3-Tert-butyl-5-[9-(3-tert-butyl-4,5-dihydroxyphenyl)fluoren-9-yl]benzene-1,2-diol | 1026015-31-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 3-Tert-butyl-5-[9-(3-tert-butyl-4,5-dihydroxyphenyl)fluoren-9-yl]benzene-1,2-diol
• CAS: 1026015-31-5
• 化学式: C₃₃H₃₄O₄
• 分子量: 494.631
• InChiKey: MYKNHXVPOZJKDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  3-Tert-butyl-5-[9-(3-tert-butyl-4,5-dihydroxyphenyl)fluoren-9-yl]benzene-1,2-diol 在 Celite 、 silver carbonate 作用下， 以 四氢呋喃 为溶剂， 以79%的产率得到9,9-bis(5'-tert-butyl-3',4'-benzoquinonyl)fluorene
  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：

  甲基2-联苯羧酸酯 在 叔丁基锂 、 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 1.33h， 生成 3-Tert-butyl-5-[9-(3-tert-butyl-4,5-dihydroxyphenyl)fluoren-9-yl]benzene-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

• 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-).