Abstract
Condensation of β-bromovinyl ether or acetate with sodium p-nitrothiophenoxide in absolute alcohol gives β-(p-nitrophenylmercapto)-vinyl ether or acetate which, by bromination, yield α, β-dibromo-β-(p-nitrophenylmercapto) -ethyl ether (Va) or acetate (Vc), respectively. By warming (Va) or (Vc) with an equivalent quantity of thiourea in dil. alcohol, 2-amino-5-(p-aminophenylmercapto) -thiazole is obtained. Condensation of glycerol-α-chlorohydrin with sodium p-nitrothiophenoxide gives 1-(p-nitrophenylmer-capto)-2, 3-dihydroxypropane (XII), which is oxidized to 1-p-nitrophenylsulfonyl-2, 3-dihy-droxypropane (XIII) with perhydrol in glacial acetic acid. (XII) and (XIII) are oxidized to p-nitrophenylmercaptoacetaldehyde (IX) and sulfonyl-acetaldehde (X), respectively, with lead tetraacetate in glacial acetic acid. The enol acetates of (IX) and (X), obtained by the acetylation of (IX) and (X) with acetic anhydride and glacial acetic acid, are tre atedwith one mole of bromine and condensed with thiourea by which 2-amino-5-(p-nitrophenylmercapto)-thiazole and -sulfonylthiazole are respectively obtained. The former can also be prepared from (IX) by bromination followed by condensation with thiourea. 2-Amino-5-(p-tolylmercapto)-thiazole and -sulfonylthiazole can also be prepared by the same method from 1-(p-tolylmercapto)- and 1-(p-tolylsulf onyl)-2, 3-di-hydroxypropane.
