methyl (1R,3S)-2,2-dichloro-3-methylcyclopropanecarboxylate | 3591-55-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (1R,3S)-2,2-dichloro-3-methylcyclopropanecarboxylate
• 英文别名: methyl (1R,3S)-2,2-dichloro-3-methylcyclopropane-1-carboxylate
• CAS: 3591-55-7；3591-56-8；89579-85-1
• 化学式: C₆H₈Cl₂O₂
• 分子量: 183.034
• InChiKey: WECBTJPNDXTQJB-IUYQGCFVSA-N

物化性质

• 沸点：
  205.6±40.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl (1R,3S)-2,2-dichloro-3-methylcyclopropanecarboxylate 在 sodium methylate 、 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 10.75h， 生成 trans-3-methyl-2,2-bis(phenylthio)cyclopropanecarboxylic acid
  参考文献：
  名称：

  暴露于苯硫酚盐亲核试剂后的手性甲基 trans-2,2-dichloro-3-methylcyclopropanecarboxylate

  摘要：

  (1R,3S)-2,2-二氯-3-甲基环丙烷羧酸甲酯中的 β-卤素原子被苯硫酚钠取代，得到二（苯硫基）酯 (1RS,3S)-4，为非对映异构体的混合物。(1RS,3S)-3-甲基-2,2-双(苯硫基)环丙烷羧酸甲酯 4 的顺反异构化、碱性水解和随后的结晶得到相应的酸 (1R,3S)-5，具有高非对映体和对映体纯度. 另一方面，酯 (1RS,3S)-4 在酸性条件下开环生成 3-甲基-4,4二(苯硫基)丙-3-烯酸甲酯 (8) 或手性 S-苯基硫酯甲酯 ( 3S)-3-methyl-4-oxo-4(phenylthio)butanoate (7)。

  DOI：

  10.3998/ark.5550190.p008.380
• 作为产物：
  描述：

  trans-2,2-dichloro-3-methylcyclopropanecarboxylic acid 在 硫酸 作用下， 以 水 、 丙酮 为溶剂， 反应 15.0h， 生成 methyl (1R,3S)-2,2-dichloro-3-methylcyclopropanecarboxylate
  参考文献：
  名称：

  The resolution of trans-2,2-dichloro-3-methylcyclopropanecarboxylic acid via crystallization of its salts with (+)- and (−)-α-phenylethylamine, and the transformation of the resulting enantiomers into (R)- and (S)-dimethyl 2-methylsuccinates

  摘要：

  The resolution of trans-2,2-dichloro-3-methylcyclopropanecarboxylic acid trans-1 was achieved by crystallization of its salts with (+)- and (-)-alpha-phenylethylamine. The chiral acids were converted into methyl esters 9, which upon reaction with sodium methoxide in methanol underwent a three-carbon ring cleavage, leading to the corresponding mono-orthoester derivatives 10. Acidic hydrolysis then gave the known (R)- and (S)-dimethyl 2-methylsuccinates 12. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.12.014

文献信息

• Cyclopropane intermediates in the synthesis of chiral alcohols with methyl-branched carbon skeleton. Application in the synthesis of insect pheromones
  作者：V. N. Kovalenko、I. V. Mineeva

  DOI：10.1134/s1070428014070033

  日期：2014.7
• The resolution of trans-2,2-dichloro-3-methylcyclopropanecarboxylic acid via crystallization of its salts with (+)- and (−)-α-phenylethylamine, and the transformation of the resulting enantiomers into (R)- and (S)-dimethyl 2-methylsuccinates
  作者：Vitaly N. Kovalenko、Oleg G. Kulinkovich

  DOI：10.1016/j.tetasy.2010.12.014

  日期：2011.1

  The resolution of trans-2,2-dichloro-3-methylcyclopropanecarboxylic acid trans-1 was achieved by crystallization of its salts with (+)- and (-)-alpha-phenylethylamine. The chiral acids were converted into methyl esters 9, which upon reaction with sodium methoxide in methanol underwent a three-carbon ring cleavage, leading to the corresponding mono-orthoester derivatives 10. Acidic hydrolysis then gave the known (R)- and (S)-dimethyl 2-methylsuccinates 12. (C) 2011 Elsevier Ltd. All rights reserved.
• Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile
  作者：Vitaly N. Kovalenko

  DOI：10.3998/ark.5550190.p008.380

  日期：——

  Substitution of the β-halogen atoms in methyl (1R,3S)-2,2-dichloro-3-methylycyclopropanecarboxylate with sodium thiophenolate leads to the di(phenylthio) ester (1RS,3S)-4 as a mixture of diastereomers. The cis-trans isomerisation of methyl (1RS,3S)-3-methyl-2,2-bis(phenylthio)cyclopropanecarboxylate 4, basic hydrolysis and subsequent crystallization gave the corresponding acid (1R,3S)-5 in high diastereomeric

  (1R,3S)-2,2-二氯-3-甲基环丙烷羧酸甲酯中的 β-卤素原子被苯硫酚钠取代，得到二（苯硫基）酯 (1RS,3S)-4，为非对映异构体的混合物。(1RS,3S)-3-甲基-2,2-双(苯硫基)环丙烷羧酸甲酯 4 的顺反异构化、碱性水解和随后的结晶得到相应的酸 (1R,3S)-5，具有高非对映体和对映体纯度. 另一方面，酯 (1RS,3S)-4 在酸性条件下开环生成 3-甲基-4,4二(苯硫基)丙-3-烯酸甲酯 (8) 或手性 S-苯基硫酯甲酯 ( 3S)-3-methyl-4-oxo-4(phenylthio)butanoate (7)。