Thermal decomposition of 2,2-bis(t-butyldioxy)alkanes.
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概要
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The thermal decomposition of 2,2-bis(<I>t</I>-butyldioxy)propane (<B>1a</B>) has been studied in cumene. The activation parameters obtained by the thermolysis of <B>la</B> are Δ<I>H</I><SUP>\neweq</SUP>=145.6kJ mol<SUP>−1</SUP> and Δ<I>S</I><SUP>\neweq</SUP>=47.3 J K<SUP>−1</SUP> mol<SUP>−1</SUP>. The decomposition products of <B>1a</B> are acetone, <I>t</I>-butyl alcohol, <I>t</I>-butyl hydroperoxide, <I>t</I>-butyl peracetate, <I>t</I>-butyl 1-methyl-1-phenylethyl peroxide, and bis(1-methyl-1-phenylethyl). The peroxyacetal cleaves homolytically at one of dioxy bonds to yield an intermediate alkoxyl radical with α-<I>t</I>-butyldioxy group, which decomposes subsequently to <I>t</I>-butyldioxyl and methyl radicals via β-elimination. The thermal decomposition of 2,2-bis(<I>t</I>-butyldioxy)butane and 2,2-bis(<I>t</I>-butyldioxy)-3-methylbutane have also been examined. Relative rates of β-elimination of radicals from alkoxyl radicals are concluded to be isopropyl: ethyl:<I>t</I>-butyldioxyl: methyl=133:33:7:1, revealing a facile scission of dioxyl radical.
- 公益社団法人 日本化学会の論文
著者
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Sawaki Yasuhiko
Department Of Applied Chemistry Faculty Of Engineering Nagoya University
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Suyama Shuji
Chemicals and Explosives Research Laboratory, Nippon Oil & Fats Co.
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Watanabe Yasumasa
Chemicals and Explosives Research Laboratory, Nippon Oil & Fats Co.
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Suyama Shuji
Chemicals & Explosives Research Laboratory, Nippon Oil & Fats Co., Ltd.
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Watanabe Yasumasa
Chemicals and Explosives Research Laboratory, Nippon Oil & Fats Co.
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