Alkylation of benzothiazolines and the Stevens rearrangement of the resulting 2,3,3-trisubstituted benzothiazolinium salts.

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概要

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• Alkylation of 2-substituted 3-methyl- or 3-ethylbenzothiazolines with Meerwein reagents gave 2-substituted 3,3-dialkylbenzothiazolinium tetrafluoroborates (<B>3</B>). The configuration of two alkyl groups on the nitrogen was assigned by NMR spectra and NOE measurement. In the Stevens rearrangement of <B>3</B> with lithium diisopropylamide ethyl group showed a much larger migratory aptitude (Et:Me≥20 :1) than methyl group irrespective of the configuration of <B>3</B>, and cyclic ammonium ylide with planar π-type carbanion was proposed as an intermediate. <B>3</B> suffered nucleophilic attack at the ring sulfur atom by butyllithium to afford a ring-opened ammonium ylide, which collapses to a radical pair to give unusual Stevens rearrangement product, where <I>o</I>-alkylthiophenyl group migrated selectively in preference to alkyl group, because of stabilization by participation of <I>o</I>-alkylthio group.

• 公益社団法人 日本化学会の論文

著者

• Akiba Kin-ya

  Department Of Chemistry Faculty Of Science Hiroshima University

• Inamoto Naoki

  Department Of Chemistry Graduate School Of Science The University Of Tokyo

• Ohara Yoshio

  Department of Chemistry, Faculty of Science, The University of Tokyo

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