Reaktionen mit Δ²‐Thiazolinonen‐(5), II. Umlagerung von 4‐Arylazo‐2‐benzylmercapto‐Δ²‐thiazolinonen‐(5) in 1.2.4‐Triazol‐Derivate

Abstract

Beim Behandeln von 4-Arylazo-2-benzylmercapto-A~-thiazolinonen-(5) (3a, b) rnit athanol. KOH tritt Umlagerung zu l-Aryl-A~-triazolinthion-(5)-carbonsauren-(3) (4a, b) ein. Andererseits reagieren 3a, b rnit k h a n 0 1 in Gegenwart von Schwefelsaure zu Athylestern (5a, b) der I-Aryl-5-benzylmercapto-lH-l.2.4-triazolcarbonsauren-(3). -Wahrend 3a-c rnit aromatischen Aminen oder Phenylhydrazin zu Benzylmercaptotriazol-Derivaten 5f -1 reagieren, bilden sich bei der Umsetzung von 3a, b rnit Methylamin oder Piperidin die Triazolinthion-Derivate 4c-f. Die Benzylmercapto-Derivate 5fh werden durch H202 zu den Benzylsulfonyl-Derivaten 7a-c oxydiert. 4-Arylazo-2-alkoxy-A2-thiazolinone-(5) (10a-f) werden beim Behandeln rnit aromatischen Aminen zu den Triazol-Derivaten 11 aj umgelagert. Reactions with 2-Thiazoline-fi-ones, I U ) . Rearrangement of 4-

Novel Rearrangement of 5-Arylazo-2-thiohydantoin Derivatives with Alkali and Aromatic Amines

“…231 °C. It was identical with an authentic sample by melting point and mixed melting point determinations [8].…”

“…This proved that the phenyl group connected to the nitrogen at position-1 stabilized the hetero-ring of 2-thiohydantoin. The structure of these products (8a-h) was inferred from the analytical data and the formation of the appropriate acid; when 8a was hydrolysed with 70% alcoholic potassium hydroxide afforded 1 -phenyl -A 2 -1,2,4-triazoline -5 -thione -3 -carboxylic acid [8]. Also 8 a was alkylated with benzyl chloride in alkyline medium and the corresponding 1-phenyl -5 -benzy Imercapto -1 H -1,2,4 -triazole -3 -car boxy anilide was separated, which on refluxing with hydrochloric acid solution till the odour of the benzylthiol could not be detected, l-phenyl-zl 2 -l,2,4-triazoline-5-one-3-carboxyanilide was separated which was proved by an authentic sample [8].…”