乙基膦酸单乙酯 | 7305-61-5

• 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: 乙基膦酸单乙酯
• 英文名称: ethyl hydrogen ethylphosphonate
• 英文别名: ethanephosphonic acid monoethylester；ethylphosphonic acid monoethyl ester；Aethyl-phosphonsaeure-monoaethylester；Aethanphosphonsaeure-monoaethylester；Phosphonic acid, ethyl-, monoethyl ester；ethoxy(ethyl)phosphinic acid
• CAS: 7305-61-5
• 化学式: C₄H₁₁O₃P
• mdl: MFCD01706297
• 分子量: 138.103
• InChiKey: YJCXKNNURGCXFQ-UHFFFAOYSA-N

物化性质

• 沸点：
  138 °C(Press: 2 Torr)
• 密度：
  1.1353 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 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

反应信息

• 作为反应物：
  描述：

  乙基膦酸单乙酯 在 COCl₂ 作用下， 生成 ethyl ethylphosphonochloridate
  参考文献：
  名称：

  The Stereochemistry of Asymmetric Phosphorus Compounds. IV. The Synthesis and Stereochemistry of Displacement Reactions of Optically Active Isopropyl Methylphosphonochloridate

  摘要：

  DOI：

  10.1021/ja00863a023
• 作为产物：
  描述：

  ethyl ethylphosphonochloridate 在 水 作用下， 生成 乙基膦酸单乙酯
  参考文献：
  名称：

  Heme Oxygenase-1 Modulates Fetal Growth in the Rat

  摘要：

  Intrauterine growth restriction is associated with increased perinatal morbidity and mortality as well as with lifelong cardiovascular and metabolic complications. Deficiency of heme oxygenase 1 (HO-1) is associated with growth restriction in mice and in humans, suggesting a role for HO-1 in fetal growth and maintenance of pregnancy. We hypothesized that modulation of HO-1 in the pregnant rat would alter fetal growth. In pregnant dams, placental HO activity was significantly inhibited with zinc deuteroporphyrin IX 2,4 bis glycol, and HO-1 protein was increased by transducing adenoviral human HO-1. Inhibition of HO-1 by zinc deuteroporphyrin IX 2,4 bis glycol resulted in a significant decrease in pup size, whereas transfection with hHO-1 resulted in increased pup size. Furthermore, the expression of IGF binding protein-1 and its receptor paralleled the expression of HO-1 in the placenta and were significantly modulated by modification of HO-1 along with the expression of vascular endothelial growth factor. These observations demonstrate that HO-1 modulates fetal growth by its effects on placental growth factors.

  DOI：

  10.1097/01.lab.0000017167.26718.f2

文献信息

• Kinetics of alkaline hydrolysis of esters of phosphorus acids in micellar and hexagonal phases in the cetyldimethylethylammonium bromide—NaOH—water system
  作者：R. F. Bakeeva、L. A. Kudryavtseva、G. Eme、E. M. Kosacheva、V. E. Bel'skii、D. B. Kudryavtsev、R. R. Shagidullin、V. F. Sopin

  DOI：10.1007/bf02495592

  日期：1998.8

  reactions in the micellar phase were determined. In micellar solutions of systemI, a tenfold increase in the rates of alkaline hydrolysis of2–4 was observed. An increase in the degree of medium ordering during the formation of the E-phase results in a twofold acceleration of alkaline hydrolysis of2 and3 and in the inhibition of this process in the case of4.

  十六烷基二甲基乙基溴化铵-NaOH-水体系(I)胶束(Mi)和六方(E)中间相对O-对硝基苯基-O,O-磷酸二乙酯(2),O-硝基苯基碱水解速率的影响通过紫外分光光度法研究了-O-乙基乙基膦酸酯(3)和O,O-二(对硝基苯基)甲基膦酸酯(4)。确定了底物的结合常数、临界胶束浓度和胶束相中反应的速率常数。在系统 I 的胶束溶液中，观察到 2-4 的碱水解速率增加了 10 倍。在 E 相形成过程中介质有序度的增加导致 2 和 3 的碱性水解的两倍加速，并在 4 的情况下抑制了该过程。
• 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。
• 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。
• Atmospheric Chemistry of Diethyl Methylphosphonate, Diethyl Ethylphosphonate, and Triethyl Phosphate
  作者：Sara M. Aschmann、Ernesto C. Tuazon、Roger Atkinson

  DOI：10.1021/jp0446938

  日期：2005.3.1

  Rate constants for the reactions of OH radicals and NO(3) radicals with diethyl methylphosphonate [DEMP, (C(2)H(5)O)(2)P(O)CH(3)], diethyl ethylphosphonate [DEEP, (C(2)H(5)O)(2)P(O)C(2)H(5)], and triethyl phosphate [TEP, (C(2)H(5)O)(3)PO] have been measured at 296 +/- 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained for the OH radical reactions (in units

  OH自由基和NO（3）自由基与甲基二膦酸二乙酯[DEMP，（C（2）H（5）O）（2）P（O）CH（3）]，乙基二膦酸二乙酯[DEEP，（ C（2）H（5）O）（2）P（O）C（2）H（5）]和磷酸三乙酯[TEP，（C（2）H（5）O）（3）PO]具有使用相对速率方法在296 +/- 2 K和大气压力下测量。OH自由基反应获得的速率常数（单位为10（-11）cm（3）分子（-1）s（-1））如下：DEMP，5.78 +/- 0.24; 深度：6.45 +/- 0.27；和TEP，5.44 +/- 0.20。NO（3）自由基反应获得的速率常数（以10（-16）cm（3）分子（-1）s（-1）为单位）为：DEMP，3.7 +/- 1.1; 深，3.4 +/- 1.4; 和TEP，2.4 +/- 1.4。对于O（3）与DEMP，DEEP和TEP的反应，速率常数的上限< 确定每种化合物的6 x 1
• 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。