Reduktive Spaltungen von Sulfamiden

Abstract

Sulfamide aliphatischer und aromatischer Amine werden durch reduktive Spaltung sowohl in alkalischem Medium (durch Natrium und Alkohole) als auch in saurer Lösung (durch Zink und Säuren, Zinn(II)‐chlorid) glatt zu den betreffenden Aminen zerlegt. Zum Studium des Reaktionsverlaufes wurde das Verhalten der möglichen Zwischenprodukte untersucht; demnach dürfte die Primärreaktion unter Bildung von Amin und Sulfinsäure verlaufen. Im sauren Medium erfolgt neben der reduktiven eine katalytische Spaltung. N‐Alkyl‐sulfanilide lassen sich auch durch Natriumamylat glatt unter Bildung von Amin und Sulfonsäure aufspalten.

Cleavage And Rearrangement Of Sulfonamides

“…The former greatly reduced the rate so that very little reaction occurred, while the latter gave rise to cleavage of the carbon-sulfur bond, as well as the nitrogen-sulfur bond (64). Similar results have been obtained with iV-substituted p-toluenesulfonamides (33). These results may be rationalized in terms of a recently proposed mechanism in which the conjugate acid of the sulfonamide is pictured as dissociating into amine and an intermediate sulfonylonium ion (34).…”

“…The maximum amount of secondary amine was obtained by using 60 per cent sulfuric acid in the case of iV-methyl-p-toluenesulfon-p-anisidide (13). For N-alkyl-p-toluenesulfonanilides with /V-alkyl groups up to butyl, the use of 85 per cent sulfuric acid is reported to be best (33).…”

The reaction of iodobenzene-p-sulphonyl chloride (pipsyl chloride) with certain amino acids and peptides, and with insulin

“…The stabilities of pipsylamino acids to acid hydrolysis are only moderate, the iodine atom having little tendency to decrease the basicity of the sulphonamide and thus to decrease the ease of formation of the conjugate acid, through which the reaction is thought to proceed (Klamann & Hofbauer, 1953). As might be expected, the stabilities of pipsylamino acids are much less influenced by the presence of other substances in the hydrolysate than are the stabilities of DNPamino acids.…”

Chemical synthesis of the 5-taurinomethyl(-2-thio)uridine modified anticodon arm of the human mitochondrial tRNALeu(UUR) and tRNALys

“…The masking of sulfonic acids as sulfonamides or ammonium salts has also been proposed (Klamann and Hofbauer 1953;Richman and Atkins 1974;Andrianov et al 2004). The cleavage of most of the reported protecting groups employs, however, strongly acidic or basic conditions unsuitable for oligoribonucleotide synthesis.…”