乙氧基(丙基)次膦酸 | 21921-96-0

• 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
• 中文名称: 乙氧基(丙基)次膦酸
• 英文名称: ethoxypropylphosphonic acid
• 英文别名: ethyl hydrogen propylphosphonate；O-Ethylhydrogenpropylphosphonat；Monoethyl propylphosphonate；ethoxy(propyl)phosphinic acid
• CAS: 21921-96-0
• 化学式: C₅H₁₃O₃P
• 分子量: 152.13
• InChiKey: FJDJZPWIPLUDIZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  9
• 可旋转键数：
  4
• 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：

  乙醇 、 乙氧基(丙基)次膦酸 在 氯化亚砜 作用下， 反应 2.0h， 生成 1-丙基膦酸二乙酯
  参考文献：
  名称：

  利用 P-烷基 2,3-氧杂磷杂双环 [2.2.2] 辛烯 3-氧化物前体对亲核试剂进行片段化相关的膦酰化

  摘要：

  新的 P-烷基 2,3-氧杂磷杂双环-[2.2.2] 辛烯 3-氧化物是通过相应的 7-磷酰冰片烯 7-氧化物的 Bayer-Villiger 氧化合成的，并用作反应性烷基偏膦酸酯的前体，可用于醇的膦酰化. 这是第一个通过 O 插入形成的两种区域异构体的反应性不同的情况，并且在微波辅助条件下实现了导致膦酸酯的断裂相关的膦酰化。

  DOI：

  10.1002/hc.21304
• 作为产物：
  描述：

  乙醇 、 丙基膦酸 在 Celite 、 N,N'-二环己基碳二亚胺 作用下， 反应 0.67h， 以83%的产率得到乙氧基(丙基)次膦酸
  参考文献：
  名称：

  DCC–Celite hybrid immobilized solid support as a new, highly efficient reagent for the synthesis of O-alkyl hydrogen alkylphosphonates under solvent-free conditions

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2008.01.016

文献信息

• 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。
• 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.
• Fragmentation-Related Phosphonylation of Nucleophiles Utilizing P-Alkyl 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide Precursors
  作者：Tamara Kovács、Laura Szandra Fülöp、György Keglevich

  DOI：10.1002/hc.21304

  日期：2016.3

  New P-alkyl 2,3-oxaphosphabicyclo-[2.2.2]octene 3-oxides were synthesized by the Bayer–Villiger oxidation of the corresponding 7-phosphanorbornene 7-oxides and were used as precursors for reactive alkylmetaphosphonates useful in the phosphonylation of alcohols. This is the first case that the reactivity of the two regioisomers formed by O-insertion was differentiated and that the fragmentation-related

  新的 P-烷基 2,3-氧杂磷杂双环-[2.2.2] 辛烯 3-氧化物是通过相应的 7-磷酰冰片烯 7-氧化物的 Bayer-Villiger 氧化合成的，并用作反应性烷基偏膦酸酯的前体，可用于醇的膦酰化. 这是第一个通过 O 插入形成的两种区域异构体的反应性不同的情况，并且在微波辅助条件下实现了导致膦酸酯的断裂相关的膦酰化。
• 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.