4,5-dimethyl-1,3,2-dioxaphospholan-2-ium 2-oxide | 16352-17-3

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 4,5-dimethyl-1,3,2-dioxaphospholan-2-ium 2-oxide
• 英文别名: 2-hydro-4,5-dimethyl-2-oxo-1,3,2-dioxaphospholane；4,5-dimethyl-1,3,2λ⁵-dioxaphospholane 2-oxide；2-hydro-2-oxo-4,5-dimethyl-1,3,2-dioxaphospholane；4,5-dimethyl-1,3,2-dioxaphospholane 2-oxide；4,5-dimethyl-[1,3,2]dioxaphospholane 2-oxide；phosphonic acid-(1,2-dimethyl-ethanediyl ester)；4,5-Dimethyl-2-oxo-[1,3,2λ⁵]dioxaphospholan
• CAS: 16352-17-3；26349-89-3；26349-90-6；26349-91-7
• 化学式: C₄H₉O₃P
• 分子量: 136.087
• InChiKey: UGKNFCJGEKQALI-UHFFFAOYSA-N

物化性质

• 沸点：
  60-63 °C(Press: 0.03 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  8.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4,5-dimethyl-1,3,2-dioxaphospholan-2-ium 2-oxide 在 sulfur 作用下， 生成 O,O-1.2-dimethylethylene hydrogen phosphorothioite
  参考文献：
  名称：

  Ovchinnikov, V. V.; Antipin, I. S.; Gareyev, R. F., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 51/52, p. 708

  摘要：

  DOI：
• 作为产物：
  描述：

  2-chloro-4,5-dimethyl-1,3,2-dioxaphospholane 在 水 、 苯 作用下， 生成 4,5-dimethyl-1,3,2-dioxaphospholan-2-ium 2-oxide
  参考文献：
  名称：

  酯交换法合成环状磷酸酯

  摘要：

  五元和六元环状亚磷酸酯是通过亚磷酸酯与 1,2- 和 1,3- 二醇的酯交换反应合成的： 亚磷酸氢二乙酯被酯交换得到环状亚磷酸氢酯。亚磷酸三-2-氯乙基酯的部分酯交换产生环状亚磷酸2-氯乙基酯。

  DOI：

  10.1139/v59-220

文献信息

• [EN] METHOD FOR THE SYNTHESIS OF HETEROCYCLIC HYDROGEN PHOSPHINE OXIDE<br/>[FR] PROCÉDÉ POUR LA SYNTHÈSE D'UN OXYDE DE D'HYDROGÉNOPHOSPHINE HÉTÉROCYCLIQUE
  申请人：STRAITMARK HOLDING AG

  公开号：WO2016026871A1

  公开（公告）日：2016-02-25

  The present invention is related to a method for the synthesis of a heterocyclic hydrogen phosphine oxide, having the general formula (I), wherein: - R is a aliphatic or aromatic divalent group optionally comprising one or more heteroatoms and optionally comprising one or more substituents and - X and Y are independently selected from -O-, -C(O)O- and -NR'- wherein R' is a monovalent group optionally comprising one or more heteroatoms comprising the steps of: a) forming a reaction mixture by mixing a compound having the general formula HX-R-YH and tetraphosphorus hexaoxide; b) recovering the resulting compound comprising the heterocyclic hydrogen phosphine oxide.

  本发明涉及一种合成杂环氢膦氧化物的方法，其具有通式（I），其中：- R是一种脂肪或芳香双价基团，可选地包含一个或多个杂原子，也可选地包含一个或多个取代基；- X和Y分别选自-O-，-C（O）O-和-NR'-，其中R'是一种可选地包含一个或多个杂原子的单价基团，包括以下步骤：a）通过混合具有通式HX-R-YH和六氧化四磷的化合物形成反应混合物；b）回收包含杂环氢膦氧化物的所得化合物。
• Celebrating 20 Years of SYNLETT - Special Essay: General Procedure for the Palladium-Catalyzed Selective Hydrophosphorylation of Alkynes
  作者：Valentine Ananikov、Irina Beletskaya、Levon Khemchyan

  DOI：10.1055/s-0029-1217739

  日期：2009.9

  A novel catalytic system has been developed to accomplish the hydrophosphorylation of terminal and internal alkynes with high isolated yields (up to 96%) and excellent regio- and stereo­selectivity (>99:1). The key factor was to apply a low-ligated palladium/triphenylphosphane (1:2) catalytic system in the presence of a catalytic amount of trifluoroacetic acid. The catalytic system so developed has been applied successfully to permit the formation of diverse alkenylphosphonates utilizing a variety of available H-phos­phonates and alkynes.

  开发了一种新型催化体系，以高分离收率（高达96%）和优异的区域及立体选择性（>99:1）实现末端和内部炔烃的亲水磷酸化。关键因素是在三氟乙酸催化剂量的存在下，应用低配位钯/三苯基膦（1:2）催化体系。所开发的催化体系已成功应用于利用多种可用H-膦酸酯和炔烃形成多种烯基膦酸酯。
• New method of alkylene phosphonate preparation
  作者：Pawel Klosinski

  DOI：10.1016/s0040-4039(00)88906-6

  日期：1990.1

  A new method of alkylene phosphonate preparation has been elaborated, based on the reaction of the corresponding cyclic ethers and phosphonic acid in the presence of acetic anhydride.

  基于相应的环醚与膦酸在乙酸酐存在下的反应，详细阐述了一种制备亚烷基膦酸酯的新方法。
• Acid-Free Nickel Catalyst for Stereo- and Regioselective Hydrophosphorylation of Alkynes: Synthetic Procedure and Combined Experimental and Theoretical Mechanistic Study
  作者：Valentine P. Ananikov、Levon L. Khemchyan、Irina P. Beletskaya、Zoya A. Starikova

  DOI：10.1002/adsc.201000606

  日期：2010.11.22

  situ from nickel bis(acetylacetonate) [Ni(acac)2] precursor and bis(diphenylphosphino)ethane (DPPE) ligand has shown excellent performance in the hydrophosphorylation of alkynes. Markovnikov-type regioselective addition to terminal alkynes and stereoselective addition to internal alkynes were carried out with high selectivity without an acidic co-catalyst (in contrast to the palladium/acid catalytic system)

  由双（乙酰丙酮酸）镍[Ni（acac）2原位制备的镍催化剂]前体和双（二苯基膦基）乙烷（DPPE）配体在炔烃的加氢磷酸化中表现出出色的性能。在没有酸性助催化剂的情况下（与钯/酸催化体系相反），以高选择性进行了向末端炔烃的马尔科夫尼科夫区域选择性加成和向内部炔烃的立体选择性加成。在开发的催化体系中，各种H-膦酸酯和炔烃反应平稳，收率高达99％。通过实验（NMR，ESI-MS，X射线）和理论（密度泛函计算）研究揭示了催化剂活化和CP键形成的机理。首次报道了炔烃在金属配位体中插入的两种不同途径。
• Cyclic organophosphorus compounds. I. Synthesis and infrared spectral studies of cyclic hydrogen phosphites and thiophosphites
  作者：A. Zwierzak

  DOI：10.1139/v67-411

  日期：1967.11.1

  A general synthetic procedure leading to cyclic hydrogen phosphites has been devised. The effect of solvent on the P==O and P—H infrared stretching modes of cyclic hydrogen phosphites and thiophosphites has been studied. It is concluded that association of cyclic hydrogen phosphites is attributable to dipole–dipole interactions rather than to hydrogen bonding.

  已经设计了导致环状亚磷酸氢酯的一般合成程序。研究了溶剂对环状亚磷酸氢酯和硫代亚磷酸酯的 P==O 和 P-H 红外伸缩模式的影响。结论是环状亚磷酸氢盐的缔合归因于偶极-偶极相互作用而不是氢键。