dimethyl 9-methyl-6-[(E,E)-4-phenylbuta-1,3-dienyl]heptalene-4,5-dicarboxylate | 253778-63-1

• 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: dimethyl 9-methyl-6-[(E,E)-4-phenylbuta-1,3-dienyl]heptalene-4,5-dicarboxylate
• 英文别名: dimethyl 7-methyl-10-[(1E,3E)-4-phenylbuta-1,3-dienyl]heptalene-1,2-dicarboxylate
• CAS: 253778-63-1
• 化学式: C₂₇H₂₄O₄
• 分子量: 412.485
• InChiKey: AERQALXUCNUYKE-INOXDZRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 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 9-methyl-6-[(E,E)-4-phenylbuta-1,3-dienyl]heptalene-4,5-dicarboxylate 在 sodium hydroxide 、 selenium(IV) oxide 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 17.0h， 生成 dimethyl 6,9-bis[(1E,3E)-4-phenylbuta-1,3-dienyl]heptalene-4,5-dicarboxylate
  参考文献：
  名称：

  New Syntheses of Di-π-Substituted Heptalenes

  摘要：

  To study the effect of double-bond shifts (DBS) in different type of heptalenes linked to extended pi- systems, several di-pi-substituted heptalenes were synthesized. 6-[(E)-Styryl]heptalene-dicarboxylate 4 was smoothly converted to 1-(chloromethyl)heptalene-dicarboxylate 5 by treatment with t-BuOK and C2Cl6 in THF at -78 degrees. The one-pot reaction of 5 and P(OEt)(3) in the presence of NaI, followed by Wittig-Horner reaction, afforded the 1,6-di-pi-substitute heptalene 6. The reaction of 6-[(1E,3E)-4-phenylbuta-1,3-dienyl]heptalenes 7 or 15 with t-BuOK and benzaldehyde in THF led to the formation of the 1,6-di-pi-substituted heptalenes 13 or 16, together with transesterification products 14 or 17. The transformation of the MeOCO group at C(4) of 6-[(E)-styryl]heptalene-dicarboxylate 4 to a phenylbuta-1,3-dienyl substituent afforded the 3,6-di-pi-substituted heptalene 21a, which is in thermal equilibrium with its DBS isomer 21b in solution. Oxidation of heptalene 22 with SeO2 in dioxane gave carbaldehyde 23, which was then subjected to a Wittig reaction to give the 6,9-di-pi-substituted heptalene-dicarboxylate 24.

  DOI：

  10.1002/(sici)1522-2675(19991215)82:12<2260::aid-hlca2260>3.0.co;2-z
• 作为产物：
  描述：

  4,7-dimethylazulene 在 三氟化硼乙醚 chromium dichloride 、 palladium diacetate 、 sodium hexamethyldisilazane 、 silver carbonate 、 mercury(II) oxide 作用下， 以 四氢呋喃 、 乙醚 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 33.0h， 生成 dimethyl 9-methyl-6-[(E,E)-4-phenylbuta-1,3-dienyl]heptalene-4,5-dicarboxylate
  参考文献：
  名称：

  Synthesis of 6-Styrylheptalenes

  摘要：

  4-Methylazulenes 3, 15, and 23 were transformed into 4-[(methylthio)methyl]azulene 4, and azulene-4-carbaldehyde dimethyl dithioacetals 16 and 24, respectively. Vilsmeier formylation of 4 and 16, and subsequent reduction led to the I-methyl derivatives 6 and 18, respectively. The thermal reaction of azulenes 6, 18, and 24 with dimethyl acetylenedicarboxylate (ADM) in toluene afforded heptalenes with a (methylthio)methyl group or a [bis(methylthio)]methyl group at C(6). Chlorination of [(methylthio)methyl]heptalene 7, followed by treatment with HgO and BF3. OEt2 in aqueous tetrahydrofuran (THF), led to 6-formylheptalene-dicarboxylate 12 in excellent yield. Similarly. hydrolysis of 18 and 24 by HgO and BF3. OEt2 in aqueous THF afforded the 6-formyl derivatives 21 and 27, respectively. Wittig reaction of the 6-formyl-substituted heptalenes and phosphonium salts 13a-e in the two-phase system CH2CI2/2N aqueous NaOH resulted in the formation of 6-styryl-substituted heptalenes.

  DOI：

  10.1002/(sici)1522-2675(19991006)82:10<1690::aid-hlca1690>3.0.co;2-d

文献信息

• Synthesis of 6-Styrylheptalenes
  作者：Jianfeng Song、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(19991006)82:10<1690::aid-hlca1690>3.0.co;2-d

  日期：1999.10.6

  4-Methylazulenes 3, 15, and 23 were transformed into 4-[(methylthio)methyl]azulene 4, and azulene-4-carbaldehyde dimethyl dithioacetals 16 and 24, respectively. Vilsmeier formylation of 4 and 16, and subsequent reduction led to the I-methyl derivatives 6 and 18, respectively. The thermal reaction of azulenes 6, 18, and 24 with dimethyl acetylenedicarboxylate (ADM) in toluene afforded heptalenes with a (methylthio)methyl group or a [bis(methylthio)]methyl group at C(6). Chlorination of [(methylthio)methyl]heptalene 7, followed by treatment with HgO and BF3. OEt2 in aqueous tetrahydrofuran (THF), led to 6-formylheptalene-dicarboxylate 12 in excellent yield. Similarly. hydrolysis of 18 and 24 by HgO and BF3. OEt2 in aqueous THF afforded the 6-formyl derivatives 21 and 27, respectively. Wittig reaction of the 6-formyl-substituted heptalenes and phosphonium salts 13a-e in the two-phase system CH2CI2/2N aqueous NaOH resulted in the formation of 6-styryl-substituted heptalenes.
• New Syntheses of Di-π-Substituted Heptalenes
  作者：Jianfeng Song、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(19991215)82:12<2260::aid-hlca2260>3.0.co;2-z

  日期：1999.12.15

  To study the effect of double-bond shifts (DBS) in different type of heptalenes linked to extended pi- systems, several di-pi-substituted heptalenes were synthesized. 6-[(E)-Styryl]heptalene-dicarboxylate 4 was smoothly converted to 1-(chloromethyl)heptalene-dicarboxylate 5 by treatment with t-BuOK and C2Cl6 in THF at -78 degrees. The one-pot reaction of 5 and P(OEt)(3) in the presence of NaI, followed by Wittig-Horner reaction, afforded the 1,6-di-pi-substitute heptalene 6. The reaction of 6-[(1E,3E)-4-phenylbuta-1,3-dienyl]heptalenes 7 or 15 with t-BuOK and benzaldehyde in THF led to the formation of the 1,6-di-pi-substituted heptalenes 13 or 16, together with transesterification products 14 or 17. The transformation of the MeOCO group at C(4) of 6-[(E)-styryl]heptalene-dicarboxylate 4 to a phenylbuta-1,3-dienyl substituent afforded the 3,6-di-pi-substituted heptalene 21a, which is in thermal equilibrium with its DBS isomer 21b in solution. Oxidation of heptalene 22 with SeO2 in dioxane gave carbaldehyde 23, which was then subjected to a Wittig reaction to give the 6,9-di-pi-substituted heptalene-dicarboxylate 24.