| Project/Area Number |
05453179
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | The University of Tokyo |
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Principal Investigator |
SHUDO Koichi Fac. Pharm. Soc. Univ Tokyo, Prof, 薬学部, 教授 (50012612)
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| Co-Investigator(Kenkyū-buntansha) |
OHWADA Tomohiko Fac. Pharm. Soc. Univ Tokyo, Prof assistant Prof, 薬学部, 助手 (20177025)
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| Project Period (FY) |
1993 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥7,500,000 (Direct Cost: ¥7,500,000)
Fiscal Year 1994: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1993: ¥4,800,000 (Direct Cost: ¥4,800,000)
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| Keywords | Friedel-Craft reaction / dication / diprotonated nitrile / molecular orbital / reaction rate / nitration / アシルカチオン / ベンゼン / フリーデル・クラフト反応 / ガッターマン反応 / 求電子試薬 / アセチル化 / 酸 / 反応機構 |
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| Research Abstract |
The active electrophile involved in the Gattermann reaction of benzene with cyanide is N,N-diprotonated hydrogen cyanide, HC^+=N^+H_2.Similarly, Houben-Hoesch acylation by benzonitrile involves N,N-diprotonated nitrile as the active species. Participation of the second proton was demonstrated by kinetic measurement of the intramolecular cyclization of phenylpropionitrile.
Acylation of benzene, toluene and chlorobenzene by CH_3COSbF_6 or C_6H_5COSbF_6 depends strongly on the acidity of the media. The major active species are the protonated acyl cations formed in the highly acidic media. The acyl cation itself contributes only to a minor extent even in the acylation of benzene and toluene.
Dications (superelectrophiles or protosolvated cations) are proposed to be the real electrophiles in these reactions of benzene and non-activated benzenes.
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