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18.12.11.1.3 Method 3: By the Alkylation of Dithiocarbamates

DOI: 10.1055/sos-SD-018-01132

Gilchrist, T. L.Science of Synthesis, (2005181044.

The S-alkylation of dithiocarbamate esters 138 is the method most widely used for the preparation of carbonimidodithioates. Dithiocarbamates are in turn made from amines and carbon disulfide under basic conditions, via the salts 137 or 140, so the method has several practical variations. These include one-pot procedures starting from compounds that incorporate the primary amino group, such as carboxamides, sulfonamides and cyanamides. The overall reaction sequence is outlined in Scheme 62.[‌67‌,‌203‌,‌224‌,‌267‌‌273‌] Either symmetrically substituted diesters or unsymmetrically substituted diesters 139 can be prepared by an appropriate choice of conditions. Phenacyl chloride reacts with the salt 137 (R1=NHTs; M=K) to give the 2-hydrazono-1,3-dithiolane 141 (yield 72%), which can be dehydrated to the dithiole 142 (Scheme 62); other α-halogenated ketones react similarly.[‌267‌]

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