1,2-bis(dibenzophospholyl)ethane | 34667-27-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1,2-bis(dibenzophospholyl)ethane
• 英文别名: 5H,5'H-5,5'-ethane-1,2-diyl-bis-benzo[b]phosphindole；5-(2-Benzo[b]phosphindol-5-ylethyl)benzo[b]phosphindole
• CAS: 34667-27-1
• 化学式: C₂₆H₂₀P₂
• 分子量: 394.392
• InChiKey: FFKXPCFGPMZGOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  1,2-bis(dibenzophospholyl)ethane 、 二(三苯基膦)环戊二烯基氯化钌(II) 以 甲苯 为溶剂， 以88%的产率得到(C5H5)RuCl(1,2-bis(dibenzophospholyl)ethane)
  参考文献：
  名称：

  Enantioselective organic syntheses using chiral transition metal complexes V. (2S,3S)-Bis(dibenzophospholyl)butane, a rigid (S,S)-CHIRAPHOS analog

  摘要：

  The P-Ph cleavage of phenyldibenzophosphole (1) with lithium in THF gives lithium dibenzophospholide (2). Reaction of 2 with ethyleneglycol ditosylate produces the known chelate ligand 1,2-bis(dibenzophospholyl)ethane (3) in good yield. Similarly, 2 and (2R,3R)-butanediol ditosylate give the new chiral chelate ligand (2S,3S)-bis(dibenzophospholyl)butane (4). Ligand exchange of [CpRu(PPh3)(2)Cl] with 3 or 4 yields the halfsandwich complexes [CpRu(C12H8PC2H4PC12H8)Cl] (5) and [CpRu((S,S)-C12H8PCHMeCHMePC12H8)Cl] (6). Complex 6 was characterized crystallographically (monoclinic, space group P2(1) (no. 4), a = 820.6(4), b = 1501.0(3), c = 1172.8(6) pm, beta = 108.87(2)degrees, V = 1.367(1) x 10(9) pm(3), Z = 2). The most conspicuous feature of the structure of 6 is the perfect coplanarity of the two dibenzophosphole moieties imposed by their steric interaction with the Cp ligand. Complex 6 and the thiophene complex [CpRu((S,S)-C12H8PCHMeCHMePC12H8)(SC4H4)]BF4 (7) derived therefrom are remarkably unreactive with regard to ligand substitutions. A possible explanation is the lack of intramolecular M ... H-C stabilization en route to the transition state of ligand substitution. The enantiomeric purity of 6 and 7 could nevertheless be demonstrated by conversion to diastereomerically pure [CpRu((S,S)-C12H8PCHMeCHMePC12H8)((S)-CNCHMePh)]BF4 (8). (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00461-6
• 作为产物：
  描述：

  1,2-双(二氯磷基)-乙烷 、 2,2'-双溴双苯 在 正丁基锂 作用下， 生成 1,2-bis(dibenzophospholyl)ethane
  参考文献：
  名称：

  的1,2-双（dibenzophospholyl-1）乙烷的替代合成，x射线晶体结构和P388活性†

  摘要：

  通过2,2'-二硫代联苯与1,2-双（二氯膦基）乙烷的偶联，以一步法完成了产率为45％的1,2-双（二苯并膦酰基-1）乙烷（2）的合成。二硫代试剂是通过将2，2'-二溴代联苯与正丁基锂金属化而原位生成的。相对于外部三甲基磷酸（1,2-双（二苯基膦基）乙烷1（不受约束的类似物1）观察到的δ12.8 ppm ，在δ11.2 ppm（氘代氯仿）处的31 P [ 1 H] nmr化学位移2稍微偏高。δ 31 P 2.0 ppm）表示。X射线晶体学显示2在空间群P2中结晶1/ c，晶格常数为a = 5.752（1），b = 12.891（2），c = 13.675（3），β= 100.74（2）°，Z =2。化合物2形成双[氯金（I） ）]以类似于已知金属络合配体1的方​​式络合。在最大耐受剂量（MTD）为20.2μmol/ kg的情况下，在ip P388白血病小鼠模型中评估2导致相对于对照，寿命（

  DOI：

  10.1002/jhet.5570270459

文献信息

• Alkali aza-, phospha- and arsacyclopentadienides and their chemical properties
  作者：E.H. Braye、I. Caplier、R. Saussez

  DOI：10.1016/s0040-4020(01)91719-3

  日期：1971.1

  is reacted with an alkali metal in an inert solvent, the phenyl group is split off yielding the corresponding alkali heterocyclopentadienide. Hydrolysis of the alkali phosphacyclopentadienides gave the first P-unsubstituted phospholes (7a, 7b, 10). Similarly, this method allows the dephenylation of N-phenyl substituted pyrroles. Reaction of the alkali phospholides with alkyl halides offers a convenient

  当1-苯基取代的吡咯，磷酸或芳醚在惰性溶剂中与碱金属反应时，苯基被分解，生成相应的碱金属杂环戊二烯。碱phosphacyclopentadienides的水解得到第一P未取代phospholes（7 A，7 B，10）。同样，该方法可以使N-苯基取代的吡咯脱苯。碱金属磷化物与烷基卤化物的反应提供了一种方便的方法来合成在P原子上带有官能团的烷基链的磷脂。因此，已经制备了对-卤代烷基磷脂，其通过自季铵化加热而得到的新的螺环（43、44）或双螺环（45）。在主链上具有P原子的杂环系统或聚phosph盐（46，47）。
• An alternate synthesis, x-ray crystal structure and p388 activity of 1,2-bis(dibenzophospholyl-1)ethane
  作者：Blaine M. Sutton、Gerald R. Girard、Drake S. Eggleston、Paul W. Baures、Leo F. Faucette、Randall K. Johnson、David T. Hill

  DOI：10.1002/jhet.5570270459

  日期：1990.5

  Synthesis of 1,2-bis(dibenzophospholyl-l)ethane (2) in 45% yield was accomplished in a single step via the coupling of 2,2′-dilithiobiphenyl with 1,2-bis(dichlorophosphino)ethane. The dilithio reagent was generated in situ by the metalation of 2,2′-dibromobiphenyl with n-butyl lithium. The 31P[1H] nmr chemical shift of 2 at δ 11.2 ppm (deuteriochloroform) is slightly upfield from the δ 12.8 ppm observed

  通过2,2'-二硫代联苯与1,2-双（二氯膦基）乙烷的偶联，以一步法完成了产率为45％的1,2-双（二苯并膦酰基-1）乙烷（2）的合成。二硫代试剂是通过将2，2'-二溴代联苯与正丁基锂金属化而原位生成的。相对于外部三甲基磷酸（1,2-双（二苯基膦基）乙烷1（不受约束的类似物1）观察到的δ12.8 ppm ，在δ11.2 ppm（氘代氯仿）处的31 P [ 1 H] nmr化学位移2稍微偏高。δ 31 P 2.0 ppm）表示。X射线晶体学显示2在空间群P2中结晶1/ c，晶格常数为a = 5.752（1），b = 12.891（2），c = 13.675（3），β= 100.74（2）°，Z =2。化合物2形成双[氯金（I） ）]以类似于已知金属络合配体1的方​​式络合。在最大耐受剂量（MTD）为20.2μmol/ kg的情况下，在ip P388白血病小鼠模型中评估2导致相对于对照，寿命（
• Enantioselective organic syntheses using chiral transition metal complexes V. (2S,3S)-Bis(dibenzophospholyl)butane, a rigid (S,S)-CHIRAPHOS analog
  作者：Wolfdieter A Schenk、Michael Stubbe、Michael Hagel

  DOI：10.1016/s0022-328x(98)00461-6

  日期：1998.6

  The P-Ph cleavage of phenyldibenzophosphole (1) with lithium in THF gives lithium dibenzophospholide (2). Reaction of 2 with ethyleneglycol ditosylate produces the known chelate ligand 1,2-bis(dibenzophospholyl)ethane (3) in good yield. Similarly, 2 and (2R,3R)-butanediol ditosylate give the new chiral chelate ligand (2S,3S)-bis(dibenzophospholyl)butane (4). Ligand exchange of [CpRu(PPh3)(2)Cl] with 3 or 4 yields the halfsandwich complexes [CpRu(C12H8PC2H4PC12H8)Cl] (5) and [CpRu((S,S)-C12H8PCHMeCHMePC12H8)Cl] (6). Complex 6 was characterized crystallographically (monoclinic, space group P2(1) (no. 4), a = 820.6(4), b = 1501.0(3), c = 1172.8(6) pm, beta = 108.87(2)degrees, V = 1.367(1) x 10(9) pm(3), Z = 2). The most conspicuous feature of the structure of 6 is the perfect coplanarity of the two dibenzophosphole moieties imposed by their steric interaction with the Cp ligand. Complex 6 and the thiophene complex [CpRu((S,S)-C12H8PCHMeCHMePC12H8)(SC4H4)]BF4 (7) derived therefrom are remarkably unreactive with regard to ligand substitutions. A possible explanation is the lack of intramolecular M ... H-C stabilization en route to the transition state of ligand substitution. The enantiomeric purity of 6 and 7 could nevertheless be demonstrated by conversion to diastereomerically pure [CpRu((S,S)-C12H8PCHMeCHMePC12H8)((S)-CNCHMePh)]BF4 (8). (C) 1998 Elsevier Science S.A. All rights reserved.