6,7-bis(chloromethyl)-8,12-diphenylbenzo[a]heptalene | 263172-10-7

• 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: 6,7-bis(chloromethyl)-8,12-diphenylbenzo[a]heptalene
• 英文别名: 1,4,6,7-bis(chloromethyl)-8,12-diphenylbenzo[a]heptalene
• CAS: 263172-10-7
• 化学式: C₃₀H₂₂Cl₂
• 分子量: 453.411
• InChiKey: SLXSZNUMPWFCGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Lithium-diphenylphosphinit 、 6,7-bis(chloromethyl)-8,12-diphenylbenzo[a]heptalene 以 四氢呋喃 为溶剂， 以77%的产率得到8,12-diphenyl-6,7-bis[(diphenylphosphinoyl)methyl]benzo[a]heptalene
  参考文献：
  名称：

  Synthesis of (P)- and (M)-6,7-Bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalenes - Potential Ligands for Homogeneous Asymmetric Catalysis

  摘要：

  The title bis(phosphane) ligands have been prepared starting from optically pure diisopropyl (P)- and (M)-8,22-diphenylbenzo[a]heptalene-6,7-dicarboxylaes ((P)-1b and (M)-1b) that had been obtained by HPLC separation of rac-1b on a semi-preparative Chiralcel OD column. Reduction of (P)-1b and (M)-1b with diisobutylaluminum hydride (DIBAH) gave optically pure (P)- and (M)-dimethanols 3 (Scheme 6 and Fig. 5). Unfortunately, the almost quantitative chlorination of rac-3 with PCl5 in CHCl3 at - 60 degrees led with (M)-3 to nearly complete loss of optical integrity However, mesylate formation of (P)-3. followed by phosphanylation with LiP(BH3)Ph-2 gave (P)-6 with only a small loss of optical activity. Optically pure (P)-6 was obtained by crystallization from Et2O/hexane, which removed the nearly insoluble rac-6. The pure bis(phosphane) ligands (P)-2 and (M)-2 can be liberated quantitatively from 6 by warming 6 in toluene in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). First Rh'-catalyzed asymmetric hydrogenation reactions of (Z)-alpha-(acetamido)cinnamic acid ((Z)-14) in the presence of (P)-2 led to (R)-N-acetylphenylalanin ((R)-15) in optical purities up to 77% (see Table 1).

  DOI：

  10.1002/(sici)1522-2675(20000119)83:1<258::aid-hlca258>3.0.co;2-a
• 作为产物：
  描述：

  diisopropyl 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylate 在 五氯化磷 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 为溶剂， 反应 5.0h， 生成 6,7-bis(chloromethyl)-8,12-diphenylbenzo[a]heptalene
  参考文献：
  名称：

  Synthesis of (P)- and (M)-6,7-Bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalenes - Potential Ligands for Homogeneous Asymmetric Catalysis

  摘要：

  The title bis(phosphane) ligands have been prepared starting from optically pure diisopropyl (P)- and (M)-8,22-diphenylbenzo[a]heptalene-6,7-dicarboxylaes ((P)-1b and (M)-1b) that had been obtained by HPLC separation of rac-1b on a semi-preparative Chiralcel OD column. Reduction of (P)-1b and (M)-1b with diisobutylaluminum hydride (DIBAH) gave optically pure (P)- and (M)-dimethanols 3 (Scheme 6 and Fig. 5). Unfortunately, the almost quantitative chlorination of rac-3 with PCl5 in CHCl3 at - 60 degrees led with (M)-3 to nearly complete loss of optical integrity However, mesylate formation of (P)-3. followed by phosphanylation with LiP(BH3)Ph-2 gave (P)-6 with only a small loss of optical activity. Optically pure (P)-6 was obtained by crystallization from Et2O/hexane, which removed the nearly insoluble rac-6. The pure bis(phosphane) ligands (P)-2 and (M)-2 can be liberated quantitatively from 6 by warming 6 in toluene in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). First Rh'-catalyzed asymmetric hydrogenation reactions of (Z)-alpha-(acetamido)cinnamic acid ((Z)-14) in the presence of (P)-2 led to (R)-N-acetylphenylalanin ((R)-15) in optical purities up to 77% (see Table 1).

  DOI：

  10.1002/(sici)1522-2675(20000119)83:1<258::aid-hlca258>3.0.co;2-a

文献信息

• Synthesis of (P)- and (M)-6,7-Bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalenes - Potential Ligands for Homogeneous Asymmetric Catalysis
  作者：Peter Mohler、Andreas Johannes Rippert、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(20000119)83:1<258::aid-hlca258>3.0.co;2-a

  日期：2000.1.19

  The title bis(phosphane) ligands have been prepared starting from optically pure diisopropyl (P)- and (M)-8,22-diphenylbenzo[a]heptalene-6,7-dicarboxylaes ((P)-1b and (M)-1b) that had been obtained by HPLC separation of rac-1b on a semi-preparative Chiralcel OD column. Reduction of (P)-1b and (M)-1b with diisobutylaluminum hydride (DIBAH) gave optically pure (P)- and (M)-dimethanols 3 (Scheme 6 and Fig. 5). Unfortunately, the almost quantitative chlorination of rac-3 with PCl5 in CHCl3 at - 60 degrees led with (M)-3 to nearly complete loss of optical integrity However, mesylate formation of (P)-3. followed by phosphanylation with LiP(BH3)Ph-2 gave (P)-6 with only a small loss of optical activity. Optically pure (P)-6 was obtained by crystallization from Et2O/hexane, which removed the nearly insoluble rac-6. The pure bis(phosphane) ligands (P)-2 and (M)-2 can be liberated quantitatively from 6 by warming 6 in toluene in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). First Rh'-catalyzed asymmetric hydrogenation reactions of (Z)-alpha-(acetamido)cinnamic acid ((Z)-14) in the presence of (P)-2 led to (R)-N-acetylphenylalanin ((R)-15) in optical purities up to 77% (see Table 1).