(R)-3-(2-bromo-phenoxy)-propane-1,2-diol | 386702-67-6

• 英文名称: (R)-3-(2-bromo-phenoxy)-propane-1,2-diol
• 英文别名: (2R)-3-(2-bromophenoxy)propane-1,2-diol
• CAS: 386702-67-6
• 化学式: C₉H₁₁BrO₃
• 分子量: 247.089
• InChiKey: LDMOQBBDWPPTNL-SSDOTTSWSA-N

物化性质

• 熔点：
  101-102 °C(Solv: dichloromethane (75-09-2))
• 沸点：
  383.9±27.0 °C(Predicted)
• 密度：
  1.563±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-3-(2-bromo-phenoxy)-propane-1,2-diol 在 4,4-diphenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene 、 N-甲基二环己基胺 、 nickel dibromide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以95%的产率得到(R)-2-(羟基甲基)-1,4-苯并二噁烷
  参考文献：
  名称：

  一种合成光学纯2-羟甲基-1,4-苯并二氧六环 及其衍生物的方法

  摘要：

  本发明公开了一种合成光学纯2‑羟甲基‑1,4‑苯并二氧六环及其衍生物的方法，该方法以廉价的2‑溴苯酚或其衍生物和丁酸缩水甘油酯为原料，通过光/镍协同催化C‑O键偶联，得到光学纯2‑羟甲基‑1,4‑苯并二氧六环或其衍生物。这些化合物是一类具有重要生物活性分子的关键中间体。本发明方法的优势在于：1)光催化剂用量低；2)以简单的镍盐为金属催化剂，无需外加配体，如溴化镍；3)反应条件温和，60～80℃可有效进行。这些显著的优势使本发明方法具有工艺简单、反应条件温和、催化剂价格便宜、绿色环保以及产率高等特点，使该发明具有良好的工业应用前景。

  公开号：

  CN109824646B
• 作为产物：
  描述：

  3-(2-溴苯氧基)丙烷-1,2-二醇 以 乙醇 、 水 为溶剂， 生成 (S)-3-(2-bromophenoxy)propane-1,2-diol 、 (R)-3-(2-bromo-phenoxy)-propane-1,2-diol
  参考文献：
  名称：

  Absolute configuration and crystal packing chirality for three conglomerate-forming ortho-halogen substituted phenyl glycerol ethers

  摘要：

  Three conglomerate-forming ortho-Hal (Hal = Cl, Br, I) substituted phenyl glycerol ethers 1-3 were investigated by single-crystal X-ray analysis, and the absolute configuration for all substances was established. The molecular structures and crystal packing details for halogen derivatives were compared with the same characteristics for ortho-OCH(3) and ortho-CH(3) analogues. Two different types of crystal packing were evaluated for these very much alike compounds. The interplay of the supramolecular crystal organization chirality sense and the single molecule absolute configuration was demonstrated. Some stabilizing and destabilizing interactions involving the ortho-substituents were revealed. The resolution of rac-2 by entrainment procedure was successfully realized. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2010.04.045

文献信息

• Crystallization of chiral compounds 3. 3-phenoxypropane-1,2-diol and 3-(2-halophenoxy)propane-1,2-diols
  作者：D. V. Zakharychev、S. N. Lazarev、Z. A. Bredikhina、A. A. Bredikhin

  DOI：10.1007/s11172-006-0243-x

  日期：2006.2

  Specific features of melting of crystalline samples of 3-(2-R-phenoxy)propane-1,2-diols with different enantiomeric compositions were studied by differential scanning calorimetry. The melting points and enthalpies of melting for the racemate and individual stereoisomers were determined. Binary phase diagrams were constructed. The entropy of mixing of individual enantiomers in the liquid phase and the free energy of formation of the racemic compound were calculated. The thermochemical data indicate that the racemates are formed upon the crystallization of phenoxy-and 2-fluorophenoxy-containing compounds, while crystallization of the chloro-, bromo-, and iodo-substituted analogs would form racemic conglomerates.

  通过差示扫描量热法研究了具有不同对映体成分的 3-(2-R-苯氧基)丙烷-1,2-二醇晶体样品熔化的具体特征。确定了外消旋体和单个立体异构体的熔点和熔焓。构建了二元相图。计算了各对映体在液相中的混合熵和外消旋化合物的形成自由能。热化学数据表明，含苯氧基和 2-氟苯氧基的化合物结晶时会形成外消旋体，而氯代、溴代和碘代类似物结晶时会形成外消旋混合物。
• Palladium-Catalyzed Intramolecular C−O Bond Formation
  作者：Shin-itsu Kuwabe、Karen E. Torraca、Stephen L. Buchwald

  DOI：10.1021/ja012046d

  日期：2001.12.1

  A number of oxygen heterocycles were synthesized using the palladium-catalyzed intramolecular etherification of aryl halides by employing di-tert-butylphosphinobiaryl ligands. The reaction proceeds under mild conditions using weak bases such as Cs2CO3 or K3PO4. A variety of functional groups are tolerated in the reaction. and enantioenriched alcohols can be coupled without erosion of optical purity. The mildness of the reaction conditions allows for the use of polyfunctionalized substrates. This method was used as the key step in the synthesis of MKC-242, an antidepressant currently in clinical trials. The synthesis of MKC-242 was achieved in 40% overall yield from commercially available sesamol and acrylonitrile,