1977
DOI: 10.1021/ja00452a029
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The photochemistry of chloroaromatic compounds. Is ".pi.-chlorobenzene" an intermediate?

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Cited by 33 publications
(12 citation statements)
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“…Electron transfer mediated dehalogenation of haloaromatic molecules in polar solvents normally proceeds via loss of halide from the anion radical followed by hydrogen abstraction by the resulting aryl radical (lower path in Scheme 4). [38][39][40][41][42][43][44][45][46] Nearly thirty years ago we reported that in the case of the DMHinduced photoconversion of DCA to DMA the hydrogen at the 10 position of MCA is provided by an alternative pathway involving protonation of the anion radical followed by loss of chlorine or disproportionation of the resulting radical (upper path in Scheme 4 or Scheme 5). This full account of our work confirms definitively that conclusion, which was disputed in a recent kinetics study.…”
Section: Discussionmentioning
confidence: 99%
See 1 more Smart Citation
“…Electron transfer mediated dehalogenation of haloaromatic molecules in polar solvents normally proceeds via loss of halide from the anion radical followed by hydrogen abstraction by the resulting aryl radical (lower path in Scheme 4). [38][39][40][41][42][43][44][45][46] Nearly thirty years ago we reported that in the case of the DMHinduced photoconversion of DCA to DMA the hydrogen at the 10 position of MCA is provided by an alternative pathway involving protonation of the anion radical followed by loss of chlorine or disproportionation of the resulting radical (upper path in Scheme 4 or Scheme 5). This full account of our work confirms definitively that conclusion, which was disputed in a recent kinetics study.…”
Section: Discussionmentioning
confidence: 99%
“…Prior to the preliminary report of our work, 8 photochemical reductive halogen displacement from haloaromatics (ArX) was thought to occur via the intermediacy of aryl radicals. 38-46 Formation of aryl radicals was attributed to excited state carbon-halogen bond homolysis [38][39][40] in the absence of electron donors, eqn (5), and to electron transfer followed by loss of halide ion from the haloaromatic radical anion, eqn (6) and (7), in the presence of electron donors (D). 41- 47 The sequence of electron-transfer in the singlet exciplex to form the radical anion and its subsequent dissociation to aryl radical and halide was proposed by several workers to account for the catalysis of photodehalogenation by amines.…”
Section: Photodehalogenation Mechanismmentioning
confidence: 99%
“…Halogen atoms are electron deficient species with high electron affinities (22) and their complexation by aromatic molecules is well known from photohalogenation (23) and flash photolysis (24) studies. Such complexation has been considered important in several photochemical problems (25), though these reactions were subsequently reinterpreted along different lines (26). Anchimeric assistance to bond homolysis by radical complexation is not a new concept, having been documented twenty years ago in thermal free radical chemistry by product analysis and activation parameters (27).…”
Section: Adtiitirjes Inclucling Energy-transfer Agentsmentioning
confidence: 99%
“…Investigations in relation to IPC persistence in the environment indicated a half-life of 254 days with unidentified metabolites in water under simulated summer sunshine [16]. However, in presence of TiO 2 /H 2 O 2 and UV, the half-life of IPC was shortened to few hours [20,21], giving a variety of degradation products including ortho-and para-hydroxy analogues, benzoquenone, isopropyl aminobenzoate and aminophenol derivatives [22][23][24][25][26][27]. In view of these conflicting reports and inadequate data on propham photo-product, herein we report the IPC photodegradation in various media with its respective photoproducts; however, such data are not fully available and the demand for it is important both to chemists and environmentalists.…”
Section: Introductionmentioning
confidence: 99%