Solvolysis in carboxamides. V. Solvolytic elimination of threo-1-methyl-2-phenylpropyl brosylate in N,N-dimethylacetamide. Kinetic, product, and deuterium tracer studies.

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概要

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• Solvolysis of a series of ring substituted <I>threo</I>-1-methyl-2-phenylpropyl brosylates has been carried out in <I>N</I>,<I>N</I>-dimethylacetamide (DMA) as solvent. Hammett treatment of the rate data indicated that the DMA solvolysis of the unsubstituted brosylate (<B>1c</B>) falls into the category of <I>k</I><SUB>s</SUB> pathway (100%). In order to gain further information of the nature of the <I>k</I><SUB>s</SUB> pathway, the DMA solvolysis of <B>1c</B> or <B>1c</B>-2-<I>d</I> (labeled at C(2)) has been conducted. The product distribution, effect of water content on it, the composition and deuterium distribution of recovered brosylate, kinetic isotope effect, and the deuterium distribution of product have been investigated. The products consisted of the olefins ((<I>E</I>)- and (<I>Z</I>)-2-pheny1-2-butenes, and 2- and 3-phenyl-1-butenes), and, in the presence of water in DMA, the carboxylates (<I>erythro</I>- and <I>thero</I>-1-methyl-2-phenylpropyl acetates) and the small amount of diastereomeric alcohols. The major product was (<I>Z</I>)-2-phenyl-2-butene, indicating the occurrence of <I>anti</I>-<I>E</I>1 process. The deuterium was substantially scrambled in each product. These findings suggest that the reaction proceeds through tight ion-pair and subsequent processes such as <I>anti</I>-<I>E</I>1, 2,1-phenyl and -hydride shifts, solvent capture, and <I>threo</I>-<I>erythro</I> interconversion take place competitively. In view of a substantial extent of intervention of such rearrangement, the involvement of nucleophilic solvent assistance is thought to be less probable in this <I>k</I><SUB>s</SUB> process.

• 公益社団法人 日本化学会の論文

著者

• Saito Seiki

  Department Of Bioengineering Science Faculty Of Engineering. Okayama University

• Okamoto Kunio

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

• Moriwake Toshio

  Department of Synthetics Chemistry, School of Engineering, Okayama University

• Saito Seiki

  Department of Synthetics Chemistry, School of Engineering, Okayama University

• Doihara Kenji

  Department of Synthetics Chemistry, School of Engineering, Okayama University

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