Add time:08/26/2019         Source:sciencedirect.com

Quantitative analysis has been performed on the products of direct as well as benzene- and acetone-sensitized photolysis of ethyl and methyl dichloroacetates in cyclohexane. Their quantum yields have been determined. It has been found that the primary mechanism is similar to that for corresponding α-monochloroacetic acid esters and consists mainly in homolytic cleavage of the CCl bond. The short-lived excited state of these esters, most likely the singlet state, is responsible for this reaction. The lack of fluorescence and the efficiency of the CCl rupture approaching unity, indicates that other decay processes for these esters does not play a considerable role. The maximum lifetime of the excited singlet state for these ester molecules is τs < 2 × 10−11 s. Photolysis of dichloroacetic acid esters can be sensitized by benzene and acetone. In the case of benzene the energy transfer occurs from the excited singlet of the donor, and both the classical energy transfer, [singlet(benzene) → singlet(ester)], and the formation of an exciplex between the excited donor molecule and the acceptor molecule in the ground state, are possible.

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