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<p>The reactivity of <i>N</i>,<i>N</i>′-bis(2,6-diisopropylphenyl)acenaphthylene-1,2-diarnine (dpp-bianH<sub>2</sub>, <b>1</b>) toward air oxygen and various quinones has been studied. An exposure of a THF solution of <b>1</b> to air oxygen at ambient temperature affords immediately H<sub>2</sub>O<sub>2</sub> (&gt;97% according to NMR data) together with the dehydrogenated product: 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian). The reaction of diamine <b>1</b> with 3,6-di-<i>tert</i>-butyl-<i>o</i>-benzoquinone depends on stoichiometry: the stable hydroxyphenoxyl radical (semiquinone, 3,6-QH<sup>•</sup>) is formed at the 1: 2 ratio of the reactants, while pyrocatechol (3,6-QH<sub>2</sub>) is formed in 92% yield (according to NMR data) at the 1: 1 ratio. The reduction of <i>p</i>-benzoquinone with diamine <b>1</b> also proceeds easily to give hydroquinone (93%), whereas anthraquinone remains inert toward diamine <b>1</b> under analogous conditions. In turn, acenaphthenequinone reacts with diamine <b>1</b> <i>via</i> reduction of only one C=O group to yield 2-hydroxyacenaphthylen-1(2<i>H</i>)-one (89%). The calculated narrow (2.20 eV) HOMO—LUMO gap in diamine <b>1</b> is consistent with its experimentally observed absorption (526 nm). A high electron-donating ability of compound <b>1</b> is due to a low ionization potential (calculated value 5.35 eV).</p>

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N,N′-Bis(2,6-diisopropylphenyl)acenaphthylene-1,2-diamine: a promising reducing agent for organic synthesis

  • 期刊论文

  • 发表日期：

    2026年3月1日

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  • Yu. I. Sozinova,
  • V. M. Makarov,
  • A. N. Lukoyanov,
  • E. A. Rychagova,
  • S. Yu. Ketkov,
  • T. S. Koptseva,
  • I. L. Fedushkin

摘要

The reactivity of N,N′-bis(2,6-diisopropylphenyl)acenaphthylene-1,2-diarnine (dpp-bianH2, 1) toward air oxygen and various quinones has been studied. An exposure of a THF solution of 1 to air oxygen at ambient temperature affords immediately H2O2 (>97% according to NMR data) together with the dehydrogenated product: 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian). The reaction of diamine 1 with 3,6-di-tert-butyl-o-benzoquinone depends on stoichiometry: the stable hydroxyphenoxyl radical (semiquinone, 3,6-QH•) is formed at the 1: 2 ratio of the reactants, while pyrocatechol (3,6-QH2) is formed in 92% yield (according to NMR data) at the 1: 1 ratio. The reduction of p-benzoquinone with diamine 1 also proceeds easily to give hydroquinone (93%), whereas anthraquinone remains inert toward diamine 1 under analogous conditions. In turn, acenaphthenequinone reacts with diamine 1 via reduction of only one C=O group to yield 2-hydroxyacenaphthylen-1(2H)-one (89%). The calculated narrow (2.20 eV) HOMO—LUMO gap in diamine 1 is consistent with its experimentally observed absorption (526 nm). A high electron-donating ability of compound 1 is due to a low ionization potential (calculated value 5.35 eV).