1-(3,4-dihydro-2H-quinolin-1-yl)-2-[2-(4-methylphenyl)sulfinylphenyl]ethanone | 172470-12-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 1-(3,4-dihydro-2H-quinolin-1-yl)-2-[2-(4-methylphenyl)sulfinylphenyl]ethanone
• CAS: 172470-12-1
• 化学式: C₂₄H₂₃NO₂S
• 分子量: 389.518
• InChiKey: DBDXHFVHQZBPLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  56.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(3,4-dihydro-2H-quinolin-1-yl)-2-[2-(4-methylphenyl)sulfinylphenyl]ethanone 在 W-2 Raney nickel 、 三乙胺 、 三氟乙酸酐 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 120.17h， 生成 5,6-dihydro-1-phenyl-4H-pyrrolo[3,2,1-ij]quinolin-2(1H)-one
  参考文献：
  名称：

  Additive and Vinylogous Pummerer Reactions of Amido Sulfoxides and Their Use in the Preparation of Nitrogen Containing Heterocycles

  摘要：

  The alpha-thiocarbocation generated from the Pummerer re action of N-methyl-N-phenyl-2-[2-(toluene-4-sulfinyl)phenyl]acetamide undergoes Friedel-Crafts reaction at the gamma-carbon with the tethered aromatic ring. Reductive removal of the phenylthio group from the resulting product using Raney nickel occurs in high yield, and the overall reaction represents a new method for the synthesis of a variety of 3-phenyl-substituted oxindoles. Treatment of the related N-benzyl-N-alkyl amido sulfoxide system with trifluoroacetic anhydride affords tetrahydroisoquinolone derivatives. The product distribution encountered coincides with the rotamer population of the starting amide. When the N-benzyl-N-methyl amide is used, only the normal Pummerer product is formed. In this case, the thionium ion is generated in the wrong conformation for pi-cyclization to occur. The corresponding N-tert-butyl amido system, however, exists in a geometric orientation which places the benzylic group in the crucial conformation necessary for pi-cyclization, and consequently, the reaction proceeds smoothly. Related cyclization reactions occur in good yield with the corresponding furanyl and cyclohexenyl N-tert-butyl amido sulfoxides. The additive Pummerer reaction of 3-phenylsulfinyl-N-benzyl-N-tert-butylacrylamide gave products derived from both 5- and 6-exo trig cyclizations. Intramolecular electrophilic aromatic substitution via six-membered ring closure ultimately afforded a dihydropyridone. The competitive process involving ipso attack of the aromatic ring on the thionium ion generates a spiro cyclohexadienyl cation that undergoes fragmentation of the adjacent a-bond. The resulting acyl iminium ion is converted to N-tert-butyl-2-phenyl-3-phenylsulfinylacrylamide upon aqueous workup. Only cyclizations leading to five-membered rings occur with the corresponding indolyl and alkenyl N-tert-butyl amido sulfoxides.

  DOI：

  10.1021/jo972093h
• 作为产物：
  描述：

  2-碘苯乙酸 在 titanium(III) chloride 、 草酰氯 、 (2,2'-bipyridine)nickel(II) dibromide 、 双氧水 、 N,N-二甲基甲酰胺 作用下， 以 甲醇 、 水 、 乙二醇 、 乙腈 、 苯 为溶剂， 反应 5.17h， 生成 1-(3,4-dihydro-2H-quinolin-1-yl)-2-[2-(4-methylphenyl)sulfinylphenyl]ethanone
  参考文献：
  名称：

  Additive and Vinylogous Pummerer Reactions of Amido Sulfoxides and Their Use in the Preparation of Nitrogen Containing Heterocycles

  摘要：

  The alpha-thiocarbocation generated from the Pummerer re action of N-methyl-N-phenyl-2-[2-(toluene-4-sulfinyl)phenyl]acetamide undergoes Friedel-Crafts reaction at the gamma-carbon with the tethered aromatic ring. Reductive removal of the phenylthio group from the resulting product using Raney nickel occurs in high yield, and the overall reaction represents a new method for the synthesis of a variety of 3-phenyl-substituted oxindoles. Treatment of the related N-benzyl-N-alkyl amido sulfoxide system with trifluoroacetic anhydride affords tetrahydroisoquinolone derivatives. The product distribution encountered coincides with the rotamer population of the starting amide. When the N-benzyl-N-methyl amide is used, only the normal Pummerer product is formed. In this case, the thionium ion is generated in the wrong conformation for pi-cyclization to occur. The corresponding N-tert-butyl amido system, however, exists in a geometric orientation which places the benzylic group in the crucial conformation necessary for pi-cyclization, and consequently, the reaction proceeds smoothly. Related cyclization reactions occur in good yield with the corresponding furanyl and cyclohexenyl N-tert-butyl amido sulfoxides. The additive Pummerer reaction of 3-phenylsulfinyl-N-benzyl-N-tert-butylacrylamide gave products derived from both 5- and 6-exo trig cyclizations. Intramolecular electrophilic aromatic substitution via six-membered ring closure ultimately afforded a dihydropyridone. The competitive process involving ipso attack of the aromatic ring on the thionium ion generates a spiro cyclohexadienyl cation that undergoes fragmentation of the adjacent a-bond. The resulting acyl iminium ion is converted to N-tert-butyl-2-phenyl-3-phenylsulfinylacrylamide upon aqueous workup. Only cyclizations leading to five-membered rings occur with the corresponding indolyl and alkenyl N-tert-butyl amido sulfoxides.

  DOI：

  10.1021/jo972093h

文献信息

• Vinylogous Pummerer Reaction of Amido-Substituted Sulfoxides as a Method for Preparing Oxindoles and Tetrahydroisoquinolones
  作者：Jeffrey T. Kuethe、John E. Cochran、Albert Padwa

  DOI：10.1021/jo00127a004

  日期：1995.11