(S)-(+)-1,2-dimethoxypropane | 76946-23-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-(+)-1,2-dimethoxypropane
• 英文别名: (2S)-1,2-dimethoxypropane
• CAS: 76946-23-1
• 化学式: C₅H₁₂O₂
• 分子量: 104.149
• InChiKey: LEEANUDEDHYDTG-YFKPBYRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  7
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (S)-(+)-1,2-丙二醇 、 碘甲烷 在 sodium hydride 作用下， 生成 (S)-(+)-1,2-dimethoxypropane
  参考文献：
  名称：

  Alkali metals dissolved in optically active solvents

  摘要：

  DOI：

  10.1021/jo00323a026

文献信息

• Mechanisms and Stereochemistry of Acid-Induced Ring Opening of Optically Active 1,2-Propene Oxides in the Gas Phase
  作者：Anna Troiani、Antonello Filippi、Maurizio Speranza

  DOI：10.1002/chem.19970031223

  日期：1997.12

  AbstractThe acid‐induced ring opening of (S)‐(—)‐1,2‐propene oxide (1S) and (R)‐(+)‐1,2‐propene oxide (1R) has been investigated in gaseous CH4 and CH3F at 720 torr and in the presence of a nucleophile, NuOH (Nu = H or CH3). The mechanism of the ring‐opening reaction has been assessed by modulating the composition of the gaseous mixture. Two reaction pathways are operative in the gas phase, both proceeding through complete inversion of configuration of the reaction center. A first process is detectable only in the CH3F/H2O systems and takes place within a persistent proton‐bound complex generated by interaction of the epoxide with the CH3OH+2 ion, formed by methylation of H2O with (CH3)2F+. Such an intracomplex ring‐opening pathway proceeds through proton transfer from the CH3OH+2 ion to the epoxide followed by motion of the neutral CH3OH moiety around the 1‐H‐oxonia‐2‐methyl‐cyclo‐propane structure (H‐1R or H‐1S) (k<108 s‐1) before attacking the ring carbons from the rear. In all the other systems with added CH3OH, this intracomplex pathway is preceded by a faster “extracomplex” pathway involving the attack of an external CH3OH molecule on the proton‐bound adduct. The regioselectivity of the intracomplex process is similar to that of the extracomplex pathway. Both are characterized by a slight preference for the Cβ center of H‐1 R (or H‐1S) (extra‐complex path regioselectivity: α/β = 0.72±0.05; intracomplex path regioselectivity: α/β = 0.71±0.05). The regioselectivity of H‐1 R (or H‐1S) is substantially different from that of the 1‐Me‐oxonia‐2‐methyl‐cyclopropanes (Me‐1 R or Me‐1 S) toward the same nucleophile NuOH (α/β = 4.1±0.35 (Nu = H); 2.28±0.16 (Nu = CH3)). This difference is attributed to a transition structure wherein the Cα–O bond rupture increases from H‐1 R (or H‐1 S) to Me‐1 R (or Me‐1 S) and in passing from CH3OH to H2O. The regioand stereoselectivity of the gas‐phase acid‐induced ring opening of 1 S and 1 R are compared with those of related reactions carried out in solution.
• Alkali metals dissolved in optically active solvents
  作者：Keith D. Cooper、Harry M. Walborsky

  DOI：10.1021/jo00323a026

  日期：1981.5