dimethyl 3,4-dihydrocyclopentazulene-1,2-dicarboxylate | 58150-96-2

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: dimethyl 3,4-dihydrocyclopentazulene-1,2-dicarboxylate
• 英文别名: dimethyl 1,2-dihydrocyclopentazulene-3,4-dicarboxylate；3.4-Dihydro-1.2-cyclopent azulen-dicarbonsaeuredimethylester；3.4-Dihydro-1.2-cyclopent (cd) azulen-dicarbonsaeuredimethylester；Dimethyl tricyclo[5.4.1.04,12]dodeca-1(11),2,4(12),7,9-pentaene-2,3-dicarboxylate
• CAS: 58150-96-2
• 化学式: C₁₆H₁₄O₄
• 分子量: 270.285
• InChiKey: UYUDPJFETYCZHA-UHFFFAOYSA-N

物化性质

• 沸点：
  424.9±45.0 °C(Predicted)
• 密度：
  1.282±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  丁炔二酸二甲酯 、 奥苷菊环 在 三氟乙酸 作用下， 以 1,2,3,4-四氢萘 为溶剂， 生成 dimethyl 3,4-dihydrocyclopentazulene-1,2-dicarboxylate
  参考文献：
  名称：

  Hafner,K. et al., Angewandte Chemie, 1976, vol. 88, p. 121 - 123

  摘要：

  DOI：

文献信息

• Ru-Catalyzed Heptalene Formation from Azulenes and Dimethyl Acetylenedicarboxylate
  作者：Andreas Johannes Rippert、Hans-J�rgen Hansen

  DOI：10.1002/hlca.19920750707

  日期：1992.11.11

  It is shown that azulenes react with dimethyl acetylenedicarboxylate (ADM) in solvents such as toluene, dioxan, or MeCN in the presence of 2 mol-% [RuH2(PPh3)4] already at temperatures as low as 100° and lead to the formation of the corresponding heptalene-1,2-dicarboxylates in excellent yields (Tables 1 and 2). The Ru-catalyzed reaction of ADM with 1-(tert-butyl)-4,6,8-trimethylazulene (31) takes

  结果表明，在2 mol％[RuH 2（PPh 3）4 ]的存在下，天青石已经在溶剂（如甲苯，二恶烷或MeCN中）与乙二甲基二羧酸二甲酯（ADM）反应，而该温度已低至100°C，并导致形成相应的庚烯1,2-二羧酸庚酯的产率很高（表1和2）。ADM与1-（的钌催化反应叔丁基）-4,6,8-trimethylazulene（31）发生即使在室温下，得到初级三环加成产物32和其热复古-狄尔斯-阿尔德产物4,6,8-三甲基az-1,2-二羧酸二甲酯（21；方案4）。在MeCN中100°时，32的产率为90％的21，而只有10％的相应的庚烯。这些观察结果表明，[RuH 2（PPh 3）4 ]催化了从天青石和ADM热形成庚烷的第一步，该第一步发生在非极性溶剂（例如，四氢化萘或十氢化萘中），温度> 180°（参见方案1）。
• Formation of Unusual Products from the Acid-Catalyzed Reaction of Azulenes with Dimethyl Acetylenedicarboxylate
  作者：Paul Brügger、Peter Uebelhart、Roland W. Kunz、Rolf Sigrist、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(19981216)81:12<2201::aid-hlca2201>3.0.co;2-7

  日期：1998.12.16

  The reaction of guaiazulene (4) and dimethyl acetylenedicarboxylate (ADM) in tetralin or toluene, catalyzed by 5 mol-% of trifluoroacetic acid (TFA) at ambient temperature, leads to the formation of the corresponding heptalene-4,5-dicarboxylate 6 and a guaiazulenyl-substituted 2,2a,4a,8b-tetrahydrocyclopent[cd]azulene derivative 7 beside the expected guaiazulenyl-substituted ethenedicarboxylates (E)-5 and (2)-5 as main products (Scheme 2). The structure of 7 was unequivocally established by an X-ray crystal-structure analysis ( Fig. I). Precursor of 7 must be the 2a,4a-dihydrocyclopent[cd]azulene-3,4-dicarboxylate 9 which reacts, under TFA catalysis, with a second molecule of 4 (Scheme 3). No formation of products of type 7 has been observed in the TFA-catalyzed reaction of 4,6,8-trimethyl- and 1,4,6,8-tetramethylazulene (13 and 16, respectively) and ADM (Scheme 4). On the other hand, the TFA-catalyzed reaction of azulene (18) itself and ADM at ambient temperature gives rise to a whole variety of new products (Scheme 5), the major part of which is derived from dimethyl 2a,4a-dihydrocyclopent[cd]azulene 3,4-dicarboxylate (25) as the main intermediate (Scheme 6). Nevertheless, for the formation of the 2a,4a,6,8b-tetrahydrocyclobut[a]azulene derivatives (E)-24a and (E)-24b, a corresponding 2a,8b-dihydro precursor 29 has to be postulated as crucial intermediate (Scheme 8).
• Hafner,K. et al., Angewandte Chemie, 1976, vol. 88, p. 121 - 123
  作者：Hafner,K. et al.

  DOI：——

  日期：——