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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

✍ Scribed by John R. Penton; Heinrich Zollinger

Publisher: John Wiley and Sons
Year: 1981
Tongue: German
Weight: 615 KB
Volume: 64
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19810640603

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✦ Synopsis

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 aminoazo derivative. At high amine concentration a second method of aminoazo formation can take place involving attack of an amine molecule on the ω~N~‐complex or on a molecular complex formed between the diazonium ion and the amine. Implication of these proposals for the diazoamino rearrangement are discussed.

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Mechanisms of Diazo Coupling Reactions.

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✍ John R. Penton; Heinrich Zollinger 📂 Article 📅 1981 🏛 John Wiley and Sons 🌐 German ⚖ 607 KB

## Abstract The __N__‐diazo coupling of __p__‐chloroaniline with __p__‐chlorobenzenediazonium tetrafluoroborate in acetonitrile at 30° shows non‐linear base catalysis by water. The results are interpreted in terms of the __S__~__E__~2 mechanism with rate‐limiting proton loss at low base concentrati

Mechanisms of Diazo Coupling Reactions.

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

✍ Richard P. Kelly; John R. Penton; Heinrich Zollinger 📂 Article 📅 1982 🏛 John Wiley and Sons 🌐 German ⚖ 591 KB

## 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 at