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Mechanisms of Diazo Coupling Reactions. Part XXXII. The Diazoamino Rearrangement in 20% Acetonitrile/Aqueous Buffers
Author(s) -
Kelly Richard P.,
Penton John R.,
Zollinger Heinrich
Publication year - 1982
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19820650112
Subject(s) - chemistry , diazo , acetonitrile , aqueous solution , amine gas treating , salt (chemistry) , ion , limiting , coupling (piping) , azo coupling , atom (system on chip) , photochemistry , medicinal chemistry , organic chemistry , mechanical engineering , computer science , engineering , embedded system
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).