a specific halide thiol compound (JP 60-36456 JP) have been proposed.
[000 4 ]
However, the process for producing cyclic disulfides shown in the above prior art has disadvantages such as low yield, expensive raw materials, or complicated processes.
[000 5 ]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a method for producing cyclic disulfides by a simpler method with a good yield using an inexpensive raw material.
[00 06 ]
[Means for Solving the Problems]
Accordingly, as a result of intensive studies to solve the above-mentioned problems, the present inventors can obtain cyclic disulfides with a good yield by a simple method of reacting the above-mentioned dihalide with sodium hydrosulfide. As a result, the present invention was completed.
[00 07 ]
Accordingly, the present invention provides a reaction of sodium hydrosulfide with a dihalide selected from 1,4-dihalogenopentan-3-one, 2,4-dihalogenopentan-3-one and 3,5-dihalogeno-2-pentanone. A ring selected from 3-methyl-1,2-dithian-4-one, 3,5-dimethyl-1,2-dithiolane-4-one and 3-acetyl-1,2-dithiolane Methods for making disulfides are provided.
[00 08 ]
DETAILED DESCRIPTION OF THE INVENTION
Cyclic disulfides above Symbol of the present invention can be produced easily and KoOsamu ratio by reacting the dihalide and sodium hydrosulfide above.
[00 09 ]
The above-mentioned dihalides used for the reaction are readily available on the market. For example, the corresponding monohalides and, for example, sulfuryl chloride, sulfuryl bromide, cupric chloride, cupric bromide, It can be easily synthesized by reacting a halogen adduct such as chlorine and bromine. Specific examples thereof include 1,4-dichloropentane-3-one and 2,4-dibromopentane-3-one. , it may be mentioned 3,5-dichloro-2-pentanol down.
[001 0 ]
In addition, sodium hydrosulfide used in the present invention is also easily available on the market, and the amount used can be appropriately selected. For example, about 2 to 10 mole times the amount of the above-mentioned dihalide of the raw material, more preferably A range of about 2 to 4 mole times can be exemplified.
[001 1 ]
The reaction can be performed directly or in the presence of a catalyst. Examples of the catalyst include trioctylmethylammonium chloride, tetrabutylammonium chloride, and benzyltrimethylammonium chloride, and the amount used is also appropriately selected. For example, a range of about 1 to 10% by weight can be preferably exemplified with respect to the raw material dihalide .
[00 12 ]
The reaction is usually carried out in the presence or absence of an organic solvent, preferably in the presence of an organic solvent, with stirring at a temperature of 20 ° C. to 30 ° C. for 3 hours to 10 hours. Examples of the organic solvent that can be used here include ether, tetrahydrofuran, hexane, toluene, and the like. The amount used can be usually 1 to 10 times the weight of the dihalide .
[00 13 ]
After completion of the reaction, if desired, extraction with an extractant such as ether, washing with an aqueous alkali solution, and distillation under reduced pressure can easily produce the desired cyclic disulfides in good yield.
[00 14 ]
Specific example above cyclic disulfides of the present invention, 3 - methyl-1,2-dithiane-4-one, 3,5-dimethyl-1,2-dithiolane-4-one, 3-acetyl -1 , it can be exemplified 2-Jichiora down.
[00 15 ]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[00 16 ]
Example 1 (Synthesis of 3-methyl-1,2-dithian-4-one)
A 500 ml four-necked flask was charged with 76.8 g (0.96 mol) of 70% sodium hydrosulfide, 1.0 g (2.47 mmol) of trioctylmethylammonium chloride and 300 ml of ether, and stirred at room temperature. To this, 37.2 g (0.24 mol) of 1,4-dichloropentan-3-one was added and stirred at room temperature for 3 hours, and then 100 ml of water was added to the reaction solution and stirred overnight. Thereafter, the ether layer was washed, dried, and the solvent was recovered. The crude product was distilled under reduced pressure to obtain 21.7 g (yield 61.1%) of the desired product.
[00 17 ]
Example 2 (Synthesis of 3,5-dimethyl-1,2-dithiolan-4-one)
A 500 ml four-necked flask is charged with 96.0 g (1.2 mol) of 70% sodium hydrosulfide, 200 ml of ether and 1 g (2.47 mmol) of trioctylmethylammonium chloride and stirred under ice-water cooling. An ether solution (100 ml) of 2,3.2-dibromopentan-3-one (73.2 g, 0.3 mol) is added dropwise thereto at 10 ± 5 ° C./1 hour, and the mixture is stirred at room temperature for 3.5 hours. After completion of the reaction, the ether layer was washed, dried, solvent recovered, and distilled under reduced pressure to obtain 28.1 g (yield 63.3%) of the desired product.
[00 18 ]
Example 3 (Synthesis of 3-acetyl-1,2-dithiolane)
In a 500 ml reaction flask, 19.2 g (0.24 mol) of 70% sodium hydrosulfide is charged and stirred under ice-water cooling. An ether solution (100 ml) of 8.8 g (0.057 mol) of 3,5-dichloro-2-pentanone was added dropwise thereto at 0 to 10 ° C. over 1 hour. After dropping, the mixture was stirred at room temperature for 3 hours, and the supernatant was distilled under reduced pressure to obtain 5.3 g of the desired product (yield 63.1%) .
[00 19 ]
【The invention's effect】
INDUSTRIAL APPLICABILITY According to the present invention, cyclic disulfides useful as various synthetic raw materials and perfume compounds can be produced in a good yield and with a simpler method using inexpensive raw materials, which is extremely useful.

Claims (1)

Characterized by reacting sodium hydrosulfide with a dihalide selected from 1,4-dihalogenopentan-3-one, 2,4-dihalogenopentan-3-one and 3,5-dihalogeno-2-pentanone. A process for preparing cyclic disulfides selected from 3-methyl-1,2-dithian-4-one, 3,5-dimethyl-1,2-dithiolane-4-one and 3-acetyl-1,2-dithiolane .