racemic 5-bromo-2,3-benzonorbornadiene | 23537-79-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: racemic 5-bromo-2,3-benzonorbornadiene
• 英文别名: (+/-)-methyl [1R,8R]-9-bromotricyclo[6.2.1.0^2,7]undeca-2,4,6,9-tetraene；(1S,8S)-9-bromotricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraene
• CAS: 23537-79-3
• 化学式: C₁₁H₉Br
• 分子量: 221.096
• InChiKey: KSEPKAZNQBRMNR-XVKPBYJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  racemic 5-bromo-2,3-benzonorbornadiene 在 溴 作用下， 以 四氯化碳 为溶剂， 以90%的产率得到(1R,4S)-2,2,3-Tribromo-1,2,3,4-tetrahydro-1,4-methano-naphthalene
  参考文献：
  名称：

  Synthesis of 2,3-dibromobenzonorbornadiene and its cyclotrimerization into 5,18:6,11:12,17-trimethanotrinaphthylene

  摘要：

  The synthesis of 2.3-dibromobenzonorbornadiene ene 11 by high temperature bromination of 2-bromobenzonorbornadiene 9 allows the synthesis of the benzoannelated trimers, syn- and anti-5,18:6,11:12,17-trimethanotrinaphthylene 8. The syn isomer is a basket shaped molecule that displays unusual geometric and electronic features including bond length fixation of the central benzene ring as shown by X-ny diffraction (exocyclic bond 1.41 Angstrom, endocyclic bond 1.36 Angstrom). (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01162-3
• 作为产物：
  描述：

  ((1R,4S)-3-Bromo-1,4-dihydro-1,4-methano-naphthalen-2-yl)-trimethyl-stannane 在 copper(l) iodide 、 lithium iodide 作用下， 以 乙二醇二甲醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以100%的产率得到racemic 5-bromo-2,3-benzonorbornadiene
  参考文献：
  名称：

  Role of Copper in the Stereoselective Metal-Promoted Cyclotrimerisation of Polycyclic Alkenes

  摘要：

  Copper-mediated stereoselective cyclotrimerisation of polycyclic alkenes is reported. The mechanism involved provides strong support for the involvement of a Cull, intermediate in cross-coupling reactions of sp(2)-carbon atoms. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2002).

  DOI：

  10.1002/1099-0690(200212)2002:23<4032::aid-ejoc4032>3.0.co;2-x

文献信息

• Triplet photoisomerization of 1-substituted 6-methoxybenzonorbornadienes. Excited-state competition between bridgehead and m-methoxy groups for intramolecular control of the dual channel di-.pi.-methane pathway. The vinyl deuterium isotope effect
  作者：Leo A. Paquette、Aravamuthan. Varadarajan、Lonnie D. Burke

  DOI：10.1021/ja00285a026

  日期：1986.12

  results reveal particularly efficient processes at one end of the spectrum to 0% reaction in the 2-bromo example. The full range of the data provides an important glimpse into how triplet deactivation can be realized in rigid bichromophoric systems possessing well-defined geometry. Finally, the secondary deuterium isotope effect associated with triplet state di-..pi..-methane rearrangement of benzonorbornadiene-d/sub

  制备了七个 1-取代的 6-甲氧基苯并降冰片二烯并对其进行了苯乙酮敏化的光异构化。在-COOCH/sub 3/、-CONH/sub 2/、-COCH/sub 3/ 和-CN 实例中，激发态1,2-芳基位移主要由桥头取代基控制。由于该基团的吸电子特性降低，如 -C(CH/sub 3/)/sub 2/OH、-NHCOCH/sub 3/ 和 -CH/sub 3/，近端 di- 的范围。 .pi.​​.-甲烷重排下降到低至 55% 的水平。值得注意的是，在本系列中，间甲氧基与位于间位的芳基碳结合的公认偏好从未占主导地位。还对 17 种苯并降冰片二烯进行了量子产率测量。结果表明，在光谱的一端，在 2-溴实例中，0% 反应的过程特别有效。完整的数据范围提供了一个重要的一瞥，可以了解如何在具有明确定义的几何形状的刚性双发色系统中实现三重态失活。最后，与苯并降冰片二烯-d/sub 2/ 的三重态二-.pi
• 10.1002/1099-0690(20022)2002:3<526::aid-ejoc526<3.0.co;2-n
  作者：Altundas, Ramazan、Dastan, Arif、Uenaldi, Nermin S.、Gueven, Kutalmis、Uzun, Orhan、Balci, Metin

  DOI：10.1002/1099-0690(20022)2002:3<526::aid-ejoc526<3.0.co;2-n

  日期：——
• 1-Substituted benzonorbornadienes
  作者：Philip J. Chenier、Steven R. Jensen、Donald A. Jess、Barnett B. Rosenblum

  DOI：10.1021/jo00964a035

  日期：1973.12
• anti-Selective Heck-type cyclotrimerization of polycyclic bromoalkenes
  作者：Sergio Cossu、Ottorino De Lucchi、Antonio Paulon、Paola Peluso、Cristiano Zonta

  DOI：10.1016/s0040-4039(01)00495-6

  日期：2001.5

  Vinyl halides can react as both substrate and reagent in the Heck reaction. In the case of bicyclic vinyl halides, the reaction leads to cyclotrimers through an anti-selective process. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Stereochemistry of the cyclotrimerisation of enantiopure polycyclic bromostannylalkenes: Mechanistic considerations on the coupling of alkenyl stannanes by copper(II) nitrate
  作者：Cristiano Zonta、Sergio Cossu、Paola Peluso、Ottorino De Lucchi

  DOI：10.1016/s0040-4039(99)01736-0

  日期：1999.11

  The cyclotrimerisation of enantiopure 1-bromo-2-trimethylstannylbenzonorbornadiene 2, contrary to the expectations, affords predominantly the trimer anti-4. This observation suggests that the reaction proceeds mainly via a Sn-Sn coupling to produce the dimer anti-5 and a tin-copper product that triggers halogen-metal exchange on the dimer thus allowing a second coupling with the starling reagent eventually leading to the anti-trimer. The little hut consistent formation of the isomer syn-4 and meso dimer 5 can arise from a racemisation of the bromine-copper-tin intermediate possibly via an alkyne structure. (C) 1999 Elsevier Science Ltd. All rights reserved.