Mechanisms of Decomposition of (Z)-2,2,2-Trifluoro-1-arylethanediazoates in Aqueous Media

A study of the kinetics of decay of three (Z)-2,2,2-trifluoro-1-arylethanediazoates at 25 °C in aqueous media, 4% 2-propanol by volume, ionic strength 1 M (NaClO4) in the pH range 4−13, as well as the results of experiments to detect deuterium incorporation into products from solvent is reported. It...

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Bibliographic Details
Published in:Journal of the American Chemical Society 1996-07, Vol.118 (30), p.7134-7138
Main Authors: Finneman, Jari I, Fishbein, James C
Format: Article
Language:English
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Summary:A study of the kinetics of decay of three (Z)-2,2,2-trifluoro-1-arylethanediazoates at 25 °C in aqueous media, 4% 2-propanol by volume, ionic strength 1 M (NaClO4) in the pH range 4−13, as well as the results of experiments to detect deuterium incorporation into products from solvent is reported. It is concluded in the case of the unsubstituted compound that the buffer-independent reaction involves rate-limiting heterolytic bond fission of the diazoic acid to yield a diazonium ion intermediate, and a similar mechanism is indicated for the other two compounds. General acid catalysis of the decay of the diazoic acids at pH < 7 is observed, and it is concluded that the reaction involves rate-limiting N−O bond cleavage of the diazoic acid that is concerted with protonation of the leaving hydroxide ion by the catalyst.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja9614629