1,2-bis(dimethylphosphino)ethane monooxide | 124393-93-7

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: 1,2-bis(dimethylphosphino)ethane monooxide
• 英文别名: dmpeO；2-Dimethylphosphorylethyl(dimethyl)phosphane
• CAS: 124393-93-7
• 化学式: C₆H₁₆OP₂
• 分子量: 166.14
• InChiKey: IRRVDTMBUVYQMU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,2-bis(dimethylphosphino)ethane monooxide 生成 2-dimethylphosphorylethyl-dimethyl-sulfanylidene-λ5-phosphane
  参考文献：
  名称：

  MADING, P., ZENTRALINST. KERNFORSCH. ROSSENDORF DRESDEN ,(1988) N 622, C. 32

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2-双(二甲基瞵)乙烷 在 盐酸 、 双氧水 、 sodium hydroxide 作用下， 以 乙醚 、 水 为溶剂， 以86%的产率得到1,2-bis(dimethylphosphino)ethane monooxide
  参考文献：
  名称：

  Catalytic Nitrile Hydration with [Ru(η⁶-p-cymene)Cl₂(PR₂R′)] Complexes: Secondary Coordination Sphere Effects with Phosphine Oxide and Phosphinite Ligands

  摘要：

  The rates of nitrile hydration reactions were investigated using [Ru(eta(6)-p-cymene)Cl-2(PR2R')] complexes as homogeneous catalysts, where PR2R' = PMe2(CH2P(O)Me-2), PMe2(CH2CH2P(O)Me-2), PPh2(CH2P(O)Ph-2), PPh2(CH2CH2P(O)Ph-2), PMe2OH, P(OEt)(2)OH. These catalysts were studied because the rate of the nitrile-to-amide,, hydration reacfion was hypothesized to be affected by the position of the io., hydrogen bond accepting group in the secondary coordination sphere of the catalyst. Experiments showed that, the rate of nitrile hydration was fastest when using [Ru(eta(6)-p-cymene)Cl2PMe2OH]: i.e., the catalyst with the hydrogen bond accepting group capable of forming the most stable ring in the transition state of the rate-limiting step. This catalyst is also active at pH 3.5. and at low temperatures-conditions where alpha-hydroxynitriles (cyanohydrins produce less cyanide, a known poison for organometallic nitrile hydration catalysts. The [Ru(eta(6)-p-cymene)Cl2PMe2OH] catalyst completely converts the cyanohydrins glycolonitrile, and, lactonitrile to their corresponding alpha-hydroxyamides faster than previously investigated Catalysts. [Ru(eta(6)-p-cymene)Cl2PMe2OH] is not, however, a good catalyst for acetone cyanohydrin hydration, because it is susceptible to cyanide poisoning. Protecting the -OH group of acetone cyanohydrin was shown to be an effective way to prevent cyanide poisoning, resulting in quantitative hydration of acetone cyanohydrin acetate.

  DOI：

  10.1021/om400380j

文献信息

• MADING, P.;SCHELLER, D., Z. ANORG. UND ALLG. CHEM., 567,(1988) N2, C. 179-191
  作者：MADING, P.、SCHELLER, D.

  DOI：——

  日期：——
• MADING, P., ZENTRALINST. KERNFORSCH. ROSSENDORF DRESDEN <BER.>,(1988) N 622, C. 32
  作者：MADING, P.

  DOI：——

  日期：——
• Catalytic Nitrile Hydration with [Ru(η⁶-<i>p</i>-cymene)Cl₂(PR₂R′)] Complexes: Secondary Coordination Sphere Effects with Phosphine Oxide and Phosphinite Ligands
  作者：Spring Melody M. Knapp、Tobias J. Sherbow、Robert B. Yelle、J. Jerrick Juliette、David R. Tyler

  DOI：10.1021/om400380j

  日期：2013.7.8

  The rates of nitrile hydration reactions were investigated using [Ru(eta(6)-p-cymene)Cl-2(PR2R')] complexes as homogeneous catalysts, where PR2R' = PMe2(CH2P(O)Me-2), PMe2(CH2CH2P(O)Me-2), PPh2(CH2P(O)Ph-2), PPh2(CH2CH2P(O)Ph-2), PMe2OH, P(OEt)(2)OH. These catalysts were studied because the rate of the nitrile-to-amide,, hydration reacfion was hypothesized to be affected by the position of the io., hydrogen bond accepting group in the secondary coordination sphere of the catalyst. Experiments showed that, the rate of nitrile hydration was fastest when using [Ru(eta(6)-p-cymene)Cl2PMe2OH]: i.e., the catalyst with the hydrogen bond accepting group capable of forming the most stable ring in the transition state of the rate-limiting step. This catalyst is also active at pH 3.5. and at low temperatures-conditions where alpha-hydroxynitriles (cyanohydrins produce less cyanide, a known poison for organometallic nitrile hydration catalysts. The [Ru(eta(6)-p-cymene)Cl2PMe2OH] catalyst completely converts the cyanohydrins glycolonitrile, and, lactonitrile to their corresponding alpha-hydroxyamides faster than previously investigated Catalysts. [Ru(eta(6)-p-cymene)Cl2PMe2OH] is not, however, a good catalyst for acetone cyanohydrin hydration, because it is susceptible to cyanide poisoning. Protecting the -OH group of acetone cyanohydrin was shown to be an effective way to prevent cyanide poisoning, resulting in quantitative hydration of acetone cyanohydrin acetate.