ethyl hydrogen butylphosphonate | 91297-42-6

• 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: ethyl hydrogen butylphosphonate
• 英文别名: Butyl(ethoxy)phosphinic acid
• CAS: 91297-42-6
• 化学式: C₆H₁₅O₃P
• 分子量: 166.157
• InChiKey: RDKFCARAWNLFDR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  5
• 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：

  ethyl hydrogen butylphosphonate 在 溶剂黄146 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.5h， 生成 ethyl 3-(4-hydroxyphenoxy)benzyl butylphosphonate
  参考文献：
  名称：

  Synthesis of ethyl 3-(hydroxyphenoxy)benzyl butylphosphonates as potential antigen 85C inhibitors

  摘要：

  All three isomers of ethyl 3-(hydroxyphenoxy)benzyl butylphosphonates as potential antigen 85C inhibitors were synthesized from 3-bromobenzoic acid using Ullman diaryl ether synthesis combined with benzyl- and trityl protection strategy for the phenol hydroxyl groups. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.07.078
• 作为产物：
  描述：

  1-丁基膦酸二乙酯 在 吡啶 、 三氟甲磺酸酐 、 水 、 sodium hydroxide 作用下， 以 二氯甲烷 、 乙醚 为溶剂， 反应 1.67h， 以79%的产率得到ethyl hydrogen butylphosphonate
  参考文献：
  名称：

  磷（V）化合物的选择性水解形成有机磷单酸

  摘要：

  已经开发了一种用于合成难以捉摸的膦酸、次膦酸和磷酸单酸的无叠氮化物和过渡金属的方法。惰性五价 P( V )-化合物（膦酸盐、次膦酸盐和磷酸盐）被三氟甲磺酸酐 (Tf 2 O)/吡啶体系活化，形成高反应性磷酰吡啶鎓中间体，该中间体经过 H 2 O 的亲核取代以选择性脱保护一个烷氧基基团形成有机磷单酸。

  DOI：

  10.1039/d1ob00881a

文献信息

• Certain N-substituted-amino-alkane phosphinic acid derivatives having
  申请人：Ciba-Geigy Corporation

  公开号：US05229379A1

  公开（公告）日：1993-07-20

  Compounds having GABA.sub.B -antagonistic properties, for example those of formula I ##STR1## wherein one of the radicals R.sub.1, R.sub.2 and R.sub.3 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical, another is hydrogen or, in the case of R.sub.1 or R.sub.2, hydroxy or, in the case of R.sub.1, halogen or, in the case of R.sub.2 together with R.sub.2 ', oxo, and the remaining radical is hydrogen, R.sub.1 ' is hydrogen or halogen, R.sub.2 ' is hydrogen, hydroxy or, together with R.sub.2, is oxo, R.sub.4 and R.sub.5 are hydrogen or R.sub.4 is an araliphatic or heteroarylaliphatic radical and R.sub.5 is hydrogen or an aliphatic radical, and R is an aliphatic, cycloaliphatic, cycloaliphatic-aliphatic, araliphatic, heteroarylaliphatic or aromatic radical having at least 2 carbon atoms or, when R.sub.1 is hydrogen or hydroxy, R.sub.2 is an aromatic radical and R.sub.1 ', R.sub.2 ' and R.sub.3 are hydrogen, R is methyl, and their pharmaceutically acceptable salts, can be used as active ingredients in medicaments for the treatment of epilepsies of the "petit mal" type. The invention relates also to novel compounds of formula I and processes for the preparation thereof.

  具有GABA.sub.B-拮抗性质的化合物，例如具有以下式I的化合物##STR1##其中R.sub.1、R.sub.2和R.sub.3中的一个是氢或脂肪族、环脂族、芳基脂肪族或芳香族基团，另一个是氢或在R.sub.1或R.sub.2的情况下是羟基或在R.sub.1的情况下是卤素或在R.sub.2与R.sub.2'一起是氧代基，其余基团是氢，R.sub.1'是氢或卤素，R.sub.2'是氢、羟基或与R.sub.2一起是氧代基，R.sub.4和R.sub.5是氢或R.sub.4是芳基脂肪族或杂环芳基脂肪族基团，R.sub.5是氢或脂肪族基团，R是至少有2个碳原子的脂肪族、环脂族、环脂族-脂肪族、芳基脂肪族、杂环芳基脂肪族或芳香族基团，当R.sub.1是氢或羟基时，R.sub.2是芳香族基团，且R.sub.1'、R.sub.2'和R.sub.3是氢时，R是甲基，以及它们的药学上可接受的盐，可用作治疗“小发作”型癫痫的药物中的活性成分。该发明还涉及具有式I的新化合物以及其制备方法。
• 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。
• Selective Esterification of Phosphonic Acids
  作者：Damian Trzepizur、Anna Brodzka、Dominik Koszelewski、Ryszard Ostaszewski

  DOI：10.3390/molecules26185637

  日期：——

  proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small- and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30 °C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic

  在这里，我们报告了膦酸单酯化和二酯化的直接和选择性合成程序。研究了一系列烷氧基供体，发现原乙酸三乙酯是进行转化的最佳试剂和溶剂。发现了对反应过程的重要温度影响。取决于反应温度，以合适的产率专门获得膦酸的单乙酯或二乙酯。所提出的方法的底物范围在芳香族和脂肪族膦酸上得到验证。所设计的方法可成功应用于小规模和大规模实验，而不会显着降低选择性或反应收率。进行了几次专门的实验以深入了解反应机理。在 30 °C 时，单酯通过中间体（膦酸的 1,1-二乙氧基乙酯）形成。在更高的温度下，类似的中间体形式产生二酯或稳定且可检测的焦膦酸盐，它们也被消耗以产生二酯。31 P NMR 光谱用于确定焦膦酸酯的结构并监测反应过程。不需要额外的试剂、良好的可及性和直接的纯化是所开发协议的重要方面。
• One-pot Synthesis of Vinyl Phosphonates from 2-hydroxyalkyl Phenyl Selenides with Monoethyl Esters of Phosphonic Acid
  作者：Shou-Ri Sheng、Wu-Kang Sun、Ming-Gang Hu、Xiao-Ling Liu、Qiu-Ying Wang

  DOI：10.3184/030823407x198221

  日期：2007.2

  Vinyl phosphonates were prepared with good yields in a one-pot, two-step transformation by Mitsunobu reaction of 2-hydroxyalkyl phenyl selenides with monoethyl esters of phosphonic acid followed by oxidation-elimination.

  通过 2-羟烷基苯基硒化物与膦酸单乙酯的 Mitsunobu 反应，然后氧化消除，在一锅两步转化中以良好的收率制备乙烯基膦酸酯。
• Mercury(II)-Catalyzed Regioselective Addition Reaction of Monoesters of Phosphonic Acid to Terminal Alkynes: Synthesis of Vinyl Phosphonates
  作者：Yixiang Ding、Aiyun Peng

  DOI：10.1055/s-2003-36818

  日期：——

  Vinyl phosphonates 3a-1 were prepared by the regioselective addition reaction of monoesters of phosphonic acid to alkynes in the presence of Hg(OAc) 2 /BF 3 .OEt 2 .

  在 Hg(OAc) 2 /BF 3 .OEt 2 存在下，通过膦酸单酯与炔烃的区域选择性加成反应制备乙烯基膦酸酯 3a-1。