(+/-)-2,2'-di-tert-butyl-7,7'-dihydroxy-8,8'-biquinolyl | 960597-74-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (+/-)-2,2'-di-tert-butyl-7,7'-dihydroxy-8,8'-biquinolyl
• 英文别名: 2-Tert-butyl-8-(2-tert-butyl-7-hydroxyquinolin-8-yl)quinolin-7-ol
• CAS: 960597-74-4
• 化学式: C₂₆H₂₈N₂O₂
• 分子量: 400.521
• InChiKey: SJPCVEKWJOKMON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  66.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-2,2'-di-tert-butyl-7,7'-dihydroxy-8,8'-biquinolyl 、 戊酰氯 在 sodium hydroxide 、 四丁基溴化铵 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 2.0h， 以31%的产率得到(+/-)-2,2'-di-tert-butyl-7,7'-di(pentanoyloxy)-8,8'-biquinolyl
  参考文献：
  名称：

  Enzymatic Resolution of 7,7‘-Dihydroxy-8,8‘- biquinolyl Dipentanoate and Its Conversion to 2,2‘-Di-tert-butyl-7,7‘-dihydroxy-8,8‘-biquinolyl

  摘要：

  [Graphics]Incubation of (+/-)-7,7'-di(pentanoyloxy)-8,8'-biquinolyl (4) with a crude cholesterol esterase preparation (from bovine pancreas) yielded highly enantioenriched unreacted dextrorotatory material, (+)-(alpha R)-4 (46%, >= -99% ee), accompanied by the expected diol product, (-)-(alpha S)-7,7'dihydroxy-8,8'-biquinolyl (1), in modest enantiomeric excess (>= 37%, >= 77% ee). Treatment of scalemic diesters 4 with t-BuLi, followed by saponification in the presence of air, gave 2,2'-di-tert-butyl-7,7'-dihydroxy-8,8'-biquinolyl (2) in enantio enriched form. Biquinolyl 2 is less configurationally stable than 1, racemizing rapidly in CHCl3 (t(1/2)(rac) = 1.9 h, rt), and with a moderate rate in MeOH (t(1/2)(rac) = 30.5 h, rt).

  DOI：

  10.1021/jo701611u
• 作为产物：
  描述：

  (+/-)-7,7'-bis[(dimethylamino)carbonyloxy]-2,2'-di-tert-butyl-8,8'-biquinolyl 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 17.0h， 以99%的产率得到(+/-)-2,2'-di-tert-butyl-7,7'-dihydroxy-8,8'-biquinolyl
  参考文献：
  名称：

  Enzymatic Resolution of 7,7‘-Dihydroxy-8,8‘- biquinolyl Dipentanoate and Its Conversion to 2,2‘-Di-tert-butyl-7,7‘-dihydroxy-8,8‘-biquinolyl

  摘要：

  [Graphics]Incubation of (+/-)-7,7'-di(pentanoyloxy)-8,8'-biquinolyl (4) with a crude cholesterol esterase preparation (from bovine pancreas) yielded highly enantioenriched unreacted dextrorotatory material, (+)-(alpha R)-4 (46%, >= -99% ee), accompanied by the expected diol product, (-)-(alpha S)-7,7'dihydroxy-8,8'-biquinolyl (1), in modest enantiomeric excess (>= 37%, >= 77% ee). Treatment of scalemic diesters 4 with t-BuLi, followed by saponification in the presence of air, gave 2,2'-di-tert-butyl-7,7'-dihydroxy-8,8'-biquinolyl (2) in enantio enriched form. Biquinolyl 2 is less configurationally stable than 1, racemizing rapidly in CHCl3 (t(1/2)(rac) = 1.9 h, rt), and with a moderate rate in MeOH (t(1/2)(rac) = 30.5 h, rt).

  DOI：

  10.1021/jo701611u

文献信息

• Determination of p<i>K</i>_aValues for Diether Derivatives of 7,7′-Dihydroxy-8,8′-biquinolyl: Dependence of Basicity on Interannular Dihedral Angle
  作者：Paul Blakemore、Selena Milicevic、Hasini Perera、Alexey Shvarev、Lev Zakharov

  DOI：10.1055/s-2008-1078448

  日期：2008.7

  7,7′-Dihydroxy-8,8′-biquinolyl and 2,2′-di-tert-butyl-7,7′-dihydroxy-8,8′-biquinolyl were O,O′-dialkylated with MeI or dihaloalkanes [X(CH2)nX′, n = 1, 3-6]. The resulting diethers were characterized by UV spectroscopy and (wherever possible) single-crystal X-ray diffraction analysis. Biquinolyl basicity was found to positively correlate with interannular dihedral angle (IDA). Two pK a points could be located for all biquinolyl diethers with IDA above ca. 65˚ (pK a1 2.3-2.7; pK a2 4.5-5.3 in aq MeOH). By contrast, methylene diethers (IDA ≤ 60˚) were only very weakly basic (pK a 2.7-3.1) and could not be doubly protonated. Lone-pair/lone-pair proximity effects are invoked to account for the observations.

  7,7'-二羟基-8,8'-双喹啉和2,2'-二叔丁基-7,7'-二羟基-8,8'-双喹啉通过甲基碘或二卤代烷[X(CH2)nX'，n = 1, 3-6]进行O,O'-二烷基化。所得的二醚通过紫外光谱分析和（在可能的情况下）单晶X射线衍射分析进行鉴定。发现双喹啉的碱性与环间二面角（IDA）正相关。对于IDA大于约65度的所有双喹啉二醚，可以定位两个pKa点（pKa1 2.3-2.7；pKa2 4.5-5.3在aq MeOH中）。相比之下，亚甲基二醚（IDA ≤ 60度）的碱性非常弱（pKa 2.7-3.1），并且不能双重质子化。孤对/孤对接近效应被用来解释这些观察结果。