2-(1-Allyl-1-benzoylmethylene)hexahydropyrimidine

• 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: 2-(1-Allyl-1-benzoylmethylene)hexahydropyrimidine
• 英文别名: 2-(1,3-Diazinan-2-ylidene)-1-phenylpent-4-en-1-one
• 化学式: C₁₅H₁₈N₂O
• 分子量: 242.321
• InChiKey: PFGVMTHBCWMAHR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  41.1
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(1-Allyl-1-benzoylmethylene)hexahydropyrimidine 、 偶氮二甲酸二乙酯 以 四氢呋喃 为溶剂， 生成 ethyl N-benzoylcarbamate 、 8-Prop-2-en-(Z)-ylidene-3,4,7,8-tetrahydro-2H-imidazo[1,5-a]pyrimidin-6-one
  参考文献：
  名称：

  的反应Ç烷基化杂环烯酮缩醛胺与偶氮二甲酸二乙酯：多官能化的季碳衍生物的合成和它们的热碎片

  摘要：

  五元环C-烷基化的杂环烯酮缩醛与偶氮二羧酸二乙酯反应，以中等至优异的收率得到含季碳的加合物，而六元类似物提供了咪唑并[1,5 - a ]嘧啶-6-一衍生物。讨论了加成产物的形成及其片段化反应途径。

  DOI：

  10.1016/s0040-4020(02)00945-6
• 作为产物：
  描述：

  1-Allyl-2-(benzoylmethylene)hexahydropyrimidine 在 zinc(II) chloride 作用下， 以 xylene 为溶剂， 反应 7.0h， 以85%的产率得到2-(1-Allyl-1-benzoylmethylene)hexahydropyrimidine
  参考文献：
  名称：

  Regiospecific Allylation of Benzoyl-Substituted Heterocyclic Ketene Aminals and Their Zinc Chloride-Promoted 3-Aza-Cope Rearrangement

  摘要：

  The regiospecific allylation of benzoyl-substituted heterocyclic ketene aminals 2 is reported. Compound 2 reacted with allyl bromide in refluxing acetonitrile to give, exclusively, C-allylated products 5 in moderate to goad yields, while only N-allylated compounds 7 were obtained in dimethylformamide with the use of sodium hydride. Under neutral conditions, reaction between 2 and allyl bromide proceeded via a six-membered transition state involving the secondary enamine segment (HNC=C) and carbon-bromine bond (C-Br). Without the secondary amino group, C-allylation was inhibited, which was illustrated by the fact that 1,3-dimethyl-2-(aroylmethylene)imidazolidines did not react with allyl bromide. No 3-aza-Cope rearrangement of N-allylated heterocyclic ketene aminals 7 was observed at temperatures up to 140 degrees C. Only with the use of zinc chloride did the rearrangement take place at 140 degrees C to give allyl-shifted products 5. N-Benzylated heterocyclic ketene aminal analogues did not undergo the rearrangement under the same conditions, indicating that the 3-aza-Cope rearrangement proceeds through a charge-accelerated concerted mechanism.

  DOI：

  10.1021/jo00114a033

文献信息

• Reaction of C-alkylated heterocyclic ketene aminals with diethyl azodicarboxylate: synthesis of polyfunctionalized quaternary carbon derivatives and their thermal fragmentation
  作者：Mei-Xin Zhao、Zhe-Ming Wang、Mei-Xiang Wang、Chun-Hua Yan、Zhi-Tang Huang

  DOI：10.1016/s0040-4020(02)00945-6

  日期：2002.9

  Five-membered ring C-alkylated heterocyclic ketene aminals react with diethyl azodicarboxylate to give the quaternary carbon-containing adducts in moderate to excellent yields while the six-membered analogs afford imidazo[1,5-a]pyrimidin-6-one derivatives. The formation of the addition products and their fragmentation reaction pathways are discussed.

  五元环C-烷基化的杂环烯酮缩醛与偶氮二羧酸二乙酯反应，以中等至优异的收率得到含季碳的加合物，而六元类似物提供了咪唑并[1,5 - a ]嘧啶-6-一衍生物。讨论了加成产物的形成及其片段化反应途径。
• Regiospecific Allylation of Benzoyl-Substituted Heterocyclic Ketene Aminals and Their Zinc Chloride-Promoted 3-Aza-Cope Rearrangement
  作者：Mei-Xiang Wang、Zhi-Tang Huang

  DOI：10.1021/jo00114a033

  日期：1995.5

  The regiospecific allylation of benzoyl-substituted heterocyclic ketene aminals 2 is reported. Compound 2 reacted with allyl bromide in refluxing acetonitrile to give, exclusively, C-allylated products 5 in moderate to goad yields, while only N-allylated compounds 7 were obtained in dimethylformamide with the use of sodium hydride. Under neutral conditions, reaction between 2 and allyl bromide proceeded via a six-membered transition state involving the secondary enamine segment (HNC=C) and carbon-bromine bond (C-Br). Without the secondary amino group, C-allylation was inhibited, which was illustrated by the fact that 1,3-dimethyl-2-(aroylmethylene)imidazolidines did not react with allyl bromide. No 3-aza-Cope rearrangement of N-allylated heterocyclic ketene aminals 7 was observed at temperatures up to 140 degrees C. Only with the use of zinc chloride did the rearrangement take place at 140 degrees C to give allyl-shifted products 5. N-Benzylated heterocyclic ketene aminal analogues did not undergo the rearrangement under the same conditions, indicating that the 3-aza-Cope rearrangement proceeds through a charge-accelerated concerted mechanism.