4-methyl-N-(m-chlorophenyl)-5-vinyl-1,3-oxazolin-2-one

• 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: 4-methyl-N-(m-chlorophenyl)-5-vinyl-1,3-oxazolin-2-one
• 英文别名: 3-(3-Chlorophenyl)-5-ethenyl-4-methyl-1,3-oxazol-2-one
• 化学式: C₁₂H₁₀ClNO₂
• 分子量: 235.67
• InChiKey: YASXBOSIULAFQC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,3-戊二酮 在 lithium carbonate 、 三乙胺 、 对苯二酚 作用下， 以 xylene 为溶剂， 反应 22.5h， 生成 4-methyl-N-(m-chlorophenyl)-5-vinyl-1,3-oxazolin-2-one
  参考文献：
  名称：

  One-Step Synthesis and Highly Regio- and Stereoselective Diels−Alder Cycloadditions of Novel exo-2-Oxazolidinone Dienes

  摘要：

  An improved synthesis of exo-heterocyclic dienes like N-substituted 4,5-dimethylene 2-oxazolidinones 1, by a one-step method from diacetyl and isocyanates, was described. This highly convergent synthetic strategy has been successfully used for the preparation of novel (Z)-5-ethylidene-4-methylene analogs 4 in fair yields. Both dienes 1 and 4 undergo efficient addition of symmetric dienophiles in thermal Diels-Alder reactions, inasmuch as they react stereo- and regioselectively with the unsymmetric olefins methyl vinyl ketone (MVK) and methyl propiolate. This regioselectivity was greatly improved by using Lewis acid catalysts (TiCl4, AlCl3). The nitrogen atom of the 2-oxazolidinone ring seems to control the orientation of the dienophile approach. These results have been rationalized in terms of the frontier molecular orbital theory by ab initio calculations. For dienes 4, addition of MVK gave the endo isomer as the major product. Dimerization of dienes 4 was also highly regio-, chemo-, and stereoselective, giving only isomer 17. This reaction furnished a second product, which corresponded to dienes 18 obtained by the [1,5] sigmatropic rearrangement of 4. The structure of the dienes and main products was established by NMR experiments and X-ray diffraction analysis.

  DOI：

  10.1021/jo962403g

文献信息

• One-Step Synthesis and Highly Regio- and Stereoselective Diels−Alder Cycloadditions of Novel <i>exo</i>-2-Oxazolidinone Dienes
  作者：Ashis B. Mandal、Adriana Gómez、Gonzalo Trujillo、Francisco Méndez、Hugo A. Jiménez、María de Jesús Rosales、Rafael Martínez、Francisco Delgado、Joaquín Tamariz

  DOI：10.1021/jo962403g

  日期：1997.6.13

  An improved synthesis of exo-heterocyclic dienes like N-substituted 4,5-dimethylene 2-oxazolidinones 1, by a one-step method from diacetyl and isocyanates, was described. This highly convergent synthetic strategy has been successfully used for the preparation of novel (Z)-5-ethylidene-4-methylene analogs 4 in fair yields. Both dienes 1 and 4 undergo efficient addition of symmetric dienophiles in thermal Diels-Alder reactions, inasmuch as they react stereo- and regioselectively with the unsymmetric olefins methyl vinyl ketone (MVK) and methyl propiolate. This regioselectivity was greatly improved by using Lewis acid catalysts (TiCl4, AlCl3). The nitrogen atom of the 2-oxazolidinone ring seems to control the orientation of the dienophile approach. These results have been rationalized in terms of the frontier molecular orbital theory by ab initio calculations. For dienes 4, addition of MVK gave the endo isomer as the major product. Dimerization of dienes 4 was also highly regio-, chemo-, and stereoselective, giving only isomer 17. This reaction furnished a second product, which corresponded to dienes 18 obtained by the [1,5] sigmatropic rearrangement of 4. The structure of the dienes and main products was established by NMR experiments and X-ray diffraction analysis.