5-[7-Bicyclo[2.2.1]heptanylidene-(3-tert-butyl-4,5-dihydroxyphenyl)methyl]-3-tert-butylbenzene-1,2-diol | 374729-47-2

• 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: 5-[7-Bicyclo[2.2.1]heptanylidene-(3-tert-butyl-4,5-dihydroxyphenyl)methyl]-3-tert-butylbenzene-1,2-diol
• CAS: 374729-47-2
• 化学式: C₂₈H₃₆O₄
• 分子量: 436.591
• InChiKey: XMMGFDONLPHYFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-[7-Bicyclo[2.2.1]heptanylidene-(3-tert-butyl-4,5-dihydroxyphenyl)methyl]-3-tert-butylbenzene-1,2-diol 在 Celite 、 silver carbonate 作用下， 以 四氢呋喃 为溶剂， 以81%的产率得到bis(5-tert-butyl-3,4-benzoquinonyl)methylenenorbornane
  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：

  7-溴双环[2.2.1]庚烷 在 LiDBB 、 叔丁基锂 、 三溴化硼 、 potassium carbonate 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 16.25h， 生成 5-[7-Bicyclo[2.2.1]heptanylidene-(3-tert-butyl-4,5-dihydroxyphenyl)methyl]-3-tert-butylbenzene-1,2-diol
  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

• Trends in Exchange Coupling for Trimethylenemethane-Type Bis(semiquinone) Biradicals and Correlation of Magnetic Exchange with Mixed Valency for Cross-Conjugated Systems
  作者：David A. Shultz、Rosario M. Fico,、Scot H. Bodnar、R. Krishna Kumar、Kira E. Vostrikova、Jeff W. Kampf、Paul D. Boyle

  DOI：10.1021/ja0367849

  日期：2003.9.1

  magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling

  介绍了双自由基复合物等结构系列内的磁结构相关性（构象电子自旋交换调制）。X射线晶体结构、变温电子顺磁共振光谱、零场分裂参数和变温磁化率测量被用来评估这一系列分子的分子构象和电子自旋交换耦合。我们的综合结果表明，交换耦合的铁磁部分通过交叉共轭 pi 系统发生，而反铁磁部分通过空间发生，相当于初始键形成。因此，分子构象控制铁磁和反铁磁对交换耦合的贡献的相对量。实际上，交换参数通过 Karplus-Conroy 型关系与平均半醌环扭转角相关。由于电子自旋交换耦合和与电子转移相关的电子耦合之间的自然联系，我们还将双自由基复合物中的交换参数与相应醌-半醌自由基阴离子中的混合价相关联。我们的结果表明，交叉共轭、混合价自由基阴离子的离域与双自由基氧化态中交换耦合的铁磁贡献成正比。我们还将双自由基复合物中的交换参数与相应醌-半醌自由基阴离子中的混合价相关联。我们的结果表明，交叉共轭、混合价自由基阴离子的离
• Synthesis of Bis(semiquinone)s and Their Electrochemical and Electron Paramagnetic Resonance Spectral Characterization
  作者：David A. Shultz、Andrew K. Boal、Gary T. Farmer

  DOI：10.1021/jo981597s

  日期：1998.12.1

  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-).