Kinetic characterization of a transient reaction by degeneration of the precursor mechanism: Application to the synthesis of 3,4-diazabicyclo[4.3.0]- non-2-ene

Autor: Jacques Berthet, Henri Delalu, Renaud Metz, M. Elkhatib
Rok vydání: 2006
Předmět:
Zdroj: International Journal of Chemical Kinetics. 38:327-338
ISSN: 1097-4601
0538-8066
DOI: 10.1002/kin.20072
Popis: The rate of the oxidation of N-amino-3-azabicyclo[3.3.0]octane by chloramine has been studied by GC and HPLC between pH 10.5 and 13.5. The second-order reaction exhibits specific acid catalysis. The formation of N,N′-azo-3-azabicyclo[3.3.0]octane or 3,4-diazabicyclo[4.3.0]non-2-ene is pH, concentration, and temperature dependent. In alkaline media, the exclusive formation of 3,4-diazabicyclo[4.3.0]non-2-ene is observed. Kinetic studies show that the oxidation of N-amino-3-azabicyclo[3.3.0]octane by chloramine is a multistep process with the initial formation of a diazene-type intermediate, which is converted by hydroxide ions into 3,4-diazabicyclo[4.3.0]non-2-ene. Because it was not possible to follow the rate of change of the intermediate concentration, to determine the kinetics of 3,4-diazabicyclo[4.3.0]non-2-ene formation, a procedure based on the degeneration of the precursor process was adopted. An appropriate mathematical treatment allowed a quantitative interpretation of all the phenomena observed over the given pH interval. The activation parameters were determined. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 327–338, 2006
Databáze: OpenAIRE
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