9,10-dibromotricyclo[6.2.2.0^2,7]dodeca-2,4,6,9,11-pentaene | 117269-34-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 9,10-dibromotricyclo[6.2.2.0^2,7]dodeca-2,4,6,9,11-pentaene
• 英文别名: 2,3-dibromo-1,4-dihydro-1,4-ethenonaphthalene；2,3-dibromobenzobarrelene；9,10-Dibromotricyclo[6.2.2.02,7]dodeca-2,4,6,9,11-pentaene
• CAS: 117269-34-8
• 化学式: C₁₂H₈Br₂
• 分子量: 312.004
• InChiKey: HVNWHKOYBLAWPB-UHFFFAOYSA-N

物化性质

• 熔点：
  71-72 °C
• 沸点：
  365.4±42.0 °C(Predicted)
• 密度：
  1.901±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  9,10-dibromotricyclo[6.2.2.0^2,7]dodeca-2,4,6,9,11-pentaene 在 tetraphenylporphyrine copper(l) iodide 、 氧气 作用下， 以 甲醇 、 四氯化碳 、 N,N-二甲基甲酰胺 为溶剂， -15.0~120.0 ℃ 、82.66 kPa 条件下， 反应 13.0h， 生成 exo-3,4-dioxa-2,5-dimethoxy-7,8-benzo<4.2.2.0^2,5>deca-7,9-diene
  参考文献：
  名称：

  烯醇醚的光氧化：exo-和endo-3,4-dioxa-2,5-dimethoxy-7,8-苯并[4.2.2.0 2,5 ] deca-7,9-二烯的合成及其化学转化

  摘要：

  单线态氧与2的反应提供了两个异构体二氧杂环丁烷3和4，它们在加热后分解为预期的二氢萘衍生物5。在硫脲存在下2的光氧合导致二酮8和缩酮7的形成。后者大概源自溶剂分子的掺入。

  DOI：

  10.1016/s0040-4020(01)80167-8
• 作为产物：
  描述：

  (1SR,3SR,4SR,10RS)-2,2,3,10-tetrabromo-1,2,3,4-tetrahydro-1,4-ethanonaphthalene 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以88%的产率得到9,10-dibromotricyclo[6.2.2.0^2,7]dodeca-2,4,6,9,11-pentaene
  参考文献：
  名称：

  Bromination of (1RS,2RS,5RS)-2,3-dibromo-6,7-benzobicyclo[3.2.1]octa-3,6-diene. A new and convenient synthesis of disubstituted benzobarrelenes

  摘要：

  DOI：

  10.1021/jo00262a040

文献信息

• The Di-p-methane Photorearrangement of 2,3-Disubstituted Benzobarrelenes: the Effect of Substituents of Opposite Polarity on the Regioselectivity
  作者：Ramazan Altundas、Metin Balci

  DOI：10.1071/c97047

  日期：——

  The solution phase photochemistry of benzobarrelene derivatives (8) and (11), containing electron-donating and electron-withdrawing substituents, has been studied. The structures of the photoproducts (16)/(20) and (17)/(21) indicate clearly that vinyl-vinyl nitrile (aldehyde) bridging is not operating. The formation of these products is discussed in terms of the stabilizing effect of the substituents on the radical and the destabilizing effect on the formation of the cyclopropane ring.

  苯并芘衍生物(8)和(11)的溶液相光化学、 的溶液相光化学进行了研究。 研究。光反应产物 (16)/(20) 和 (17)/(21) 的结构 结构清楚地表明，乙烯基-乙烯基腈（醛）桥接不 醛桥接。这些产物的形成可以从以下方面进行讨论 取代基对自由基的稳定作用和对形成环状化合物的不稳定作用进行了讨论。 对环丙烷环形成的破坏作用。
• The differing mechanisms of photo-formation of 7-cyanobenzocyclooctatetraene from 7- and 6-cyano-2,3-benzobicyclo[4.2.0]octa-2,4,7-triene
  作者：Christopher Owen Bender、Douglas Dolman、Jeremy Christian Foesier、Sherry Lee Lawson、Kathryn Elvia Preuss

  DOI：10.1139/v02-204

  日期：2003.1.1

  It is known that 7-cyanobenzocyclooctatetraene (COT 2) is a product of the thermolysis and direct photolysis of 7- and 6-cyano-2,3-benzobicyclo[4.2.0]octa-2,4,7-triene (1 and 5), though the mechanisms of these rearrangements have not been reported. In the present study experiments have been carried out using the deuterium-labelled trienes 1a (93%-d₁ at C-6) and 5a (93%-d₁ at C-8), which were formed from 2π + 2π photo-closure (direct irradiation) of COT 2a labelled at C-8. The results reveal that whereas the thermolysis of 1a and 5a and the direct irradiation of 5a reform COT 2a, probably via cleavage of the strained cyclobutene C-1—C-6 bond, the direct irradiation of triene 1a gives a differently labelled COT product, containing the deuterium exclusively at C-9. The mechanism proposed for the latter phototransformation is a modification of the Zimmerman di-π-methane rearrangement.Key words: mechanisms, rearrangements, photochemistry, di-π-methane rearrangement.

  已知7-氰基苯并环辛四烯（COT 2）是7-和6-氰基-2,3-苯并[4.2.0]辛二烯（1和5）的热解和直接光解的产物，尽管这些重排的机制尚未报告。在本研究中，使用了标记在C-6处的氘标记三烯1a（93%-d1）和标记在C-8处的氘标记三烯5a（93%-d1），它们是从标记在C-8处的COT 2a经过2π + 2π光闭合（直接照射）形成的。结果表明，虽然1a和5a的热解以及5a的直接照射会重新形成COT 2a，可能是通过断裂应力环丁烷C-1-C-6键，但三烯1a的直接照射会产生一个标记不同的COT产物，其中氘完全位于C-9。对于后者的光转化提出的机制是Zimmerman双π-甲烷重排的改进。关键词：机制，重排，光化学，双π-甲烷重排。
• Substituent effect on regioselectivity in the di-π-methane rearrangement: synthesis of disubstituted benzobarrelene derivatives and their photochemistry
  作者：Nermin S Ünaldi、Metin Balci

  DOI：10.1016/s0040-4039(01)01770-1

  日期：2001.11

  es 5 and 6 have been synthesized and subjected to triplet-sensitized photoisomerization. 2,3-Dicyanobenzobarrelene 5 gave two di-π-methane rearrangement products 7 and 8 and a [2π+2π]-cycloaddition product 9. However, 2,5-dicyanobenzobarrelene 6 formed a single di-π-methane product 13. The formation of these products is discussed in terms of the radical stabilizing effect of the substituents and the

  已经合成了2，3-和2，5-二氰基苯并戊烯5和6，并对其进行了三重态敏化的光异构化。2,3-二氰基苯并戊烯5给出两个二-π-甲烷重排产物7和8和一个[2π+2π]-环加成产物9。但是，2，5-二氰基苯并戊烯6形成单一的二-π-甲烷产物13。根据取代基的自由基稳定作用和对环丙烷环形成的去稳定作用来讨论这些产物的形成。
• Low and high temperature bromination of 2,3-dicarbomethoxy and 2,3-dicyano benzobarrelene: unexpected substituent effect on bromination
  作者：Sara Taşkesenlioğlu、Arif Daştan、Erdin Dalkılıç、Murat Güney、Rza Abbasoğlu

  DOI：10.1039/b9nj00372j

  日期：——

  The bromination of 2,3-dicarbomethoxy benzobarrelene yielded the dibromide regio- and stereospecifically arising from the aryl shift where the bromine exclusively attacks the double bond from the exo face of the double bond. High temperature bromination of this compound yielded aryl-shift products. From the low temperature bromination of 2,3-dicyano benzobarrelene, non-rearranged products were obtained

  溴化 2,3-二苯甲氧基苯并三氢萘产生二溴化物的区域和立体特异性，这是由芳基转移引起的，其中溴仅从双键的外表面攻击双键。该化合物的高温溴化产生芳基转移产物。从低温溴化2,3-二氰基与重排产物一起获得了苯并戊烯，未重排产物。出乎意料的是，我们观察到未重排产物的产率随温度升高而降低。使用DFT计算模型化合物讨论了取代基的可能作用。
• Synthesis of 2,3-, 2,5-, and 2,6-dibromobenzobarrelenes High temperature bromination 1
  作者：Osman Çakmak、Metin Balci

  DOI：10.1016/0040-4039(90)80225-b

  日期：1990.1

  2-Bromobenzobarrelene 7 has been brominated at 78 °C. Four bromine addition products 8, 9, 10, 11 with bicyclo [2.2.2]skaleton have been isolated whose structures were established on the basis of the 1H- and 13C-NMR spectral measurements. The dehydrobromination of 8, 9, 10, and 11 was achieved using potassium tert.-Butoxide and sodium methoxide to give 2,3-, 2.4-, and 2,5-dibromobenzobarrelenes, respectively

  2-溴苯并barrelene7已在78°C溴化。已分离出具有双环[2.2.2]骨架的四个溴加成产物8、9、10、11，其结构是根据1 H-和13 C-NMR光谱测量确定的。用叔丁醇钾和甲醇钠分别完成8、9、10和11的脱氢溴化反应，分别得到2，3-，2.4-和2，5-二溴苯并戊烯。