Kinetics of the autocatalytic oxidation of N‐amino‐3‐azabicyclo[3,3,0]octane by chloramine in aqueous medium

Abstract

The kinetics of the degradation of N-amino-3-azabicyclo[3,3, Oloctane by chloramine has been studied by GC and HPLC in stoichiometric conditions in a solution buffered with NaOH/KHaP04 and NaaB407.10 H2O between pH = 10.5 and 13.5. The second-order reaction exhibits specific acid catalysis which indicates competitive oxidation between the haloamine and the neutral and ionic forms of the bicyclic hydrazine. The enthalpy and entropy of activation were determined a t pH = 12.89.In a nonbuffered solution, the interaction is autocatalyzed due to acidification of the mixture by the ammonium ions. In basic medium, the reaction forms a n endocyclic hydrazone. A mathematical treatment based on an implicit equation allows a quantitative interpretation of all the phenomena observed over the above pH interval. This takes both the acid/base dissociation equilibria and the alkaline hydrolysis of the chloro-derivative into account. 0 1995 John Wiley & Sons, Ine.

Kinetics of the oxidation of N-aminopiperidine with chloramine

“…Methodological details on the apparatus and the experimental procedure have been published previously [23,24]. In a second step, the isobestic point disappeared while UV absorption increased and simultaneously deviated to lower wavelengths.…”

Kinetics of dehydrohalogenation ofN-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

“…: RRЈNNH ϩ HCl (1) 2 2 Where R, RЈ ϭ H, alkyl, aryl, and alicyclic. During the synthesis of this molecule and under certain pH conditions, one can observe the forma- NMR spectrum at of 3-azabicy- 13 C t ϭ 0 clo [3,3,0]oct-2-ene after dissolution of the dimer in CDCl 3 . tion of several by-products, in particular 3,4-diazabicyclo [4,3,0]non-2-ene 2, N,NЈ-azo-3-azabicyclo [3,3,0]octane 3, and 3-aza-bicyclo [3,3,0]oct-2-ene 4 which precipitates in the form of a white solid. The first two of these were the object of previous investigations [1 -4].…”

“…Analysis of the reaction mixture during the preparation of hydrazine reveals the existence of small quantities of an organohaloamine 5, Nchloro-3-azabicyclo [3,3,0]octane (ClAZA). In these conditions, imine would result from the following two consecutive reactions: chlorine exchange between the chloramine and 3-aza-bicyclo [3,3,0]octane [5 -11] followed by a dehydrohalogenation [12 -27] of the substituted haloamine (reactions 2 and 3):…”

“…The present study has the objective of researching the mechanism of the formation of 4 and of determining the kinetic parameters in order to define the optimal synthesis conditions. The most simple reaction scheme would consist of a direct dehydrogenation of 3-azabicyclo [3,3,0]octane (AZA) to form imine:…”

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ABSTRACT: The formation of 3-azabicyclo [3,3,0]oct-2-ene in the course of the synthesis of 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 44ЊC), and the concentrations of NaOH (0.1 to ) and the chlorinated derivative (1 to ).

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