Thio carbamates and their derivatives

Details Thio carbamates and their derivatives Thio carbamates and their derivatives

1986-11-26

1992-09-29

Lee, M.

Organic compounds -- part of the class 532-570 series

Organic compounds

Esters having the thiocarboxylate group, -cx-, wherein the...

558242, 558234, 558241, 564428, C07C33300, C07C21100

Patent

active

051515407

ABSTRACT:
A method is provided for preparing N-acylaminothiophenols, e.g., N-acetyl-para-aminothiophenol, or aminothiophenols, e.g., para-aminothiophenol, or N,S-diacylaminothiophenols, e.g., N,S-diacetyl-para-aminothiophenol, by reacting any of certain sulfur-containing ketones, viz., an S-(acylaryl) N,N-di(organo)thiocarbamate, e.g., S-(4'-acetophenyl)-N,N-dimethylthiocarbamate, an acylthiophenol acylate ester, e.g., 4-acetothiophenol acetate, or a free acylthiophenol, e.g., 4-acetothiophenol with hydroxylamine or a hydroxylamine salt, to form the oxime of the ketone, subjecting the oxime to a Beckmann rearrangement in the presence of a catalyst to form an S-(N-acyl-aminoaryl) N,N-di(organo)thiocarbamate, e.g., S-(N-acetyl-para-aminophenyl) N,N-dimethylthiocarbamate, an N,S-diacylaminothiophenol, e.g., N,S-diacetyl-paraaminothiophenol, or an N-acyl aminothiophenol, e.g., N-acetyl-para-aminothiophenol, respectively. The S-(N-acyl-aminoaryl) N,N-di(organo)thiocarbamate may be hydrolyzed to the N-acyl aminothiophenol or aminothiophenol. The S-(acylaryl) N,N-di(organo)thiocarbamate may be produced by reacting a hydroxy aromatic ketone, e.g., 4-hydroxyacetophenone (4-HAP) with an N,N-di(organo)thiocarbamoyl halide, e.g., N,N-dimethylthiocarbamoyl chloride (DMTC) to form an O-(acylaryl) N,N-di(organo)thiocarbamate, e.g., O-(4'-acetophenyl) N,N-dimethylthiocarbamate, and pyrolytically rearranging the latter compound. The acylthiophenol may be produced by hydrolyzing the S-(acylaryl) N,N-di(organo)thiocarbamate.

REFERENCES:
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patent: 4524217 (1985-06-01), Davenport et al.
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Pearson, et al., J. Am. Chem. Soc., 1953, pp. 5905-5908.
Newman, et al., J. Org. Chemistry, vol. 31, pp. 3980-3984 (1966).
Kwart, et al., J. Org. Chemistry, vol. 31, pp. 410-413 (1966).

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