Organische Synthesen im Plasma von Glimmentladungen. XIII¹⁾ Umlagerungen von N‐alkylierten in kernalkylierte Aniline²⁾

Abstract

N‐Alkylaniline lagern sich in Glimmentladungen in ortho‐ und para‐substituierte Aniline um. Parallel dazu laufen eine Entalkylierungsreaktion sowie die Bildung von N‐Methylenanilinen ab. Die Reaktion verläuft über Ion‐Molekül‐Komplexe.

Photorearrangement of Quinoline-Protected Dialkylanilines and the Photorelease of Aniline-Containing Biological Effectors

“…The rearrangement of N -alkylanilines to ring-alkylated products was first described by Hofmann in the 19th century , and later investigated by several other groups. − The reaction requires harsh conditions and furnishes a mixture of para- and ortho-rearranged products (generally preferring the para isomer) in low to moderate yields together with numerous side products. The photochemical equivalent of this rearrangement has also been described; it generates a mixture of regioisomers, favoring the ortho derivative. , The reaction requires high irradiation power, causing the formation of a complex mixture of byproducts and ultimately resulting in low yields. Ogata and Takagi investigated the photochemical rearrangement of N -alkylanilines, but the study was limited to para-blocked anilines and probed only the electronics of the migrating benzylic group.…”

“…The photochemical equivalent of this rearrangement has also been described; it generates a mixture of regioisomers, favoring the ortho derivative. 39,40 The reaction requires high irradiation power, causing the formation of a complex mixture of byproducts and ultimately resulting in low yields. Ogata and Takagi investigated the photochemical rearrangement of N-alkylanilines, 41 but the study was limited to para-blocked anilines and probed only the electronics of the migrating benzylic group.…”