1-n-butyl-2,5-dihydro-3-methyl-1H-phosphole 1-oxide | 62891-09-2

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: 1-n-butyl-2,5-dihydro-3-methyl-1H-phosphole 1-oxide
• 英文别名: 1-oxo-1-butyl-3-methyl-3-phospholene；1-n-butyl-3-methyl-3-phospholene 1-oxide；Oxid von 1-Butyl-3-methyl-3-phospholen-1；1-butyl-3-methyl-3-phospholene-1-oxide；1-butyl-3-methyl-3-phospholene oxide；1-butyl-3-methyl-2,5-dihydro-1λ5-phosphole 1-oxide
• CAS: 62891-09-2
• 化学式: C₉H₁₇OP
• 分子量: 172.207
• InChiKey: JNQSVKDXPKQCOP-UHFFFAOYSA-N

物化性质

• 沸点：
  128 °C(Press: 0.3 Torr)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-n-butyl-2,5-dihydro-3-methyl-1H-phosphole 1-oxide 在 phase-transfer cat sodium hydroxide 、 silver nitrate 作用下， 以 水 为溶剂， 生成 1-butyl-4-chloro-3-methoxy-3-methyl-2,6-dihydro-1λ5-phosphinine 1-oxide
  参考文献：
  名称：

  Keglevich, Gy.; Petnehazy, I.; Toeke, L., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 51/52, p. 744

  摘要：

  DOI：
• 作为产物：
  描述：

  正溴丁烷 、 1-chloro-3-methyl-3-phospholene-1-oxide 在 magnesium 作用下， 生成 1-n-butyl-2,5-dihydro-3-methyl-1H-phosphole 1-oxide
  参考文献：
  名称：

  Ring expansion in the addition of dichlorocarbene to 2,5-dihydro-1H-phosphole 1-oxides

  摘要：

  DOI：

  10.1021/jo00227a008

文献信息

• Dynamic kinetic resolution of 1-substituted-3-methyl-3-phospholene oxides via the formation of diastereomeric alkoxyphospholenium salts
  作者：Péter Bagi、Réka Herbay、Péter Ábrányi-Balogh、Béla Mátravölgyi、Elemér Fogassy、György Keglevich

  DOI：10.1016/j.tet.2018.07.058

  日期：2018.10

  then rearranged into the corresponding optically active 3-phospholene oxides upon heating. After a screening of chiral auxiliaries and the optimization of the reaction conditions, several scalemic 1-aryl- or 1-alkyl-3-methyl-3-phospholene oxides were prepared in excellent yields and with ee-s up to 35%. The key steps of this resolution were investigated by quantum chemical calculations to get some insights

  阐述了一种基于形成共价非对映中间体的动态动力学拆分方法，以制备对映体富集的1-取代-3-甲基-3-氧化膦。首先将3-环氧丙烷氧化物转化为相应的氯-3-磷鎓氯化物。氯磷鎓盐的对映异构体之间的动态相互转化已通过实验验证，因为这是动态拆分的关键步骤。使环状氯代磷鎓盐与带有羟基官能团的手性助剂反应，以不等量形成相应的非对映体烷氧基磷鎓盐。然后在加热时将非对映异构物质重新排列成相应的旋光的3-氧化茂氧化物。在筛选了手性助剂并优化了反应条件后，以极高的收率和高达35％的ee制备了几种规模的1-芳基-或1-烷基-3-甲基-3-膦基环氧丙烷。通过量子化学计算研究了该分辨率的关键步骤，以深入了解造成立体选择的因素。
• Isomerization and application of phospholene oxides
  作者：Réka Herbay、Nikolett Péczka、Gábor Györke、Péter Bagi、Elemér Fogassy、György Keglevich

  DOI：10.1080/10426507.2018.1553043

  日期：2019.5.27

  Abstract In this research, an investigation of the isomerization and the applications of 3-phospholene oxides were elaborated. The isomerization of 3-phospholene oxides to 2-phospholene oxides was investigated under thermal condition. The application of bases and acids was also tested in this reaction. Moreover, the isomerization was also elaborated via the formation of halophosphonium salt intermediates

  摘要 本研究对3-磷烯氧化物的异构化及其应用进行了研究。在热条件下研究了 3-磷烯氧化物异构化为 2-磷烯氧化物。在该反应中还测试了碱和酸的应用。此外，异构化也通过形成卤代鏻盐中间体来进行。3-磷烯氧化物被脱氧并转化为相应的钯配合物。图形概要
• A novel preparation of chlorophospholenium chlorides and their application in the synthesis of phospholene boranes
  作者：Réka Herbay、Péter Bagi、Zoltán Mucsi、Béla Mátravölgyi、László Drahos、Elemér Fogassy、György Keglevich

  DOI：10.1016/j.tetlet.2016.12.059

  日期：2017.2

  A novel preparation of 1-chloro-3-methyl-3-phospholenium chlorides was developed by reacting 1-substituted-3-methyl-3-phospholene 1-oxides with oxalyl chloride. The obtained cyclic chlorophosphonium salts were reacted with LiBH4 to afford the corresponding 1-substituted-3-methyl-3-phospholene boranes. The latter protocol involves a silane-free deoxygenation, and borane complex formation. In one instance

  通过使1-取代的-3-甲基-3-膦-1-氧化物与草酰氯反应，开发了一种新型的1-氯-3-甲基-3-磷酰氯的制备方法。使获得的环状氯盐与LiBH 4反应，得到相应的1-取代的-3-甲基-3-膦基硼烷。后一种方案涉及无硅烷的脱氧和硼烷络合物的形成。在一种情况下，通过在环氯phosph盐中双键的重排来合成2-膦硼烷和相应的P-氧化物。通过量子化学计算研究了这种双键迁移。
• Preparation of 2-phospholene oxides by the isomerization of 3-phospholene oxides
  作者：Péter Bagi、Réka Herbay、Nikolett Péczka、Zoltán Mucsi、István Timári、and György Keglevich

  DOI：10.3762/bjoc.16.75

  日期：——

  obtained by heating the 3-phospholene oxides in methanesulfonic acid, or via the formation of cyclic chlorophosphonium salts. Whereas mixtures of the 2- and 3-phospholene oxides formed, when the isomerization of 3-phospholene oxides was attempted under thermal conditions, or in the presence of a base. The mechanisms of the various double bond migration pathways were elucidated by quantum chemical calculations

  通过双键重排，由相应的3-氧化膦制备一系列1-取代的-3-甲基-2-氧化膦。可以通过在甲磺酸中加热3-氧化膦或通过形成环状氯膦盐来获得2-氧化膦。然而，当在热条件下或在碱的存在下尝试3-环氧丙烷的异构化时，形成了2-环氧丙烷和3-环氧丙烷的混合物。量子化学计算阐明了各种双键迁移途径的机理。
• Platinum(II) complexes incorporating racemic and optically active 1-alkyl-3-phospholenes and 1-propyl-phospholane P-ligands: Synthesis, stereostructure, NMR properties and catalytic activity
  作者：György Keglevich、Péter Bagi、Áron Szöllősy、Tamás Körtvélyesi、Péter Pongrácz、László Kollár、László Drahos

  DOI：10.1016/j.jorganchem.2011.08.006

  日期：2011.8

  Racemic and optically active 1-propyl- and 1-butyl-3-methyl-3-phospholene oxides, as well as 1-propyl-3-methylphospholane oxides were converted after deoxygenation to the corresponding phosphine-borane and phopshine-platinum complexes. Stereostructure of the novel platinum complexes with a propyl group on the phosphorus atom was evaluated by quantum chemical calculations. The complexes displayed characteristic

  在消氧后，外消旋和旋光的1-丙基-和1-丁基-3-甲基-3-氧化膦以及1-丙基-3-甲基氧化膦被转化为相应的膦-硼烷和磷-铂络合物。通过量子化学计算评估了在磷原子上带有丙基的新型铂配合物的立体结构。该配合物在其NMR光谱方面显示出特征性，并且在苯乙烯衍生物的加氢甲酰化中作为催化剂表现出不同寻常的区域选择性。在光学活性的Pt-络合物前体的存在下，获得的Ee-s高达21％。