JPH0449540B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing phenyl chlorothioformates. Phenyl chlorothioformates are extremely useful as intermediates for pharmaceuticals and agricultural chemicals. [Prior Art] It is known that phenyl chlorothioformates can be produced by the reaction of phenols and thiophosgene in the presence of a dehydrohalogenating agent. [Problems to be solved by the invention] Since thiophosgene is highly toxic, it must be handled with great care. Considering abnormal situations such as leakage, it is desirable to avoid storing or moving large quantities as much as possible. An object of the present invention is to avoid storing or transferring large amounts of thiophosgene and to easily and safely produce phenylchlorothioformates. [Means for Solving the Problems of the Invention] As a result of intensive study of various tests, the present inventors found that
Phenyl chlorothioformates can be produced by adding phenols and perchloromethyl mercaptan to a mixed solvent of an organic solvent and water, then blowing sulfur dioxide into the mixed solvent, and then adding a dehydrohalogenation reagent. They discovered this and completed the present invention. [Function] Next, the method of implementing the present invention will be described in detail. Perchloromethyl mercaptan is added to the mixed solvent of an organic solvent and water in an amount equal to or more than about the same molar amount as the phenol. Examples of the organic solvent include chlorinated hydrocarbons such as chloroform, dichloromethane, and carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene, and xylene. It is desirable to use water at least about twice the mole of perchloromethyl mercaptan. A small amount of alkali metal iodide can be added to facilitate the reaction. Sulfur dioxide is blown into the mixed solution in an amount of approximately equal to 20 times the mole of perchloromethyl mercaptan, and then a dehydrohalogenation reagent is added. Examples of dehydrohalogenation reagents include inorganic bases such as alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal carbonates, and organic bases such as triethylamine, pyridine, quinoline, and isoquinoline. , sodium hydroxide, potassium hydroxide, and other alkali metal hydroxides are used by dissolving them in water. The dehydrohalogenation reagent may be used in an amount approximately equivalent to that of phenol, provided that the aqueous layer is removed from the reaction solution before addition. The reaction temperature is usually about -10°C to room temperature, and the reaction can be completed within about 10 hours. [Effects of the invention] A simple and safe method can be obtained by adding phenols and perchloromethyl mercaptan to a mixed solvent of an organic solvent and water, then blowing sulfur dioxide into the mixed solvent, and then adding a dehydrohalogenation reagent. phenyl chlorothioformates can be produced. Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 1 with stirrer, thermometer and 300ml dropping funnel
In a three-necked flask, add 60 g of 3-tert-butylphenol, 75 g of perchloromethyl mercaptan, 240 ml of carbon tetrachloride, 240 ml of water, and 3 ml of potassium iodide.
g was removed and the flask was cooled on ice. Then 100 g of sulfur dioxide was bubbled into the solution with stirring. The temperature inside the flask was maintained at 0-10°C. After blowing in sulfur dioxide, the aqueous layer was removed from the reaction solution, and 42 ml of a 40% aqueous sodium hydroxide solution was added dropwise to the remaining organic layer. After the dropwise addition, the mixture was further stirred for 2 hours. After the reaction is complete,
The organic layer was separated from the reaction solution and distilled to obtain 46.6 g of 3-tert-butylphenyl chlorothioformate. The yield of 3-tert-butylphenyl chlorothioformate was 51% based on 3-tert-butylphenol. The physical properties of the obtained 3-tert-butylphenyl chlorothioformate were as follows. Elemental analysis (%) C H Cl S Analysis value 57.86 5.84 15.47 14.06 Calculated value 57.76 5.72 15.50 14.02 Infrared absorption spectrum (NaCl: cm ^-1 ) 2960, 1618, 1582, 1494, 1242, 1010 Examples 2 to 4 Examples The phenols shown in Table 1 were placed in the same reaction apparatus as in Example 1, and the phenols shown in Table 1 were reacted under the reaction conditions shown in Table 1, followed by the same treatment as in Example 1 to obtain phenyl chlorothioformates. The results are shown in Table-1. The obtained 5,6,7,8-tetrahydro-2-
The physical properties of naphthyl chlorothioformate were as follows. Elemental analysis (%) C H Cl S Analytical value 57.91 4.87 15.89 14.01 Calculated value 58.72 4.89 15.64 14.14 Infrared absorption spectrum (NaCl: cm ^-1 ) 2930, 1616, 1588, 1496, 1250, 1008 Obtained 4-methylphenyl chloro The physical properties of thioformate were as follows. Elemental analysis (%) C H Cl S Analytical value 51.25 3.57 19.12 17.02 Calculated value 51.47 3.77 18.99 17.17 Infrared absorption spectrum (NaCl: cm ^-1 ) 3030, 2920, 1598, 1502, 1250, 1010 Obtained phenyl chlorothiophor The physical properties of the mate were as follows. Elemental analysis (%) C H Cl S Analysis value 48.96 2.71 20.31 18.63 Calculated value 48.70 2.91 20.53 18.57 Infrared absorption spectrum (NaCl: cm ^-1 ) 3060, 1600, 1590, 1488, 1240, 1008 [Table]

Claims (1)

[Claims] 1 Phenyl chlorothioformates characterized by adding phenols and perchloromethyl mercaptan to a mixed solvent of an organic solvent and water, then blowing sulfur dioxide into the mixed solvent, and then adding a dehydrohalogenation reagent. manufacturing method.