2-(o-Bromobenzyl)-1-methylenecyclohexane | 138616-59-8

• 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-(o-Bromobenzyl)-1-methylenecyclohexane
• 英文别名: 1-Bromo-2-[(2-methylidenecyclohexyl)methyl]benzene
• CAS: 138616-59-8
• 化学式: C₁₄H₁₇Br
• 分子量: 265.193
• InChiKey: PYPAUDDLZMUQRR-UHFFFAOYSA-N

物化性质

• 沸点：
  320.1±11.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 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-(o-Bromobenzyl)-1-methylenecyclohexane 在 叔丁基锂 、 甲醇 作用下， 以 乙醚 、 正庚烷 、 正戊烷 为溶剂， 以98%的产率得到1-methylene-2-(phenylmethyl)cyclohexane
  参考文献：
  名称：

  Cyclization of Aryllithiums Tethered to Methylenecycloalkanes:  Stereoselective Synthesis of 4a-Substituted cis-Hexahydrofluorenes

  摘要：

  The cyclization of an aryllithium tethered to a methylenecycloalkane, generated from 2-(o-bromobenzyl)-1-methylenecycloalkanes 1, 2, and 3 by low-temperature lithium-bromine exchange, has been found to be a kinetically slow but thermodynamically favorable process that proceeds at a convenient rate in an exclusively 5-exo fashion when solutions of the aryllithium in n-heptane-di-n-butyl ether (9:1 v/v) are warmed to 45 degreesC. The cyclization affords stereoisomerically pure cis-fused products (7 and 8) when the methylenecycloalkane is five- or six-membered but it is less stereoselective when the methylenecycloalkane is seven-membered. The ring-closure of the aryllithium derived from 2-(o-bromobenzyl)-1-methylenecyclohexane (2) provides an experimentally convenient route to stereoisomerically pure 4a-substituted cis-hexahydrofluorenes in 60-90% isolated yield.

  DOI：

  10.1021/jo020593r
• 作为产物：
  描述：

  2-溴溴苄 在 potassium tert-butylate 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 2-(o-Bromobenzyl)-1-methylenecyclohexane
  参考文献：
  名称：

  Cyclization of Aryllithiums Tethered to Methylenecycloalkanes:  Stereoselective Synthesis of 4a-Substituted cis-Hexahydrofluorenes

  摘要：

  The cyclization of an aryllithium tethered to a methylenecycloalkane, generated from 2-(o-bromobenzyl)-1-methylenecycloalkanes 1, 2, and 3 by low-temperature lithium-bromine exchange, has been found to be a kinetically slow but thermodynamically favorable process that proceeds at a convenient rate in an exclusively 5-exo fashion when solutions of the aryllithium in n-heptane-di-n-butyl ether (9:1 v/v) are warmed to 45 degreesC. The cyclization affords stereoisomerically pure cis-fused products (7 and 8) when the methylenecycloalkane is five- or six-membered but it is less stereoselective when the methylenecycloalkane is seven-membered. The ring-closure of the aryllithium derived from 2-(o-bromobenzyl)-1-methylenecyclohexane (2) provides an experimentally convenient route to stereoisomerically pure 4a-substituted cis-hexahydrofluorenes in 60-90% isolated yield.

  DOI：

  10.1021/jo020593r

文献信息

• A highly regioselective 6-endo-aryl radical cyclisation: stereocontrolled synthesis of trans-octahydroanthracenes
  作者：Sitaram Pal、Monika Mukherjee、Debi Podder、Alok K. Mukherjee、Usha Ranjan Ghatak

  DOI：10.1039/c39910001591

  日期：——

  The sterocontrolled synthesis of trans-octahydroanthracenes 3, 11 and 14 through implementation of an efficient and highly regioselective 6-endo-trig-aryl radical cyclisation of the respective 2-(o-bromobenzyl)-1-methylenecyclohexanes 2, 10 and 13, with tri-n-butyltin hydride is reported, along with a single crystal X-ray structure determination of 11.

  报告了通过实施高效且高度区域选择性的6-内环三芳基自由基环化反应，将相应的2-(邻溴苄基)-1-亚烯基环己烷2、10和13合成为反式八氢蒽3、11和14，使用了三正丁基锡氢化物，并对11进行了单晶X射线结构测定。
• Regiochemistry in Aryl Radical Cyclization onto Methylenecycloalkanes
  作者：Hiroyuki Ishibashi、Tetsuya Kobayashi、Sayaka Nakashima、Osamu Tamura

  DOI：10.1021/jo001086h

  日期：2000.12.1

  Bu(3)SnH-mediated aryl radical cyclization onto methylenecycloalkanes having a phenylthio, an ester, or a nitrile group at the terminus of the alkenic bond provides exclusively exo cyclization products. The results are in sharp contrast to those reported for nonsubstituted methylenecycloalkanes, which give exclusively endo cyclization products. Formation of endo cyclization products has been suggested

  Bu（3）SnH介导的芳基自由基环化成在烯键末端具有苯硫基，酯或腈基的亚甲基环烷烃，仅提供外环化产物。结果与未取代的亚甲基环烷烃报告的结果形成鲜明对比，后者仅产生内环化产物。内环化产物的形成已被认为是芳基连续5-外向环化和新叶重排的结果。选择性外芳基自由基环化提供了一种合成含苄基季碳原子的稠合芳族化合物的新方法。
• An Efficient Palladium Catalyzed Stereocontrolled Synthesis of 4a-Angular Methyl Substituted Hydrofluorenes
  作者：Jayanta K. Mukhopadhyaya、Sitaram Pal、Usha Ranjan Ghatak

  DOI：10.1080/00397919508015849

  日期：1995.6

  A high yield s tereoselective synthesis of 4a-angularly methyl substituted cis-hexahydrofluorenes 5a-h and tetrahydrofluorenes 7a,b has been developed by palladium-catalyzed intramolecular Heck-type cyclization of the respective exo-olefins 4a-h and 4a,b through exclusive 5-exo-trig mode.
• Regioselective Aryl Radical Cyclization. 1. Stereocontrolled Synthesis of Linearly Condensed Hydroaromatic Carbocyclic Systems through 6-endo-Ring Closures
  作者：Sitaram Pal、Jayanta K. Mukhopadhyaya、Usha Ranjan Ghatak

  DOI：10.1021/jo00089a009

  日期：1994.5

  The stereocontrolled synthesis of trans-octahydroanthracenes 3, 11a-c, and 14a-c and trans-octahydro-5aH-cyclohepta[b] naphthalene (27) through implementation of an efficient and highly regioselective 6-endo-trig-aryl radical cyclization of the respective 2-(o-bromoaryl)-1-methylenecyclohexanes 2, 10a-c, and 13a-c and 2-(o-bromobenzyl)-1-methylenecycloheptane (41) with tri-n- butyltin-hydride-is described. The radical cyclization of 2-(o-bromobenzyl)-1-methylenecyclopentane (43), in contrast, produced a mixture of the cis- and trans-hexahydro-1H-benz[f]indenes (38) and (37).
• Sulfur-Controlled <i>Exo</i> Selective Aryl Radical Cyclization onto <i>Exo</i>-Methylenecycloalkanes
  作者：Hiroyuki Ishibashi、Tetsuya Kobayashi、Daisuke Takamasu

  DOI：10.1055/s-1999-2826

  日期：1999.8