Reactivities of stable rotamers. XII. Reactions of 9-(2-bromomethyl-6-methylphenyl)fluorene rotamers with nucleophiles.
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概要
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Rates of some substitution reactions of 9-(2-bromomethyl-6-methylphenyl)fluorene rotamers with nucleophiles are compared. Methanolysis of the rotamers proceeded smoothly in the <I>sp</I> form but was sluggish in the <I>ap</I>. Reactions of the <I>sp</I> form with sodium methoxide afforded 6-methylspiro[benzocyclobutene-1(2<I>H</I>), 9′-[9<I>H</I>]fluorene] and <I>sp</I>-9-(2-methoxymethyl-6-methylphenyl)fluorene, the former being a minor product. In addition to these, isomerization to the <I>ap</I> was detected. In contrast, the <I>ap</I> form afforded the spiro compound as a major product and the <I>ap</I> form of the methoxy compound as a minor product. Menschutkin reactions with pyridine bases were much faster in the <I>sp</I> form than in the <I>ap</I>. These results are attributed to the steric effect in the transition states of the reactions: the <I>sp</I> form reacts much faster than the <I>ap</I> because of the presence of the fluorene moiety in proximity of the reaction site in the latter.
- 公益社団法人 日本化学会の論文
著者
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Murata Shigeru
Department Of Basic Science Graduate School Of Arts And Sciences The University Of Tokyo
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Oki Michinori
Department Of Chemistry Faculty Of Science Okawama University Of Science
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Nakamura Mikio
Department Of Anatomy Jikei-kai School Of Medicine
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Nakamura Mikio
Department of Chemistry, Faculty of Science, The University of Tokyo
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Kanno Seiichiro
Department of Chemistry, Faculty of Science, The University of Tokyo
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Tanabe Yo
Department of Chemistry, Faculty of Science, The University of Tokyo
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Tanabe Yo
Department of Chemistry, Faculty of Science, Kyoto University
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