isopropyl phosphinate | 51963-59-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: isopropyl phosphinate
• 英文别名: isopropyl hypophosphite；Oxido(propan-2-yloxy)phosphanium；oxido(propan-2-yloxy)phosphanium
• CAS: 51963-59-8
• 化学式: C₃H₉O₂P
• 分子量: 108.077
• InChiKey: BGLDJAVKFHETGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  isopropyl phosphinate 在 Ni-doped silica 作用下， 以 环己烷 、 水 为溶剂， 反应 18.0h， 以4.15 g的产率得到亚磷酸二异丙酯
  参考文献：
  名称：

  Synthesis of H-Phosphonate Intermediates and Their Use in Preparing the Herbicide Glyphosate

  摘要：

  亚磷酸酯化后，在镍催化剂的作用下，与另一分子醇发生反应，提供了一种绿色方法来制备H-膦酸二酯。该方法避免了基于三氯化磷的方法中需要任何等化物氯的需求。

  公开号：

  US20140303394A1
• 作为产物：
  描述：

  正硅酸四异丙酯 在 次磷酸 作用下， 以 水 、 乙腈 为溶剂， 反应 2.0h， 生成 isopropyl phosphinate
  参考文献：
  名称：

  Novel Cyclic Phosphinic Acids as GABA_C ρ Receptor Antagonists: Design, Synthesis, and Pharmacology

  摘要：

  Understanding the role of GABA(C) receptors in the central nervous system is limited due to a lack of specific ligands. Novel gamma-aminobutyric acid (GABA) analogues based on 3-(aminomethyl)-1-oxo-1-hydroxy-phospholane 17 and 3-(guanido)-1-oxo-1-hydroxy-phospholane 19 were investigated to obtain selective GABA(C) receptor antagonists. A compound of high potency (19, K-B = 10 mu M) and selectivity (greater than 100 times at rho(1) GABA(C) receptors as compared to alpha(1)beta(2)gamma(2L) GABA(A) and GABA(B(1b,2)) receptors) was obtained. The cyclic phosphinic acids (17 and 19) are novel lead agents for developing into more potent and selective GABA(C) receptor antagonists with increased lipophilicity for future in vivo studies.

  DOI：

  10.1021/ml1001344

文献信息

• Organophosphorus Chemistry without PCl₃: A Bridge from Hypophosphorous Acid to H-Phosphonate Diesters
  作者：Henry C. Fisher、Lucie Prost、Jean-Luc Montchamp

  DOI：10.1002/ejoc.201301412

  日期：2013.12

  A process for the conversion of hypophosphorous acid (H3PO2, HPA) and alcohols into various H-phosphonate diesters [(RO)2P(O)H] is described. The new reaction provides a missing bridge between HPA and important H-phosphonates, completely avoiding the use of PCl3. Nickel chloride or nickel on silica catalyze the oxidative phosphorylation of alkyl phosphinates with various alcohols or water. The reaction

  描述了将次磷酸 (H3PO2, HPA) 和醇转化为各种 H-膦酸二酯 [(RO)2P(O)H] 的过程。新反应在 HPA 和重要的 H-膦酸盐之间提供了一个缺失的桥梁，完全避免了 PCl3 的使用。氯化镍或二氧化硅上的镍催化烷基次膦酸盐与各种醇或水的氧化磷酸化。该反应是原子经济的，避免了废物的形成。完全避免了以前对氯和碱的需求。
• A novel and convenient preparation of hypophosphite esters
  作者：Sylvine Deprèle、Jean-Luc Montchamp

  DOI：10.1016/s0022-328x(01)01204-9

  日期：2002.2

  Only a few methods have been described for the preparation of hypophosphite esters (alkyl phosphinates, ROP(O)H2). As a result, comparatively few applications have been reported, and these intermediates have not been widely exploited in organophosphorus chemistry despite their synthetic potential. Herein, we describe a very general, practical, and high-yielding synthesis of hypophosphite esters, based

  仅描述了几种制备次磷酸酯的方法（次膦酸烷基酯，ROP（O）H 2）。结果，已经报道了相对较少的应用，尽管这些中间体具有合成潜力，但尚未在有机磷化学中得到广泛利用。在此，我们基于次磷酸及其某些盐与烷氧基硅烷的反应，描述了一种非常通用，实用且高产的次磷酸酯合成方法。该方法学解决了与先前报道的反应有关的许多问题。我们的酯化反应是在各种溶剂中于中等温度下进行的，在这些条件下，酯具有明显的热稳定性。此外，所使用的试剂是廉价的，并且不必是严格无水的。讨论了该方法的范围和局限性，
• Direct Monoalkylation of Alkyl Phosphinates to Access H-Phosphinic Acid Esters
  作者：Jean-Luc Montchamp、Isabelle Abrunhosa-Thomas、Patrice Ribière、Alicia C. Adcock

  DOI：10.1055/s-2005-924768

  日期：——

  Simple alkyl phosphinates prepared by the silicate esterification method can be alkylated under Barbier-like conditions with butyl lithium at -78 °C followed by warming to room temperature. The method is limited to the more reactive electrophile such as allylic bromides and alkyl iodides. With these electrophiles good yields of H-phosphinic acid esters are generally obtained in a straightforward manner

  通过硅酸酯化方法制备的简单烷基次膦酸盐可以在类似巴比尔的条件下与丁基锂在 -78 °C 下烷基化，然后升温至室温。该方法仅限于反应性更强的亲电子试剂，例如烯丙基溴化物和烷基碘化物。使用这些亲电子试剂，通常以简单的方式获得高产率的 H-次膦酸酯。
• Synthesis of Novel 5′-Hydrogenphosphonothioate Derivatives of AZT, d4T and ddI
  作者：Ying Jin、Ming Sun、Hua Fu、Yu-Fen Zhao

  DOI：10.1246/cl.2004.116

  日期：2004.2

  5′-hydrogenphosphonothioate derivatives of AZT, d4T, and ddI as anti-HIV prodrug candidates were synthesized in 61–76% yields under mild conditions through sequential one-pot reactions, i.e., couple of triethylammonium phosphinate with different alcohols in the presence of pivaloyl chloride (PV-Cl), following oxidation with elemental sulfur and further condensation with AZT, d4T, or ddI in the presence of PV-Cl.

  AZT、d4T 和 ddI 的 5′-氢磷酰硫酸酯衍生物作为抗 HIV 前药候选物，在温和条件下通过顺序一锅反应合成，产率为 61-76%。该反应过程包括将三乙胺磷酸酯与不同醇在有格氏氯（PV-Cl）存在下偶联，随后用元素硫氧化，最后在 PV-Cl 存在下与 AZT、d4T 或 ddI 进一步缩合。
• Phosphitylation via the Mitsunobu reaction
  作者：I.Darren Grice、Peta J. Harvey、Ian D. Jenkins、Michael J. Gallagher、Millagahamada G. Ranasinghe

  DOI：10.1016/0040-4039(95)02282-1

  日期：1996.2

  Treatment of a dialkyl phosphite with triphenylphosphine and diisopropyl azodicarboxylate in toluene, followed by addition of an alcohol, results in the formation of the corresponding trialkyl phosphite. Similarly, dialkyl phosphonites can be synthesised from monoalkyl phosphites (alkyl phosphinates).

  用三苯基膦和偶氮二羧酸二异丙酯在甲苯中处理亚磷酸二烷基酯，然后加入醇，导致形成相应的亚磷酸三烷基酯。类似地，二烷基亚膦酸酯可以由亚磷酸单烷基酯（亚膦酸烷基酯）合成。