• Title/Summary/Keyword: Thianthrene

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Reaction of Thianthrene Cation Radical Perchlorate with Cumene Hydroperoxides (티안트렌 양이온 자유라디칼 과염소산염과 큐멘과산화수소의 반응)

  • Jongheon Shin;Kyongtae Kim
    • Journal of the Korean Chemical Society
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    • v.27 no.2
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    • pp.142-149
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    • 1983
  • Reaction of thianthrene cation radical perchlorate (1) with cumene (4), p-chlorocumene (2), and p-nitrocumene (3) hydroperoxides in acetonitrile at room temperature afforded, inter alia, thianthrene as a common product and 5-(4'-hydroxyphenyl) thianthrenium perchlorate (5) for 4, 5-(5'-chloro-2'-hydroxyphenyl) thianthrenium perchlorate (7) and 5-acetonylthianthrenium perchlorate (6) for 2 and 6 for 3, respectively. Stoichiometry of these reactions showed that 2 moles of 1 gave rise to 1mole of thianthrene and 1 mole of thianthrenium salt (or salts). Nucleophilic reactivity to 1 was found to be in the order of phenol > > p-chlorophenol ${\sim}$ acetone > > p-nitrophenol. Apart from acid-catalyzed heterolytic decomposition of hydroperoxides, small amount of homolytic decomposition products were found from 3 and 4.

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Reaction of Thianthrene Cation Radical Perchlorate with Thioxanthene. Synthesis of Thioxanthene Derivatives (티안트렌 양이온 자유라디칼과 염소산염과 티오크잔틴의 반응. 티오크잔틴 유도체의 합성)

  • Kyongtae Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.34-43
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    • 1980
  • The reaction of thianthrene cation radical perchlorate with thioxanthene in acetonitrile gave thianthrene and dark reddish thioxanthylium ion instead of thioxanthene cation radical. Addition of aromatic nucleophiles such as anisole, aniline, N,N-diethylaniline, catechol, ethylbenzene, to the above mixture yielded the corresponding thioxanthenes with substituent at 9 position. Reactions with dibenzo-18-crown-6-ether, diphenylmercury, and triphenylphosphine gave similar products. However, reactions with aromatics with electron-withdrawing group were either too slow or inert to such a reaction.

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Reactions of Thianthrene Cation Radical Perchlorate with N-(p-Methoxyphenyl)benzene- and Methanesulphonamides

  • Sung Hoon Kim;Jung Hyu Shin;Kyongtae Kim
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.509-514
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    • 1989
  • Reactions of thianthrene cation radical perchlorate (1) with N-(p-methoxyphenyl)benzenesulphonamide (14) in acetonitrile at room temperature afforded various products : thianthrene (3), N-(p-hydroxyphenyl)benzenesulphonamide (16), benzenesulphonamide (18), hydroquinone (20); 5-(5-benzenesulphonamido-2-methoxyphenyl)-thia nthrenium perchlorate(21), 2-benzenesulphonamido-2'-hydroxy-5,5'-dimethoxy biphenyl(24), 2-benzenesulphonamido-2',5'-dihydroxy-5-methoxy -biphenyl(25), and a traceable amount of p-quinone(23). The formations of part of (3) and (21) can be explained by either disproportionation or half-regeneration mechanism but those of the remainders by diverse reactions of sulphonamidyl radical (27) derived from (14) (through single electron transfer, followed by deprotonation processes). Similar results were observed from the reaction with N-(p-methoxyphenyl)methanesulphonamide (15).

A Route for Sulfuranyl Radical by an Electron Transfer from Sodium Naphthalenide to a Triarylsulfonium Salt$^1$

  • Kim, Kyong-Tae;Bae, Hye-Kyung
    • Bulletin of the Korean Chemical Society
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    • v.8 no.3
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    • pp.165-167
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    • 1987
  • Reaction of 5-(2-thianthreniumyl)thianthrene perchlorate with sodium naphthalenide in the presence of benzenethiol in tetrahydrofuran at -$78^{\circ}C$ proceeded via a formation of a sulfuranyl radical to give thianthrene (66%), 2-phenylthiothianthrene (33%), phenyl 2-(2-thianthrenylthio)phenyl sulfide (traceable amount), and some unknowns, along with naphthalene and very small amount of 1,4-dihydronaphthalene.

Photopolymerization of Vinyl Monomers Using Organic Initiators

  • Kim, Myoung-Hee;Lee, Jun;Cha, Hyo Chang;Ham, Heui-Suk;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.2 no.1
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    • pp.1-12
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    • 2009
  • This miniaccount presents the selective examples of our recent discoveries in the photopolymerization of vinyl monomers using the organic initiators such as hydrosilanes, poly(hydroarylsilane)s, benzoin silyl ethers, and thianthrene cation radical. In the photopolymerization of vinyl monomers with silanes polysilanes, while the polymerization yields and polymer molecular weights of the poly(MMA)s containing the silyl moieties decreased, the TGA residue yields and intensities of SiH stretching IR bands increased as the mole ratio of the silanes over MMA increased. The hydroarylsilane and poly(hydroarylsilane) seemed to influence strongly on the photopolymerizaiton of olefinic monomers as both chain initiation and chain transfer agents. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. Benzoin silyl ethers and thianthrene cation radical also exhibit the photoinitiating ability in the photopolymerization of MMA.

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