dimethyl 8-(tert-butyl)-1,6,10-trimethylheptalene-4,5-dicarboxylate | 98506-44-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 8-(tert-butyl)-1,6,10-trimethylheptalene-4,5-dicarboxylate
• 英文别名: dimethyl 8-(tert-butyl)-5,6,10-trimethylheptalene-1,2-dicarboxylate；Dimethyl 8-tert-butyl-5,6,10-trimethylheptalene-1,2-dicarboxylate
• CAS: 98506-44-6
• 化学式: C₂₃H₂₈O₄
• 分子量: 368.473
• InChiKey: LKOAMBUFXYHGED-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl 8-(tert-butyl)-1,6,10-trimethylheptalene-4,5-dicarboxylate 在 氢氧化钾 作用下， 以 乙醇 、 水 为溶剂， 反应 4.0h， 以95%的产率得到13-(tert-butyl)-1-(methoxycarbonyl)-9,11,15-trimethylheptalene-2-carboxylic acid
  参考文献：
  名称：

  庚二烯-1,2-二羧酸环状'邻'酸酐的形成

  摘要：

  1-（烷氧羰基）庚二烯-2-羧酸以及2-（烷氧基羰基）庚二烯-1-羧酸在醇存在下与由N，N-二甲基甲酰胺（DMF）和草酰氯形成的亚胺盐反应，得到相应的环状“邻”-酸酐（ψ-酯；参见方案2、3、6和8）。当酸和醇的烷氧基部分不同时，由于庚烯骨架的非平面性，形成非对映异构的“邻”-酸酐。强烈建议从β侧使用醇（参见方案5和表1））。该效应可以归因于庚烯骨架的弯曲拓扑，其在空间上阻碍亲核试剂从假定的中间体，即19型带电荷的O-烷基化的酸酐的α-侧接近（参见方案6）。而“邻位‘-anhydrides与在‘围’的庚搭烯骨架的位上四个取代基是结构稳定达100°时，’邻位” -anhydrides只有三个“围” -取代基差向异构化缓慢，在100℃（CF方案7）归因于庚烯骨架的构型的热诱导反转。

  DOI：

  10.1002/hlca.19870700602
• 作为产物：
  描述：

  6-(tert-butyl)-1,4,8-trimethylazulene 、 丁炔二酸二甲酯 以 萘烷 为溶剂， 反应 1.67h， 生成 tetramethyl (1RS,2RS,5RS,8RS)-13-(tert-butyl)-2,6,8-trimethyltetracyclo<6.2.2.2^2.50^1.7>tetradeca-3,6,9,11,13-pentaene-3,4,9,10-tetracarboxylate 、 dimethyl 6-(tert-butyl)-4,8-dimethylazulene-1,2-dicarboxylate 、 dimethyl 8-(tert-butyl)-1,6,10-trimethylheptalene-4,5-dicarboxylate
  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.
• Thermal Reaction of Highly Alkylated Azulenes with Dimethyl Acetylenedicarboxylate: HOMO(Azulene)vs. SHOMO(Azulene) Control in the Primary Thermal Addition Step
  作者：Yi Chen、Roland W. Kunz、Peter Uebelhart、Roland H. Weber、Hans-J�Rgen Hansen

  DOI：10.1002/hlca.19920750803

  日期：1992.12.16

  substituents. However, the main reaction channel of A is its retro-Diels-Alder reaction to the starting materials (azulene and ADM). The highly reversible Diels-Alder reaction of ADM to the five-membered ring of the azulenes is HOMO(azulene)/LUMO(ADM)-controlled, in contrast to the at 200° irreversible ADM addition to the seven-membered ring of the azulenes to yield the Diels-Alder products of type

  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
• Formation of Cyclic ‘<i>ortho</i>’-Anhydrides of Heptalene-1,2-dicarboxylic Acids
  作者：Roland H. Weber、Paul Brügger、Wolf Arnold、Peter Schönholzer、Hans-Jürgen Hansen

  DOI：10.1002/hlca.19870700602

  日期：1987.9.23

  oxylic acids as well as 2-(alkoxycarbonyl)heptalene-1-carboxylic acids react with the iminium salt formed from N,N-dimethylformamide (DMF) and oxalyl chloride, in the presence of an alcohol, to yield the corresponding cyclic ‘ortho’ -anhydrides (ψ-esters; cf. Schemes 2,3,6, and 8). When the alkoxy moiety of the acids and the alcohols is different, then diastereoisomeric ‘ortho’ -anhydrides are formed

  1-（烷氧羰基）庚二烯-2-羧酸以及2-（烷氧基羰基）庚二烯-1-羧酸在醇存在下与由N，N-二甲基甲酰胺（DMF）和草酰氯形成的亚胺盐反应，得到相应的环状“邻”-酸酐（ψ-酯；参见方案2、3、6和8）。当酸和醇的烷氧基部分不同时，由于庚烯骨架的非平面性，形成非对映异构的“邻”-酸酐。强烈建议从β侧使用醇（参见方案5和表1））。该效应可以归因于庚烯骨架的弯曲拓扑，其在空间上阻碍亲核试剂从假定的中间体，即19型带电荷的O-烷基化的酸酐的α-侧接近（参见方案6）。而“邻位‘-anhydrides与在‘围’的庚搭烯骨架的位上四个取代基是结构稳定达100°时，’邻位” -anhydrides只有三个“围” -取代基差向异构化缓慢，在100℃（CF方案7）归因于庚烯骨架的构型的热诱导反转。