((1S,2R,3R)-2-chloro-1-methyl-3-phenylcyclopropyl)methanol | 179091-13-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮
• 英文名称: ((1S,2R,3R)-2-chloro-1-methyl-3-phenylcyclopropyl)methanol
• 英文别名: [(1S,2R,3R)-2-chloro-1-methyl-3-phenylcyclopropyl]methanol
• CAS: 179091-13-5
• 化学式: C₁₁H₁₃ClO
• 分子量: 196.677
• InChiKey: WMPNBXVJVFGESI-HBNTYKKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  间苯氧基溴化苄 、 ((1S,2R,3R)-2-chloro-1-methyl-3-phenylcyclopropyl)methanol 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以84%的产率得到(1S,2R,3R)-(-)-2-Chloro-1-methyl-3-phenylcyclopropylmethyl 3-phenoxybenzyl ether
  参考文献：
  名称：

  Synthesis and stereostructure–activity relationship of a synthetic pyrethroid, 2-chloro-1-methyl-3-phenylcyclopropylmethyl-3-phenoxybenzyl ether

  摘要：

  Of the four diastereoisomers of 2-chloro-1-methyl-3-phenylcyclopropylmet 3-phenoxybenzyl ether 5, a new type of synthetic pyrethroid, which have been synthesized, only the (1R*,2S*,3S*)-isomer 5a showed significant insecticidal activity against the tobacco cutworm and the common mosquito. Two enantiomers (1R,2S,3S)-(-)-5a and (1S,2R,3R)-(+)-5a were prepared by the optical resolution process, and their absolute configurations were determined by chemical derivatization via predictable asymmetric cyclopropanation. Bioassay showed that the (1R,2S,3S)-(-)-5a was active, while (1S,2R,3R)-(+)-5a was not. The geometry around the asymmetric centre of the (1R,2S,3S)-enantiomer was correlated with that of representative pyrethroids which are both optically active and have insecticidal activity.

  DOI：

  10.1039/p19960001243
• 作为产物：
  描述：

  (E)-2-Methyl-3-phenyl-2-propen-1-ol-tetrahydro-2-pyranylether 在 三乙基硼 、 苄基三乙基氯化铵 甲醇 、 potassium fluoride 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 jones' reagent 、 三正丁基氢锡 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 21.0h， 生成 ((1S,2R,3R)-2-chloro-1-methyl-3-phenylcyclopropyl)methanol
  参考文献：
  名称：

  Synthesis and stereostructure–activity relationship of a synthetic pyrethroid, 2-chloro-1-methyl-3-phenylcyclopropylmethyl-3-phenoxybenzyl ether

  摘要：

  Of the four diastereoisomers of 2-chloro-1-methyl-3-phenylcyclopropylmet 3-phenoxybenzyl ether 5, a new type of synthetic pyrethroid, which have been synthesized, only the (1R*,2S*,3S*)-isomer 5a showed significant insecticidal activity against the tobacco cutworm and the common mosquito. Two enantiomers (1R,2S,3S)-(-)-5a and (1S,2R,3R)-(+)-5a were prepared by the optical resolution process, and their absolute configurations were determined by chemical derivatization via predictable asymmetric cyclopropanation. Bioassay showed that the (1R,2S,3S)-(-)-5a was active, while (1S,2R,3R)-(+)-5a was not. The geometry around the asymmetric centre of the (1R,2S,3S)-enantiomer was correlated with that of representative pyrethroids which are both optically active and have insecticidal activity.

  DOI：

  10.1039/p19960001243

文献信息

• Spectroscopic Characterization of Heterohalogenic Dihalomethylzinc Carbenoids: Application to a More Efficient Chlorocyclopropanation Reaction
  作者：Sylvain Taillemaud、André B. Charette

  DOI：10.1021/acs.organomet.1c00631

  日期：2022.1.10

  Dihalomethylmetal reagents are important species that can be used in halocyclopropanation reactions (metal = zinc) as well as in alkenyl halide synthesis. When trihalomethanes containing two or more different halogen atoms are used to prepare zinc carbenoids, several species can be formed through a halogen scrambling process. This affects which halocyclopropane, or haloalkene, is generated in the subsequent reaction

  二卤甲基金属试剂是可用于卤代环丙烷化反应（金属 = 锌）以及烯基卤化物合成的重要物质。当使用含有两个或多个不同卤素原子的三卤甲烷来制备锌类化合物时，可以通过卤素加扰过程形成几种物质。这会影响在后续反应中生成哪种卤代环丙烷或卤代烯烃。在论文的第一部分，我们报告了通过 NMR 对二卤代碳烯锌的广泛表征，以确定当各种二卤代甲烷和三卤代甲烷试剂用作类碳烯前体时形成的主要物种。在论文的第二部分中，直接应用该信息使得能够从廉价且易于获得的前体开发烯丙醇的高效氯环丙烷化反应。