[ethane-1,2-diylbis(oxyethane-2,1-diyl)]bis[dibenzylphosphin] dioxide | 470454-02-5

• 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: [ethane-1,2-diylbis(oxyethane-2,1-diyl)]bis[dibenzylphosphin] dioxide
• 英文别名: [benzyl-[2-[2-(2-dibenzylphosphorylethoxy)ethoxy]ethyl]phosphoryl]methylbenzene
• CAS: 470454-02-5
• 化学式: C₃₄H₄₀O₄P₂
• 分子量: 574.637
• InChiKey: ZZDDWBNSDFPOKX-UHFFFAOYSA-N

物化性质

• 沸点：
  797.7±60.0 °C(Predicted)
• 密度：
  1.155±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.55
• 重原子数：
  40.0
• 可旋转键数：
  17.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  [ethane-1,2-diylbis(oxyethane-2,1-diyl)]bis[dibenzylphosphin] dioxide 在 lithium aluminium tetrahydride 、 cerium(III) chloride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 72.0h， 生成 7,7,13,13-tetrabenzyl-1,4,10-trioxa-7,13-diphosphoniacyclopentadecane dibromide
  参考文献：
  名称：

  Diphosphapodanden,[12]-,[15]- und[18]Diphosphacoronanden, Diphosphacryptand-8 und Alkalimetall-Komplexe

  摘要：

  The cyclizing bis-phosphonium-salt formation of the open-chain bih-phosphine 17a (1,1,7,7-tetrabenzyl(P.O.P-podand-7)) with diethylene glycol derived dibromide 13a yields the 12-membered cyclic bib-phosphonium salt 20 (4,4,10,10-tetrabenzyl-12(.P.O.P-coronand-4)-4,10-diium dibromide) in yields as high as 50-60%. The 1,1,10,10-tetrabenzyl(P.O-2.P-podand-10) 17b forms with 13a the 15-membered cyclic bis-phosphonium salt 21 (7,7,13,13-tetrabenzyl-15(O.P.O.P-coronand-5)-7,13-diium dibromide) with the same high yield. By quaternization of the bis-phosphine 17b with triethylene glycol derived dibromide 13b, the 18-membered 7,7,16,16-tetrabenzyl-18(O-2.P.O-2.P-coronand-6)-7,16-diium dibromide 24 is obtained in 501,10 yield, too. The Wittig reaction of the cyclic phosphonium salts with benzaldehyde yields the 12, 15-, and 18-membered cyclic bis-benzylphosphine dioxides 9, 10, and 11 as cis- and trans-isomers beside trans-stilbene, The 7,13-dioxido-7,13-dibenzyl-15(O-2.P.O-2.P-coronand-5 10 forms a crystalline 1: 1 Na-complex 23, which exists as a dimer. The structure of 23 was established by an X-ray analysis and spectroscopic data. The 7,16-dibenzyl-18(O-2.PO2.P-coronand-6) 28 that is available by reduction of 11 with CeCl3/LiAlH4 reacts with triethylene glycol derived dibromide 13b under Ruggly-Ziegler-dilution conditions to give the bicyclic bis-phosphonium salt 29 (1.10-dibenzyl(P[O-2](3).P-cryptand-8)-1,10-diium dibromide) in 18% yield. Again, by the Wittig procedure with benzaldehyde, the 7,16-dioxido(P[O-2](3)P-cryptand-8) 12 is obtained as the first diphosphacryptand. The FD-MS (CH2Cl2) of the cyclic bis-phosphine dioxides 10 - 12 show that they exist as [2M + Na](+) complexes. The complex formation constants K-a of 9 - 11 with alkali-metal cations are studied and compared with the complex formation of corresponding crown ethers.

  DOI：

  10.1002/1522-2675(200206)85:6<1714::aid-hlca1714>3.0.co;2-8
• 作为产物：
  描述：

  1,2-双(2-溴乙氧基)乙烷 在 sodium hydroxide 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 48.0h， 生成 [ethane-1,2-diylbis(oxyethane-2,1-diyl)]bis[dibenzylphosphin] dioxide
  参考文献：
  名称：

  Diphosphapodanden,[12]-,[15]- und[18]Diphosphacoronanden, Diphosphacryptand-8 und Alkalimetall-Komplexe

  摘要：

  The cyclizing bis-phosphonium-salt formation of the open-chain bih-phosphine 17a (1,1,7,7-tetrabenzyl(P.O.P-podand-7)) with diethylene glycol derived dibromide 13a yields the 12-membered cyclic bib-phosphonium salt 20 (4,4,10,10-tetrabenzyl-12(.P.O.P-coronand-4)-4,10-diium dibromide) in yields as high as 50-60%. The 1,1,10,10-tetrabenzyl(P.O-2.P-podand-10) 17b forms with 13a the 15-membered cyclic bis-phosphonium salt 21 (7,7,13,13-tetrabenzyl-15(O.P.O.P-coronand-5)-7,13-diium dibromide) with the same high yield. By quaternization of the bis-phosphine 17b with triethylene glycol derived dibromide 13b, the 18-membered 7,7,16,16-tetrabenzyl-18(O-2.P.O-2.P-coronand-6)-7,16-diium dibromide 24 is obtained in 501,10 yield, too. The Wittig reaction of the cyclic phosphonium salts with benzaldehyde yields the 12, 15-, and 18-membered cyclic bis-benzylphosphine dioxides 9, 10, and 11 as cis- and trans-isomers beside trans-stilbene, The 7,13-dioxido-7,13-dibenzyl-15(O-2.P.O-2.P-coronand-5 10 forms a crystalline 1: 1 Na-complex 23, which exists as a dimer. The structure of 23 was established by an X-ray analysis and spectroscopic data. The 7,16-dibenzyl-18(O-2.PO2.P-coronand-6) 28 that is available by reduction of 11 with CeCl3/LiAlH4 reacts with triethylene glycol derived dibromide 13b under Ruggly-Ziegler-dilution conditions to give the bicyclic bis-phosphonium salt 29 (1.10-dibenzyl(P[O-2](3).P-cryptand-8)-1,10-diium dibromide) in 18% yield. Again, by the Wittig procedure with benzaldehyde, the 7,16-dioxido(P[O-2](3)P-cryptand-8) 12 is obtained as the first diphosphacryptand. The FD-MS (CH2Cl2) of the cyclic bis-phosphine dioxides 10 - 12 show that they exist as [2M + Na](+) complexes. The complex formation constants K-a of 9 - 11 with alkali-metal cations are studied and compared with the complex formation of corresponding crown ethers.

  DOI：

  10.1002/1522-2675(200206)85:6<1714::aid-hlca1714>3.0.co;2-8

文献信息

• Diphosphapodanden,[12]-,[15]- und[18]Diphosphacoronanden, Diphosphacryptand-8 und Alkalimetall-Komplexe
  作者：Gottfried Märkl、Josef Reisinger、Peter Kreitmeier、Jens Langer、H. Nöth

  DOI：10.1002/1522-2675(200206)85:6<1714::aid-hlca1714>3.0.co;2-8

  日期：2002.6

  with benzaldehyde, the 7,16-dioxido〈P[O2]3P-cryptand-8〉 12 is obtained as the first diphosphacryptand. The FD-MS (CH2Cl2) of the cyclic bis-phosphine dioxides 10–12 show that they exist as [2M+Na]+ complexes. The complex formation constants Ka of 9–11 with alkali-metal cations are studied and compared with the complex formation of corresponding crown ethers.