2,4-Bis(ethoxycarbonyl)-5,6,7,8-tetrahydropyrido<2,3-d>pyrimidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶并嘧啶类
• 英文名称: 2,4-Bis(ethoxycarbonyl)-5,6,7,8-tetrahydropyrido<2,3-d>pyrimidine
• 英文别名: Diethyl 5,6,7,8-tetrahydropyrido[2,3-d]pyrimidine-2,4-dicarboxylate
• 化学式: C₁₃H₁₇N₃O₄
• 分子量: 279.296
• InChiKey: HFNCFXSKHLJVJP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  90.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  1,3,5-三嗪-2,4,6-三甲酸三乙酯 、 2-亚氨基哌啶盐酸盐 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以75%的产率得到2,4-Bis(ethoxycarbonyl)-5,6,7,8-tetrahydropyrido<2,3-d>pyrimidine
  参考文献：
  名称：

  Inverse Electron Demand Diels-Alder Reactions of Heterocyclic Azadienes: [4 + 2] Cycloaddition Reaction of Amidines with 1,3,5-Triazines

  摘要：

  A detailed study of the scope of the amidine Diels-Alder reaction with 1,3,5-triazines is described. The thermal reaction of amidines with symmetrical 1,3,5-triazines proceeds with in situ amidine to 1,1-diaminoethene tautomerization, [4 + 2] cycloaddition with the 1,3,5-triazine, loss of ammonia from the initial Diels-Alder adduct with imine generation, imine to enamine tautomerization, and retro Diels-Alder loss of ethyl cyanoformate to provide substituted 4-aminopyrimidines in excellent conversions. The reaction proceeds best with the amidine hydrochloride salts at intermediate reaction temperatures (90-100 degrees C) in polar, aprotic solvents, is rather invariant to the ratio of dienophile-diene used (1:2 congruent to 1:1 congruent to 2:1), and is subject to triazine substitutent effects characteristic of an inverse electron demand Diels-Alder reaction (R = CO(2)Et > R = H >> R = SCH3). Notably, the generality of the amidine [4 + 2] cycloaddition reaction with 1,3,5-triazines which has been extended to include cyclic amidines effectively addresses the limitations of the alternative ynamine or N,O-ketene acetal dienophiles. A comparative examination of amidines, thioimidates, and imidates revealed that amidines are uniquely suited for use in this reaction cascade.

  DOI：

  10.1021/jo00096a044

文献信息

• Inverse Electron Demand Diels-Alder Reactions of Heterocyclic Azadienes: [4 + 2] Cycloaddition Reaction of Amidines with 1,3,5-Triazines
  作者：Dale L. Boger、Monica J. Kochanny

  DOI：10.1021/jo00096a044

  日期：1994.8

  A detailed study of the scope of the amidine Diels-Alder reaction with 1,3,5-triazines is described. The thermal reaction of amidines with symmetrical 1,3,5-triazines proceeds with in situ amidine to 1,1-diaminoethene tautomerization, [4 + 2] cycloaddition with the 1,3,5-triazine, loss of ammonia from the initial Diels-Alder adduct with imine generation, imine to enamine tautomerization, and retro Diels-Alder loss of ethyl cyanoformate to provide substituted 4-aminopyrimidines in excellent conversions. The reaction proceeds best with the amidine hydrochloride salts at intermediate reaction temperatures (90-100 degrees C) in polar, aprotic solvents, is rather invariant to the ratio of dienophile-diene used (1:2 congruent to 1:1 congruent to 2:1), and is subject to triazine substitutent effects characteristic of an inverse electron demand Diels-Alder reaction (R = CO(2)Et > R = H >> R = SCH3). Notably, the generality of the amidine [4 + 2] cycloaddition reaction with 1,3,5-triazines which has been extended to include cyclic amidines effectively addresses the limitations of the alternative ynamine or N,O-ketene acetal dienophiles. A comparative examination of amidines, thioimidates, and imidates revealed that amidines are uniquely suited for use in this reaction cascade.