The Reaction of Benzene, Chlorine and Maleic Anhydride. An Interception Reaction

Ecke, George G.; Buzbee, Lloyd R.; Kolka, Alfred J.

doi:10.1021/ja01582a024

Cited by 13 publications

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“…39 Cl-CHD adduct formation in the photochemical chlorination of benzene was already postulated in the fifties supported by trapping experiments with maleic anhydride. 45 Cl-CHD formation is also a contributing pathway in the reaction of Cl • with benzene in the gas phase though its main fate is decomposition to reform the reactants. 44 Formation of Cl-CHD radicals was proposed to be the main species responsible for the increased selectivity in the abstraction of tertiary with respect to primary hydrogen observed in the chlorination of alkanes in aromatic solvents.…”

Section: Discussionmentioning

confidence: 99%

“…44 Formation of Cl-CHD radicals was proposed to be the main species responsible for the increased selectivity in the abstraction of tertiary with respect to primary hydrogen observed in the chlorination of alkanes in aromatic solvents. [45][46][47] Moreover, the apparent reactivity of such Cl-adducts toward 2,3-dimethylbutane, as observed in time-resolved experiments, was reported to reflect the extent of their reversible dissociation to free Cl • . 49 The difference in the behavior of the Cl-CHD radicals in the gas phase and in organic solvents compared with that in the aqueous phase seems to be the lack of dissociation of Cl-CHD in aqueous solutions.…”

Section: Discussionmentioning

confidence: 99%

“…Cl−CHD adduct formation in the photochemical chlorination of benzene was already postulated in the fifties supported by trapping experiments with maleic anhydride . Cl−CHD formation is also a contributing pathway in the reaction of Cl • with benzene in the gas phase though its main fate is decomposition to reform the reactants …”

Section: Discussionmentioning

confidence: 99%

“…Formation of Cl−CHD radicals was proposed to be the main species responsible for the increased selectivity in the abstraction of tertiary with respect to primary hydrogen observed in the chlorination of alkanes in aromatic solvents. − Moreover, the apparent reactivity of such Cl-adducts toward 2,3-dimethylbutane, as observed in time-resolved experiments, was reported to reflect the extent of their reversible dissociation to free Cl • …”

Section: Discussionmentioning

confidence: 99%

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Kinetic Study of the Reactions of Chlorine Atoms and Cl₂^•- Radical Anions in Aqueous Solutions. II. Toluene, Benzoic Acid, and Chlorobenzene

et al. 2001

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Laser and conventional flash photolysis of Na 2 S 2 O 8 aqueous solutions containing Clions were employed to investigate the reactions of chlorine atoms and Cl 2 •radical ions with toluene, benzoic acid, and chlorobenzene. A mechanism is proposed which accounts for the faster decay of Cl 2 •in aqueous solutions containing increasing concentrations of the organic substrates. Interpretation of the experimental data is supported by kinetic computer simulations. Chlorine atoms react with the three substituted aromatics studied here almost with diffusioncontrolled rate constants, k ) (1.8 ( 0.3) × 10 10 M -1 s -1 . The high reactivity observed for Cl atoms contrasts with that of the Cl 2 •radical ions, for which the rate constant for its reactions with the substituted benzenes is e 1 × 10 6 M -1 s -1 . The organic radicals produced from these reactions, as well as the nature of the reaction products are discussed. The observed results seem to support an addition mechanism yielding chlorocyclohexadienyl radicals (Cl-CHD) as the most significant reaction channel following reaction of Cl atoms and the organic compounds. In air-saturated solutions, subsequent thermal reactions of Cl-CHD radicals lead both to chlorination and oxidation of the aromatics.

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Section: Discussionmentioning

confidence: 99%