2-Chloro-3-methyl-5-tert-butyl-1,3,2-oxazaphosphorinane | 167895-92-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧氮杂膦
• 英文名称: 2-Chloro-3-methyl-5-tert-butyl-1,3,2-oxazaphosphorinane
• 英文别名: 5-Tert-butyl-2-chloro-3-methyl-1,3,2-oxazaphosphinane
• CAS: 167895-92-3
• 化学式: C₈H₁₇ClNOP
• 分子量: 209.656
• InChiKey: LMFZQGHIUXJWRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 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：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  六氟异丙醇 、 2-Chloro-3-methyl-5-tert-butyl-1,3,2-oxazaphosphorinane 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以91%的产率得到cis-2-(1,1,1,3,3,3-Hexafluoroisopropoxy)-3-methyl-5-tert-butyl-1,3,2-oxazaphosphorinane
  参考文献：
  名称：

  Study of the Conformational Equilibria of 2-Z-3-Methyl-1,3,2-oxazaphosphorinanes. Steric and Stereoelectronic Influences on the Orientation of the Me2N Substituent on Three-Coordinate Phosphorus

  摘要：

  The conformations of a series of 1,3,2-oxazaphosphorinanes containing three-coordinate phosphorus, 1-9, have been determined by the use of H-1, P-31, and C-13 NMR spectroscopy. The rings were substituted at ring nitrogen, N(3), with a methyl group to compare its effect on conformational energies with those of 1,3,2-oxazaphosphorinanes reported earlier that featured a larger substituent at N(3), Ph or i-Pr. Quite expectedly, like those rings previously studied with Ph or i-Pr at N(3), a MeO or (CF3)(2)CHO substituent at phosphorus has a strong preference to be axial on a chair-form ring, 1-4, cis-7, and cis-8, or pseudoaxial on a ring in a twist/boat conformation, trans-7. However, when Me(2)N is attached to phosphorus, the newly studied N(3)Me rings display a chair-chair conformational equilibrium, 10 reversible arrow 11, with the Me(2)N equatorial ring, 11, mildly dominant (58/42, 5; 65/35, 6). This contrasts with ratios of 17/83 and 20/80 for the corresponding N(3)Ph analogs, A, and 23/77 for the N(S)-i-Pr compound, B. The observed change in the free energy of the equilibrium 10 reversible arrow 11, 1.2-1.3 kcal/mol, is ascribed to the dominant influence of a decrease in repulsion experienced in conformation 11 between the equatorial Me(2)NP and the smaller Me at N(3)(Me(2)N(eq)/N(3)Me destabilization) compared to that experienced with the N(3)Ph and N(3)-i-Pr analogs. This steric influence of N(3) substituents on the equilibrium 10 reversible arrow 11 is opposite to that found for four-coordinate phosphorus containing 1,3,2-oxazaphosphorinanes in which Me(2)NP(ax/N(3)Ph repulsions that destabilize 10 appear to be dominant.

  DOI：

  10.1021/jo00120a020
• 作为产物：
  描述：

  N-methyl-2-(hydroxymethyl)-3,3-dimethylbutylamine 在 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以57%的产率得到2-Chloro-3-methyl-5-tert-butyl-1,3,2-oxazaphosphorinane
  参考文献：
  名称：

  Study of the Conformational Equilibria of 2-Z-3-Methyl-1,3,2-oxazaphosphorinanes. Steric and Stereoelectronic Influences on the Orientation of the Me2N Substituent on Three-Coordinate Phosphorus

  摘要：

  The conformations of a series of 1,3,2-oxazaphosphorinanes containing three-coordinate phosphorus, 1-9, have been determined by the use of H-1, P-31, and C-13 NMR spectroscopy. The rings were substituted at ring nitrogen, N(3), with a methyl group to compare its effect on conformational energies with those of 1,3,2-oxazaphosphorinanes reported earlier that featured a larger substituent at N(3), Ph or i-Pr. Quite expectedly, like those rings previously studied with Ph or i-Pr at N(3), a MeO or (CF3)(2)CHO substituent at phosphorus has a strong preference to be axial on a chair-form ring, 1-4, cis-7, and cis-8, or pseudoaxial on a ring in a twist/boat conformation, trans-7. However, when Me(2)N is attached to phosphorus, the newly studied N(3)Me rings display a chair-chair conformational equilibrium, 10 reversible arrow 11, with the Me(2)N equatorial ring, 11, mildly dominant (58/42, 5; 65/35, 6). This contrasts with ratios of 17/83 and 20/80 for the corresponding N(3)Ph analogs, A, and 23/77 for the N(S)-i-Pr compound, B. The observed change in the free energy of the equilibrium 10 reversible arrow 11, 1.2-1.3 kcal/mol, is ascribed to the dominant influence of a decrease in repulsion experienced in conformation 11 between the equatorial Me(2)NP and the smaller Me at N(3)(Me(2)N(eq)/N(3)Me destabilization) compared to that experienced with the N(3)Ph and N(3)-i-Pr analogs. This steric influence of N(3) substituents on the equilibrium 10 reversible arrow 11 is opposite to that found for four-coordinate phosphorus containing 1,3,2-oxazaphosphorinanes in which Me(2)NP(ax/N(3)Ph repulsions that destabilize 10 appear to be dominant.

  DOI：

  10.1021/jo00120a020