Metal ion initiated halogenation reactions of N-haloamines

1969 ◽  
Vol 47 (5) ◽  
pp. 715-721 ◽  
Author(s):  
Dennis D. Tanner ◽  
Melvyn W. Mosher
Keyword(s):  
Metal Ion ◽  
Cuprous Chloride ◽  
Chain Process ◽  
Chain Mechanism ◽  
Molecular Chlorine ◽  
Ferrous Chloride ◽  
Radical Chain ◽  
Acid Media ◽  
Hydrocarbon Substrates ◽  
Radical Chain Process

The metal ion catalyzed chlorination of hydrocarbon substrates by N-chloroamines and imides in acid media proceeds by a free radical chain mechanism. Reactions of four different N-chloro halogenating reagents with cuprous chloride, ferrous sulfate, and ferrous chloride initiators have been investigated. Contrary to the previously reported observations no experimental differences were observed in the halogenation reactions of individual N-halo compounds or with the different initiators. The chain carrying species in all cases was shown to be the chlorine atom and the radical chain process showed identical reactivity to that of photo-chlorination by molecular chlorine.

Kinetics and mechanisms of the pyrolysis of diethyl ether I. The uninhibited reaction

1964 ◽  
Vol 278 (1375) ◽  
pp. 505-516 ◽  
Keyword(s):  
Diethyl Ether ◽  
Chain Process ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Elementary Reactions ◽  
First Order ◽  
First Order Kinetics ◽  
Steady State Rate ◽  
State Rate ◽  
Radical Chain Process

The uninhibited thermal decomposition of diethyl ether was studied from 560 to 620 °C and at pressures ranging from 15 to 320 mmHg . The order of the overall reaction was between 1 and 3/2, the order being greater the higher the pressure. Analytical and kinetic data provide strong evidence that there is a molecular split of diethyl ether into ethanol and ethylene. The reaction leading to acetaldehyde and ethane, on the other hand, is concluded to be almost entirely a free-radical chain process. A detailed chain mechanism is postulated, involving first-order initiation and the reaction between C 2 H 5 and CH 2 CH 2 OC 2 H 5 as the chain-ending step. This mechanism is shown to give a steady-state rate equation which leads to first-order kinetics at lower ether pressures and three-halves-order kinetics at higher ones. The kinetic results lead to activation energies which are in satisfactory agreement with values calculated on the basis of the elementary reactions.

Halogenation with N-haloamines in strong acids. I. The nature of the chain propagating radical

1970 ◽  
Vol 48 (4) ◽  
pp. 546-553 ◽  
Author(s):  
J. Spanswick ◽  
K. U. Ingold
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Hydrogen Atom ◽  
Chloride Ion ◽  
Chain Process ◽  
Molecular Chlorine ◽  
Radical Chain ◽  
Atom Chain ◽  
Strong Acids ◽  
Radical Chain Process

The N-haloamine halogenation of 1-chlorobutane in 4 M sulfuric acid in acetic acid as solvent is a radical chain process in which aminium radicals are the principal hydrogen atom abstracting species. With N-chloroamines, a concurrent chlorine atom chain is promoted by impurities such as molecular chlorine, hydrogen chloride, and chloride ion.

Metal ion initiated halogenation reaction of N-haloamines

1970 ◽  
Vol 48 (4) ◽  
pp. 544-545 ◽  
Author(s):  
F. Minisci ◽  
G. P. Gardini ◽  
F. Bertini
Keyword(s):  
Free Radical ◽  
Radical Cation ◽  
Chlorine Atom ◽  
Metal Ion ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Radical Chain Mechanism ◽  
Halogenation Reaction ◽  
Amino Radical Cation ◽  
Methyl Heptanoate

The metal ion catalyzed chlorination of 1-chlorobutane, 1-chlorohexane, methyl-pentanoate, and methyl-heptanoate by protonated N-chloroamines proceeds by a free radical chain mechanism and the chain carrying species was shown not to be a chlorine atom, but an amino radical cation.

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