2-hydroxy-5-(2-phthalimidoethyl)-1,4-benzoquinone | 155592-11-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 2-hydroxy-5-(2-phthalimidoethyl)-1,4-benzoquinone
• CAS: 155592-11-3
• 化学式: C₁₆H₁₁NO₅
• 分子量: 297.267
• InChiKey: CUYOZOGTYBDDJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.19
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  91.75
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  4-硝基苯肼 、 2-hydroxy-5-(2-phthalimidoethyl)-1,4-benzoquinone 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 生成 4-<(4-nitrophenyl)azo>-6-(2-phthalimidoethyl)benzene-1,3-diol
  参考文献：
  名称：

  Synthesis and Characterization of Models for the 2,4,5-Trihydroxyphenylalanine (TOPA)-Derived Cofactor of Mammalian Copper Amine Oxidases, and Initial Amine Reactivity Studies

  摘要：

  The mammalian copper amine oxidases effect the oxidative deamination of primary amines through utilization of an ''active carbonyl'' cofactor, shown recently to be the quinone form (TPQ) of a protein-based 2,4,5-trihydroxyphenylalanine (TOPA) residue. We synthesized three models for the cofactor in both reduced (benzenetriol) and oxidized (hydroxyquinone) forms, which differ in the nature of the alkyl substituent mimicking the connection to the protein backbone: hydantoinylmethyl, phthalimidoethyl, and pivalamidoethyl. The quinone forms were capable of deaminating benzylamine in aqueous CH3CN both stoichiometrically and catalytically (in the presence of O-2), but incapable of deaminating non-benzylic amines. In order to clarify the various reactions potentially occurring during aerobic autorecycling deamination, we studied the pH-dependent benzenetriol --> hydroxyquinone autoxidation as well as the possible reaction of amines with the benzenetriol forms. The latter undergo stoichiometric substitution with amines to give (alkylamino)resorcinols, not via cyclohexadienone tautomerization previously proposed, but via a redox cycling mechanism involving condensation of the amines with traces of hydroxyquinone present in the benzenetriol preparations. This observed substitution regiochemistry, as well as structural characterization of the hydroxyquinone arylhydrazine derivatives, confirms that amines react exclusively at the electrophilic C5 carbonyl position of TPQ models. Both the hydroxyquinone and benzenetriol forms were found to react with ethylenediamine in the presence of O-2 to give 6-hydroxy-7-(2-pivalamidoethyl)quinoxaline, consistent with the postulated generation of such moiety when lysyl oxidase is inactivated by ethylenediamine.

  DOI：

  10.1021/jo00088a023
• 作为产物：
  描述：

  2,4,5-tris(benzyloxy)-β-nitrostyrene 在 palladium on activated charcoal lithium aluminium tetrahydride 、 氢气 、 三氯化铁 作用下， 以 四氢呋喃 、 乙醇 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 50.0~115.0 ℃ 、413.69 kPa 条件下， 反应 26.0h， 生成 2-hydroxy-5-(2-phthalimidoethyl)-1,4-benzoquinone
  参考文献：
  名称：

  Synthesis and Characterization of Models for the 2,4,5-Trihydroxyphenylalanine (TOPA)-Derived Cofactor of Mammalian Copper Amine Oxidases, and Initial Amine Reactivity Studies

  摘要：

  The mammalian copper amine oxidases effect the oxidative deamination of primary amines through utilization of an ''active carbonyl'' cofactor, shown recently to be the quinone form (TPQ) of a protein-based 2,4,5-trihydroxyphenylalanine (TOPA) residue. We synthesized three models for the cofactor in both reduced (benzenetriol) and oxidized (hydroxyquinone) forms, which differ in the nature of the alkyl substituent mimicking the connection to the protein backbone: hydantoinylmethyl, phthalimidoethyl, and pivalamidoethyl. The quinone forms were capable of deaminating benzylamine in aqueous CH3CN both stoichiometrically and catalytically (in the presence of O-2), but incapable of deaminating non-benzylic amines. In order to clarify the various reactions potentially occurring during aerobic autorecycling deamination, we studied the pH-dependent benzenetriol --> hydroxyquinone autoxidation as well as the possible reaction of amines with the benzenetriol forms. The latter undergo stoichiometric substitution with amines to give (alkylamino)resorcinols, not via cyclohexadienone tautomerization previously proposed, but via a redox cycling mechanism involving condensation of the amines with traces of hydroxyquinone present in the benzenetriol preparations. This observed substitution regiochemistry, as well as structural characterization of the hydroxyquinone arylhydrazine derivatives, confirms that amines react exclusively at the electrophilic C5 carbonyl position of TPQ models. Both the hydroxyquinone and benzenetriol forms were found to react with ethylenediamine in the presence of O-2 to give 6-hydroxy-7-(2-pivalamidoethyl)quinoxaline, consistent with the postulated generation of such moiety when lysyl oxidase is inactivated by ethylenediamine.

  DOI：

  10.1021/jo00088a023