Diethyl 2-methoxyazulene-1,3-dicarboxylate | 969-52-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Diethyl 2-methoxyazulene-1,3-dicarboxylate
• 英文别名: 2-Methoxy-azulen-1,3-dicarbonsaeure-diethylester；diethyl 2-methoxyazulene-1,3-dicarboxylate
• CAS: 969-52-8
• 化学式: C₁₇H₁₈O₅
• 分子量: 302.327
• InChiKey: BRHMFCVINPGXDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Diethyl 2-methoxyazulene-1,3-dicarboxylate 在 氢氧化钾 、 乙醇 作用下， 生成 2-Methoxy-azulen-1,3-dicarbonsaeure-dimethylester
  参考文献：
  名称：

  The Synthesis of Diethyl 2-Hydroxyazulene-1, 3-dicarboxylate from Troponoids and Some Reactions of 2-Hydroxyazulene Derivatives

  摘要：

  DOI：

  10.1246/bcsj.37.1644
• 作为产物：
  描述：

  2-氯-2,4,6-环庚三烯-1-酮 在 sodium ethanolate 作用下， 生成 Diethyl 2-methoxyazulene-1,3-dicarboxylate
  参考文献：
  名称：

  The Synthesis of Diethyl 2-Hydroxyazulene-1, 3-dicarboxylate from Troponoids and Some Reactions of 2-Hydroxyazulene Derivatives

  摘要：

  DOI：

  10.1246/bcsj.37.1644

文献信息

• Reactions of diethyl azulene-1,3-dicarboxylate derivatives and 1-azaazulene derivatives with Grignard reagents, and alkyl- and aryllithium
  作者：Tadayoshi Morita、Noritaka Abe、Kahei Takase

  DOI：10.1039/b003078n

  日期：——

  Reactions of diethyl azulene-1,3-dicarboxylate (1) and diethyl 2-chloroazulene-1,3-dicarboxylate (11) with Grignard reagents, followed by dehydration with tetrachloro-1,2-benzoquinone, gave 2-, 4,- and 6-substituted addition–oxidation products. Grignards reagents have a tendency to react with 1 at the positions in the order of 2 > 4 > 6, while steric hindrance has a greater influence at the positions in order of 2 > 4 > 6. Reactions of 1 and 11 with phenyllithium and methyllithium gave similar results. On the other hand, on the reaction of diethyl 2-methoxyazulene-1,3-dicarboxylate (15), Grignard reagents attacked preferentially at the methoxy group, and 2-substituted products were obtained. Use of excess molar equivalents of Grignard reagents led to diaryl-substituted products. Reaction of 2-chloro-1-azaazulenes with Grignard reagents also gave similar addition–oxidation products, and reacted at the positions in the order 8 ≫ 4 > 6, whereas reaction of 2-methoxy-1-azaazulene with a Grignard reagent gave 1-azaazulen-2(1H)-one.

  二乙基azulene-1,3-二羧酸酯（1）和二乙基2-氯azulene-1,3-二羧酸酯（11）与格氏试剂反应，随后与四氯-1,2-苯并醌脱水，生成了2-、4-和6-取代的加成-氧化产物。格氏试剂倾向于按照2 > 4 > 6的顺序与1反应，而立体位阻在2 > 4 > 6的位置上有更大的影响。1和11与苯基锂和甲基锂的反应结果相似。另一方面，二乙基2-甲氧基azulene-1,3-二羧酸酯（15）的反应中，格氏试剂优先攻击甲氧基，得到2-取代产物。使用过量的格氏试剂会导致二芳基取代产物的形成。2-氯-1-氮杂azulenes与格氏试剂的反应也生成类似的加成-氧化产物，反应位置的顺序为8 ≫ 4 > 6，而2-甲氧基-1-氮杂azulene与格氏试剂的反应则生成1-氮杂azulen-2(1H)-酮。
• Impact of 2,6-connectivity in azulene: optical properties and stimuli responsive behavior
  作者：Michael Koch、Olivier Blacque、Koushik Venkatesan

  DOI：10.1039/c3tc31610f

  日期：——

  small donor acceptor molecule azulene as a core structure for potential optoelectronic applications has been evaluated. The synthesis and characterization of different isomers of di(phenylethynyl)azulene 1–4 have been successfully carried out. The photophysical properties as well as their stimuli responsive behavior reflecting their corresponding electronic properties were also investigated. The experimental

  已经评估了氧化还原活性，小的施主受体分子氮杂作为潜在光电应用的核心结构的可能。合成和二（苯基乙炔基）甘菊环的不同异构体的表征1-4已被成功地进行。还研究了光物理性质及其反映其相应电子性质的刺激响应行为。实验观察表明，2,6-连接（3）表现出强烈的发光，并显示出在酸处理后最强的刺激响应行为。DFT计算3 揭示了在氮杂烯的2和6位上炔取代基对基态和激发态的最大贡献，这使得在氮杂烯上的2，6-连接性成为低带隙共轭材料的非常有希望的候选者。
• Charge Transport and Conductance Switching of Redox‐Active Azulene Derivatives
  作者：Florian Schwarz、Michael Koch、Georg Kastlunger、Heinz Berke、Robert Stadler、Koushik Venkatesan、Emanuel Lörtscher

  DOI：10.1002/anie.201605559

  日期：2016.9.19

  evaluated. The conductance of the 1,3 Az derivative is at least one order of magnitude lower than those of the 2,6 Az and 4,7 Az derivatives, in agreement with density functional theory (DFT) calculations. In addition, only 1,3 Az exhibits pronounced nonlinear current–voltage characteristics with hysteresis, indicating a bias‐dependent conductance switching. DFT identifies the LUMO to be nearest to

  Azulene（Az）是一种非交替的芳香烃，由五元富电子和七元贫电子环组成；提供固有氧化还原活性的电子分布。通过改变两个桥接电极的取代基与Az中心的连接点，可以评估氧化还原功能对电荷传输的影响。与密度泛函理论（DFT）计算相一致，1,3 Az衍生物的电导比2,6 Az和4,7 Az衍生物的电导低至少一个数量级。此外，只有1,3 Az表现出明显的非线性电流-电压特性，并具有滞后现象，表明与偏置有关的电导率开关。DFT确定LUMO最接近电极的费米能，但仅在2,6和4,7 Az衍生物的情况下才是有效的传输通道，而1,3 Az衍生物在低偏压下使用HOMO而在高偏压下使用LUMO + 1。反过来，局域的，弱耦合的1,3 Az LUMO会由于占据单个分子轨道（MO）而产生一个缓慢的电子跳跃通道，该通道负责电压诱导的转换。
• The Synthesis of Diethyl 2-Hydroxyazulene-1, 3-dicarboxylate from Troponoids and Some Reactions of 2-Hydroxyazulene Derivatives
  作者：Tetsuo Nozoe、Kahei Takase、Noboru Shimazaki

  DOI：10.1246/bcsj.37.1644

  日期：1964.11