dimethyl 9,10-benzotricyclo<6.2.2.2.0^1,7>dodeca-2,4,6,9,11-pentaene-11,12-dicarboxylate | 153651-77-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: dimethyl 9,10-benzotricyclo<6.2.2.2.0^1,7>dodeca-2,4,6,9,11-pentaene-11,12-dicarboxylate
• 英文别名: dimethyl 4b,10-etheno-10H-benz[a]azulene-11,12-dicarboxylate
• CAS: 153651-77-5
• 化学式: C₂₀H₁₆O₄
• 分子量: 320.345
• InChiKey: DGLLGIRDHHBVTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  dimethyl 9,10-benzotricyclo<6.2.2.2.0^1,7>dodeca-2,4,6,9,11-pentaene-11,12-dicarboxylate 生成 dimethyl benzo[a]cyclopent[c,d]azulene-1,2-dicarboxylate
  参考文献：
  名称：

  二甲基-8,12-二苯基[合成和手性光学属性d ]庚搭烯-6,7-二羧酸二乙酯†

  摘要：

  在2摩尔％[RuH 2（PPh 3）4 ]的存在下，于100°在MeCN中使6,10-二苯基苯并[ a ] azulene（3）与乙酰二羧酸二甲酯（ADM）反应，得到7：1混合物2,6-二苯基-9,10-苯并三环[6.2.2.0 1,7 ] dodeca-2,4,6,9,11-戊烯-11,12-二羧酸酯（4）和二甲基8,12-二苯基苯甲酸酯的合成[ d ]庚二烯-6，7-二羧酸酯（5；方案2）。当在DMF中于150°加热1小时时，三轮车4导致形成81.5％的庚烯-6,7-二羧酸酯5和15％的起始氮杂3。。当在假异丙苯中将三轮车4加热到高达180°的温度时，未观察到三轮车4的重排。庚烯-6,7-二羧酸酯5在Chiracel色谱柱上很容易分离成其对映体（PM）和（MP）-5（参见图2）。在150°加热1小时后，（MP）-5完全没有消旋。苯并[ a ] azulene（6）与ADM的Ru催化反应导致形成二甲基9

  DOI：

  10.1002/hlca.19930760814
• 作为产物：
  描述：

  benzo[a]azulene 、 丁炔二酸二甲酯 在 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以15%的产率得到dimethyl 9,10-benzotricyclo<6.2.2.2.0^1,7>dodeca-2,4,6,9,11-pentaene-11,12-dicarboxylate
  参考文献：
  名称：

  二甲基-8,12-二苯基[合成和手性光学属性d ]庚搭烯-6,7-二羧酸二乙酯†

  摘要：

  在2摩尔％[RuH 2（PPh 3）4 ]的存在下，于100°在MeCN中使6,10-二苯基苯并[ a ] azulene（3）与乙酰二羧酸二甲酯（ADM）反应，得到7：1混合物2,6-二苯基-9,10-苯并三环[6.2.2.0 1,7 ] dodeca-2,4,6,9,11-戊烯-11,12-二羧酸酯（4）和二甲基8,12-二苯基苯甲酸酯的合成[ d ]庚二烯-6，7-二羧酸酯（5；方案2）。当在DMF中于150°加热1小时时，三轮车4导致形成81.5％的庚烯-6,7-二羧酸酯5和15％的起始氮杂3。。当在假异丙苯中将三轮车4加热到高达180°的温度时，未观察到三轮车4的重排。庚烯-6,7-二羧酸酯5在Chiracel色谱柱上很容易分离成其对映体（PM）和（MP）-5（参见图2）。在150°加热1小时后，（MP）-5完全没有消旋。苯并[ a ] azulene（6）与ADM的Ru催化反应导致形成二甲基9

  DOI：

  10.1002/hlca.19930760814

文献信息

• A Detailed Investigation of the Reaction of 5,9-Diphenylbenz[a]azulene with Dialkyl Acetylenedicarboxylates Leading to Dialkyl 8,12-Diphenylbenzo[a]heptalene-6,7-dicarboxylates
  作者：Anthony Linden、Markus Meyer、Peter Mohler、Andreas J. Rippert、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(19991215)82:12<2274::aid-hlca2274>3.0.co;2-9

  日期：1999.12.15

  The synthesis of 5,9-dipbenylbenz[a]azulene (1) from 1,3-diphenylcyclopent[a]indene-2,8-dione (4) and cyclopropene has been re-investigated. The reduction of the decarbonylated cycloadduct 5 with LiAlH4/AlCl3 in Et2O leads not only to the expected 7,10-dihydrobenz[a]azulene 6, but also to small amounts of the cyclopropa[b]fluorenes exo-7 and endo-7 (cf Scheme 2), the structures of which have been determined by X-ray crystal-structure analysis (cf. Fig. 1). The reaction of 1 with dialkyl acetylenedicarboxylates (ADR) in MeCN at 100 degrees in the presence of 2 mol-% of catalysts such as [RuH2(PPh3)(4)] results mainly in the formation of the expected 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylates 3. A thorough investigation of the reaction mixture of 1 and dimethyl acetylenedicarboxylate (ADM) revealed the presence of a number of intermediates and side products (Scheme 5). Most important was the isolation and identification of the cyclobutene intermediate 9a (cf. Fig. 4), which is formed by a zwitterionic rearrangement of the primary adduct 2a of 1 and ADM and represents the direct precursor of the heptalene-diester 3a. Compounds of type 9a have so far only been postulated as necessary intermediates in the thermal reaction of azulenes and ADR to give corresponding heptalenedicarboxylates. Compound 9a is photochemically unstable and undergoes rearrangement even under the influence of normal laboratory light into a mixture of trans-10a and cis-10a (Scheme 8). Both diastereoisomers are also found in the original reaction mixture of 1 and ADM, but not when the reaction is performed under exclusion of light. On heating in MeCN at 100 degrees, or better in DMF at 150 degrees, trans-10a and cis-10a undergo rearrangement to the fluoranthene-1,2-dicarboxylate 11a (Scheme 9), which is also present in the original reaction mixture of 1 and ADM. The catalysts do not accelerate the reaction of 1 and ADR, but they lead to better yields of the benzo[a]heptalene-6,7-dicarboxylates 3, especially in the reaction of 1 with diisopropyl acetylenedicarboxylate (ADiP) (cf. Tables 1 and 2).