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Yuasa, Kanako; Enomoto, Kazuyuki*; Maekawa, Yasunari; Kato, Jun*; Yamashita, Takashi*; Yoshida, Masaru
Journal of Photopolymer Science and Technology, 17(1), p.21 - 28, 2004/07
Times Cited Count：9 Percentile：31.07(Polymer Science)The electron beam (EB)-induced reactions of arylsulfonic acid esters, phenyl p-toluenesulfonate (1a), phenyl benzenesulfonate (1b), and phenyl 1-naphthalenesulfonate (1c), were examined in the balk state. The EB irradiation of 1a afforded the Fries rearrangement products, o- and p-hydroxyphenyl p-tolylsulfones (2a and 3a), phenol (5), and the oxidation product of 2a, o,p-dihydroxyphenyl p-tolylsulfone (4a), which has not been observed in photolysis. The irradiation of 1b, which is liquid at room temperature, gave Fries products, 5, and the oxidation product, o,p-dihydroxyphenyl phenylsulfone. On the other hand, the EB-induced reaction of 1c proceeded with the lowest reactivity through crystal to crystal transformation to afford Fries products and 5, but not oxidation product. The mechanistic study reveals that oxidation product 4a generated by the oxidation reaction of ortho-Fries product 2a but not para-isomer 3a with an active oxidant, which should result from the decomposition of 1a.
Enomoto, Kazuyuki*; Maekawa, Yasunari; Moon, S.; Shimoyama, Junji*; Goto, Kazuyuki*; Narita, Tadashi*; Yoshida, Masaru
Journal of Photopolymer Science and Technology, 17(1), p.41 - 44, 2004/06
Times Cited Count：2 Percentile：9.04(Polymer Science)The Electron beams (EB)-induced reactions of triphenylsulfonium methanesulfonate (1) in the crystalline state gave benzene-substituted product, biphenylsulfonium methanesulfonate (2), which has not been observed by either photolysis. In this paper, the EB-induced reactions of triphenylsulfonium salt derivatives, which possesses aromatic/aliphatic counter anions, have been examined. The anionic moiety of sulfonium salts has practically little effect on the formation of biphenyl salt 2 as well as the other products. The consumption rates of the sulfonium salts containing aromatic counter anions are somewhat smaller in a crystalline state and about two times larger than those of the salts with aliphatic counter anions. The greater decomposition rates of the sulfonium salts with aromatic counter anions than those of aliphatic counter anions in an amorphous state are elucidated by lower ionization potential of the salts with aromatic counter anions such as tosyl and naphthyl groups than those with aliphatic counter anions.
