Methylphosphonsaeure-monopropylester | 4546-11-6

• 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: Methylphosphonsaeure-monopropylester
• 英文别名: Methylphosphonsaeure-propylester；methyl-phosphonic acid n-propyl ester；Propyl hydrogen methylphosphonate；methyl(propoxy)phosphinic acid
• CAS: 4546-11-6
• 化学式: C₄H₁₁O₃P
• mdl: MFCD08275623
• 分子量: 138.103
• InChiKey: WPEAFCGWTBGVNU-UHFFFAOYSA-N

物化性质

• 沸点：
  112-116 °C(Press: 0.1 Torr)
• 密度：
  1.1249 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  8
• 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

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  Methylphosphonsaeure-monopropylester 、 异丙醇 在 polymer supported sulfonated magnetic resin 作用下， 以 甲苯 为溶剂， 反应 0.75h， 以92%的产率得到O-isopropyl O'-propyl methylphosphonate
  参考文献：
  名称：

  聚合物负载的磺化磁性树脂：O-烷基烷基膦酸和羧酸酯化的有效试剂

  摘要：

  已经开发了一种温和而有效的合成方法，该方法使用聚合物负载的磺化磁性树脂对O-烷基烷基膦酸和羧酸进行酯化。使用外部磁体回收聚合物负载的树脂，并重复使用几次。

  DOI：

  10.1016/j.tetlet.2014.10.086
• 作为产物：
  描述：

  methyl-phosphonic acid-chloride propyl ester 在 sodium hydroxide 作用下， 生成 Methylphosphonsaeure-monopropylester
  参考文献：
  名称：

  有机磷化合物的反应性。第二十七部分。烷基膦酸氢烷基酯与对硝基苯甲腈氧化物的反应：酸性水解得到的α-羟基亚氨基对硝基苯甲酸烷基膦酸酯的无规辅助的P-O裂变

  摘要：

  p -Nitrobenzonitrile与烷基氢烷基膦容易氧化物反应（I; R 1 =我，R 2 =甲基，乙基，镨，镨我，卜吨CH 2，或卜吨CHME）和（I; R 1 =的Et，卜t或Ph; R 2 = Et），磷酸二乙基氢和二乙基次膦酸氢生成相应的1：1加合物，即烷基α-羟基亚氨基-对硝基苄基烷基膦酸酯（II; R 1 = Me; R 2 = Me，乙基，丙基，镨我，卜吨CH 2，或卜吨CHME）和（II; R 1=的Et，卜吨或pH; [R 2 = ET），二乙基α羟基亚p硝基苄酯（II; R 1 =环氧乙烷，R 2 = ET），和α羟基亚p分别硝基苄二乙基次膦酸（III）。除了在酸性条件下稳定的最后一种情况外，加合物在稀有的二恶烷水溶液中在pH 2-3·5的条件下，以非常快速的，通过手性辅助的方式发生了P–O裂变（动力学研究表明，其快约10 7，比在相似条件下经历烷基-氧裂变的简单

  DOI：

  10.1039/j29710001988
• 作为试剂：
  描述：

  六乙基亚磷酸胺 在 Methylphosphonsaeure-monopropylester 作用下， 生成 tetraethyldiamidophosphite
  参考文献：
  名称：

  Reaction of amidophosphites with alkylmethylphosphonic and thiophosphonic acids

  摘要：

  DOI：

  10.1007/bf00862202

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。
• Surface Mediated Synthesis of Unsymmetrical <i>O,O</i>-dialkyl Alkyl Pyrophosphonates using Neutral Alumina: Potential Chemical Weapons Convention Related Compounds
  作者：Rajesh Kumar、Devendra K. Dubey、Arvind K. Gupta、M.P. Kaushik

  DOI：10.3184/030823408x318316

  日期：2008.5

  The surface mediated synthesis of unsymmetrical O,O’- dialkyl alkyl pyrophosphonates from O-alkyl alkylphosphonic acid is described. These pyrophosphonates are listed in schedule 2B4 of Chemical Weapon Convention (CWC). The effect of the presence of chromatographic grade of Al₂O₃on the phosphorylation of a series of alkyl phosphonic acids has also been investigated. For phosphonic acids having different alkyl groups, it was observed that higher yields of the more hindered pyrophosphonates were formed in the presence of Al₂O₃. This method has an advantage over the conventional methods in terms of easy work-up, reduced reaction time and high yields.

  介绍了以 O-烷基烷基膦酸为原料，通过表面介导合成非对称 O,O'-二烷基烷基焦磷酸盐的方法。这些焦磷酸盐被列入《化学武器公约》（CWC）附表 2B4。此外，还研究了色谱级 Al2O3 的存在对一系列烷基膦酸磷化的影响。对于具有不同烷基的膦酸，观察到在 Al2O3 的存在下形成的受阻程度较高的焦磷酸盐的产率较高。与传统方法相比，该方法具有操作简便、反应时间短和产率高等优点。
• Synthesis of Phosphonates with Identical and Different Alkyl Groups by the Microwave‐Assisted Alkylation of Phosphonic Ester‐Acid Derivatives
  作者：György Keglevich、Nikoletta Harsági、László Drahos、Nóra Zsuzsa Kiss

  DOI：10.1002/cplu.202200342

  日期：2023.2

  Dialkyl alkylphosphonates with identical or different alkoxy groups were synthesized by the alkylation of monoalkylphosphonic derivatives by haloalkanes in the presence of triethylamine at 135 °C under solvent-free microwave-assisted conditions. After an easy work-up comprising flash chromatography, the products were obtained in 80–93 % yields.

  在无溶剂微波辅助条件下，在三乙胺存在下，在 135 °C 下，通过卤代烷烃对单烷基膦酸衍生物进行烷基化，合成具有相同或不同烷氧基的烷基膦酸二烷基酯。经过包括快速色谱在内的简单后处理后，以 80–93% 的收率获得了产品。
• 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.
• PREPARATION, DERIVATIZATION WITH TRIMETHYLSILYLDIAZOMETHANE, AND GC/MS ANALYSIS OF A “POOL” OF ALKYL METHYLPHOSPHONIC ACIDS FOR USE AS QUALITATIVE STANDARDS IN SUPPORT OF COUNTERTERRORISM AND THE CHEMICAL WEAPONS CONVENTION
  作者：Michael D. Crenshaw、David B. Cummings

  DOI：10.1080/10426500490459632

  日期：2004.6

  There are hundreds of nerve agents in the class of alkyl methylphosphonofluoridates covered by Schedule 1 of the CWC (Chemical Weapons Convention). Hydrolysis of these sarin-like nerve agents results in all equal number of alkyl methylphosphonic acids. These allkyl methylphosphonic acids are persistent and provide good evidence of specific agent production or use. In order to support the CWC and counterterrorism activities, it is desirable to have ready access to each of these hydrolysis products for use as qualitative standards. A means for simultaneously producing multiple alkyl methylphosphonates from methylphosphonic acid and the corresponding alcohols was developed. Derivatization of these alkyl methylphosphonic acids with trimethylsilyldiazomethane yields the corresponding methyl esters which are suitable for GC/MS analysis.