KINETICS DEHYDROHALOGENATION OF N-CHLORO-3-AZABICYCLO[3,3,0]OCTANE INALKALINE-MEDIUM - NMR AND ES MS EVIDENCE OF THE DIMERIZATION OF 3-AZABICYCLO[3,3,0]OCT-2-ENE/

The formation of 3-azabicyclo[3,3,0]oct-2-ene in the course of the syn thesis of N-amino-3-azabicyclo[3,3,0]octane using the Raschig process results from the following two consecutive reactions: chlorine transfe r between the monochloramine and the 3-azabicyclo[3,3,0]octane followe d by a dehydrohalogenation of the substituted haloamine. The kinetics of the reaction were studied by HPLC and UV as a function of temperatu re (15 to 44 degrees C), and the concentrations of NaOH (0.1 to 1 M) a nd the chlorinated derivative (1 to 4 X 10(-3) M). The reaction is bim olecular (k = 103 x 10(-6) M-1 s(-1); Delta H-0# = 89 kJ mol(-1); and Delta S-0# = -33.6 J mol(-1) K-1) and has an E2 mechanism. The spectra l data of 7-azabicyclo[3,3,0]oct-2-ene were determined. 1R, NMR, and E S/MS analysis show dimerization of the water-soluble monomer into a wh ite insoluble dimer. (C) 1998 John Wiley & Sons, Inc.