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Mechanisms of Diazo Coupling Reactions. Part XXXII. The Diazoamino Rearrangement in 20% Acetonitrile/Aqueous Buffers

✍ Scribed by Richard P. Kelly; John R. Penton; Heinrich Zollinger

Publisher: John Wiley and Sons
Year: 1982
Tongue: German
Weight: 591 KB
Volume: 65
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19820650112

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✦ Synopsis

Abstract

The rearrangements of 4′‐methoxy‐N‐methyl‐ and N‐methyl‐4′‐nitro‐diatzoaminobenzene have been studied in 20% acetonitrile/aqueous buffers. The reactions are specifically acid catalyzed and involve pre‐equilibrium formation of amine and diazonium salt followed by rate‐limiting attack of the diazonium ion at a C‐atom (C‐coupling) to give the corresponding aminoazo compounds. There is no evidence to suggest that, under the present conditions, mechanisms other than the established Friswell‐Green mechanism occur. The traditional two‐stage synthesis of aminoazo compounds via isolated diazoamino compounds can therefore be replaced by a one stage process for amines which undergo initial attack at a N‐atom by diazonium ion (N‐coupling).

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Mechanisms of Diazo Coupling Reactions.

Mechanisms of Diazo Coupling Reactions. Part XXXI. Aminoazo formation in the diazo coupling of N, N-dimethylaniline and m-toluidine with p-methoxybenzenediazonium tetrafluoroborate in acetonitrile

✍ John R. Penton; Heinrich Zollinger 📂 Article 📅 1981 🏛 John Wiley and Sons 🌐 German ⚖ 615 KB

## Abstract In the title reactions it is shown that aminoazo formation does not occur by direct attack of diazonium ion at C‐atom. Initial attack is at N‐atom, but proton loss from the ω~N~‐complex formed is relatively slow. Hence, at low amine concentration this rearranges intermolecularly to the