Electron-Beam-Induced Fries Rearrangement and Oxidation Reactions of Sulfonic Acid Esters in Crystalline State
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-to...
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Published in | Journal of Photopolymer Science and Technology Vol. 17; no. 1; pp. 21 - 27 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
Hiratsuka
The Society of Photopolymer Science and Technology(SPST)
2004
Japan Science and Technology Agency |
Subjects | |
Online Access | Get full text |
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Summary: | 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-tolylsulfoes (2a and 3a), phenol (5) and the oxidation products of 2a, o,p-dihyroxyphenyl p-tolysulfon (4a), which has not been observed in photolysis. The EB-induced reaction of 1a exhibits higher ortho-regioselectivity at the early stage owing to crystal lattice control. The radiation of 1b, which is liquid at room temperature, give Fries rearrangement products with lower ortho/para regioselectivity. On the other hand, the EB-induced reaction of 1c proceeded with the lowest reactivity through crystal to crystal transformation to afford Fries rearrangement products, o- and p-hydroxyohenyl 1-naphthylsulfones (2c and 3c), and 5, but not oxidation product. The mechanistic study reveals that oxidation rpoduct 4a generated by the oxidation reaction of ortho-Fries rearrangement product 2a but not para-isomer 3a with an active oxidant, which should result from the decomposition of 1a. |
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ISSN: | 0914-9244 1349-6336 |
DOI: | 10.2494/photopolymer.17.21 |