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Kinetics of dehydrohalogenation of N ‐chloro‐3‐azabicyclo[3,3,0]octane in alkaline medium. NMR and ES/MS evidence of the dimerization of 3‐azabicyclo[3,3,0]oct‐2‐ene
Author(s) -
Elkhatib M.,
Peyrot L.,
Scharff J. P.,
Delalu H.
Publication year - 1998
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1998)30:2<129::aid-kin4>3.0.co;2-u
Subject(s) - chemistry , dehydrohalogenation , dimer , octane , ene reaction , kinetics , chlorine , proton nmr , monomer , medicinal chemistry , derivative (finance) , stereochemistry , organic chemistry , polymer , catalysis , physics , quantum mechanics , financial economics , economics
The formation of 3‐azabicyclo[3,3,0]oct‐2‐ene in the course of the synthesis of N ‐amino‐3‐azabicyclo[3,3,0]octane using the Raschig process results from the following two consecutive reactions: chlorine transfer between the monochloramine and the 3‐azabicyclo[3,3,0]octane followed by a dehydrohalogenation of the substituted haloamine. The kinetics of the reaction were studied by HPLC and UV as a function of temperature (15 to 44°C), and the concentrations of NaOH (0.1 to 1 M) and the chlorinated derivative (1 to 4×10 −3 M). The reaction is bimolecular ( k =103×10 −6 M −1 s −1 ; Δ H 0# =89 kJ mol −1 ; and Δ S 0# =−33.6 J mol −1 K −1 ) and has an E2 mechanism. The spectral data of 3‐azabicyclo[3,3,0]oct‐2‐ene were determined. IR, NMR, and ES/MS analysis show dimerization of the water‐soluble monomer into a white insoluble dimer. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 129–136, 1998.