11,12-bis(bromomethyl)-9,10-dihydro-9,10-ethenoanthracene | 131760-70-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 11,12-bis(bromomethyl)-9,10-dihydro-9,10-ethenoanthracene
• 英文别名: 11,12-bis(bromomethyl)-9,10-etheno-9,10-dihydroanthracene；11,12-di(bromomethyl)-9,10-dihydro-9,10-ethenoanthracene；15,16-Bis(bromomethyl)tetracyclo[6.6.2.02,7.09,14]hexadeca-2,4,6,9,11,13,15-heptaene
• CAS: 131760-70-8
• 化学式: C₁₈H₁₄Br₂
• 分子量: 390.117
• InChiKey: IEQCYKXWMDPHCO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  11,12-bis(bromomethyl)-9,10-dihydro-9,10-ethenoanthracene 在 锌 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以93%的产率得到9,10-dihydro-11,12-dimethylene-9,10-ethanoanthracene
  参考文献：
  名称：

  Reduction of DMAD-anthracene adducts. Synthesis and conformations of substituted cyclodecadienes

  摘要：

  A general method for reducing DMAD-anthracene adducts to the corresponding enediols is described. Thus, the ester groups of 1 were reduced without C = C reduction using the DIBAH-nBuLi ''ate'' complex to give previously unknown 2 in high yield. Analogous enediols 5-7 were similarly prepared. Base treatment of dibromide 3 and dithiol 9, both prepared from 2 by standard methods, gave conformationally rigid dithiacyclodecadiene 10. With o-, m-, and p-xylylenedithiols, dibromide 3 gave respectively the conformationally labile cyclophanes 12 and 13 and the rigid cyclophane 14. Tetrabromide 16 and dithiol 9 gave cuppedophane 17, but tetrabromide 18 and 9 formed bis-m-cyclophane 19 instead.

  DOI：

  10.1021/jo00003a019
• 作为产物：
  描述：

  11,12-bis(hydroxymethyl)-9,10-etheno-9,10-dihydroanthracene 在 2,4,6-三甲基吡啶 、 三溴化磷 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以63%的产率得到11,12-bis(bromomethyl)-9,10-dihydro-9,10-ethenoanthracene
  参考文献：
  名称：

  Reduction of DMAD-anthracene adducts. Synthesis and conformations of substituted cyclodecadienes

  摘要：

  A general method for reducing DMAD-anthracene adducts to the corresponding enediols is described. Thus, the ester groups of 1 were reduced without C = C reduction using the DIBAH-nBuLi ''ate'' complex to give previously unknown 2 in high yield. Analogous enediols 5-7 were similarly prepared. Base treatment of dibromide 3 and dithiol 9, both prepared from 2 by standard methods, gave conformationally rigid dithiacyclodecadiene 10. With o-, m-, and p-xylylenedithiols, dibromide 3 gave respectively the conformationally labile cyclophanes 12 and 13 and the rigid cyclophane 14. Tetrabromide 16 and dithiol 9 gave cuppedophane 17, but tetrabromide 18 and 9 formed bis-m-cyclophane 19 instead.

  DOI：

  10.1021/jo00003a019

文献信息

• Medium-Dependent Type Selectivity in Photoreactions of a Crown Ether-Annelated Dibenzobarrelene Derivative
  作者：Heiko Ihmels、Michael Schneider、Michael Waidelich

  DOI：10.1021/ol026482w

  日期：2002.9.1

  [reaction: see text] A concept for modifying the photochemical properties of a dibenzobarrelene derivative by the combination of supramolecular assembly and solid-state photochemistry is presented. The irradiation of dibenzobarrelene 1b and alkali metal complexes thereof (1:1) in acetonitrile or benzene solution leads preferentially to the dibenzocyclooctatetraene 4b as the photoproduct. In contrast

  [反应：见正文]提出了一种通过超分子组装和固态光化学的结合来改变二苯并桶烯衍生物的光化学性质的概念。在苯腈或苯溶液中辐照二苯并戊烯1b及其碱金属配合物（1：1）优先产生作为光产物的二苯并环辛酸酯四烯4b。相反，由于强的阳离子作用，二苯并半bullvalene 5b形成为固态的主要光产物。
• Stereoselective Di-pi-Methane Rearrangement of a BINOL-Substituted Dibenzobarrelene Derivative
  作者：Heiko Ihmels、Jia Luo

  DOI：10.1515/zpch-2014-0462

  日期：2014.3.28

  Two dibenzobarrelene derivatives were synthesized that are covalently linked to a (S)-BINOL unit through an oxymethylene (1b) or ethylenedioxymethylene (1c) unit, and their photoreactivity was examined. Irradiation of 1b in acetone resulted in a di-π-methane rearrangement to give diastereoselectively one dibenzosemibullvalene isomer. Experimental and theoretical data point to a directing effect of the BINOL auxiliary based on steric repulsion. The derivative 1c with a longer linker between the BINOL unit and the dibenzobarrelene is photoinert, presumably because of fast competing relaxation processes in the excited state.

  摘要：合成了两种二苯并[4,5]环戊二烯衍生物，它们通过氧亚甲基（1b）或乙二醇亚甲基（1c）单元与（S）-BINOL单元共价连接，并研究了它们的光反应性。在丙酮中照射1b导致二π-甲烷重排反应，选择地形成了一个二苯并半牛烯异构体。实验和理论数据表明，基于立体排斥，BINOL辅助剂具有定向作用。具有较长连接剂的1c衍生物在光激发态中是光惰性的，可能是因为存在竞争性的快速弛豫过程。
• 11,12-Bis(diethylaminomethyl)-9,10-dihydro-9,10-ethenoanthracene: A probe for the heavy atom effect in solid state photoreactions
  作者：Heiko Ihmels、Brian O. Patrick、John R. Scheffer、James Trotter

  DOI：10.1016/s0040-4020(99)00024-1

  日期：1999.2

  The photochemistry of title compound 2 and its hydrogen halide salts was investigated in solution and in the solid state. In the solid state the halide ions were shown to cause a heavy atom effect that was not observed in solution. The orientation of the halide ions towards the chromophore was determined on the basis of the corresponding structures in the solid state as determined by X-ray crystallography. (C) 1999 Elsevier Science Ltd. All rights reserved.
• ANANTANARAYAN, ASHOK;HART, HAROLD, J. ORG. CHEM., 56,(1991) N, C. 991-996
  作者：ANANTANARAYAN, ASHOK、HART, HAROLD

  DOI：——

  日期：——
• Reduction of DMAD-anthracene adducts. Synthesis and conformations of substituted cyclodecadienes
  作者：Ashok Anantanarayan、Harold Hart

  DOI：10.1021/jo00003a019

  日期：1991.2

  A general method for reducing DMAD-anthracene adducts to the corresponding enediols is described. Thus, the ester groups of 1 were reduced without C = C reduction using the DIBAH-nBuLi ''ate'' complex to give previously unknown 2 in high yield. Analogous enediols 5-7 were similarly prepared. Base treatment of dibromide 3 and dithiol 9, both prepared from 2 by standard methods, gave conformationally rigid dithiacyclodecadiene 10. With o-, m-, and p-xylylenedithiols, dibromide 3 gave respectively the conformationally labile cyclophanes 12 and 13 and the rigid cyclophane 14. Tetrabromide 16 and dithiol 9 gave cuppedophane 17, but tetrabromide 18 and 9 formed bis-m-cyclophane 19 instead.