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24
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(b) Evidence for a similar mechanism in the reduction of the analoguous 4-aminophenyl cation has been presented; see ref 2b. A study on the mechanism of the photoreaction of 1 in alcoholic solvents is underway.
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We have no positive evidence for the phenonium structure of the adduct cation, but this is calculated to be the lowest-lying adduct with an alkene; see ref 2a.
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For example, the quantum yield of photodegradation in MeOH is reported to be φ = 0.1, whereas in cyclohexane it is somewhat higher at φ = 0.35. See ref 11.
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The effect of addition of cesium carbonate is complex. It somewhat enhances the conversion of chlorophenol 1, reasonably because some phenolate anion is then present, which absorbs a large proportion of the light used for irradiation (lamps centered at 310 nm) since its absorption is red-shifted by ca. 10 nm. This effect seems more important for 1 in polar nonprotic solvents despite the slight solubiblity of the base in this medium. In particular, in ethyl acetate the addition of cesium carbonate increased the conversion of 1 from 11% to 50%, with a concomitant increase of the photoreduction yield. Even if the phenolate absorbs part of the light, the photoproducts distribution did not change, in accord with previous reports.8a,25 In accord with this rationalization, the reactivity of a nonacidic compound such as anisole 2 was affected to a much lower degree.
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