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Dediazoniation of Arenediazonium Ions in Homogeneous Solutions. Part XVII. Kinetics and mechanisms of dediazoniation of p-chlorobenzenediazonium tetrafluoroborate in weakly alkaline aqueous solutions in the presence of oxygen

✍ Scribed by Jacques Besse; Heinrich Zollinger

Publisher
John Wiley and Sons
Year
1981
Tongue
German
Weight
928 KB
Volume
64
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The kinetics of dediazoniation of p‐chlorobenzenediazonium tetrafluoroborate have been studied in buffer solutions in the pH‐range 9.0–10.0, ionic strength I = 0.10, at 20.0° in glass and polytetrafluoroethylene vessels. The presence of oxygen (<5 ppb of O~2~, 60 to 100 ppb of O~2~, air, > 99% of O~2~) has a decisive influence on the rate and kinetic order of the dediazoniation. Iodoacetic acid inhibits the reaction, whereas p‐chlorophenol has a catalytic effect, and in air and >99% of O~2~ it acts as an autocatalyst. The reaction is subject to general‐base catalysis by water, hydroxyl ions, hydrogen carbonate and carbonate ions. The kinetic results are interpreted in conjunction with data concerning the reaction products [2] and a ^15^N‐CIDNP. investigation of a related system [3]. Specific radical chain mechanisms are consistent with the results.

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Dediazoniations of Arenediazonium Ions in Homogeneous Solutions. Part XV. Products of dediazoniation of p-chlorobenzenediazonium tetrafluoroborate in weakly alkaline aqueous solutions
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Dediazoniation of Arenediazonium Ions in Homogeneous Solutions. Part XVI. Kinetics and mechanisms of dediazoniation of p-chlorobenzenediazonium tetrafluoroborate in weakly alkaline aqueous solutions under nitrogen gas
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The kinetics of reactions of p-chlorobenzenediazonium ions in aqueous buffer solutions (pH 9.0-10.6) under N, (< 5 ppb of 0,) have been measured between 20 and 50°C. The formation of trans-diazotate is first-order with respect to the concentration of hydroxyl ions and to the equilibrium concentratio

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## Abstract ^15^N‐CIDNP. spectra recorded during the reaction of diazonium cations with OH^−^ in weakly alkaline aqueous solutions show that the dediazoniation is at least __partially__ homolytic. The polarizations observed for the diazonium and __trans__‐diazotate ions can be explained by reaction

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## Abstract __p__‐Nitrobenzenediazonium tetrafluoroborate dissolved in dimethylsulfoxide (DMSO) at 50° forms __p__‐nitrophenol in 88–90% yield. The phenolic oxygen atom originates exclusively from the oxygen atom of DMSO as demonstrated by the use of ^18^O‐labelled DMSO. The first‐order rate of ded

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## Abstract The mechanism of dediazoniation of arenediazonium tetrafluoroborates in 2,2,2‐trifluoroethanol (TFE) is strongly dependent on the concentration of added pyridine. The added base complexes with the diazonium ion and diverts it to a homolytic pathway. Complex formation is indicated by the