Methyl dithiophenylacetate

Prior to the 1947 report by Cook and Heilbron on their novel synthesis, 5-aminothiazoles were mostly unknown in the literature. Previous syntheses included the Curtius degradation of ethyl thiazole-5-carboxylates which did not have general applicability there was also difficultly in obtaining the necessary starting materials. During a study on penicillin, Cook and Heilbron found that the reaction between methyl dithiophenylacetate and ethyl aminocyanoacetate gave what was initially believed to be ethyl phenylthionacetamidocyanoacetate 4. However further studies proved the compound to be 5-amino-4-carbethoxy-2-benzyl-thiazole 5, which was basic. 

The synthesis of 5-amino-4-carbethoxy-2-benzylthiazole 17 via the reaction of ethyl aminocyanoacetate 15 with methyl dithiophenylacetate 16 provided the first general synthesis of the previously little known 5-aminothiazoles. Similarly, the reaction between aminoacetonitrile 18 and sodium dithiophenylacetate 19 at room temperature gave 5-amino-2-benzylthiazole 20 in excellent yield. 

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