ethyl 2,5-di-tert-butyl-3,4-dihydroxybenzpate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl 2,5-di-tert-butyl-3,4-dihydroxybenzpate
• 英文别名: Ethyl 2,5-ditert-butyl-3,4-dihydroxybenzoate
• 化学式: C₁₇H₂₆O₄
• 分子量: 294.391
• InChiKey: RSKYGUFCMSLMLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3,5-二-叔-丁基-4-羟基苯甲酸乙酯 在 tetrakis(acetonitrile)copper(I)tetrafluoroborate 、 Co(II)(Salpr) 氧气 、 四氯化锡 、 三乙胺 、 N,N-bis[2-(N-methylbenzimidazol-2-yl)ethyl]benzylamine 作用下， 以 盐酸 、 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 4.03h， 生成 ethyl 2,5-di-tert-butyl-3,4-dihydroxybenzpate
  参考文献：
  名称：

  Novel tert-Butyl Migration in Copper-Mediated Phenol Ortho-Oxygenation Implicates a Mechanism Involving Conversion of a 6-Hydroperoxy-2,4-cyclohexadienone Directly to an o-Quinone

  摘要：

  Copper mediated ortho-oxygenation of phenolates may proceed through the generation of a 6-peroxy-2,4-cyclohexadienone intermediate. To test this theory, we studied the fate of sodium 4-carbethoxy2,6-di-tert-butylphenolate, where the ortho-oxygenation sites are blocked by tert-butyl groups. Using the Cu(I) complex of N,N-bis(2-(N-methylbenzimidazol-2-yl)ethyl)benzylamine, isolation of the major oxygenated product and characterization by single-crystal X-ray crystallography and NMR spectroscopy revealed it to be 4-carbethoxy-3,6-di-tert-butyl-1,2-benzoquinone, resulting from a 1,2-migration of a tert-butyl group. The independently prepared B-hydroperoxide is transformed by the Cu(I)- (or Cu(II)-) ligand complex to the same o-quinone. The observed 1,2-migration of the tert-butyl group appears to reflect an electron demand created by rearrangement of the postulated peroxy intermediate. A mechanism proceeding alternatively through a catechol and subsequent oxidation to the o-quinone seems ruled out by a control study demonstrating that the requisite intermediate to catechol formation would instead eliminate the 2-tert-butyl group.

  DOI：

  10.1021/jo991625m

文献信息

• Novel <i>tert</i>-Butyl Migration in Copper-Mediated Phenol <i>Ortho</i>-Oxygenation Implicates a Mechanism Involving Conversion of a 6-Hydroperoxy-2,4-cyclohexadienone Directly to an <i>o</i>-Quinone
  作者：Subrata Mandal、Dainius Macikenas、John D. Protasiewicz、Lawrence M. Sayre

  DOI：10.1021/jo991625m

  日期：2000.8.1

  Copper mediated ortho-oxygenation of phenolates may proceed through the generation of a 6-peroxy-2,4-cyclohexadienone intermediate. To test this theory, we studied the fate of sodium 4-carbethoxy2,6-di-tert-butylphenolate, where the ortho-oxygenation sites are blocked by tert-butyl groups. Using the Cu(I) complex of N,N-bis(2-(N-methylbenzimidazol-2-yl)ethyl)benzylamine, isolation of the major oxygenated product and characterization by single-crystal X-ray crystallography and NMR spectroscopy revealed it to be 4-carbethoxy-3,6-di-tert-butyl-1,2-benzoquinone, resulting from a 1,2-migration of a tert-butyl group. The independently prepared B-hydroperoxide is transformed by the Cu(I)- (or Cu(II)-) ligand complex to the same o-quinone. The observed 1,2-migration of the tert-butyl group appears to reflect an electron demand created by rearrangement of the postulated peroxy intermediate. A mechanism proceeding alternatively through a catechol and subsequent oxidation to the o-quinone seems ruled out by a control study demonstrating that the requisite intermediate to catechol formation would instead eliminate the 2-tert-butyl group.