Amino acids dithiocarbamate synthesis

N-Bis(methylthio)methylene derivatives of amines (iminodithiocarbonates) were first introduced by Hoppe and Beckmann468 for the synthesis of a-amino acids from glycine. The A bis(methylthio)methyleneamines are prepared by reaction of a primary amine with carbon disulfide (HAZARD) in the presence of triethylamine and iodomethane to form a methyl dithiocarbamate derivative, which is then S-alkylated with a second equivalent of iodomethane in the presence of potassium carbonate as the base. Scheme 8,233 illustrates an alternative one pot procedure applied to the synthesis of /erf-butyl N-[bis(methylthio)-methylene]glycinate and its use in diastereoselective conjugate addition under... 

The X-ray crystal structures of Pt(S2CNEt2)2 and PtCl(S2CNEt2)(PPh3) show sulfur coordination of the dithiocarbamate ligand, with respective Pt-—S distances of 2.349(7) A and 2.294(7) A for S atoms tram to P and a.i804,i805 Analogous complexes can be prepared with an amino acid substituent on the dithiocarbamate. Other variations include the synthesis of bis... 

Further reports on other octahedral nickel(II) mono(dithiocarbamate) species include the synthesis of a range of 1,10-phen complexes [Ni(phen)2(S2CNR2)], in which the dithiocarbamates are derived from a-amino acids. Here, on the basis of IR and electronic spectroscopy, molecular association is proposed to occur as a result of hydrogen bonding between the NH and carboxylate groups (119). 

Even though the most widely used preparation is still the reaction of alkali isothiocyanates or alkyl and aryl isothiocyanates with a-amino carboxylic acid derivatives, the reaction of dithiocarbamic acid esters (CCX) with a-amino carboxylic acids (CCXI) has certain advantages especially in the synthesis of heterocyclically substituted imidazolidin-4-one-2-thiones (221). 

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