diethyl 1,2-dibromoethylphosphonate | 63637-75-2

• 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: diethyl 1,2-dibromoethylphosphonate
• 英文别名: Phosphonic acid, (1,2-dibromoethyl)-, diethyl ester；1,2-dibromo-1-diethoxyphosphorylethane
• CAS: 63637-75-2
• 化学式: C₆H₁₃Br₂O₃P
• 分子量: 323.949
• InChiKey: TVYWGXSIQASYJS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  6
• 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

• 作为反应物：
  描述：

  diethyl 1,2-dibromoethylphosphonate 在 potassium carbonate 作用下， 以 四氢呋喃 、 乙醇 、 二甲基亚砜 为溶剂， 反应 5.0h， 生成 (3-氨丙基)磷酸二乙酯
  参考文献：
  名称：

  Cyclopropanation of 1,2-dibromoethylphosphonate: a synthesis of β-aminocyclopropylphosphonic acid and derivatives

  摘要：

  Diethyl (1,2-dibromoethyl)phosphonate was found to undergo cyclopropanation with nitromethane in good yield. The resulting trans beta-nitrocyclopropylphosphonate was converted to the trans N-protected aminocyclopropylphosphonate through a reduction-protection sequence. Subsequent hydrolysis gave the free beta-aminocyclopropylphosphonic acid without any formation of ring-opening byproduct. Cyclopropanation of 1,2-dibromoethylphosphonates with nitroalkanes and their reduction are also discussed. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.09.035
• 作为产物：
  描述：

  乙烯基磷酸二乙酯 以 四氯化碳 为溶剂， 反应 12.5h， 以95%的产率得到diethyl 1,2-dibromoethylphosphonate
  参考文献：
  名称：

  对映体α，β-二氨基乙基膦酸作为氨基肽酶的有效抑制剂—立体选择性合成和生物活性

  摘要：

  α，β-二氨基乙基膦酸是丙氨酰氨基肽酶和内质网氨基肽酶2的有效过渡态类似物抑制剂，是M01蛋白酶的生物医学重要成员。在这项工作中，分离所选抑制剂的单个对映异构体，并验证其抑制能力。合成涉及使用手性α-甲基苄胺来获得非对映体氮丙啶膦酸酯，作为多步工艺的关键中间体。非对映体氮丙啶经色谱分离，杂环用适当的胺打开。抑制研究表明，绝对构型与抑制活性之间存在有趣的相关性。某些对映体膦酸氨基酸类似物在纳摩尔范围内表现出抑制常数。

  DOI：

  10.1016/j.tetlet.2016.09.051

文献信息

• A structural insight into the P1 S1 binding mode of diaminoethylphosphonic and phosphinic acids, selective inhibitors of alanine aminopeptidases
  作者：Ewelina Węglarz-Tomczak、Łukasz Berlicki、Małgorzata Pawełczak、Bogusław Nocek、Andrzej Joachimiak、Artur Mucha

  DOI：10.1016/j.ejmech.2016.04.018

  日期：2016.7

  and porcine), revealed several potent compounds (e.g., Ki = 65 nM of 1u for HsAPN). Two structures of an M1 representative (APN from Neisseria meningitidis) in complex with N-benzyl-1,2-diaminoethylphosphonic acid and N-cyclohexyl-1,2-diaminoethylphosphonic acid were determined by the X-ray crystallography. The analysis of these structures and the models of the phosphonic acid complexes of the human

  研究了N'-取代的1,2-二氨基乙基膦酸和1,2-二氨基乙基次膦酸二肽，以揭示这些抑制剂对M1丙氨酸氨基肽酶（APNs）相对于M17亮氨酸氨基肽酶（LAP）的意外选择性的结构背景。通过氮丙啶以改进的合成方法获得二氨基膦酸，将其进一步扩大用于次膦酸假二肽系统。对不同来源（细菌，人和猪）的三个M1和一个M17金属氨肽酶测定的抑制活性显示出几种有效的化合物（例如，对于Hs APN ，K i  = 65 nM，1u）。M1代表（脑膜炎奈瑟氏球菌的APN ）的两个结构与通过X射线晶体学测定N-苄基-1,2-二氨基乙基膦酸和N-环己基-1,2-二氨基乙基膦酸。这些结构的分析和人类直系同源物的膦酸配合物的模型提供了对S1活性位点区域内其他氨基基团和配体的疏水取代基的作用的深入了解。
• Synthesis of 5-Phosphonoisoxazol­ine<i>N</i>-Oxides by Selective<i>O</i>-Alkylation of Nitronate Anions
  作者：Vincent Perez、Nicolas Rabasso、Antoine Fadel

  DOI：10.1002/ejoc.201501243

  日期：2016.1

  5-phosphonoisoxazoline N-oxides were prepared in good to excellent yields by selective O-alkylation of nitronate anions with (α-tosyloxyvinyl)phosphonates. A comprehensive study was undertaken to limit the competitive formation of the (β-nitrocyclopropyl)phosphonate resulting from C-alkylation of the ambident nitronate anions. The 5-phosphonoisoxazoline N-oxides thus formed were reduced to the corresponding 5-phosphonoisoxazolines

  通过选择性 O-烷基化硝基阴离子与 (α-甲苯磺酰氧基乙烯基) 膦酸盐，制备了一系列 5-膦酰基异恶唑啉 N-氧化物，收率良好至极好。进行了一项全面的研究以限制由双亲硝基阴离子的 C-烷基化产生的（β-硝基环丙基）膦酸盐的竞争性形成。由此形成的5-膦酰基异恶唑啉N-氧化物被还原为相应的5-膦酰基异恶唑啉。
• Design and Synthesis of Exocyclic Cyclitol Aziridines as Potential Mechanism‐Based Glycosidase Inactivators
  作者：Tim P. Ofman、Gijsbert A. van der Marel、Jeroen D. C. Codée、Hermen S. Overkleeft

  DOI：10.1002/ejoc.202300186

  日期：——

  Eight exocyclic aziridine cyclitols were synthesized, envisioned as putative covalent inhibitors of inverting glucosidases. The constructs, bearing a range of electron withdrawing moieties, were obtained efficiently through an aza-Michael initiated ring closure reaction (aza-MIRC) on validamine or 1-epi-validamine. The synthetic methodologies and inhibitor design presented here can fuel the future

  合成了八个环外氮丙啶环醇，被设想为转化糖苷酶的推定共价抑制剂。通过对有效胺或 1- epi -validamine 的氮杂迈克尔引发的闭环反应 (aza-MIRC)，可以有效地获得带有一系列吸电​​子部分的构建体。这里介绍的合成方法和抑制剂设计可以推动未来发现转化糖苷酶的共价抑制剂。
• Synthesis, Molecular Structure, and Spectroscopical Properties of Alkenylphosphonic Derivatives. 1. Vinyl-, Propenyl-, (Bromoalkenyl)-, and (Cyanoalkenyl)phosphonic Compounds
  作者：C. I. Sainz-Diaz、E. Galvez-Ruano、A. Hernandez-Laguna、J. Bellanato

  DOI：10.1021/jo00106a017

  日期：1995.1

  Several vinyl-, propenyl-, (bromoalkenyl)-, and (cyanoalkenyl)phosphonate derivatives have been synthesized. The (2-cyanovinyl)phosphonates have been obtained with an important improvement in the yield (40% versus 6%). The separation of the E and Z isomers of the cyano derivatives and their hydrolysis to the corresponding phosphonic acids have been studied. The bromination and dehydrobromination of some alkenylphosphonic derivatives have also been studied. Spectroscopical studies from UV, IR, Raman, and H-1, C-13, and P-31 NMR have been performed in most of these derivatives. The C=C/P-O pi conjugation exists but it is weak in all these compounds. Dipole moments and C=C/P=O conformational populations have been calculated theoretically by ab initio methods. The effect of the solvent polarity on the conformational population has been observed by IR spectroscopy disclosing two C=C/P=O conformers. Experimental and theoretical results have been compared, a high level of agreement has been found.
• Berdnikov,E.A. et al., Journal of general chemistry of the USSR, 1979, vol. 49, p. 257 - 262
  作者：Berdnikov,E.A. et al.

  DOI：——

  日期：——