Solvolysis in carboxamides. VI. Kinetic, product, and deuterium tracer studies on the N,N-dimethylacetamide solvolysis of threo-2-(p-methoxyphenyl)-1-methylpropyl brosylate. Nature of the k.DELTA. pathway.
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概要
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Solvolysis of <I>threo</I>-2-(<I>p</I>-methoxyphenyl)-1-methylpropyl brosylate (<B>1</B>) and its deuterium derivative (<B>1</B>-2-<I>d</I>) has been carried out in <I>N</I>,<I>N</I>-dimethylacetamide (DMA) as solvent at 50.0 and 75.0 °C. Product examination revealed that in the presence of water (0.17 mol/dm<SUP>3</SUP>) the main product is <I>threo</I>-2-(<I>p</I>-methoxyphenyl)-1-methylpropyl acetate (73% at 50 °C), but in the absence of water (<I>Z</I>)-2-(<I>p</I>-methoxyphenyl)-2-butene (<B>5</B>) (<I>ca.</I> 70% at 50 °C). Both of these products are derived from a <I>threo</I>-imidatonium ion [<I>threo</I>-R-Amide]<SUP>+</SUP> which is produced by DMA capture of the tight ion-pair [R<SUP>+</SUP>OBs<SUP>−</SUP>] (<B>2</B>) from the front-side. A part (<I>ca.</I> 14% yield) of the (<I>Z</I>)-olefin <B>5</B> is directly led from the tight ion-pair <B>2</B>. The formation of the olefin <B>5</B> can not be explained by intervention of the phenyl-bridged ion. Although the rate of the brosylate <B>1</B> exhibits the <I>k</I><SUB>Δ</SUB> portion deviating upwards from the Hammett plot for a series of <I>threo</I>-2-aryl-1-methylpropyl brosylates, the Schleyer's <I>k</I><SUB>Δ</SUB>-<I>k</I><SUB>s</SUB> treatment for the rate-(retained)product correlation was unsatisfactory. The classical simple <I>S</I><SUB>N</SUB>1 mechanism can preferably elucidate the product distribution, including the isotope distribution, without intervention of the phenyl-bridged ion intermediate.
- 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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Doihara Kenji
Department of Synthetics Chemistry, School of Engineering, Okayama University
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Moriwake Toshro
Department of Synthetics Chemistry, School of Engineering, Okayama University
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