4-methyl-1,3,2-dioxaphosphinan-2-ium 2-oxide | 16368-20-0

• 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: 4-methyl-1,3,2-dioxaphosphinan-2-ium 2-oxide
• 英文别名: 4-methyl-[1,3,2]dioxaphosphinane 2-oxide；2-Hydro-4-methyl-2-oxo-1,3,2λ⁵-dioxaphosphorinane；2-oxo-4-methyl-1,3,2-dioxaphosphorinane；2-oxo-4-methyl-1,3,2-dioxaphosphorinan；Phosphorigsaeure-(1-methyltrimethylen)ester；4-Methyl-1,3,2-dioxaphosphorinan-2-oxid；4-Methyl-2-oxo-1.3.2-dioxaphosphorinan
• CAS: 16368-20-0
• 化学式: C₄H₉O₃P
• 分子量: 136.087
• InChiKey: BRNIZUWNRYIOEU-UHFFFAOYSA-N

物化性质

• 熔点：
  49-50 °C
• 沸点：
  138-140 °C(Press: 3 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-methyl-1,3,2-dioxaphosphinan-2-ium 2-oxide 、 苯甲醛吖嗪 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Nifant'ev,E.E. et al., Journal of general chemistry of the USSR, 1975, vol. 45, p. 1424 - 1428

  摘要：

  DOI：
• 作为产物：
  描述：

  2-formyloxy-4-methyl-[1,3,2]dioxaphosphinane 以 乙醚 为溶剂， 生成 4-methyl-1,3,2-dioxaphosphinan-2-ium 2-oxide
  参考文献：
  名称：

  Fursenko,I.V. et al., Journal of general chemistry of the USSR, 1968, vol. 38, # 6, p. 1251 - 1255

  摘要：

  DOI：

文献信息

• Chemoselective Reduction of the P=O Bond in the Presence of P-O and P-N Bonds in Phosphonate and Phosphinate Derivatives
  作者：Sylwia Sowa、K. Michał Pietrusiewicz

  DOI：10.1002/ejoc.201801518

  日期：2019.2.7

  The chemoselective reduction of P=O bond in α‐hydroxy and α‐amino phosphonic/phosphinic acid derivatives can be achieved without concomitant scission of their ester and amide bonds using commercially available BH3 complexes. The reduction involves an intramolecular assistance by the proximal OH or NH groups enabling preferential removal of the phosphoryl oxygen.

  使用市售BH 3络合物，无需伴随其酯键和酰胺键的断裂即可实现α-羟基和α-氨基膦酸/次膦酸衍生物中P = O键的化学选择性还原。还原涉及通过近端的OH或NH基团的分子内协助，从而能够优先去除磷酰氧。
• Iodoform, a New Reagent in the Todd-Atherton Reaction
  作者：Grażyna Mielniczak、Andrzej Bopusiński

  DOI：10.1081/scc-120026306

  日期：2003.12

  Abstract An innovative and convenient application of the iodoform (1) as the reagent in the synthesis of phosphoramidates via Todd-Atherton reaction is described. The full stereoselectivity of this transformation using a 4-methyl-1,3,2-dioxaphosphinane model system was demonstrated.

  摘要 描述了碘仿 (1) 作为试剂在 Todd-Atherton 反应合成氨基磷酸酯中的创新和便捷应用。使用 4-甲基-1,3,2-二氧杂膦模型系统证明了这种转化的完全立体选择性。
• 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。
• One-step transformation of ammonium dialkyl phosphoroselenoates into dialkyl phosphoramidates
  作者：Gra?yna Mielniczak、Andrzej ?opusi?ski

  DOI：10.1002/hc.10110

  日期：——

  Ammonium dialkyl phosphoroselenoates are directly converted into the dialkyl phosphoramidates by iodosobenzene and iodoxybenzene. The inversion of configuration at the phosphorus atom, using model diastereoisomeric ammonium cis- and trans-2-oxo-2-seleno-4-methyl-1,3,2-dioxaphosphinan system, was observed. The mechanistic scheme of this transformation is discussed. © 2003 Wiley Periodicals, Inc. Heteroatom

  二烷基磷酸硒酸铵被碘代苯和碘氧基苯直接转化为氨基磷酸二烷基酯。使用模型非对映异构铵顺式和反式 2-oxo-2-seleno-4-methyl-1,3,2-dioxaphosphinan 系统观察到磷原子的构型反转。讨论了这种转换的机制方案。© 2003 Wiley Periodicals, Inc. 杂原子化学 14:121–127, 2003; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.10110
• Kinetically Controlled Stereoselective Synthesis of 2-Oxo-2-aryl-1,3,2-dioxaphosphorinane Derivatives via a Palladium-Catalyzed Reaction
  作者：Hongming Cui、Daizong Lin、Dang Qun、Xu Bai

  DOI：10.1021/acs.joc.3c02151

  日期：2024.3.1

  Chiral phosphonate esters have been widely applied in the fields of organic chemistry, medicine, and photoelectric materials. However, it requires the challenging enantioselective synthesis of cyclic phosphonate esters with the desired chiral configuration. The two epimers of 2-oxo-2H-1,3,2-dioxaphosphorinane derivatives should have different reactivities in Pd-catalyzed coupling reactions, which could lead

  手性膦酸酯在有机化学、医药、光电材料等领域有着广泛的应用。然而，它需要具有所需手性构型的环状膦酸酯的对映选择性合成，具有挑战性。 2-oxo-2 H -1,3,2-二氧杂膦烷衍生物的两种差向异构体在Pd催化的偶联反应中应具有不同的反应活性，这可能为2-oxo-2-aryl-的不对称合成提供有效的方法。 1,3,2-二氧杂膦烷衍生物。通过计算和实验对偶联反应进行彻底研究，实现了手性环状膦酸酯的立体选择性合成。在动力学控制的条件下，由2-oxo-2 H -1,3,2-二氧杂膦烷衍生物的混合物可以得到具有高非对映选择性和良好化学收率的轴向异构体产物。