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41.7.1.1.2 Method 2: Synthesis from Triazenes

DOI: 10.1055/sos-SD-041-00494

Kubik, S.Science of Synthesis, (201041511.

The acid-induced decomposition of alkyl(aryl)triazenes, prepared by the reaction of alkylamines with arenediazonium compounds, leads initially to alkanediazonium compounds from which the final products are formed by nucleophilic replacement of the nitrogen with the conjugated base of the acid, the solvent, or the simultaneously formed amine.[‌42‌] If decomposition of the triazene is induced by silica gel, alkyl(aryl)amines are formed in addition to the corresponding arylamine and alkyl alcohol.[‌43‌] Scheme 10 shows that the first step of the reaction consists of the tautomerization of the predominant 3-alkyl-1-aryl form of the triazene 11[‌44‌‌47‌] into the 1-alkyl-3-aryl form. Alkyl(aryl)triazenes derived from chiral alkylamines with a stereogenic center at the carbon atom carrying the amino group react preferentially with retention of configuration.[‌48‌] Detailed kinetic investigations showed that alkyl(aryl)triazenes can decompose according to three different mechanisms: buffer catalyzed, general acid catalyzed, and uncatalyzed unimolecular by NN heterolysis.[‌49‌,‌50‌] In contrast, the hydrolysis of 1,3-dialkyltriazenes has been shown to involve either specific acid or specific acid/general base catalysis depending on the type of buffer,[‌51‌,‌52‌] whereas 1,3,3-trialkyltriazenes[‌53‌] and 1-alkyl-3-pyridyltriazenes[‌54‌] have been shown to decompose exclusively by a specific acid-catalyzed pathway.

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