4,8-dimethyl-6-phenylazulene | 42758-88-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 4,8-dimethyl-6-phenylazulene
• 英文别名: 4,8-dimethyl-6-phenyl-azulene；4,8-Dimethyl-6-phenyl-azulen
• CAS: 42758-88-3
• 化学式: C₁₈H₁₆
• 分子量: 232.325
• InChiKey: VZINPMRSBOEDPV-UHFFFAOYSA-N

物化性质

• 沸点：
  379.1±22.0 °C(Predicted)
• 密度：
  1.049±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  4,8-dimethyl-6-phenylazulene 在 sodium tetrahydroborate 作用下， 以 二氯甲烷 、 三氟乙酸 为溶剂， 生成 1,4,8-trimethyl-6-phenylazulene
  参考文献：
  名称：

  New Products from the Heptalene-Forming Reaction of Azulenes and Acetylenedicarboxylates in Polar Media

  摘要：

  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.

  DOI：

  10.1002/1522-2675(200201)85:1<27::aid-hlca27>3.0.co;2-f
• 作为产物：
  描述：

  2,6-dimethyl-4-phenyl-pyrylium; perchlorate 在 四氢呋喃 、 Sodium cyclopentadienide 作用下， 生成 4,8-dimethyl-6-phenylazulene
  参考文献：
  名称：

  Hafner; Kaiser, Justus Liebigs Annalen der Chemie, 1958, vol. 618, p. 140,148

  摘要：

  DOI：

文献信息

• Hafner,K.; Schneider,G., Justus Liebigs Annalen der Chemie, 1964, vol. 672, p. 194 - 214
  作者：Hafner,K.、Schneider,G.

  DOI：——

  日期：——
• Hafner,K. et al., Justus Liebigs Annalen der Chemie, 1961, vol. 650, p. 35 - 41
  作者：Hafner,K. et al.

  DOI：——

  日期：——
• Hafner,K.; Moritz,K.L., Angewandte Chemie, 1960, vol. 72, p. 918
  作者：Hafner,K.、Moritz,K.L.

  DOI：——

  日期：——
• Hafner; Kaiser, Justus Liebigs Annalen der Chemie, 1958, vol. 618, p. 140,148
  作者：Hafner、Kaiser

  DOI：——

  日期：——
• 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.