2-丙炔-1-基2-嘧啶羧酸酯 | 139584-77-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 中文名称: 2-丙炔-1-基2-嘧啶羧酸酯
• 英文名称: 2-<(prop-2-ynyloxy)carbonyl>pyrimidine
• 英文别名: Prop-2-yn-1-yl pyrimidine-2-carboxylate；prop-2-ynyl pyrimidine-2-carboxylate
• CAS: 139584-77-3
• 化学式: C₈H₆N₂O₂
• 分子量: 162.148
• InChiKey: UCQYFZMONOQHJC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  52.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-丙炔-1-基2-嘧啶羧酸酯 以 硝基苯 为溶剂， 反应 24.0h， 以80%的产率得到呋喃并[3,4-b]吡啶-5(7H)-酮
  参考文献：
  名称：

  Intramolecular Diels-Alder reactions of pyrimidines and a computational study toward their structure and reactivity

  摘要：

  The syntheses of 2-[(prop-2-ynyloxy)carbonyl]pyrimidine (1), 5-[(prop-2-ynyloxy)carbonyl]pyrimidine (2), 5-phenyl-2-[2-(1-prop-2-ynylpyrryl)]pyrimidine (8),5-phenyl-2-[2-(1-prop-2-ynylpyrrolidinyl)]pyrimidine (9) and 2-[2-(prop-2-ynyloxy)phenyl]-4,6-R2-5-R1-pyrimidine (R1 = H, Cl, Ph; R2 = H, Me) (14a-d) are described. Upon heating, the compounds 1, 9, and 14 undergo an intramolecular Diels-Alder reaction and a subsequent retro Diels-Alder reaction to yield the annelated pyridines 15, 16, and 17, respectively. The compounds 2 and 8 did not react. The nonreactivity of the compounds 2 and 8 is ascribed to conjugation of the pyrimidine aromatic system with part of the dienophilic side chain, giving rise to conformations in which the diene and dienophile moieties cannot interact. For the compounds 1, 9, and 14 conjugation is absent, due to steric hindrance. To support this, semiempirical (MDNO-PM3) and molecular mechanics (MMX, CHEMX) calculations were performed. The HOMO-LUMO energy separation of the compounds did not consequently reflect the observed reactivity. However, the probability of the compounds to be in a reactive conformation appeared to correlate with the observed rate of reaction (9 > 14a > 1 >> 2, 8).

  DOI：

  10.1021/jo00037a011
• 作为产物：
  描述：

  2-氰基嘧啶 、 2-丙炔-1-醇 在 盐酸 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以4.5%的产率得到2-丙炔-1-基2-嘧啶羧酸酯
  参考文献：
  名称：

  Intramolecular Diels-Alder reactions of pyrimidines and a computational study toward their structure and reactivity

  摘要：

  The syntheses of 2-[(prop-2-ynyloxy)carbonyl]pyrimidine (1), 5-[(prop-2-ynyloxy)carbonyl]pyrimidine (2), 5-phenyl-2-[2-(1-prop-2-ynylpyrryl)]pyrimidine (8),5-phenyl-2-[2-(1-prop-2-ynylpyrrolidinyl)]pyrimidine (9) and 2-[2-(prop-2-ynyloxy)phenyl]-4,6-R2-5-R1-pyrimidine (R1 = H, Cl, Ph; R2 = H, Me) (14a-d) are described. Upon heating, the compounds 1, 9, and 14 undergo an intramolecular Diels-Alder reaction and a subsequent retro Diels-Alder reaction to yield the annelated pyridines 15, 16, and 17, respectively. The compounds 2 and 8 did not react. The nonreactivity of the compounds 2 and 8 is ascribed to conjugation of the pyrimidine aromatic system with part of the dienophilic side chain, giving rise to conformations in which the diene and dienophile moieties cannot interact. For the compounds 1, 9, and 14 conjugation is absent, due to steric hindrance. To support this, semiempirical (MDNO-PM3) and molecular mechanics (MMX, CHEMX) calculations were performed. The HOMO-LUMO energy separation of the compounds did not consequently reflect the observed reactivity. However, the probability of the compounds to be in a reactive conformation appeared to correlate with the observed rate of reaction (9 > 14a > 1 >> 2, 8).

  DOI：

  10.1021/jo00037a011

文献信息

• Intramolecular Diels-Alder reactions of pyrimidines and a computational study toward their structure and reactivity
  作者：Werner A. W. Stolle、August E. Frissen、Antonius T. M. Marcelis、Henk C. Van der Plas

  DOI：10.1021/jo00037a011

  日期：1992.5

  The syntheses of 2-[(prop-2-ynyloxy)carbonyl]pyrimidine (1), 5-[(prop-2-ynyloxy)carbonyl]pyrimidine (2), 5-phenyl-2-[2-(1-prop-2-ynylpyrryl)]pyrimidine (8),5-phenyl-2-[2-(1-prop-2-ynylpyrrolidinyl)]pyrimidine (9) and 2-[2-(prop-2-ynyloxy)phenyl]-4,6-R2-5-R1-pyrimidine (R1 = H, Cl, Ph; R2 = H, Me) (14a-d) are described. Upon heating, the compounds 1, 9, and 14 undergo an intramolecular Diels-Alder reaction and a subsequent retro Diels-Alder reaction to yield the annelated pyridines 15, 16, and 17, respectively. The compounds 2 and 8 did not react. The nonreactivity of the compounds 2 and 8 is ascribed to conjugation of the pyrimidine aromatic system with part of the dienophilic side chain, giving rise to conformations in which the diene and dienophile moieties cannot interact. For the compounds 1, 9, and 14 conjugation is absent, due to steric hindrance. To support this, semiempirical (MDNO-PM3) and molecular mechanics (MMX, CHEMX) calculations were performed. The HOMO-LUMO energy separation of the compounds did not consequently reflect the observed reactivity. However, the probability of the compounds to be in a reactive conformation appeared to correlate with the observed rate of reaction (9 > 14a > 1 >> 2, 8).