Process for producing thionocarboxylic acid ester
A technology of aryl thiocarboxylates and sulfur halides, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of strong toxicity of hydrogen sulfide, low synthesis yield of thiocarboxylic acid chlorides, Not suitable for industrial manufacturing methods and other issues
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Embodiment 1
[0087] Under a nitrogen atmosphere, magnesium (1.6 g, 64.0 mmol), LiCl (2.7 g, 64.0 mmol) and tetrahydrofuran (hereinafter referred to as "THF") (10.0 mL ). After adding chlorobenzene (7.2 g, 64 mmol), the mixture was stirred at room temperature for 2 hours to prepare a Grignard compound.
[0088] Subsequently, under a nitrogen atmosphere, phenyl chlorothioformate (11.0 g, 64.0 mmol), tris(2,4-pentanedione)iron(III) were added to a 200 mL three-necked flask equipped with a stirring bar and a thermometer ((Fe(acac) 3 )) (0.7 g, 1.9 mmol) and THF (50.0 mL). After cooling the mixture to -30°C, the Grignard compound obtained through the above process was added, and the resulting mixture was stirred for 2 hours to complete the reaction.
[0089] The mixture was brought to room temperature and extracted with toluene / hydrochloric acid. The organic layer was evaporated under reduced pressure. The resulting solid was purified by silica gel column chromatography to provide phenylth...
Embodiment 2～19
[0091] Using the starting materials shown in Table 1 and Table 2, the reaction was performed in the same manner as in Example 1. Tables 1 and 2 show the species and yields of the obtained products. Each Grignard compound shown in the compound (2) column of the table was obtained by reacting magnesium with a halide that is a precursor of each Grignard compound in the same manner as in Example 1. The values shown in the catalyst column of the table are catalyst amounts expressed in mol% relative to compound (1).
[0092] Table 1
[0093]
[0094] *Depend on 19 FNMR determination
[0095] Table 2
[0096]
[0097] *Depend on 19 FNMR determination
Embodiment 20
[0099] Under a nitrogen atmosphere, magnesium (1.6 g, 64.0 mmol), dibromoethane (0.6 g, 3.2 mmol) and cyclopentyl methyl ether (CPME) were added to a 50 ml three-necked flask equipped with a stirring bar and a thermometer ( 10.0 mL). After bromocyclohexane (10.4 g, 64 mmol) was added, the mixture was stirred at 60°C for 1 hour to prepare a Grignard compound.
[0100] Subsequently, under a nitrogen atmosphere, phenyl chlorothioformate (11.0 g, 64.0 mmol), 0.1 M dilithium tetrachlorocopper(II) was added to a 200 mL three-necked flask equipped with a stirring bar and a thermometer. Tetrahydrofuran solution (19 mL, 1.9 mmol) and THF (10 mL). After cooling the mixture to -30°C, the Grignard compound obtained through the above process was added, and the resulting mixture was stirred for 2 hours to complete the reaction. The mixture was brought to room temperature and extracted with toluene / hydrochloric acid. The organic layer was evaporated under reduced pressure. The resulting ...
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