JPH06179663A - Production of glycidylarylsulfonates - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject compound useful as a synthetic inter mediate, etc., for agricultural chemicals and medicines in high purity and yield by adding glycidol and a tert. amine compound in this order to arylsulfonyl chlorides and reacting these components. CONSTITUTION:Glycidol and a tert. amine compound such as trimethylamine are added in this order to arylsulfonyl chlorides such as benzenesulfonyl chloride and reaction of these components is carried out to provide the objective compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing glycidyl aryl sulfonates. More specifically, it relates to a method for producing sulfonic acid ester glycidyl aryl sulfonates from glycidol and aryl sulfonyl chlorides.

[0002]

2. Description of the Related Art Glycidyl aryl sulfonates, which are the object compounds of the present invention, are important compounds as synthetic intermediates for agricultural medicine and the like. In particular, it is a compound effective in producing aryl glycidyl ether by reacting with phenol, naphthol, quinolinol and the like.

Conventionally, as a method for producing the glycidyl aryl sulfonates, a method for producing glycidyl aryl sulfonates by oxidizing allyl aryl sulfonates with a peroxide has also been used. Generally, glycidol is an aromatic hydrocarbon. Alternatively, a method of producing glycidyl aryl sulfonates by reacting with aryl sulfonyl chlorides in the presence of a tertiary amine compound in a halogenated hydrocarbon solvent is often used. At that time, it is produced by dropping the aromatic hydrocarbon or halogenated hydrocarbon solution of the arylsulfonyl chlorides into an aromatic hydrocarbon or halogenated hydrocarbon solution of glycidol and a tertiary amine compound, and then recrystallizing or reducing pressure. The method of isolation and purification by distillation is common. The manufacturing method is shown below.

1) A method in which arylsulfonyl chlorides are added to a dichloromethane or toluene solution of glycidol and triethylamine and then isolated by recrystallization [J. Org. Chem. , 51, 3701, (1
986); Org. Chem. , 54,129
5, (1989); S. P. , 49469
74]

2) A method in which a sulfonyl chloride is added dropwise to a benzene solution of glycidol and triethylamine and isolated by recrystallization or vacuum distillation [Organic Synthetic Chemistry, 22, 558, (1964)].

However, in these methods, glycidol as one of the starting materials has poor stability in the reaction system and easily causes side reactions such as polymerization, so that the yield and purity of the glycidyl aryl sulfonates formed are low. The yield of glycidyl aryl sulfonates is 37 to 59 in the above production method 1).
%, And 66 to 72% in the above production method 2). this is,
This is because the purity of the glycidyl aryl sulfonates formed is low and requires an isolation operation such as recrystallization or distillation, and these operations complicate the manufacturing process.

Further, in a halogenated hydrocarbon solvent such as dichloromethane, the solubility of the raw materials is high, but on the other hand, a large amount of by-products are produced and the yield of glycidyl sulfonates is low. On the other hand, in the case of an aromatic hydrocarbon solvent such as toluene, the yield of glycidyl aryl sulfonates is high, but the solubility of aryl sulfonyl chlorides is low, so a large amount of solvent is required. From these points as well, the conventionally known manufacturing method is not industrially preferable.

The inventors of the present invention thought that it is necessary to find an industrially useful process for producing glycidyl aryl sulfonates in addition to these conventionally known techniques, and conducted earnest studies.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have improved the charging method when glycidyl aryl sulfonates are produced by reacting glycidol with arylsulfonyl chlorides. By doing so, it is possible to produce low-colored arylsulfonyl chlorides in a high yield, and to further purify the glycidyl arylsulfonates simply by washing with water and distilling off the reaction solvent without performing recrystallization or distillation. They have found that sulfonates can be obtained, and completed the present invention.

That is, the present invention provides a method for producing glycidyl aryl sulfonates by reacting glycidol with aryl sulfonyl chlorides, in which glycidol and then a tertiary amine compound are added in this order to the reaction. And a method for producing glycidyl aryl sulfonates.

An object of the present invention is to provide a method for producing glycidyl aryl sulfonates by reacting glycidol with aryl sulfonyl chlorides, further improving the productivity, and obtaining high yield of glycidyl aryl sulfonates. And a method of manufacturing with high quality.

[0012] In the method of the present invention, a specific implementation method will be described. A predetermined amount of glycidol is added to an aromatic hydrocarbon solvent in which arylsulfonyl chlorides are dissolved or suspended, and then a predetermined amount of a tertiary amine compound is added. Add dropwise to react. The order of charging the raw materials other than the above is not preferable because it causes a decrease in the yield and quality of the obtained glycidyl aryl sulfonates. After the reaction is completed, the reaction solution obtained is washed with water to remove the hydrochloride salt of the tertiary amine compound, and then the solvent is distilled off. The yield of glycidyl aryl sulfonates in the obtained product in terms of purity is 90% or more, which is extremely high as compared with the prior art, and since the by-product of impurities is small, a complicated purification operation is required for its isolation. do not do.

The present invention is usually practiced in a solvent. The solvent used is not particularly limited as long as it is inert to the raw materials and products, but aromatic hydrocarbons are preferably used. Specific examples include benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, chlorotoluene and nitrobenzene. These solvents are usually used alone, but there is no problem in using two or more kinds of solvents together.

In the present invention, the arylsulfonyl chlorides used in the production of glycidyl aryl sulfonates by reacting glycidol with aryl sulfonyl chlorides include benzenesulfonyl chloride and p-toluenesulfonyl chloride. , O-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride and the like.

In the present invention, when glycidol is reacted with arylsulfonyl chlorides to produce glycidyl aryl sulfonates, the tertiary amine compound used is not particularly limited as long as it is a tertiary amine having an alkyl or aryl group. Not a thing. Specifically, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, tribenzylamine, tetramethylethylenediamine, N, N-dimethylaniline,
Examples thereof include N, N-diethylaniline, N-alkylpiperidines, N-alkylpyrrolidines, and substituted or unsubstituted pyridines.

In the method of the present invention, the amount of glycidol used is from 0.9 to 0.9% based on the arylsulfonyl chlorides.
The molar ratio is 1.2, preferably 0.95 to 1.10. Also, the amount of the tertiary amine compound used is 0.9 to 0.9 with respect to the arylsulfonyl chlorides.
The molar ratio is 1.2, preferably 0.95 to 1.10. There is no problem in the reaction if any of these raw materials is extremely small or too large, but it is industrially not preferable because an excessive amount of the raw material remains.

If the reaction temperature is too low, the reaction rate will be slow, and if it is too high, the reaction rate will remarkably increase, but a polymerization reaction of glycidol will occur, and on the contrary, the yield of glycidyl aryl sulfonates will be lowered. 60 ° C
The range is good.

The reaction time is not uniquely determined by the raw material concentration and the reaction temperature, but usually the reaction is completed within 20 hours, and high yield and high quality glycidyl aryl sulfonates can be obtained.

[0019]

The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Example 1 76.5 g (0.38) of p-toluenesulfonyl chloride
9 mol) was suspended in 137 g of toluene, and 32.4 g of glycidol (0.
420 mol) and then 41.4 g (0.
406 mol) was added dropwise. After that, the liquid temperature is 25 to 30 ° C.
The temperature was raised to, and the reaction was carried out for 16 hours while maintaining the same temperature. After completion of the reaction, the reaction solution was washed with 280 g of water, and the solvent was distilled off under reduced pressure to obtain 86.4 g of a product. As a result of analysis by HPLC,
The purity of glycidyl p-toluenesulfonate is 94.6.
%, And the yield in terms of purity was 92.1%.

Example 2 When 75.3 g (0.391 mol) of benzenesulfonyl chloride was used in the same manner as in Example 1, the purity of glycidyl benzene sulfonate was 93.9% and the yield in terms of purity was 9%.
It was 0.8%.

Example 3 92.6 g of p-nitrobenzenesulfonyl chloride
(0.390 mol) in the same manner as in Example 1,
Purity of glycidyl p-nitrobenzene sulfonate 9
The yield was 5.1% and the purity conversion yield was 91.4%.

Example 4 By following the same procedure as in Example 1 except that the reaction temperature was 40 to 45 ° C. for 12 hours, the purity of glycidyl p-toluenesulfonate was 91.8% and the yield in terms of purity was 90.4%. Met.

Comparative Example 1 32.4 g (0.420 mol) of glycidol was dissolved in 140 g of toluene and 41.4 g (0.406 mol) of triethylamine and then p-toluenesulfonyl were added while stirring and maintaining the temperature at 2 to 5 ° C. Chloride 76.5 g (0.
389 mol) was added dropwise. After that, the liquid temperature is 25 to 30 ° C.
The temperature was raised to and kept at the same temperature for 20 hours for reaction. After completion of the reaction, the reaction solution was washed with 280 g of water and the solvent was distilled off under reduced pressure to obtain 69.4 g of glycidyl p-toluenesulfonate. As a result of analysis by HPLC, the purity of glycidyl p-toluenesulfonate was 86.9%, and the yield in terms of purity was 67.9%.

Comparative Example 2 76.5 g (0.38 p-toluenesulfonyl chloride)
(9 mol) was suspended in 140 g of toluene, and 41.4 g of triethylamine was added while stirring and maintaining the temperature at 2 to 5 ° C.
(0.406 mol) then 32.4 g of glycidol
(0.420 mol) was added dropwise. After that, increase the liquid temperature to 25 ~
The temperature was raised to 30 ° C., and the reaction was carried out for 20 hours while maintaining the same temperature.
After completion of the reaction, the reaction solution was washed with 280 g of water and the solvent was distilled off under reduced pressure to give glycidyl p-toluenesulfonate 84.5.
g was obtained. As a result of analysis by HPLC, the purity of glycidyl p-toluenesulfonate was 87.3%, and the yield in terms of purity was 83.1%.

[0025]

According to the method of the present invention, glycidyl aryl sulfonates, which are synthetic intermediates for agricultural medicine and the like, can be obtained in high yield from glycidol and aryl sulfonyl chlorides. Moreover, the obtained glycidyl aryl sulfonates can be isolated in high yield and high quality by washing the reaction solution with water and distilling off the solvent without complicated purification operation. Therefore, it is a method for producing glycidyl aryl sulfonates which is extremely valuable industrially.

Claims (2)

[Claims] 1. A method for producing glycidyl aryl sulfonates by reacting glycidol with aryl sulfonyl chlorides, wherein glycidol and then a tertiary amine compound are sequentially added to the aryl sulfonyl chlorides and reacted. A process for producing glycidyl aryl sulfonates, which is characterized. 2. Arylsulfonyl chlorides such as benzenesulfonyl chloride, p-toluenesulfonyl chloride, o-nitrobenzenesulfonyl chloride, m-
The method according to claim 1, wherein nitrobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride, or p-chlorobenzenesulfonyl chloride is used.