ethyl methyl methylphosphonate | 18755-36-7

• 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: ethyl methyl methylphosphonate
• 英文别名: O-ethyl O-methyl methylphosphonate；EMMP；1-[methoxy(methyl)phosphoryl]oxyethane
• CAS: 18755-36-7
• 化学式: C₄H₁₁O₃P
• 分子量: 138.103
• InChiKey: YDVMILOIKRSPEO-UHFFFAOYSA-N

物化性质

• 沸点：
  74-75 °C(Press: 15 Torr)
• 密度：
  1.050±0.06 g/cm3(Predicted)
• 保留指数：
  952;952;951.5

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：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  甲基磷酸乙酯 、 三甲基硅烷化重氮甲烷 在 甲醇 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 ethyl methyl methylphosphonate
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1080/10426500490459632

文献信息

• Facile Hydrolysis-Based Chemical Destruction of the Warfare Agents VX, GB, and HD by Alumina-Supported Fluoride Reagents
  作者：E. Gershonov、I. Columbus、Y. Zafrani

  DOI：10.1021/jo8019972

  日期：2009.1.2

  A facile solvent-free hydrolysis (chemical destruction) of the warfare agents VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate), GB (O-isopropyl methylphosphonofluoridate or sarin), and HD (2,2′-dichloroethyl sulfide or sulfur mustard) upon reaction with various solid-supported fluoride reagents is described. These solid reagents include different alumina-based powders such as KF/Al2O3

  简便的无溶剂水解剂（战争破坏剂VX（O-乙基S -2-（二异丙氨基氨基）乙基甲基硫代磷酸酯），GB（O-异丙基甲基氟代磷酸酯或沙林）和HD（2,2'-二氯乙基硫醚）描述了在与各种固体负载的氟化物试剂反应后产生的硫芥末或硫芥末）。这些固体试剂包括不同的氧化铝基粉末，例如KF / Al 2 O 3，AgF / KF / Al 2 O 3和KF / Al 2 O 3，它们富含所谓的配位不饱和氟化物离子（我们称其为ECUF- KF / Al 2 O 3）。当吸附在这些吸附剂上时，神经毒剂VX迅速水解（t 1/2范围在0.1-6.3 h之间）水解成相应的无毒膦酸主要成分EMPA（> 90％）和相对毒性的脱乙基VX（< 10％）。后者的副产物进一步水解为无毒的MPA产物（t 1/2范围为2.2-161 h）。发现反应速率和产物分布强烈地取决于KF / Al 2 O 3基质中氟离子的性质及其含水量。所研
• Solvent Effects on the Reactions of the Nerve Agent VX with KF/Al₂O₃: Heterogeneous or Homogeneous Decontamination?
  作者：Gil Fridkin、Lea Yehezkel、Ishay Columbus、Yossi Zafrani

  DOI：10.1021/acs.joc.5b02733

  日期：2016.3.4

  Solvent effects on the reactions of the extremely toxic nerve agent VX with KF/Al2O3 powder were explored. Small quantities of water or methanol (5–10 wt %), which effectively mobilized all components while maintaining the heterogeneous nature of the reaction, promoted much faster rates than those obtained with larger quantities. Any amount of acetonitrile resulted in extremely slow transformations

  探索了溶剂对剧毒神经毒剂VX与KF / Al 2 O 3粉末反应的影响。少量的水或甲醇（5-10 wt％）可以有效地转移所有组分，同时保持反应的非均质性，其速率要比大量获得的快得多。任意数量的乙腈都会导致极慢的转化。出人意料的是，由于5-50 wt％的庚烷介导VX快速扩散的能力和MAS离心作用的结合，导致快速反应。
• Destruction of chemical warfare agents VX and soman by ?-nucleophiles as oxidizing agents
  作者：Thierry Cassagne、Henri-Jean Cristau、G�rard Delmas、Michel Desgranges、Claude Lion、Gilbert Magnaud、�liane Torreilles、David Virieux

  DOI：10.1002/hc.1074

  日期：——

  ethyl methylphosphonothiolate, VX 1, were investigated with five oxidizing agents. In all the cases, the formation of the VX N-oxide 7 was observed prior to the subsequent oxidation and hydrolysis into the nontoxic O-ethyl methylphosphonate 2. Magnesium monoperoxyphthalate (MMPP) is probably one of the most active reagents to achieve the complete detoxification of VX 1. The decontamination using MMPP

  O-乙基S-(2-二异丙基-氨基)乙基甲基硫代膦酸酯，VX 1，与五种氧化剂的反应进行了研究。在所有情况下，在随后的氧化和水解成无毒的 O-乙基甲基膦酸酯 2 之前观察到 VX N-氧化物 7 的形成。 单过氧邻苯二甲酸镁 (MMPP) 可能是实现完全解毒的最活跃的试剂之一VX 1. 使用 MMPP 的净化也成功地扩展到 soman 13，一种 G 型试剂。© 2001 John Wiley & Sons, Inc. 杂原子化学 12:485–490, 2001
• The nucleophilic reactivity of organophosphorus compounds. Part 4. The alkylation of phosphorus acid anions with 'onium keten acetals
  作者：Alexander T. Zaslona、C. Dennis Hall

  DOI：10.1039/p19810003059

  日期：——

  The preparations of phosphonium and pyridinium keten acetals are reported and their reactions with a variety of phosphorus acid anions are described. The novel pyridinium keten acetals are useful reagents for the alkylation of various acid anions in aprotic, aqueous and aqueous-emulsion media.

  报告了of和吡啶酮酮缩醛的制备，并描述了它们与各种磷酸根阴离子的反应。新型吡啶酮酮缩醛是用于非质子，水性和水性乳液介质中各种酸阴离子烷基化的有用试剂。
• Alkali Metal Alkoxide Clusters:  Convenient Catalysts for the Synthesis of Methylphosphonates
  作者：Rebecca M. Kissling、Michel R. Gagné

  DOI：10.1021/jo9820521

  日期：1999.3.1

  interchange reaction between carbonyl and phosphorus esters. This reactivity leads to convenient methodologies for the synthesis of symmetric and unsymmetric alkyl-substituted methylphosphonates from dimethyl methylphosphonate (DMMP). Reactions rates are high with initial turnover frequencies (N(t)) in excess of 1 x 10(6) h(-)(1) observed and with KO(t)Bu > NaO(t)Bu > LiO(t)Bu. The reactions were sensitive

  碱金属醇盐是用于促进羰基酯和磷酸酯之间的交换反应的良好催化剂（1-8 mol％）。这种反应性导致了由甲基膦酸二甲酯（DMMP）合成对称和不对称烷基取代的甲基膦酸酯的简便方法。初始转换频率（N（t））超过1 x 10（6）h（-）（1）且KO（t）Bu> NaO（t）Bu> LiO（t）Bu时，反应速率很高。反应对产物甲基膦酸酯中的空间效应敏感，反应速率与转移醇盐的大小平行（正烷基>异烷基>叔烷基）。对于测试反应DMMP +乙酸异丙酯，取代动力学与依次替换每种甲醇的情况一致，并且第二位移的替代率明显低于第一位移。第一次取代过程的动力学研究表明了浓度依赖性速率定律。一种最容易解决的方案是偶联酯交换反应，其中醇盐可逆地独立地添加到膦酸酯和酯中。

表征谱图