dibenzo[b,e]bicyclo[2.2.2]octadiene-1-carboxylic acid | 20202-05-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: dibenzo[b,e]bicyclo[2.2.2]octadiene-1-carboxylic acid
• 英文别名: Dibenzobicyclo[2.2.2]octadien-1-carbonsaeure；9,10-Ethanoanthracene-9(10h)-carboxylic acid；tetracyclo[6.6.2.02,7.09,14]hexadeca-2,4,6,9,11,13-hexaene-1-carboxylic acid
• CAS: 20202-05-5
• 化学式: C₁₇H₁₄O₂
• 分子量: 250.297
• InChiKey: BVLVSIVPACIYAV-UHFFFAOYSA-N

物化性质

• 溶解度：
  可溶于DMSO（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dibenzo[b,e]bicyclo[2.2.2]octadiene-1-carboxylic acid 在 氯化亚砜 作用下， 以 甲苯 为溶剂， 反应 2.0h， 生成 11-(chlorocarbonyl)-9,10-dihydro-9,10-eyhanoanthracene
  参考文献：
  名称：

  Geometry−Affinity Relationships of the Selective Serotonin Receptor Ligand 9-(Aminomethyl)-9,10-dihydroanthracene

  摘要：

  With the exception of its two aromatic rings and basic nitrogen atom, 9-(aminomethyl)-9,10-dihydroanthracene (AMDA; 1) is remarkably devoid of the pharmacophore features usually associated with high-affinity receptor ligands such as the heteroatom hydrogen bonding features of the endogenous ligand serotonin. AMDA does contain a phenylethylamine skeleton within a tricyclic ring system, and the presence of the second aromatic group is necessary for optimal receptor affinity. The structural requirements for the binding of AMDA at 5-HT2A receptors were investigated with respect to the geometric relationship between the two aromatic rings. It appears that the geometry of the AMDA parent is in the optimal range for fold angle between aromatic moieties. Evaluation of conformationally constrained derivatives of AMDA suggests that a chain extended trans, gauche form is most likely responsible for high affinity.

  DOI：

  10.1021/jm010354g
• 作为产物：
  描述：

  乙烯 、 9-蒽甲酸 以 N,N-二甲基甲酰胺 为溶剂， 170.0 ℃ 、2.76 MPa 条件下， 反应 48.0h， 生成 dibenzo[b,e]bicyclo[2.2.2]octadiene-1-carboxylic acid
  参考文献：
  名称：

  Substituent-Dependent Nitration of 9-Substituted 9,10-Dihydro-9,10-ethanoanthracenes

  摘要：

  研究发现，桥头碳上含有 Me、But、F、Br、I、OMe、NO2、CN、CHO 或 CO2Me 取代基的 9-取代乙蒽的单硝化作用只发生在芳香环的β位。单硝基产物被分离出来，并通过 1H n.m.r. 光谱进行鉴定，其相对比例则通过定量 g.l.c .和/或 1H n.m.r. 光谱进行估算。对于上述所有底物，在含有取代基的桥头碳的β-元位置上的硝化比例[得到一般形式 (4) 的化合物]大于在桥头取代基的相应β-对位位置上的硝化比例[得到一般形式 (3) 的化合物]。虽然芳香环 β 位的优先硝化与之前报道的 9,10-二氢-9,10-乙桥蒽 (2a) 本身的硝化一致，但之前并没有观察到这种优先元攻击。由于本研究中使用的取代基在立体和电子方面存在很大差异，因此无法将这种行为与现有的取代基参数联系起来，而且这种优先偏置的起源仍不清楚。 对该体系中的二硝化作用仅进行了表面研究。桥头取代基和一个芳香环上已经存在的硝基的影响，似乎在确定进入的硝基对另一个（未硝化的）芳香环的攻击位置时，产生了难以预测的结果。

  DOI：

  10.1071/ch9951949

文献信息

• Electrochemical Studies on the Competition Between Intramolecular Electron Transfer and Intermolecular Protonation of Nitroaryl Radical Anions in the Reductions of Apical Carboxylic Acid Substituents of 2- and 3-Nitro- 9,10-dihydro-9,10-ethanoanthracene-9-carboxylic Acids
  作者：Peter A. Lay、Robert K. Norris、Paul K. Witting

  DOI：10.1071/c97076

  日期：——

  The results obtained from variable scan rate cyclic voltammetry (c.v.) on 2-nitro- and 3-nitro-9,10- dihydro-9,10-ethanoanthracene-9-carboxylic acids [(4) and (5), respectively], combined with simulations of various c.v. responses, are consistent with reduction of a benzylic acid group being facilitated by an intramolecular electron transfer process. This intramolecular process involves a one-electron reduction of the nitroaromatic group, followed by a rapid and irreversible π*(ArNO2)•- → π*(RCO2H)•- intramolecular electron transfer to the carboxylic acid group at a benzylic bridgehead position of the acids (4) and (5). The reduction potentials of the acid groups are shifted more than 0·3 V to positive potentials at slow scan rates (20-100 mV s-1) compared with the unnitrated acid derivative (6). The reduction potentials and the relative peak currents for the reductions of the nitro and acid groups for each of compounds (4) and (5) are dependent on the concentrations of the reactants. At concentrations of substrate >1 mM, reduction of the acid moiety is increasingly dependent on complex intermolecular processes. These intermolecular processes compete with intramolecular electron transfer from the nitroaryl anion to the apical acid group at the benzylic bridgehead position. Digital simulations of the voltammetric data were confined to substrate concentrations <1 mM, and show that the intramolecular reductions of the apical carboxylic acid protons of (4) and (5) are complicated by competing intermolecular electron transfer and intermolecular self-protonations of the nitro radical anions. The value of the intramolecular electron transfer rate constant for the meta compound is an order of magnitude larger than that for the para compound, which is the opposite reactivity pattern to that generally found in the SRN1 reactions of m- and p-nitrobenzyl halides. This indicates that there is likely to be an important contribution from an intramolecular through-space electron transfer mechanism for the former reaction

  可变扫描速率循环伏安法（C.V. 2-硝基和 3-硝基-9,10-二氢-9,10-乙硫杂蒽-9-羧酸 [(4) 和 (5)]，并结合模拟各种 c.v. 反应一致，苄基酸基的还原是由分子内电子 分子内电子转移过程。这种 分子内电子转移过程包括硝基芳香族基团的单电子还原 分子内过程包括硝基芳香族基团的一电子还原，然后是快速且不可逆的 π*(ArNO2)-- → π*(RCO2H) π*(RCO2H)-- 分子内电子转移到羧酸基团的苄基桥头位置 酸 (4) 和 (5) 的桥头位置上的羧酸基团进行分子内电子转移。酸基的还原电位 酸基的还原电位在慢扫描速率下（20-100 mV s）向正电位移动超过 0-3 V。 扫描速率（20-100 mV s-1）时，酸基的还原电位会向正电位移动 0-3 V 以上。 酸衍生物 (6)。与未硝化的酸衍生物（6）相比，在慢扫描速率下（20-100 mV-1 化合物 (4) 和 (5) 中硝基和酸基的还原电位和相对峰值电流与浓度有关。 (5) 的还原电位和还原硝基和酸基的相对峰值电流取决于反应物的浓度。当底物浓度为 1 mM 时，酸基的还原越来越依赖于复杂的分子间过程。 复杂的分子间过程。这些分子间过程与 分子内电子从硝基芳基阴离子转移到位于苄基桥顶端的酸基的竞争过程 基的分子内电子传递发生竞争。伏安数据的数字模拟 伏安数据仅限于底物浓度为 1 毫摩尔的情况，结果表明 的顶端羧酸质子的分子内还原。 (4) 和 (5) 的顶端羧酸质子的分子内还原因相互竞争的分子间电子转移和 硝基阴离子的分子间自质子化。分子内电子转移速率常数 分子内电子转移速率常数 元化合物的分子内电子转移速率常数比对位化合物的分子内电子转移速率常数大一个数量级。 对位化合物的分子内电子转移速率常数的数量级，这与 这与 SRN1 反应中发现的反应模式相反。 间硝基和对硝基苄基卤化物 SRN1 反应的反应模式相反。这表明 这表明，前者的分子内通空电子转移机制可能对 分子内空间电子转移机制对前一反应的重要贡献。 反应
• Verfahren zur Herstellung von 9,10-Dihydro-9,10-ethanoanthracen-9-carbonsäuren durch Oxidation der entsprechenden Aldehyde
  申请人：BAYER AG

  公开号：EP0878459A1

  公开（公告）日：1998-11-18

  9,10-Dihydro-9,10-ethanoanthracen-9-carbonsäuren werden durch Oxidation der entsprechenden Aldehyde in besonders vorteilhafter Weise erhalten, wenn man die Oxidation mit Sauerstoff oder einem Sauerstoff enthaltenden Gas und in Gegenwart eines Katalysators und eines organischen Verdünnungsmittels durchführt.

  9,10-二氢-9,10-乙炔基蒽-9-羧酸是通过氧化相应的醛类得到的，如果氧化是在有催化剂和有机稀释剂存在的情况下，用氧气或含氧气体进行，会特别有利。
• Synthese und Eigenschaften von 1-Aminoalkyl-dibenzo[b,e]bicyclo[2.2.2]octadienen
  作者：M. Wilhelm、P. Schmidt

  DOI：10.1002/hlca.19690520602

  日期：——

  AbstractThe syntheses of dibenzo [b, e] bicyclo [2.2.2] octadienes substituted at the bridgehead by aminomethyl, aminoethyl or aminopropyl groups are described. The influence of this substitution on the fragmentation upon electron impact and on the nmr spectra of the new compounds is discussed.
• JPH10316612A
  申请人：——

  公开号：JPH10316612A

  公开（公告）日：1998-12-02
• Geometry−Affinity Relationships of the Selective Serotonin Receptor Ligand 9-(Aminomethyl)-9,10-dihydroanthracene
  作者：Scott P. Runyon、Srinivas Peddi、Jason E. Savage、Bryan L. Roth、Richard A. Glennon、Richard B. Westkaemper

  DOI：10.1021/jm010354g

  日期：2002.4.1

  With the exception of its two aromatic rings and basic nitrogen atom, 9-(aminomethyl)-9,10-dihydroanthracene (AMDA; 1) is remarkably devoid of the pharmacophore features usually associated with high-affinity receptor ligands such as the heteroatom hydrogen bonding features of the endogenous ligand serotonin. AMDA does contain a phenylethylamine skeleton within a tricyclic ring system, and the presence of the second aromatic group is necessary for optimal receptor affinity. The structural requirements for the binding of AMDA at 5-HT2A receptors were investigated with respect to the geometric relationship between the two aromatic rings. It appears that the geometry of the AMDA parent is in the optimal range for fold angle between aromatic moieties. Evaluation of conformationally constrained derivatives of AMDA suggests that a chain extended trans, gauche form is most likely responsible for high affinity.