Non-conventional Aromatic Electrophilic Reactions Occurring via "ipso" Arenium Ion Intermediates

Research Project

Project/Area Number	60470024
Research Category	Grant-in-Aid for General Scientific Research (B)
Allocation Type	Single-year Grants
Research Field	有機化学一般
Research Institution	Ehime University
Principal Investigator	SUZUKI Hitomi Professor, 理学部, 教授 (50025342)
Project Period (FY)	1985 – 1986
Project Status	Completed (Fiscal Year 1986)
Budget Amount *help	¥7,700,000 (Direct Cost: ¥7,700,000) Fiscal Year 1986: ¥500,000 (Direct Cost: ¥500,000) Fiscal Year 1985: ¥7,200,000 (Direct Cost: ¥7,200,000)
Keywords	Aromatics / Nitration / Electrophilic Reaction / 反応機構
Research Abstract	Non-conventional reactions of benzenoid compounds which occur as a consequence of "ipso" attack of electrophiles have been investigated, with a special emphasis on the elucidation of the anomalies observed during the side-chain nitration of polysubstituted arenes; nitrooxylation with <HNO_3> / <CH_2> <Cl_2> and nitration with <HNO_3> / <(CH_3CO)_2> O. Based on the evidence obtained from product variations with substituents, electrochemical nitrodecarboxylation of arylacetates, and ESR examination of the initial stage of the side-chain reactions, a proposal is made that the side-chain substitution of polysubstituted arenes occurs via heterolytic path with <HNO_3> / <CH_2> <Cl_2> and via a homolytic path with <HNO_3> / <(CH_3CO)_2> O. The first isolation of a proposed methylenecyclohexadiene intermediate for the side-chain substitution of arenes under heterolytic conditions is also included.