4-tert-butyl-1-hydroxyphosphorinane 1-oxide | 171668-51-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 磷环化合物
• 英文名称: 4-tert-butyl-1-hydroxyphosphorinane 1-oxide
• 英文别名: 4-Tert-butyl-1-hydroxy-1lambda5-phosphinane 1-oxide；4-tert-butyl-1-hydroxy-1λ5-phosphinane 1-oxide
• CAS: 171668-51-2
• 化学式: C₉H₁₉O₂P
• 分子量: 190.222
• InChiKey: OLPYKNJMRBCVGU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-tert-butyl-1-hydroxyphosphorinane 1-oxide 在 氯化亚砜 作用下， 以 乙醇 为溶剂， 生成 trans-4-tert-butyl-1-ethoxyphosphorinane 1-oxide
  参考文献：
  名称：

  Preparation, Reactions, and Stereochemistry of 4-tert-Butyl-1-chlorophosphorinane 1-Oxide and Derivatives

  摘要：

  The title compound 6 was synthesized as a model structure to study the stereochemical and mechanistic aspects of nucleophilic substitution at the phosphorus atom in a six-membered ring. Several synthetic methods were used to prepare 6, but in every case a mixture of diastereomers was obtained, in almost the same ratio. This mixture was used for the investigation of the reaction with several alcohols (methanol, ethanol, isopropyl alcohol) under acidic and/or basic conditions. Reactions with phenyllithium and two nitrogen nucleophiles, aniline and morpholine, were also carried out. The reactions led to mixtures of diastereomeric products; the ratio of these products did not always correspond to the diastereomeric ratio of starting material. Reactions of phosphinate esters were also studied, including kinetic measurements; the results strongly suggest an S(N)2 reaction mechanism. 4-tert-Butyl-1-fluorophosphorinane 1-oxide (mixture of isomers) was synthesized and its reactions with phenoxide ions and phenyllithium were studied; the overall stereochemical results of these transformations were similar to those of the title chlorides. The stereochemical assignments of the phenyl- (4), methoxy- (7), phenoxy- (10), and anilino (13) derivatives of 6 have been firmly anchored by X-ray studies; assignments for other compounds are tentative and based on spectroscopic measurements, including H-1, C-13, P-31, and O-17 NMR data.

  DOI：

  10.1021/jo00125a012
• 作为产物：
  描述：

  1-溴-3-(2-溴乙基)-4,4-二甲基戊烷 在 ammonium hypophosphite 、 六甲基二硅氮烷 作用下， 以 均三甲苯 为溶剂， 反应 12.0h， 以55%的产率得到4-tert-butyl-1-hydroxyphosphorinane 1-oxide
  参考文献：
  名称：

  使用实验和计算的NMR化学位移确定六元饱和杂环（N，P，S，Se）及其氧化产物中的构型

  摘要：

  六元饱和杂环-4-叔丁基-1-甲基哌啶，4-叔丁基-1-甲基膦，4-叔丁基-四氢-2 H-噻喃和4-叔丁基-四氢-2将H-硒代吡喃制备为具有明确几何结构的合适模型化合物，用于其氧化产物的NMR研究。通过标准化学制备以及通过直接在NMR管中用间-氯过苯甲酸原位氧化获得相应的差向异构N-氧化物，次膦氧化物，亚砜和亚硒酸盐。实验1 H和13将C化学位移与通过GIAO方法使用DFT，MP2和HF方法以及各种基础集获得的相应计算数据进行比较。实验数据与计算数据的相关性表明，可以使用快速DFT B3LYP / 6-31G *方法确定差向异构氧化产物的立体化学，以进行几何优化和NMR化学位移计算。

  DOI：

  10.1016/j.tet.2014.04.047