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18.2.6.1.3.1 Variation 1: Synthesis of Dithiocarbamates

DOI: 10.1055/sos-SD-018-00070

Braverman, S.; Cherkinsky, M.; Birsa, M. L.Science of Synthesis, (200518174.

The nucleophilic addition of an amine to carbon disulfide provides derivatives of dithiocarbamic acid. Since the free acids thus obtained are unstable, the reaction is conducted in the presence of a base or using an excess of amine in order to isolate the corresponding dithiocarbamate salts. Although, in most cases, crude dithiocarbamates are pure enough for subsequent transformations, their purification is a challenging problem. Usually, this is achieved by recrystallization, but the yields can be very low since the dithiocarbamates may decompose, particularly upon heating. A high-yield preparative procedure for the synthesis of pure dithiocarbamates has been accomplished via temporary protection of this functional group. Thus, reaction of amines with carbon disulfide in the presence of 0.5 equivalents of bis(tributyltin) oxide provides stannyl dithiocarbamates 332 in high yields. These compounds are stable toward water, alcohols, amines, or strong nonnucleophilic bases and can be safely purified by various methods. Pure stannyl dithiocarbamates are converted quantitatively into the corresponding sodium salts 333 by treatment with sodium hydrogen sulfide (Scheme 169).[‌658‌]

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