6-(tert-butyl)-1,4,8-trimethylazulene | 98506-45-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 6-(tert-butyl)-1,4,8-trimethylazulene
• 英文别名: 6-Tert-butyl-1,4,8-trimethylazulene
• CAS: 98506-45-7
• 化学式: C₁₇H₂₂
• 分子量: 226.362
• InChiKey: CULILXUYBNYUTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  6-(tert-butyl)-1,4,8-trimethylazulene 在 sodium tetrahydroborate 、 三氟化硼乙醚 、 三氯氧磷 作用下， 以 乙醚 、 二乙二醇二甲醚 为溶剂， 生成 6-(tert-butyl)-1,3,4,8-tetramethylazulene
  参考文献：
  名称：

  高度烷基化的安祖烯与乙二甲酸二甲酯的热反应：HOMO（Azulene ）与SHOMO（Azulene）对照在主要热加成步骤中的反应

  摘要：

  在十氢化萘或四氢化萘乙炔二（ADM）高度烷基化的薁在180-200°的产率的反应，旁边的预期heptalene-和甘菊环-1,2-二羧酸酯，式的四环化合物的“反” - V和的三环化合物类型E（请参阅方案2-4和8-11）。'抗' -V型化合物代表主要的三环中间体A与ADM的Diels - Alder加合物。在某些情况下，E型三环化合物也经历了连续的Diels - Alder与ADM反应，得到类型“的四环化合物的抗‘ -或’ SYN ” - VI（参见方案2和8-11）。类型的三环化合物ë，即4和8，可逆地重新排列通过[1,5] -C转移到异构体的三环结构（CF。18和19，分别在方案6）已经在温度> 50℃。光化学4重排为对应的四环化合物20经由二π-甲烷反应。所观察到的heptalene-和甘菊环-1,2-二羧酸酯，以及“型的四环化合物的抗‘’ - V从初级三环中间体形成甲经由重排（he

  DOI：

  10.1002/hlca.19920750803

文献信息

• Light-Induced and Thermal π-Skeletal Rearrangement of Heptalenes with Retention of Configuration
  作者：Werner Bernhard、Paul Brügger、Peter Schönholzer、Roland H. Weber、Hans-Jürgen Hansen

  DOI：10.1002/hlca.19850680216

  日期：1985.3.27

  (tert-butyl)-5,6,10-trimethylheptalene-1, 2-dicarboxylate (5), and their derivatives rearrange reversibly on irradiation or on heating to yield the corresponding 1,6,8,10-tetramethyl- (4) and 8-(tert-butyl)-1,6,10-trimethylheptalene-1,2-dicarboxylate (6), and their derivatives by double-bond shift (π-skeletal rearrangement) via a transition state with D2 symmetry as the highest possible one. This follows

  结果表明，5、6、8、10-四甲基-二甲基（3）和8，（叔丁基）-5,6,10-三甲基庚二烯-1，2-二羧酸酯（5）及其衍生物在甲基上可逆地重排。辐射或加热产生相应的1,6,8,10-四甲基-（4）和8-（叔丁基）-1,6,10-三甲基庚二烯-1,2-二羧酸酯（6）及其衍生物通过双键移位（π-骨架重排）通过与过渡状态d 2对称性最高可能的一个。这是由于以下事实：（-）-（P）-3被光化学和热重排以得到（-）-（P）-4，即，在保持庚烯骨架的构型且不损失光学纯度的情况下，发生π-骨架重排。
• New Products from the Heptalene-Forming Reaction of Azulenes and Acetylenedicarboxylates in Polar Media
  作者：Gurmit Singh、Anthony Linden、Khaled Abou-Hadeed、Hans-Jürgen Hansen

  DOI：10.1002/1522-2675(200201)85:1<27::aid-hlca27>3.0.co;2-f

  日期：2002.1

  A number of azulenes; 1, in particular those with pi-substituents at C(6) such as phenyl, 3,5-dimethylphenyl, and 4-biphenyl, have been reacted with 3 mol-equiv. of dimethyl acetylenedicarboxylate (ADM) in MeCN at 110degrees (cf. Scheme 1). Main products had been, in all cases, the corresponding heptalene-4,5-dicarboxylates 2. However, a whole number of side products, mainly rearranged (1 + 2)-adducts with two molecules of ADM, in amounts of 0.2-9% were also isolated and characterized (cf. Scheme 2). The 2a,8a-dihydro-3,4-ethenoazulene-1,2-dicarboxylates 14, formed by energetically favorable ring closure from the solvent-stabilized zwitterions 15, resulting from bond heterolysis in the primary cycloadducts 12 (cf. Scheme 3), have been mechanistically identified as the pivotal intermediates responsible for the formation of all side product (cf. Schemes 5, 9, 12, and 13). Deuterium-labeling experiments were in agreement with the proposed mechanisms, indicating that si,gmatropic [1,5s]-H shifts in 14 (cf. Scheme 6) as well as isoconjugate [1,4s]-H shifts in resonance-stabilized zwitterions of type 21 (cf. Scheme 9) are the crucial steps for side-product formation. It is postulated that a concluding antarafacial 8e-dyotropic rearrangement is responsible for the appearance of the 2,4a-dihydrophenanthrene-tetracarboxylates of type trans-6 (cf. Scheme 9) in the reaction mixtures, which further rearrange thermally by a not fully understood mechanism into the isomeric tetracarboxylates 7 (cf. Schemes 10 and 11). Most surprising is the presence of a small amount (0.3-1%) of the azulene-4,5,7,8-tetracarboxylate 9 in the reaction mixture of azulene 1a and ADM. It is proposed that the formation of 9 is the result of a [1,5s]-C shift in the spiro-linked intermediates 24, which, after prototropic shift and take-up of a third molecule of ADM, disintegrate by a retro-Diels-Alder reaction into 9 and the phthalic diesters 30 (cf. Scheme 12). The UV/VIS spectra of the pi-substituted heptalene-4,5-dicarboxylates 2d-2f and their double-bond shifted (DBS) forms 2d-2f (cf Table 4 and Figs. 9-12) exhibit in comparison with the heptatene-dicarboxylates 2a and 2'a, carrying a t-Bu group at C(8), only marginal differences, which are mainly found in the relative intensity and position of heptatene bands II and III.