2-Methoxy-3-methyl-1,3,2-oxazaphosphorinane | 167895-84-3

• 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-Methoxy-3-methyl-1,3,2-oxazaphosphorinane
• 英文别名: 2H-1,3,2-Oxazaphosphorine, tetrahydro-2-methoxy-3-methyl-；2-methoxy-3-methyl-1,3,2-oxazaphosphinane
• CAS: 167895-84-3
• 化学式: C₅H₁₂NO₂P
• 分子量: 149.13
• InChiKey: FOIXOMXUMDLECB-UHFFFAOYSA-N

物化性质

• 沸点：
  86.7±7.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  9
• 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：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  溴乙酸乙酯 、 2-Methoxy-3-methyl-1,3,2-oxazaphosphorinane 以 苯 为溶剂， 反应 24.0h， 生成 (3-Methyl-2-oxo-2λ⁵-[1,3,2]oxazaphosphinan-2-yl)-acetic acid ethyl ester 、 Ethyl 2-[[3-bromopropyl(methyl)amino]-methoxyphosphoryl]acetate
  参考文献：
  名称：

  1,3,2-氧氮杂膦系列中的Arbuzov重排

  摘要：

  2-烷氧基-1,3,2-氧氮杂膦（包括 3-烷基衍生物）与溴乙酸甲酯和乙酯的反应产生两种类型的 Arbuzov 重排产物（环状和非环状产物）。它们的产率之比实际上与起始试剂 3 位取代基的性质无关，主要由磷键合烷氧基中取代基的性质决定，范围为 96:4 至 2:98。 无环产物可以转换成循环的。

  DOI：

  10.1007/s11172-005-0061-6
• 作为产物：
  描述：

  甲醇 、 2-chlorotetrahydro-3-methyl-2H-1,3,2-oxazaphosphorine 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以83%的产率得到2-Methoxy-3-methyl-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

文献信息

• Reactions of 2-alkoxy-3-alkyl-1,3,2-oxazaphosphinanes with alkyl chloroformates
  作者：A. E. Shipov、G. K. Genkina、P. V. Petrovskii、K. A. Lyssenko、T. A. Mastryukova

  DOI：10.1007/s11172-008-0029-4

  日期：2008.1

  Abstract2-Alkoxy-3-alkyl-1,3,2-oxazaphosphinanes containing a sterically hindered N atom react with alkyl chloroformates according to the Arbuzov mechanism only. The ratio of the open and cyclic reaction products depends on the nature of the alkoxy group in the starting phosphinane. With a less hindered N atom, acylation at the N atom gives acyclic chloridophosphites, in addition to the Arbuzov-type

  摘要 含有位阻 N 原子的 2-烷氧基-3-烷基-1,3,2-氧氮杂膦仅根据 Arbuzov 机理与氯甲酸烷基酯反应。开环和环状反应产物的比例取决于起始膦烷中烷氧基的性质。对于受阻较少的 N 原子，除了 Arbuzov 型产物外，N 原子上的酰化还产生无环亚磷酸氯酯。氯化亚磷酸酯的结构通过它们向稳定硫代磷酸盐的化学转化得到证实。获得了磷酰甲酰胺和磷酰甲酰肼的氧氮杂膦类似物。
• 1,3,2-Oxazaphosphinane analogs of phosphorylacetic acid derivatives: synthesis and properties
  作者：A. E. Shipov、G. K. Genkina、P. V. Petrovskii、T. A. Mastryukova

  DOI：10.1007/s11172-006-0167-5

  日期：2005.11

  the ring (Alk = Et). In aqueous solution, cyclic products with the N-isopropyl group are only stable, while the rest undergo hydrolysis with cleavage of the P-N bond of the ring. Oxazaphosphinane analogs of phosphorylacetamide and phosphorylacetohydrazide were synthesized.

  2-AlkO-1,3,2-氧氮杂膦与烷基 N-卤代乙酰氨基或 N-氯甲基-N-甲氧基羰基氨基羧酸盐的反应主要产生具有保留 (Alk = Me) 和开环 (Alk = Et) 的产物。在水溶液中，带有 N-异丙基的环状产物是稳定的，而其余的则发生水解，环的 PN 键断裂。合成了磷酰乙酰胺和磷酰乙酰肼的氧氮杂膦类似物。
• 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
  作者：Yande Huang、Jaehoon Yu、Wesley G. Bentrude

  DOI：10.1021/jo00120a020

  日期：1995.7

  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.
• Arbuzov rearrangement in the 1,3,2-oxazaphosphinane series
  作者：A. E. Shipov、G. K. Genkina、P. V. Petrovskii、T. A. Mastryukova

  DOI：10.1007/s11172-005-0061-6

  日期：2004.9

  Reactions of 2-alkoxy-1,3,2-oxazaphosphinanes (including 3-alkyl derivatives) with methyl and ethyl bromoacetates give two types of Arbuzov rearrangement products (cyclic and acyclic ones). The ratio between their yields is virtually independent of the nature of the substituent in position 3 of the starting reagent, being mainly determined by the nature of the substituent in the phosphorus bound alkoxy

  2-烷氧基-1,3,2-氧氮杂膦（包括 3-烷基衍生物）与溴乙酸甲酯和乙酯的反应产生两种类型的 Arbuzov 重排产物（环状和非环状产物）。它们的产率之比实际上与起始试剂 3 位取代基的性质无关，主要由磷键合烷氧基中取代基的性质决定，范围为 96:4 至 2:98。 无环产物可以转换成循环的。