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Radiation-induced reactions of cinnamic acid derivatives have been examined and compared with photoreactions in the crystalline state; all the reaction products were exactly the same as those of the photoreactions, indicating that the reactions proceed only via the lowest excited state to give [2 + 2] cycloadducts, E/Z isomerization products, or starting molecules.

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Articles you may be interested inOptimization of postgrowth electron-beam curing for focused electron-beam-induced Pt deposits Electron-beam exposure mechanisms in hydrogen silsesquioxane investigated by vibrational spectroscopy and in situ electron-beam-induced desorption Comparative study of thermally cured and electron-beam-exposed hydrogen silsesquioxane resistsThe electron-beam ͑EB͒-induced reaction of triphenylsulfonium methanesulfonate ͑1-Ms͒ in the solid state afforded the benzene-substituted product, biphenyldiphenylsulfonium methanesulfonate ͑2-Ms͒, which has not been observed by either photolysis or EB-induced reaction in a solution. Biphenyl salt 2-Ms was accumulated as an intermediate product at an early stage and consequently decomposed to diphenylsulfide ͑3͒ and three regioisomers of phenylthiobiphenyls ͑4͒. The kinetic data of both formation and consumption of 2-Ms revealed that the biphenyl salt 2-Ms exhibited 3.7 times greater kinetic constants for consumption than that of 1-Ms. The EB-induced reaction of benzene-substituted triphenylsulfonium salts, p-biphenyldiphenylsulfonium methanesulfonate ͑2p-Ms͒ and ͑4-phenylthiophenyl͒diphenylsulfonium methanesulfonate ͑7͒, showed the consumption rates of 3.8 and 5.7 times greater than that of 1-Ms. The sulfonium salts with aromatic counteranions showed somewhat higher reactivity than those with aliphatic counteranions. Accordingly, it is concluded that the triphenylsulfonium salts having aryl groups, which exhibit lower ionization potential, in both cation and anion moieties should exhibit greater decomposition rates. Detailed kinetic analysis of 1-Ms revealed that the EB-induced reaction of 1-Ms comprises two disparate pathways, one pathway is a unimolecular rearrangement via the lowest excited state leading to only orthoisomer of 4 and the other is a bimolecular displacement of phenyl radical via the upper excited state leading to 2-Ms and 3.