Solvolysis of <I>cis</I>- and <I>trans</I>-4-<I>t</I>-Butylcyclohexyl Tosylates in <I>N</I>-Methylacetamide. Rates and Products Distribution
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概要
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Solvolysis of <I>cis</I>- and <I>trans</I>-4-<I>t</I>-butylcyclohexyl tosylates (RX) in wet <I>N</I>-methylacetamide (H<SUB>2</SUB>O content: 0.06–0.94 wt%) was carried out to give olefins (77–93%), 4- and 3-<I>t</I>-butylcyclohexyl acetates (ROAc) (6–22%), and 4- and 3-<I>t</I>-butylcyclohexanols (ROH) (2–4%). In <I>N</I>-methylacetamide with water (0.06%, wt) <I>trans</I>-4-RX gave <I>cis</I>-4-ROAc containing 18% <I>trans</I>-4-ROAc whereas <I>cis</I>-4-RX yielded <I>trans</I>-4-ROAc containing only 3% of <I>cis</I>-4-ROAc. In the course of solvolysis (75% completion) <I>trans</I>-4-RX was isomerized to <I>cis</I>-4-RX (5.9%), whereas <I>cis</I>-4-RX gave only 0.3% <I>trans</I>-4-RX. These results are characteristic of solvolysis in this amide solvent when compared with those in other hydroxylic solvents. Stereochemical results obtained from the present studies on the solvolysis in <I>N</I>-methylacetamide can not be explained by the hypothetical hydrogen-bridged carbonium ion intermediate proposed for the solvolysis of <I>cis</I>-4-RX. The nature of <I>N</I>-methylacetamide as a solvolytic solvent is discussed especially with regard to the effect of its polymeric structure on the steric course of solvolysis.
- 公益社団法人 日本化学会の論文
著者
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Saito Seiki
Department Of Bioengineering Science Faculty Of Engineering. Okayama University
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Okamoto Kunio
Department of Fuel Chemistry Faculty of Engineering Kyoto University
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Yabuki Tatsumi
Department of Synthetic Chemistry, School of Engineering, Okayama University
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Moriwake Toshio
Department of Synthetic Chemistry, School of Engineering, Okayama University
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