3-Methyl-cyclohexa-1,4-diene-1,3-dicarboxylic acid dimethyl ester | 131249-98-4

• 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: 3-Methyl-cyclohexa-1,4-diene-1,3-dicarboxylic acid dimethyl ester
• 英文别名: Dimethyl 3-methylcyclohexa-1,4-diene-1,3-dicarboxylate
• CAS: 131249-98-4
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: ROHHDBBUZFCPJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  3-Methyl-cyclohexa-1,4-diene-1,3-dicarboxylic acid dimethyl ester 在 叔丁基过氧化氢 、 重铬酸吡啶 、 Celite 作用下， 以 苯 为溶剂， 反应 22.0h， 以29%的产率得到Dimethyl 3-methyl-6-oxocyclohexa-1,4-diene-1,3-dicarboxylate
  参考文献：
  名称：

  Photochemical and acid-catalyzed dienone-phenol rearrangements. The effect of substituents on the regioselectivity of 1,4-sigmatropic rearrangements of the type A intermediate

  摘要：

  Birch reduction of isophthalic acid and 3-cyanobenzoic acid followed by (1) methylation of the resulting enolate with methyl iodide and (2) esterification with diazomethane provided 2-carbomethoxy- and 2-cyano-6-methyl-6-carbomethoxy-1,4-cyclohexadienes 9 and 25. Type A photorearrangements of a series of 2-carbomethoxy-, 2-cyano-, 2-methoxy-, and 2-methyl-4-carbomethoxy-4-methyl-2,5-cyclohexadien-1-ones 11, 26, 45a, and 45b gave 4-carbomethoxy-3-methyl-2-substituted-phenols 12, 28, 46, and 31. It has been demonstrated that the regioselectivity of type A photorearrangement of C(2) substituted 2,5-cyclohexadien-1-ones is governed by electronic rather than steric effects to give the intermediate C(1) rather than C(3) substituted bicyclo [3.1.0(1,5)]hex-3-en-2-ones. Regioselectivities of the acid-catalyzed dienone-phenol rearrangements of C(2) substituted 2,5-cyclohexadienones 11, 45a, and 45b appear to be dependent upon the relative stabilities of carbocations resulting from migration of the C(4) carbomethoxy group.

  DOI：

  10.1021/jo00003a037
• 作为产物：
  描述：

  Dilithium isophthalate 、 四氢呋喃 、 碘甲烷 生成 3-Methyl-cyclohexa-1,4-diene-1,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  SCHULTZ, ARTHUR G.;HARDINGER, STEVEN A., J. ORG. CHEM., 56,(1991) N, C. 1105-1111

  摘要：

  DOI：

文献信息

• Synthesis of 2,5- and 2,4-Cyclohexadiene-1,3-dicarboxylates via Reductive Alkylation of Isophthalates
  作者：Pierfausto Seneci、Marco Caspani、Federica Monti、Lucia Carrano、Sergio Lociuro、Romeo Ciabatti

  DOI：10.1080/00397919708004199

  日期：1997.3

  Abstract Substituted 2,5-(structure 1) and 2,4-(structure 2) cyclohexadiene-1,3-dicarboxylates were prepared via Birch reductive alkylation of substituted isophthalates with alkylating agents such as alkyl and allyl halides, allkyl dihalides, α-halocarboxylates and epoxides. A brief discussion about their reactivity and stability is presented.

  摘要 取代的 2,5-（结构 1）和 2,4-（结构 2）环己二烯-1,3-二羧酸酯是通过取代间苯二甲酸酯的 Birch 还原烷基化与烷基化剂如烷基和烯丙基卤化物、烷基二卤化物、α-卤代羧酸盐和环氧化物。简要讨论了它们的反应性和稳定性。
• Allylic Functionalization of 2,5- and 2,4-Cyclo-Hexadiene-1,3-Dicarboxylates
  作者：Pierfausto Seneci §、Marco Caspani、Federica Monti $、Lucia Carrano、Sergio Lociuro §

  DOI：10.1080/00397919808007186

  日期：1998.6

  of 2,4- and 2,5-cyclohexadiene-1,3-dicarboxylates were functionalized at the allylic position via oxidation (SeO2, PDC/t-BuOOH) and halogenation (NBS). The regiochemical outcome for different substrates and reactions was studied and the importance of factors such as reaction mechanism, steric hindrance and reaction intermediates stability was discussed. §Present address: GlaxoWellcomc Medicines Research

  摘要 通过氧化 (SeO2, PDC/t-BuOOH) 和卤化 (NBS) 在烯丙基位置将一系列 2,4- 和 2,5- 环己二烯-1,3-二羧酸酯官能化。研究了不同底物和反应的区域化学结果，并讨论了反应机理、位阻和反应中间体稳定性等因素的重要性。§当前地址：GlaxoWellcomc Medicines Research Centre, Via Fleming 4, Verona, Italy $当前地址：Hoechst Marion Roussel, Paris, France
• SCHULTZ, ARTHUR G.;HARDINGER, STEVEN A., J. ORG. CHEM., 56,(1991) N, C. 1105-1111
  作者：SCHULTZ, ARTHUR G.、HARDINGER, STEVEN A.

  DOI：——

  日期：——
• Photochemical and acid-catalyzed dienone-phenol rearrangements. The effect of substituents on the regioselectivity of 1,4-sigmatropic rearrangements of the type A intermediate
  作者：Arthur G. Schultz、Steven A. Hardinger

  DOI：10.1021/jo00003a037

  日期：1991.2

  Birch reduction of isophthalic acid and 3-cyanobenzoic acid followed by (1) methylation of the resulting enolate with methyl iodide and (2) esterification with diazomethane provided 2-carbomethoxy- and 2-cyano-6-methyl-6-carbomethoxy-1,4-cyclohexadienes 9 and 25. Type A photorearrangements of a series of 2-carbomethoxy-, 2-cyano-, 2-methoxy-, and 2-methyl-4-carbomethoxy-4-methyl-2,5-cyclohexadien-1-ones 11, 26, 45a, and 45b gave 4-carbomethoxy-3-methyl-2-substituted-phenols 12, 28, 46, and 31. It has been demonstrated that the regioselectivity of type A photorearrangement of C(2) substituted 2,5-cyclohexadien-1-ones is governed by electronic rather than steric effects to give the intermediate C(1) rather than C(3) substituted bicyclo [3.1.0(1,5)]hex-3-en-2-ones. Regioselectivities of the acid-catalyzed dienone-phenol rearrangements of C(2) substituted 2,5-cyclohexadienones 11, 45a, and 45b appear to be dependent upon the relative stabilities of carbocations resulting from migration of the C(4) carbomethoxy group.