Transfer of active chlorine from chloramine to nitrogenous organic compounds.  2.  Mechanism

Isaac, Russell A.; Morris, J. Carrell

doi:10.1021/es00139a007

Cited by 49 publications

(48 citation statements)

References 5 publications

(8 reference statements)

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“…N-chloro-3-azabicyclo [3,3,0]octane " Cl-AZA" was obtained by chlorination of 3-azabicyclo [3,3,0]octane by hypochlorite ion (1 -2% excess AZA). This product, which is slightly soluble in water, decomposes at 70ЊC during distillation (760 torr) to liberate gases and leave a carbonaceous deposit.…”

Section: Methodsmentioning

confidence: 99%

“…In comparison with pH ϭ 8.16, one observes a decrease in the rate of disappearance of reactants and formation of N-chloro-3-azabicyclo [3,3,0]octane. In order to quantify this phenomenon, a series of analogous measurements were performed at different pH values.…”

Section: Influence Of Phmentioning

confidence: 99%

“…The mechanism proposed by Snyder and Margerum [1] and again by Isaac and Morris [2,3] involves the reaction of the chloroammonium ion with free amine despite a low concentration of reactants. This implicates a nucleophilic attack of the ammoniacal nitrogen lone pair on the positive chlorine site:…”

Section: Aza/nh2cl/nh3cl1 Systemmentioning

confidence: 99%

“…(1), in the synthesis of asymmetric bicyclic hydrazines, in particular N-amino-3-azabicyclo [3,3,0] octane " NAZA": (1) where R, RЈ ϭ H, alkyl, aryl, and alicyclic.…”

mentioning

confidence: 99%

“…This is due to the fact that the majority of these studies were performed in a limited pH region and did not simultaneously take the halogenation and amination properties of haloamine into account. The objective of this work is to study the chlorine transfer kinetics for the case of 3-azabicyclo [3,3,0]octane and to establish a mathematical model which describes the dual properties of chloramine towards the ammoniacal nitrogen.…”

mentioning

confidence: 99%

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Halogenation and amination dual properties of haloamines in Raschig environment: A chlorine transfer reaction between chloramine and 3-azabicyclo[3,3,0]octane

Elkhatib

Marchand

Peyrot

et al. 1997

Int. J. Chem. Kinet.

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The chlorine transfer reaction between 3‐azabicyclo[3,3,0]octane “AZA” and chloramine was studied over pH 8–13 in order to follow both the amination and halogenation properties of NH2Cl. The results show the existence of two competitive reactions which lead to the simultaneous formation of N‐amino‐ and N‐chloro‐ 3‐azabicyclo[3,3,0]octane by bimolecular kinetics. The halogenation reaction is reversible and the chlorine derivative obtained, which is thermolabile and unstable in the pure state, was identified by electrospray mass spectrometry. These phenomena were quantified by a reaction between neutral species according to an apparent SN2‐type mechanism for the amination process and a ionic mechanism involving a reaction between chloramine and protonated amine for the halogenation process. Amination occurs only in strongly basic solutions (pH ≥ 13) while chlorination occurs at lower pH's (pH ≤ 8). At intermediate pH's, a mixture of these two compounds is obtained. The relative proportions of the products are a function of intrinsic rate constants, pH and pKa of the reactants. The rate constants and thermodynamic activation parameters are the following: k1 = 45.5 × 10−3 M−1 s−1; ΔH10# = 59.8 kJ mol−1; ΔS10# = − 86.5 J mol−1 K−1 for amination; k2 = 114 × 10−3 M−1 s−1; ΔH20# = 63.9 kJ mol−1; and ΔS20# = − 48.3 J mol−1 K−1 for chlorination. The ability of an interaction corresponding to a specific (NH3Cl+/RR′NH) or general (NH2Cl/RR′NH) acid catalysis has been also discussed. © 1997 John Wiley & Sons, Inc.

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Section: Methodsmentioning

confidence: 99%

Section: Influence Of Phmentioning

confidence: 99%

Section: Aza/nh2cl/nh3cl1 Systemmentioning

confidence: 99%

“…(1), in the synthesis of asymmetric bicyclic hydrazines, in particular N-amino-3-azabicyclo [3,3,0] octane " NAZA": (1) where R, RЈ ϭ H, alkyl, aryl, and alicyclic.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Halogenation and amination dual properties of haloamines in Raschig environment: A chlorine transfer reaction between chloramine and 3-azabicyclo[3,3,0]octane

Elkhatib

Marchand

Peyrot

et al. 1997

Int. J. Chem. Kinet.

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Halogenation and amination dual properties of haloamines in Raschig environment: A chlorine transfer reaction between chloramine and 3‐azabicyclo[3,3,0]octane

Elkhatib¹,

Marchand²,

Peyrot³

et al. 1997

Int. J. Chem. Kinet.

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This work comes as a part of the reactivity of chloramine with mono-and disubstituted amines with the ABSTRACT The chlorine transfer reaction between 3-azabicyclo[3,3,0]octane "AZA" and chloramine was studied over pH 8 -13 in order to follow both the amination and halogenation properties of NH 2 Cl. The results show the existence of two competitive reactions which lead to the simultaneous formation of N-amino-and N-chloro-3-azabicyclo[3,3,0]octane by bimolecular kinetics. The halogenation reaction is reversible and the chlorine derivative obtained, which is thermolabile and unstable in the pure state, was identified by electrospray mass spectrometry. These phenomena were quantified by a reaction between neutral species according to an apparent S N 2-type mechanism for the amination process and a ionic mechanism involving a reaction between chloramine and protonated amine for the halogenation process. Amination occurs only in strongly basic solutions (pH Ն 13) while chlorination occurs at lower pH's (pH Յ 8). At intermediate pH's, a mixture of these two compounds is obtained. The relative proportions of the products are a function of intrinsic rate constants, pH and pK a of the reactants. The rate constants and thermodynamic activation parameters are the following: k 1 ϭ 45.5 ϫ 10 Ϫ3 M Ϫ1 s Ϫ1 ; ⌬H 1 0# ϭ 59.8 kJ mol Ϫ1 ; ⌬S 1 0# ϭ Ϫ 86.5 J mol Ϫ1 K Ϫ1 for amination; k 2 ϭ 114 ϫ 10 Ϫ3 M Ϫ1 s Ϫ1 ; ⌬H 2 0# ϭ 63.9 kJ mol Ϫ1 ; and ⌬S 2 0# ϭ Ϫ 48.3 J mol Ϫ1 K Ϫ1 for chlorination. The ability of an interaction corresponding to a specific (NH 3 Cl ϩ /RRЈNH) or general (NH 2 Cl/RRЈNH) acid catalysis has been also discussed.

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2012

Oxidation of Amino Acids, Peptides, and Proteins

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Transfer of active chlorine from chloramine to nitrogenous organic compounds. 2. Mechanism

Cited by 49 publications

References 5 publications

Halogenation and amination dual properties of haloamines in Raschig environment: A chlorine transfer reaction between chloramine and 3-azabicyclo[3,3,0]octane

Halogenation and amination dual properties of haloamines in Raschig environment: A chlorine transfer reaction between chloramine and 3-azabicyclo[3,3,0]octane

Halogenation and amination dual properties of haloamines in Raschig environment: A chlorine transfer reaction between chloramine and 3‐azabicyclo[3,3,0]octane

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