1,3,2-Dioxaphosphorinane, 2-chloro-5-methyl- | 38206-42-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环化合物
• 英文名称: 1,3,2-Dioxaphosphorinane, 2-chloro-5-methyl-
• 英文别名: 2-chloro-5-methyl-1,3,2-dioxaphosphorinanes；cis-2-chloro-5-methyl-1,3,2-dioxaphosphorinane；cis-2-chloro-5-methyl-[1,3,2]dioxaphosphinane
• CAS: 38206-42-7；51851-57-1；157522-89-9
• 化学式: C₄H₈ClO₂P
• 分子量: 154.533
• InChiKey: VEWQKSMFHJESJJ-SWUQSZJBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.13
• 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：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  2-甲基-1,3-丙二醇 在 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 生成 1,3,2-Dioxaphosphorinane, 2-chloro-5-methyl- 、 2-Chloro-5-methyl-[1,3,2]dioxaphosphinane
  参考文献：
  名称：

  Conformational Equilibria of Phosphoranes with 5-Alkyl-Substituted 1,3,2-Dioxaphosphorinane Rings Attached Diequatorially to Five-Coordinated Phosphorus. Are Boat/Twist Conformations Populated?

  摘要：

  The conformational equilibria of 1,3,2-dioxaphosphorinanes 4-8, featuring diequatorial attachment of the ring to five-coordinate phosphorus, were perturbed by a series of substituents at C5 (Me, Ph, t-Bu). Unlike the analogous phosphoranes that feature equatorial/apical ring attachment and populate boat/twist conformations even when unbiased by ring substituents, no H-1 NMR evidence could be found for population of a nonchair conformation, even in the presence of an axial 5-t-Bu (8). The failure to readily form boat/twist conformations also is contradictory to their known ease of population by 1,3,2-dioxaphosphorinanes containing three- or four-coordinate phosphorus. Both steric and stereoelectronic rationales are offered for this highly significant but hitherto unrecognized conformational property of 1,3,2-dioxaphosphorinane rings attached diequatorially to five-coordinate phosphorus. Perturbation of a chair-chair equilibrium (A reversible arrow B) was observed that allowed the determination of conformational energies (A values, kcal/mol, in C6D6) for the groups at C5: Me, 0.8; Ph, 1.6; t-Bu, 1.7. These values are similar to those for C5 substituents on 1,3-dioxane rings with the exception of 5-Ph (A value 1.0 kcal/mol for 1,3-dioxane). The similarity of the A values for the Ph and t-Bu substituents in the 1,3,2-dioxaphosphorinane ring is tentatively assigned to increased steric repulsions present when the 5-Ph is axial because of the apical P-O bond of the five-coordinate phosphorus.

  DOI：

  10.1021/ja00155a003