Group 15 Element Compounds N, P, As, Sb, Bi

A variety of thiocarboxylic acid ammonium salts have been synthesized by the reaction of thiocarboxylic acids with amines such as piperidine and by salt-exchange reactions of alkali metal thiocarboxylate with tetraalkylammo-nium halides [ 141,142]. Most of the lower aliphatic thiocarboxylic acid piperi- 

Thiocarboxylic acid arsenic derivatives 107 (E=S x=l-3) have been synthesized by the following four methods (1) R PhAsO+RCOSH [316] (2) R2PhAsS+ RCOBr [317] (3) Ph3 AsClx+M(ArCOS) (M=K, (CH2)4NH2) [305] (4) AS2O3+ RCOSH [to (RCOS)3As] [292]. Among these, the methods (3) and (4) are preferable in terms of yield and simplicity of procedure. A series of selenium isologues 

107 (E=Se) have been prepared in good yields using selenocarboxylic acid sodium salts or 0-trimethylsilyl esters [132,139]. Diphenylarsanyl selenocar-boxylates 107 (E=Se,x=l) also are obtained by treating piperidinium diphenyl-selenoarsinate or -diselenoarsanate with acyl chlorides [137]. 

Although antimony tris(thiocarboxylate) (RCOS)3Sb (R=CH3 [88,89],Ph [292]) can be readily obtained in good yields from stoichiometric reactions of Sb203 with thiocarboxylic acids [88,292] or SbCl3 with potassium thiocarboxylates [181], the preparation and isolation of the organoantimony thiocarboxylates 

Like the antimony derivatives, bismuth tris(arenecarbothioate) 109 (E=S x=3) can be easily prepared using the reaction of (CH3COO)3Bi [39], (PhS)3Bi [39], Bi203 [292] and BiX3 [181] as the bismuth source. The organobismuth thiocar- 

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