isopropyl hydrogen ethylphosphonate | 170135-50-9

• 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: isopropyl hydrogen ethylphosphonate
• 英文别名: isopropyl ethylphosphonate；Ethylphosphonsaeureisopropylester；propan-2-yl hydrogen (R)-ethylphosphonate；ethyl(propan-2-yloxy)phosphinic acid
• CAS: 170135-50-9
• 化学式: C₅H₁₃O₃P
• mdl: MFCD08275621
• 分子量: 152.13
• InChiKey: QSYAHOJZVYVHEY-UHFFFAOYSA-N

物化性质

• 沸点：
  98-100 °C(Press: 0.1 Torr)
• 密度：
  1.090±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 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：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  isopropyl hydrogen ethylphosphonate 生成 ethyl-phosphonic acid diethylamide-isopropyl ester
  参考文献：
  名称：

  Rasumow et al., Zhurnal Obshchei Khimii, 1957, vol. 27, p. 2394; engl. Ausg. S. 2455

  摘要：

  DOI：
• 作为产物：
  描述：

  Ethyl-phosphonic acid cyclohex-2-enyl ester isopropyl ester 生成 isopropyl hydrogen ethylphosphonate
  参考文献：
  名称：

  Sosnovsky,G.; Karas,G.A., Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1978, vol. 33, p. 1165 - 1176

  摘要：

  DOI：

文献信息

• Resolution of Chiral Phosphate, Phosphonate, and Phosphinate Esters by an Enantioselective Enzyme Library
  作者：Charity Nowlan、Yingchun Li、Johannes C. Hermann、Timothy Evans、Joseph Carpenter、Eman Ghanem、Brian K. Shoichet、Frank M. Raushel

  DOI：10.1021/ja0658618

  日期：2006.12.1

  phosphotriesterase and 15 mutant enzymes. For each substrate, the leaving group was 4-hydroxyacetophenone while the other two groups attached to the phosphorus core consisted of an asymmetric mixture of methyl, methoxy, ethyl, ethoxy, isopropoxy, phenyl, phenoxy, cyclohexyl, and cyclohexoxy substituents. For the wild-type enzyme, the relative rates of hydrolysis for the two enantiomers ranged from 3 to 5.4 x 10(5)

  一系列 16 个手性磷酸酯、膦酸酯和次膦酸酯的对映体对用于确定细菌磷酸三酯酶和 15 种突变酶内固有的立体选择性歧视的广度。对于每种底物，离去基团是 4-羟基苯乙酮，而与磷核相连的其他两个基团由甲基、甲氧基、乙基、乙氧基、异丙氧基、苯基、苯氧基、环己基和环己氧基取代基的不对称混合物组成。对于野生型酶，两种对映异构体的相对水解速率范围为 3 到 5.4 x 10(5)。使用活性位点内的位点特异性突变的各种组合来创建修饰酶，其对映选择性特性发生改变。对于单点突变酶 G60A，立体选择性相对于野生型酶提高了 1-3 个数量级。获得了额外的突变体，其中对于本研究测试的 16 对对映异构体中的 13 对，立体选择性与野生型酶相反。最引人注目的例子是 4-乙酰苯基甲基苯基磷酸酯的水解。G60A 突变体优先水解 SP 对映异构体的因子为 3.7 x 10(5)。I106G/F132G/H257Y 突变体以
• Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids—An Experimental and a Theoretical Study
  作者：Nikoletta Harsági、Réka Henyecz、Péter Ábrányi-Balogh、László Drahos、György Keglevich

  DOI：10.3390/molecules26175303

  日期：——

  It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C2–C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol−1) that may be overcome only by MW irradiation. The major role of the [bmim][BF4] additive is to increase the absorption of MW energy. The specific chemical role of the [BF4] anion of the ionic liquid in an alternative mechanism was also raised by the computations.

  众所周知，包括膦酸在内的P-酸不易直接酯化。然而，发现一系列烷基膦酸在微波（MW）辐射下与C2-C4醇在[bmim][BF4]存在下可以进行单酯化反应。选择性达到80-98％，而分离收率在61-79％的范围内。所开发的方法是一种绿色的P-酸酯化方法。在M062X/6-311+G(d,p)理论水平上进行的DFT计算（考虑了相应醇的溶剂效应）探索了三步机制，并证明了较高的活化焓（160.6-194.1 kJ·mol-1），只有通过MW辐射才能克服。[bmim][BF4]添加剂的主要作用是增加MW能量的吸收。计算还提出了离子液体中[BF4]阴离子的特定化学作用在另一种机制中的作用。
• DCC–Celite hybrid immobilized solid support as a new, highly efficient reagent for the synthesis of O-alkyl hydrogen alkylphosphonates under solvent-free conditions
  作者：A.K. Gupta、Rajesh Kumar、H.K. Gupta、Vijay Tak、D.K. Dubey

  DOI：10.1016/j.tetlet.2008.01.016

  日期：2008.3

  An efficient and solvent-free synthesis of O-alkyl hydrogen alkyl phosphonates is described. The methodology involves the condensation of alkyl phosphonic acids using DCC-Celite under solvent-free conditions. (c) 2008 Elsevier Ltd. All rights reserved.
• SYNTHESIS OF ALKYL HYDROGEN ALKYLPHOSPHONATES
  作者：André Pienaar、Cornelis M. Erasmus、Mauritz Wentzel、Eugene H. Cowley

  DOI：10.1080/10426509908037007

  日期：1999.5.1

  The synthesis of alkyl hydrogen alkylphosphonates 1 was studied. Different synthetic routes were investigated and it was found that alkylphosphonic anhydrides can serve as ideal precursors for the synthesis of those half-acids, It was also shown that isopropyl phosphonic dichloride reacts in a unique fashion to produce alkyl hydrogen isopropylphosphonates in moderate yields.
• Sosnovsky,S.; Konieczny,M., Phosphorus and the Related Group V Elements, 1974, vol. 4, p. 255 - 264
  作者：Sosnovsky,S.、Konieczny,M.

  DOI：——

  日期：——