CIDNP investigation of aminyl radicals formed by thermolysis of triazenes.
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概要
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Thermolysis of asymmetric triazenes Ar–N=N–NH–R <B>1</B> produces anilines Ar–NH<SUB>2</SUB> <B>2</B>, hydrocarbons R–H <B>3</B>, and <I>N</I>-alkylated anilines Ar–NH–R <B>4</B> as the main reaction products. <SUP>1</SUP>H- and <SUP>13</SUP>C-CIDNP experiments show polarization of nuclei in Ar–NH<SUB>2</SUB>, Ar–NH–R, R–H and some additional products (especially ring alkylated anilines). These observations are in agreement with the formation of an intermediate radical pair [Ar–NH··R] which must have been formed <I>via</I> homolysis of the tautomeric form ArNH–N=N–R <B>1</B>′. Temperature-dependent <SUP>13</SUP>C-NMR spectra show a rapid equilibrium between <B>1</B> and <B>1</B>′ at room temperature and above, the tautomeric form <B>1</B> being predominant. From the CIDNP spectra the signs of the <SUP>1</SUP>H and <SUP>13</SUP>C hyperfine couplings of aminyl radicals Ar–NH and alkyl radicals R. have been determined.
- 公益社団法人 日本化学会の論文
著者
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Iwamura Hiizu
Department Of Chemistry Faculty Of Science The University Of Tokyo
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Dangel Karl-Michael
Department of Organic Chemistry, University of Tübingen
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Albert Klaus
Department of Organic Chemistry, University of Tübingen
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Rieker Anton
Department of Chemistry, Faculty of Science, The University of Tokyo
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Imahashi Yuzo
Department of Chemistry, Faculty of Science, The University of Tokyo
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