diethyl (1E)-3-hydroxyprop-1-enylphosphonate | 76242-00-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl (1E)-3-hydroxyprop-1-enylphosphonate
• 英文别名: diethyl 3-hydroxy-1(E)-propenylphosphonate；E-1-diethylphosphonyl-3-hydroxyprop-1-ene；diethyl 3-hydroxy-1-propenylphosphonate；diethyl 1-propen-3-ol phosphonate；(E)-3-diethoxyphosphorylprop-2-en-1-ol
• CAS: 76242-00-7
• 化学式: C₇H₁₅O₄P
• 分子量: 194.167
• InChiKey: OHDLHOZXSKAVEI-FNORWQNLSA-N

物化性质

• 沸点：
  150-155 °C(Press: 1 Torr)
• 密度：
  1.1455 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl (1E)-3-hydroxyprop-1-enylphosphonate 生成 (E)-3-chloro-1-diethoxyphosphorylprop-1-ene
  参考文献：
  名称：

  BELYX, O. A.;DOGADINA, A. V.;IONIN, B. I.;PETROV, A. A., ZH. OBSHCH. XIMII, 57,(1987) N 12, 2699-2711

  摘要：

  DOI：
• 作为产物：
  描述：

  3-溴-1-丙烯膦酸二乙酯 在 sodium hydroxide 作用下， 以 甲醇 、 丁酮 为溶剂， 反应 15.0h， 生成 diethyl (1E)-3-hydroxyprop-1-enylphosphonate
  参考文献：
  名称：

  Enantioselective synthesis of threo-α,β-dihydroxyphosphonates by asymmetric dihydroxylation of 1(E)-alkenylphosphonates with AD-mix reagents

  摘要：

  Asymmetric dihydroxylation (AD) of 1(E)-alkenylphosphonates with an AD-mix -alpha or -beta reagent was examined to give a series of optically active threo-alpha,beta-dihydroxyphosphonates. Good enantioselectivity (>88% eel was observed in the AD reaction of 1(E)-alkenylphosphonates with conjugated aromatic substituents. The steric effects of the ester functionality in the course of the dihydroxylation were also evaluated. Enantioselectivity and yield were significantly improved when the AD reaction was carried out with dimethyl phosphonate instead of diethyl phosphonate. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(97)10341-6

文献信息

• Phosphonates containing sulfur and selenium. Synthesis of vinylphosphonates bearing α-sulfenyl, α-selenenyl, α-sulfinyl and α-seleninyl moieties and studies on nucleophilic addition
  作者：Wanda H. Midura、Jerzy A. Krysiak

  DOI：10.1016/j.tet.2004.10.026

  日期：2004.12

  efficiently to α-phosphorylvinyl sulfoxides or α-phosphorylvinyl selenides depending on the reaction conditions. Oxidation of α-phosphorylvinyl selenides and subsequent thermolysis of selenoxides afford alkynylphosphonates. Studies of the stereochemical course of nucleophilic addition to α-phosphoryl sulfoxides show high facial stereoselectivity of the reaction, however, epimerisation at the α-carbon atom leads

  根据反应条件，外消旋和旋光性α-磷酰基亚砜的硒烯基化是关键步骤，可有效地导致α-磷酰基乙烯基亚砜或α-磷酰基乙烯基硒化物。α-磷酰基乙烯基硒化物的氧化和随后硒氧化物的热解提供了炔基膦酸酯。对亲核加成至α-磷酰基亚砜的立体化学过程的研究表明，该反应具有较高的面部立体选择性，但是，在α-碳原子上的差向异构化会导致非对映异构体的混合物。
• Copper (II)-catalyzed regio- and stereoselective addition of H/P(O)R2 to alkynes
  作者：Inna G. Trostyanskaya、Irina P. Beletskaya

  DOI：10.1016/j.tet.2014.02.037

  日期：2014.4

  catalyst for β-E regio- and stereoselective syn-addition of the H–P(O)-bond of diphenylphosphine oxide, H-phosphinates, dialkylphosphites to various alkynes in the synthesis of P(O)-containing alkenes. Without additives and ligands Cu(II)-compounds showed better results than CuI or Ni(acac)2. The catalytic system developed is tolerant to typical organic functional groups present in the alkynes and to the

  Cu（acac）2是在P（O）合成中，β- E区域和立体选择性地将二苯膦氧化物，H-次膦酸酯，二烷基亚磷酸酯的H–P（O）键加成到各种炔烃上的新型通用催化剂）的烯烃。没有添加剂和配体，Cu（II）化合物显示出比CuI或Ni（acac）2更好的结果。所开发的催化系统对炔烃中存在的典型有机官能团以及H-P（O）化合物中不同取代基的性质具有耐受性。
• An Efficient Synthesis of Enantiomeric (S)-Phosphocarnitine
  作者：Andrzej E. Wróblewski、Anetta Hałajewska-Wosik

  DOI：10.1002/1099-0690(200208)2002:16<2758::aid-ejoc2758>3.0.co;2-q

  日期：2002.8

  Diethyl (S)-2,3-epoxypropylphosphonate [(S)-3] was transformed into (S)-phosphocarnitine [(S)-2] in the following sequence of reactions: a C-3 regioselective opening of the oxirane ring with magnesium bromide, quantitative bromide displacement with trimethylamine, and ester hydrolysis. The epoxide ring opening of 3 with HCl/EtOAc gave a 92:8 mixture of 3- and 2-chloro-substituted phosphonates. Reaction

  (S)-2,3-环氧丙基膦酸二乙酯 [(S)-3] 在以下反应序列中转化为 (S)-磷酸肉碱 [(S)-2]：环氧乙烷环的 C-3 区域选择性打开与溴化镁、用三甲胺定量溴化物置换和酯水解。3用HCl/EtOAc的环氧化物开环得到3-和2-氯-取代的膦酸酯的92:8混合物。(S)-3与NMe3水溶液的反应得到3-羟基-1-丙烯基膦酸二乙酯作为主要产物。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
• Synthesis of Novel Enantiomerically Pure<i>C</i> ₃-Symmetric Trialkanolamine Ligand­ Containing Phosphoryl Groups
  作者：Andrzej E. Wróblewski、Anetta Hałajewska-Wosik

  DOI：10.1055/s-2006-926349

  日期：——

  Catalytic activity of ten metal salts in the reaction of benz­hydrylamine and benzylamine with diethyl 2,3-epoxypropylphosphonate (1) was studied. Only in the presence of copper(I) iodide pure diethyl 3-benzhydrylamino- and 3-benzylamino-2-hydroxy­propylphosphonates were produced quantitatively. Although the reactions­ catalysed by calcium(II) triflate were the fastest, they led to the contamination of the major products with the respective bisphosphonates. Enantiomerically pure (S,S)-bis[2-(O,O-diethyl­phosphorylmethyl)ethanol]amine (10) was prepared in a Ca(OTf)2-catalysed reaction of (S)-1 (ee 94%) with 0.4 equivalent benzyl­amine followed by hydrogenolysis. The bisphosphonate (S,S)-10 was transformed into enantiomerically pure (S,S,S)-tris[2-(O,O-diethylphosphorylmethyl)ethanol]amine (2), when reacted with (S)-1 (ee 94%) or into (R,S,S)-2, when (R)-1 (ee 94%) was used.

  研究了十种金属盐在苯海拉明和苄胺与 2,3-环氧丙基膦酸二乙酯（1）反应中的催化活性。只有在碘化铜（I）存在的情况下，才能定量生成纯净的 3-苄基氨基和 3-苄基氨基-2-羟基丙基膦酸二乙酯。虽然三酸钙（II）催化的反应速度最快，但它们会导致主要产物受到相应双膦酸盐的污染。(S,S)-双[2-(O,O-二乙基磷酰甲基)乙醇]胺(10)是在 Ca(OTf)2 催化下，由(S)-1（ee 94%）与 0.4 等量的苄胺反应，然后加氢分解制备的对映体纯品。当与(S)-1（ee 94%）反应时，双膦酸盐(S,S)-10 转化为对映体纯的(S,S,S)-三[2-(O,O-二乙基磷酰甲基)乙醇]胺(2)；当使用(R)-1（ee 94%）时，则转化为(R,S,S)-2。
• The Design and Synthesis of Inhibitors of Imidazoleglycerol Phosphate Dehydratase as Potential Herbicides
  作者：John M. Cox、Timothy R. Hawkes、Peter Bellini、Russell M. Ellis、Roger Barrett、Joseph J. Swanborough、Sally E. Russell、Peter A. Walker、Nigel J. Barnes、Andrew J. Knee、Terence Lewis、Paul R. Davies

  DOI：10.1002/(sici)1096-9063(199708)50:4<297::aid-ps592>3.0.co;2-2

  日期：1997.8