Substituent effects on 15N and 17O NMR chemical shifts in 4'-substituted trans-NNO-azoxybenzenes.

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概要

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• <SUP>15</SUP>N and <SUP>17</SUP>O NMR spectra have been measured for a series of 4′-substituted <I>trans</I>-<I>NNO</I>-azoxybenzenes (AZOXY) and the obtained substituent chemical shift (SCS) values have been analyzed by means of the LSFE equation. Both the resonance and the polar contribution of substituents are important in determining the <SUP>15</SUP>N(β) SCS and the adjacent terminal <SUP>17</SUP>O SCS in the –N<SUB>α</SUB>=N<SUB>β</SUB>(O)– function of the AZOXY set. The resonance contributions of the AZOXY sets differ from those of the corresponding PYNO sets in view of a depressed pi-acceptor resonance contribution. That is, the resonance susceptibility ratio in the LSFE equation, ρ<SUB>π</SUB><SUP>+</SUP>⁄ρ<SUB>π</SUB><SUP>−</SUP>, varies from 1.4 (PYNO) to 2–4 (AZOXY) for both <SUP>15</SUP>N and <SUP>17</SUP>O SCS. The results are compared with the <SUP>13</SUP>C SCS of the corresponding positions in the relevant aromatic side-chain systems, and characterized in terms of repulsive pi-acceptor interaction between the substituents and the side-chain pi-electron systems. The importance of such dual resonance susceptibility has been shown for understanding characteristic features of the <SUP>15</SUP>N and the adjacent <SUP>17</SUP>O SCS.

• 公益社団法人 日本化学会の論文

著者

• Tsuno Yuho

  Department Of Chemistry Faculty Of General Education Kumamoto University

• Takai Yoshio

  Material Analysis Center, The Institute of Scientific and Industrial Research, Osaka University

• TSUNO Yuho

  Department of Chemistry, Faculty of Science, Kyushu University

• SAWADA Masami

  Material Analysis Center, The Institute of Scientific and Industrial Research, Osaka University

• Tanaka Takanori

  Material Analysis Center, The Institute of Scientific and Industrial Research, Osaka University

• Hanafusa Terukiyo

  Material Analysis Center, The Institute of Scientific and Industrial Research, Osaka University

• Okubo Masao

  Department of Chemistry, Faculty of Science and Engineering, Saga University

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