N-Dithiocarboxylation

Abbreviations used salen, ethylenebis(salicylaldimine) pyrr-dtc, pyrrolidine-N-dithiocarboxylate PPIXDME, protoporphyrin IXdimethyl ester S2-o-xyl, a,a-dimercapto-o-xylene... 

Tetramethyleneaminocarbodithioic acid (pyrrolidine-N-dithiocarboxylic 57Ja,69JA,73SSC acid) (C H NS2)... 

Pentamethyleneaminocarbodithioic acid (piperidine-N-dithiocarboxylic 57Ja,73SSC acid)... 

Katritzky, A.R., Ch.V Marson, and H. Faid-AUah. 1987. Heterocyclic N-dithiocarboxylic acids. Heterocycles 26 1657-1670. 

Kano N, Kawashima T (2005) Dithiocarboxylic Acid Salts of Group 1-17 Elements (Except for Carbon). 251 141-180... 

Thione-S-oxides react regiospecifically with allyl and benzylsilanes in the presence of a stoichiometric amount of tetra-n-butylammonium fluoride to produce allyl and benzyl sulphoxides [8], cf. the analogous fluoride initiated reaction of thio-ketones and dithiocarboxylic esters with silanes [9, 10]. The yields of sulphoxides... 

BC13 convert 0=0 groups of ketones, lactones, and lactams to G=S groups119 and H2S-Me3SiCl-i-Pr2NLi converts carboxylic esters to thiono esters.120 Carboxylic acids RCOOH can be converted directly to dithiocarboxylic esters RCSSR, 120a in moderate yield, with P4S, and a primary alcohol R OH.121 Thioketones can also be prepared by treatment of ketones with P4SI0,122 and from oximes or various types of hydrazone (overall conversion C=N------> C=S).123... 

Fluorodcsulfurizations of thiols,311 phenyl thioglycosides,290 1,2-dithiolans.312 aromatic dithiocarboxylic acids,399 or orthothioesters313 in hydrogen fluoride systems with N-chloro-or N-bromosuccinimide as a coagcnt are facile methods for the generation of monofluorides, gem-difluorides, and trifluoromethyl derivatives, e.g. formation of 11,311 12,312 13,313 and... 

Nag et al. have investigated the coordination chemistry of ligands related to or derived from 2-aminocyclopentene-l-dithiocarboxylic acid, concluding N—S bidentate behaviour for the complexes in general.103 With MoVI, however, this ligand and iV-alkyl derivatives are observed to function rather as S—S bidentates.104... 

Perregaard, J. and Lawesson, S. O., Studies on organophosphorus compounds - XVI. On 0,0-Dialkyl dithiophosphoric acids and N,N,N, N -tetramethylthiophosphoric diamide as thiation agents conversion of carboxamide into thiocarboxamides, alkyl dithiocarboxylates, or nitriles, Bull Soc. Chim. Belg., 1977, 86,321. 

Tellurium bis[dithiocarboxylates] lose one dithiocarboxylate group in reactions with equimolar amounts of chlorine, bromine, iodine, (V-chlorosuccinimide, or N-bromosuccinimide. The products, tellurium dithiocarboxylate halides, precipitate from the reaction mixtures . 

An interesting example of a Lewis acid/base reaction between neutral reactants is the formation of tris(n-butyl)phosphonium-dithiocarboxylate, ( -Bu)3P" — 82 , from tris(n-butyl)phosphane and carbon disulfide in solution. As expected, this equilibrium is strongly shifted in favour of the dipolar zwitterion with increasing solvent polarity (diethyl ether dimethyl sulfoxide) [272, 273]. 

Another remarkable example of reaction type (c) in Table 5, somewhat related to the Menschutkin reaction, is the Sn2 reaction between tris(n-butyl)phosphane and carbon disulfide, to give zwitterionic tris( -butyl)phosphonium dithiocarboxylate via a corresponding dipolar activated complex [790, 791],... 

Complexes with other dithiocarboxylates such as n-C6Hi3CS2 (Fig. 10) (37), PhCH2CS2 (38,39), and Me2CHCS2 (38—40) have been reported. 

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