Thioformate, O-ethyl

The mechanism of the condensation in Part D probably involves thioformylation of the metallated isocyanoacetate followed by intramolecular 1,1-addition of the tautomeric enethiol to the isonitrile. This thi2izole synthesis is analogous to the formation of oxazoles from acylation of metallated isonitriles with acid chlorides or anhydrides. " Interestingly, ethyl formate does not react with isocyanoacetate under the conditions of this procedure. Ethyl and methyl isocyanoacetate have been prepared in a similar manner by dehydration of the corresponding N-formylglycine esters with phosgene and trichloromethyl chloroformate, respectively. The phosphoryl chloride method described here was provided to the submitters by Professor U. Schollkopf and is based on the procedure of Bohme and Fuchs. The preparation of O-ethyl thioformate in Part C was developed from a report by Ohno, Koi/.uma, and Tsuchihaski. " ... 

O-Ethyl thioformate Formic acid, thio-, O-ethyl ester (8) Methanethioic acid, O-ethyl ester (9) (29392-46-9)... 

A one-pot synthesis of 4-substituted 3-amino-2-cyanothiophenes involving o-ethyl thioformate was reported (140L2522). The thiophene core in these 4-subsitututed 2-cyanothiophenes can be readily incorporated into more elaborate pharmaceutically relevant structures as... 

O-Ethyl thioformate added dropwise at room temp, during 10 min. to an ethanolic soln. of benzophenone hydrazone, and stirred until HgS-evolution ceases -> N2,N -bis(diphenylmethylene)formohydrazide hydrazone. Y 77%. F. e. s. P. Jakobsen, Acta Chem. Scand. B29, 281 (1975). 

A soln. of O-ethyl thioformate and ethyl isocyanoacetate in dry ethanol added drop wise with vigorous stirring to an ethanolic suspension of NaCN, and warmed 0.5 hr. at 50° ethyl thiazole-4-carboxylate. Y 92%. F. e. s. G. D. Hartman and L. M. Weinstock, Synthesis 1976, 681. 

OGEN DISULFIDE DITHIOBIS(THIOFORMIC ACID)-o,o-DIETHYL ESTER DIXANTHOGEN ETHYL XANTHOGEN DISULFIDE EXD K PREPARATION THIOPEROXYDICARBONIC ACID DIETHYL ESTER... 

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