4-[Bis-(3-tert-butyl-4,5-dihydroxy-phenyl)-methylene]-2,6-di-tert-butyl-cyclohexa-2,5-dienone | 220548-38-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4-[Bis-(3-tert-butyl-4,5-dihydroxy-phenyl)-methylene]-2,6-di-tert-butyl-cyclohexa-2,5-dienone
• CAS: 220548-38-9
• 化学式: C₃₅H₄₆O₅
• 分子量: 546.747
• InChiKey: PDSGRONMDKGVOI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.43
• 重原子数：
  40.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  97.99
• 氢给体数：
  4.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  4-[Bis-(3-tert-butyl-4,5-dihydroxy-phenyl)-methylene]-2,6-di-tert-butyl-cyclohexa-2,5-dienone 在 Celite 、 silver carbonate 作用下， 以 四氢呋喃 为溶剂， 以87%的产率得到bis(5'-tert-butyl-3',4'-benzoquinonyl)-3,5-di-tert-butyl-4-oxophenylmethane
  参考文献：
  名称：

  Synthesis of Bis(semiquinone)s and Their Electrochemical and Electron Paramagnetic Resonance Spectral Characterization

  摘要：

  The syntheses of three new bis(semiquinone)s (2(..2-), 3(..2-), and 5(..2-)) linked through carbon-carbon double bonds in a geminal fashion (2(..2-) and 3(..2-)), and through an sp(3) carbon (5(..2-)), are presented, as well as the results of variable-temperature EPR CVT-EPR) spectroscopy on these biradicals and two previously reported bis(semiquinone)s, 1(..2-) and 4(..2-). We suggest that the potential difference in redox couples associated with a biradical is useful for qualitatively assessing changes in the exchange parameter within an isostructural series. The zero-field-splitting parameters for 1(..2-)- 5(..2-) are consistent with their electronic structures: biradicals 1(..2-)-3(..2-) which have conjugating groups attached to the semiquinone rings have D-values less than 5(..2-), a bis(semiquinone) that lacks such a conjugating group. Also, the D-value of 3(..2-) is significantly less than those of 1(..2-) and 2(..2-), in greement with larger interelectron separation in 3(..2-), a biradical with quinone-methide pi-system delocalization. Changes in counterion Lewis acidity are not manifested in the D-values of the biradical dianion 4(..2-). The EPR spectrum of biradical 5(..2-) is consistent with the existence of at least two rotamers having different zero-field-splitting parameters. Biradicals 1(..2-)-4(..2-) gave linear Curie plots, consistent with J > 0 (ferromagnetic coupling) or J = 0, The temperature-dependent intensity of EPR signals of 5(..2-) are characteristic of antiferromagnetic coupling. Best fit results give J = -114 +/- 6 cal/mol for the \D/hc\ = 0.01309 cm(-1) rotamer of 5(..2-), and J = -76 +/-: 3 cal/mol for the \D/hc\ = 0.01026 cm(-1) rotamer of 5(..2-).

  DOI：

  10.1021/jo981597s
• 作为产物：
  描述：

  methyl 3,5-di-tert-butyl-4-(trimethylsilyloxy)benzoate 在 盐酸 作用下， 以 甲醇 为溶剂， 生成 4-[Bis-(3-tert-butyl-4,5-dihydroxy-phenyl)-methylene]-2,6-di-tert-butyl-cyclohexa-2,5-dienone
  参考文献：
  名称：

  Synthesis of Bis(semiquinone)s and Their Electrochemical and Electron Paramagnetic Resonance Spectral Characterization

  摘要：

  The syntheses of three new bis(semiquinone)s (2(..2-), 3(..2-), and 5(..2-)) linked through carbon-carbon double bonds in a geminal fashion (2(..2-) and 3(..2-)), and through an sp(3) carbon (5(..2-)), are presented, as well as the results of variable-temperature EPR CVT-EPR) spectroscopy on these biradicals and two previously reported bis(semiquinone)s, 1(..2-) and 4(..2-). We suggest that the potential difference in redox couples associated with a biradical is useful for qualitatively assessing changes in the exchange parameter within an isostructural series. The zero-field-splitting parameters for 1(..2-)- 5(..2-) are consistent with their electronic structures: biradicals 1(..2-)-3(..2-) which have conjugating groups attached to the semiquinone rings have D-values less than 5(..2-), a bis(semiquinone) that lacks such a conjugating group. Also, the D-value of 3(..2-) is significantly less than those of 1(..2-) and 2(..2-), in greement with larger interelectron separation in 3(..2-), a biradical with quinone-methide pi-system delocalization. Changes in counterion Lewis acidity are not manifested in the D-values of the biradical dianion 4(..2-). The EPR spectrum of biradical 5(..2-) is consistent with the existence of at least two rotamers having different zero-field-splitting parameters. Biradicals 1(..2-)-4(..2-) gave linear Curie plots, consistent with J > 0 (ferromagnetic coupling) or J = 0, The temperature-dependent intensity of EPR signals of 5(..2-) are characteristic of antiferromagnetic coupling. Best fit results give J = -114 +/- 6 cal/mol for the \D/hc\ = 0.01309 cm(-1) rotamer of 5(..2-), and J = -76 +/-: 3 cal/mol for the \D/hc\ = 0.01026 cm(-1) rotamer of 5(..2-).

  DOI：

  10.1021/jo981597s

文献信息

• Paramagnetic Zinc(II) Complexes of a Bis(catechol):  Dependence of Product Spin State on Tautomerization of the Bis(catechol) Ligand
  作者：David A. Shultz、Scot H. Bodnar

  DOI：10.1021/ic981092k

  日期：1999.2.1

  We report the preparation and characterization of zinc(II) hydrotris(3-cumenyl-5-methylpyrazolyl)borate (LZn) complexes, (LZn)(2)()1'-H and (LZn)(2)()1, of a bis(catechol) ligand. The formation of (LZn)(2)()1'-H, an S = (1)/(2) complex, rather than (LZn)(2)()1, an S = 1 complex, is observed due to tautomerization of a reaction intermediate. The biradical complex, (LZn)(2)()1, can be prepared from (LZn)(2)()1'-H

  我们报告制备和表征的锌（II）氢三（3-枯烯基5-甲基吡唑基）硼酸（LZn）配合物（LZn）（2）（）1'-H和（LZn）（2）（）1，双（邻苯二酚）配体的结构。观察到（LZn）（2）（）1'-H（S =（1）/（2）配合物）的形成，而不是（LZn）（2）（）1（S = 1配合物）的形成是由于反应中间体的互变异构。双自由基配合物（LZn）（2）（）1可通过氧化从（LZn）（2）（）1'-H制备，该转换伴随着蓝绿色到红紫色的变色和从（1）/（2）到1的自旋增加。双自由基配合物（LZn）（2）（）1的冻结溶液EPR谱显示零场分裂，并且Deltam（s）（）= 2跃迁特性三重态