(2-chlorocyclopropyl)benzene | 17650-99-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2-chlorocyclopropyl)benzene
• 英文别名: [(1S,2S)-2-chlorocyclopropyl]benzene
• CAS: 17650-99-6
• 化学式: C₉H₉Cl
• 分子量: 152.623
• InChiKey: GBXROAOUSDRIOO-IUCAKERBSA-N

物化性质

• 沸点：
  80-90 °C(Press: 5 Torr)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (2-chlorocyclopropyl)benzene 在 硝酸 、 乙酸酐 作用下， 反应 3.0h， 生成 2-nitrocinnamaldehyde
  参考文献：
  名称：

  Novokreshchennykh, V. D.; Mochalov, S. S.; Lukashova, E. A., Journal of Organic Chemistry USSR (English Translation), 1984, vol. 20, # 1, p. 96 - 101

  摘要：

  DOI：
• 作为产物：
  描述：

  (2,2-二溴环丙基)苯 在 正丁基锂 、 1,1,2-三氯三氟乙烷（CFC-113） 、 lithium tri-n-butylzincate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 24.75h， 生成 (2-chlorocyclopropyl)benzene
  参考文献：
  名称：

  Stereoselective carbon-carbon bond-forming reaction of 1,1-dibromocyclopropanes via 1-halocyclopropylzincates

  摘要：

  Lithium trialkylzincates react efficiently with 1,1-dibromocyclopropanes 5 to give the corresponding alkylation products 7 nonstereoselectively. The reaction proceeds through a 1,2-alkyl migration of the intermediately formed zincate carbenoid 3 in an invertive manner. Reaction of 5 with BuLi followed by successive treatment of the resulting trans-lithium carbenoid 8 with ZnCl2 and an alkyllithium (R2Li) produces the zincate carbenoid trans-3, which, in turn, gives cis-7 stereoselectively (Method B). Reaction of lithium trialkylzincates and trans-1-bromo-1-chlorocyclopropanes 11 prepared in situ by chlorination of the trans-lithium carbenoid with CF2ClCFCl2 yields trans-7 stereoselectively (Method C). 1-Alkylcyclopropylzinc 4, an intermediate of the alkylation reaction, reacts smoothly with acyl, aryl, and alkenyl halides in the presence of a palladium(0) catalyst to give the corresponding coupling products 15 and 16. By generating the cyclopropylzinc intermediate 4 stereoselectively by using method B or C, one can obtain the desired stereoisomers of the coupling products with high selectivity.

  DOI：

  10.1021/jo00063a010

文献信息

• Free radical chlorination and one-electron oxidation of arylcyclopropanes. Designer probes for cytochrome P-450 hydroxylation mechanisms
  作者：Pamela Riley、Robert P. Hanzlik

  DOI：10.1016/s0040-4039(00)99390-0

  日期：1989.1

  Arylcyclopropyl radicals can be formed under mild conditions (phase-transfer-catalyzed chlorination) and give rise to cyclopropyl products; in contrast one-electron oxidation of arylcyclopropanes by Mn(OAc)3 leads to fragmentation of the cyclopropane ring and the formation of acyclic products.

  可以在温和的条件下（相转移催化的氯化）形成芳基环丙基自由基，并生成环丙基产物。相比之下，Mn（OAc）3对芳基环丙烷的单电子氧化会导致环丙烷环断裂并形成无环产物。
• Stereoselective Monoalkylation of α-Halocyclopropyllithiums. A Versatile Method for the Synthesis of α-Alkylcyclopropyl Acetates and Alkylidenecyclopropanes
  作者：Katuzi Kitatani、Tamejiro Hiyama、Hitosi Nozaki

  DOI：10.1246/bcsj.50.3288

  日期：1977.12

  The title carbenoids (7 and 8) prepared by the action of butyllithium on dihalocyclopropanes are smoothly methylated with methyl iodide. The product ratio of cis-methylated product (3)/trans-methylated one (4) (or endo-methylated product (5)/exo-methylated one (6) is found to depend on the aging period of the carbenoids; thermodynamic equilibration gives almost 3 or 5. This procedure has been extended to general alkylation by utilizing HMPA co-solvent. The resulting α-alkylated cyclopropyl halides are converted into allylic acetates or cyclopropyl acetates upon acetolysis and also into alkylidenecyclopropanes upon base treatment. The protonolysis of 8 gives trans- or exo-bromocyclopropanes stereoselectively.

  通过二卤环丙烷与丁基锂作用制备的碳宾（7和8）能顺利地用甲基碘进行甲基化。顺式甲基化产物（3）/反式甲基化产物（4）（或内型甲基化产物（5）/外型甲基化产物（6）的产率比取决于碳宾的老化时间；热力学平衡几乎给予3或5。该方法已通过利用六甲基磷酰胺（HMPA）作为共溶剂扩展到一般烷基化。得到的α-烷基化环丙基卤代物在乙酰解后转化为烯丙基乙酸酯或环丙基乙酸酯，并且在碱处理下转化为烷基亚甲基环丙烷。8的质子分解选择性地得到反式或外型溴代环丙烷。
• Synthesis of monohalocyclopropane derivatives from olefins by the reaction with trihalomethanes and copper
  作者：Nariyoshi Kawabata、Masami Tanimoto、Shigehiro Fujiwara

  DOI：10.1016/0040-4020(79)85049-8

  日期：1979.1

  bromo-, and iodocyclopropane derivatives were obtained in 10–80% yields by the reaction of FCHI2, ClCHI2, BrCHI2, and CHI3, respectively, with Cu in the presence of olefins. The reaction was electrophilic, and proceeded stereospecifically, i.e., cis and trans olefins afforded cyclopropane derivatives whose configurations with respect to the substituents from original olefins were cis and trans, respectively

  在烯烃存在下，通过FCHI 2，ClCHI 2，BrCHI 2和CHI 3分别与Cu反应，可以以10-80％的产率获得氟代，氯代，溴代和碘代环丙烷衍生物。该反应是亲电的，并且立体定向地进行，即，顺式和反式烯烃提供环丙烷衍生物，其相对于来自原始烯烃的取代基的构型为顺式和反式。， 分别。由于在反应混合物中未检测到异构烯烃，这是通过将相应的游离单卤代碳烯插入CH键所预期的，因此该反应似乎是通过有机铜中间体而不是游离的单卤代碳烯进行的。关于通过新反应引入的卤素的构型，通常主要在相应的反式或外型异构体上获得顺式或内式异构体。
• Photoinduced Reduction of<i>gem</i>-Dichlorocyclopropanes with SmI₂and Benzenethiol
  作者：Akiya Ogawa、Syoji Ohya、Toshikazu Hirao

  DOI：10.1246/cl.1997.275

  日期：1997.3

  Upon irradiation with visible light, gem-dichlorocyclopropanes undergo reductive dechlorination with samarium diiodide and benzenethiol to provide the corresponding cyclopropanes in good yields. The reaction may proceed via the hydrogen abstraction from PhSH by cyclopropyl radicals formed in situ by the reduction with SmI2.

  在可见光照射下，钆-二氯环丙烷与二碘化钐和苯硫醇进行还原脱氯，以良好的收率提供相应的环丙烷。反应可以通过用 SmI 2 还原原位形成的环丙基自由基从 PhSH 夺氢而进行。
• Photoreductive Dehalogenation of Organic Halides in the Presence of Lithium Aluminum Hydride
  作者：Nobujiro Shimizu、Kenji Watanabe、Yuho Tsuno

  DOI：10.1246/bcsj.57.885

  日期：1984.3

  Lithium aluminum hydride markedly accelerates photoreductive dehalogenation of cyclopropyl, aromatic, and olefinic halides carried out in ether.

  氢化铝锂显着加速环丙基、芳族和烯属卤化物在醚中进行的光还原脱卤。