6,8-dimethyl 7-oxo-7H-benzo[7]annulene-6,8-dicarboxylate | 24790-67-8

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物 - 环庚三烯酮
• 英文名称: 6,8-dimethyl 7-oxo-7H-benzo[7]annulene-6,8-dicarboxylate
• 英文别名: 7-oxo-7H-benzocycloheptene-6,8-dicarboxylic acid dimethyl ester；7-Oxo-7H-benzocyclohepten-6,8-dicarbonsaeure-dimethylester；7H-Benzocycloheptenon-(7)-dicarbonsaeure-(6.8)-dimethylester；Dimethyl 7-oxo-7H-benzo[a]cycloheptene-6,8-dicarboxylate；dimethyl 7-oxobenzo[7]annulene-6,8-dicarboxylate
• CAS: 24790-67-8
• 化学式: C₁₅H₁₂O₅
• 分子量: 272.257
• InChiKey: DCTQUEIYCQWNRS-UHFFFAOYSA-N

物化性质

• 熔点：
  186-188 °C
• 沸点：
  349.6±31.0 °C(Predicted)
• 密度：
  1.307±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6,8-dimethyl 7-oxo-7H-benzo[7]annulene-6,8-dicarboxylate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 5,6,8,9-Tetrahydro-5,9-(dicarboxy-methano)-7H-benzocycloheptenon-(7)
  参考文献：
  名称：

  Additionsreaktionen CH-acider verbindungen an 7H-benzocycloheptenon-(7)-dicarbonsäureester-(6.8)

  摘要：

  DOI：

  10.1016/s0040-4039(01)88163-6
• 作为产物：
  描述：

  7-oxo-7H-benzocycloheptene-6,8-dicarboxylic acid diethyl ester 在 硫酸 作用下， 生成 6,8-dimethyl 7-oxo-7H-benzo[7]annulene-6,8-dicarboxylate
  参考文献：
  名称：

  Thiele; Schneider, Justus Liebigs Annalen der Chemie, 1909, vol. 369, p. 293

  摘要：

  DOI：

文献信息

• Synthesis and Characterization of 1-Hydroxy-4,5-arene-Fused Tropylium Derivatives
  作者：Takuya Kodama、Yuki Kawashima、Kenta Uchida、Zhirong Deng、Mamoru Tobisu

  DOI：10.1021/acs.joc.1c01818

  日期：2021.10.1

  The properties of 1-hydroxy-4,5-arene-fused tropyliums were assessed based on experimental and theoretical investigations. An X-ray crystallographic analysis revealed a decrease of bond alternation in the seven-membered ring of 1-hydroxy-4,5-benzotropylium derivatives compared with that of the parent 4,5-benzotropones, which is indicative of an increase in aromaticity upon protonation. NICS and AICD

  基于实验和理论研究评估了 1-羟基-4,5-芳烃稠合的 tropyliums 的性质。X 射线晶体学分析显示，与母体 4,5-苯并托酮相比，1-羟基-4,5-苯并托鎓衍生物的七元环中的键交替减少，这表明芳香性增加质子化。NICS 和 AICD 计算也支持 1-羟基-4,5-芳烃稠合的 tropylium 的芳香性增加。还测定了一系列 1-羟基-4,5-芳烃稠合的托鎓衍生物的 p K a值。
• Synthesis of 4,5-Benzotropone π Complexes of Iron, Rhodium, and Iridium and Their Potential Use in Catalytic Borrowing-Hydrogen Reactions
  作者：Takuya Kodama、Yuki Kawashima、Zhirong Deng、Mamoru Tobisu

  DOI：10.1021/acs.inorgchem.0c03587

  日期：2021.4.5

  The syntheses of rhodium, iridium, and iron π complexes bearing 4,5-benzotropone ligands are reported. X-ray crystallographic analyses revealed that a tropone core coordinates to a metal center in a η4 manner with a tub-form geometry. Some of the benzotropone π complexes exhibited catalytic activity for N-alkylation of aniline by borrowing hydrogen.

  报道了带有4，5-二苯甲酮配体的铑，铱和铁π配合物的合成。X射线结晶分析表明环庚三烯酮芯坐标到金属中心的η 4与桶形式的几何形状的方式。某些苯甲酮π配合物通过借入氢对苯胺的N-烷基化表现出催化活性。
• Polarized Helical Coumarins: [1,5] Sigmatropic Rearrangement and Excited-State Intramolecular Proton Transfer
  作者：Łukasz Kielesiński、Olaf W. Morawski、Cristina A. Barboza、Daniel T. Gryko

  DOI：10.1021/acs.joc.0c02978

  日期：2021.5.7

  facilitates excited-state intramolecular proton transfer (ESIPT). This process leads to a barrierless conical intersection with the ground electronic state and opens a radiationless deactivation channel effectively competing with fluorescence. Solvent stabilization of the CT state increases the barrier for ESIPT and decreases the efficiency of the nonradiative channel. This results in the observed correlation

  将苯酚加到环状α，β-不饱和酯中，然后进行分子内酯交换和[1,5]σ重排的串联过程，可得到一系列基于先前未知的3-氨基-7-羟基苯并[3,4]的螺旋香豆素。环庚[1,2 - c ] chromen-6-核。这些具有β-酮酸酯部分的新型极化香豆素已被用于合成显示绿色荧光的更硬的和螺旋状的香豆素-吡唑啉酮。极性溶剂中香豆素-吡唑啉酮的排放增加取决于S 1状态的性质。预计香豆素-吡唑啉酮具有两个垂直的能量态：一个弱吸收的S 1（1 LE），然后一个明亮的S2状态（1 CT）。在极性溶剂中，1 CT可以稳定在1以下LE并可能变成荧光状态。荧光光谱的溶剂变色证实了这一理论预测。这些香豆素-吡唑啉酮杂合物中存在NH···O═C分子内氢键，可促进激发态分子内质子转移（ESIPT）。该过程导致与基态电子状态的无障碍圆锥形相交，并打开了与荧光有效竞争的无辐射失活通道。CT状态的溶剂稳定化会增加ESIPT的势
• Synthesis of benzo-homotriasterenedione
  作者：Christopher B. Chapleo、Andr� S. Dreiding

  DOI：10.1002/hlca.19740570814

  日期：——

  Kondensation von 6,8-dimethoxycarbonyl-benzocycloheptan-7-on (4,5-Benzo-tropon-2, 7-dicarbonsäure-dimethylester) ((4)4) mit Aceton-dicarbonsäuredimethylester ergab 68% 1,5-Hydroxy, methoxy-2,4,6,8-tetramethoxycarbonyl-10, 10a-benzo-9-oxa-10a-homoadamant-10-en (6) und 17% des bekannten 3,7-Dihydroxy-4,8,2β,6β-tetramethoxycarbonyl-9,10-benzo-bicyclo[3.3.2]dec-3,7,9-triens (7). Hydrolyse und Decarboxylierung

  6,8-二甲氧基羰基-苯并环庚烷-7-一（4,5-苯并tropon-2，7-二羧酸二甲酯）（（4）4）与丙酮二羧酸二甲酯的缩合反应生成68％的1,5-羟基，甲氧基-2,4,6,8-四甲氧基羰基-10、10a-苯并-9-oxa-10a-纯水合-10-en（6）和17％的已知3,7-二羟基-4,8,2β， 6β-四甲氧基羰基-9,10-苯并双环[3.3.2] dec-3,7,9-三烯（7）。水解和脱羧将四酯6（如针对7所述）转化为9,10-苯并双环[3.3.2] dec-9-en-3,7-二酮（9）。根据1 H-NMR测定的Spinsimulierung，参数为9派生出9 cc的扶手椅扶手椅合规性。
• Synthesis, GluN2B affinity and selectivity of benzo[7]annulen-7-amines
  作者：Sandeep Gawaskar、Dirk Schepmann、Alessandro Bonifazi、Bernhard Wünsch

  DOI：10.1016/j.bmc.2014.10.004

  日期：2014.12

  Due to their beneficial side effect profile, NMDA receptor antagonists interacting selectively with the allosteric ifenprodil binding site of the GluN2B subunit are of major interest for the treatment of neurological and neurodegenerative disorders. A series of benzo[7]annulen-7-amines 6 was designed by conformational restriction of ifenprodil (1). At first the benzo[7]annulen-7-one 11 was prepared in a three-step synthesis comprising of a double Knoevenagel condensation of phthalaldehyde (7) with dimethyl 3-oxoglutarate (8), hydrogenation of 9 and saponification/decarboxylation of 10. Reductive amination of the ketone 11 with primary amines and NaBH(OAc)(3) led to the secondary amines 6a-d, cis-6h and trans-6i. The tertiary amines 6e-g were obtained by S(N)2-substitution of the nosylate 13. Although H-bond forming substituents in 2- and 5-position are missing, the amines 6 exhibit high affinity towards GluN2B containing NMDA receptors. A distance of four to five bond lengths between the basic amino moiety and the phenyl ring in the side chain appears to be optimal for high GluN2B affinity. The phenylcyclohexylamine cis-6h and the 4-benzylpiperidine 6g show the highest GluN2B affinities (K-i = 2.3 nM and 2.9 nM, respectively). With respect to selectivity against the PCP binding site, sigma(1) and sigma(2) receptors the phenylpiperazine 6f is the most promising GluN2B antagonist. (C) 2014 Elsevier Ltd. All rights reserved.