dimethyl (Z)-1-(4,6,8-trimethylazulen-3-yl)ethene-1,2-dicarboxylate | 58151-00-1

• 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 (Z)-1-(4,6,8-trimethylazulen-3-yl)ethene-1,2-dicarboxylate
• 英文别名: (4.6.8-Trimethyl-1-azulenyl)-maleinsaeuredimethylester；dimethyl (Z)-2-(4,6,8-trimethylazulen-1-yl)but-2-enedioate
• CAS: 58151-00-1
• 化学式: C₁₉H₂₀O₄
• 分子量: 312.365
• InChiKey: WCAFWSBCSAHUHV-YBEGLDIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  23.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  4,6,8-三甲基甘菊蓝 、 丁炔二酸二甲酯 在 三氟乙酸 作用下， 生成 dimethyl (Z)-1-(4,6,8-trimethylazulen-3-yl)ethene-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

• 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).