hexahydro-3-(4-penten-1-yl)-2H-azepin-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: hexahydro-3-(4-penten-1-yl)-2H-azepin-2-one
• 英文别名: 3-(Penten-5-yl)-2(1H)-azepinone；3-Pent-4-enylazepan-2-one
• 化学式: C₁₁H₁₉NO
• 分子量: 181.278
• InChiKey: MRTYHCYZYWCEAW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-氧代-2-苯基丙烯酰氯化物 、 hexahydro-3-(4-penten-1-yl)-2H-azepin-2-one 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以25%的产率得到1-phenyl-14-oxa-12-azatetracyclo[10.3.1.03,13.07,13]hexadecane-15,16-dione
  参考文献：
  名称：

  Intramolecular 1,4-Dipolar Cycloadditions of Cross-Conjugated Heteroaromatic Betaines. Synthesis of Hexahydrojulolidines and Related Peri- and Ortho-Fused Ring Systems

  摘要：

  3-Alkenyl 2-lactams react with (chlorocarbonyl)phenylketene to give nonisolable anhydro-4-hydroxy-2-oxo-1,3-oxazinium hydroxides which undergo regio- and stereospecific 1,4-dipolar cycloaddition in moderate yields to produce cycloadducts containing a carbon dioxide bridge. Thermolysis of the cycloadduct led to extrusion of carbon dioxide via a nonconcerted 1,5-hydrogen shift to give julolidine-type derivatives. Two of the cycloadducts were characterized by single-crystal X-ray determinations. A significant enhancement in the overall yield of the cycloaddition occurred in related reactions using anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides obtained from 3-alkenyl-3-ethyl(or methyl) 2-thiolactams and a variety of 1,3-bielectrophiles such as (chlorocarbonyl)phenylketene, carbon suboxide, substituted malonyl dichlorides, and ethyl (chlorocarbonyl)acetate. The thiazinium betaines were often isolable, and in one instance, a single-crystal X-ray characterization was possible. Cycloaddition of the thiazinium betaines occurred in a regiospecific manner. The initially formed cycloadducts which retained the carbonyl sulfide bridge could be induced to lose COS on further heating. Julolidine-type derivatives were obtained principally via a nonconcerted process. Variation in lactam ring size, coupled with tether length and substituent in the 1,3-bielectrophile , enabled control of ring size, substituents, and whether an ortho- or peri-fused tricyclic system resulted from the overall cycloaddition. In contrast to the lactam system, the thiolactams require disubstitution in the 3-position to avoid proton loss in the intermediate betaine with formation of a 1,3-thiaioline-4,6-dione.

  DOI：

  10.1021/jo00117a035
• 作为产物：
  描述：

  己内酰胺 、 5-溴-1-戊烯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以35%的产率得到hexahydro-3-(4-penten-1-yl)-2H-azepin-2-one
  参考文献：
  名称：

  Intramolecular 1,4-Dipolar Cycloadditions of Cross-Conjugated Heteroaromatic Betaines. Synthesis of Hexahydrojulolidines and Related Peri- and Ortho-Fused Ring Systems

  摘要：

  3-Alkenyl 2-lactams react with (chlorocarbonyl)phenylketene to give nonisolable anhydro-4-hydroxy-2-oxo-1,3-oxazinium hydroxides which undergo regio- and stereospecific 1,4-dipolar cycloaddition in moderate yields to produce cycloadducts containing a carbon dioxide bridge. Thermolysis of the cycloadduct led to extrusion of carbon dioxide via a nonconcerted 1,5-hydrogen shift to give julolidine-type derivatives. Two of the cycloadducts were characterized by single-crystal X-ray determinations. A significant enhancement in the overall yield of the cycloaddition occurred in related reactions using anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides obtained from 3-alkenyl-3-ethyl(or methyl) 2-thiolactams and a variety of 1,3-bielectrophiles such as (chlorocarbonyl)phenylketene, carbon suboxide, substituted malonyl dichlorides, and ethyl (chlorocarbonyl)acetate. The thiazinium betaines were often isolable, and in one instance, a single-crystal X-ray characterization was possible. Cycloaddition of the thiazinium betaines occurred in a regiospecific manner. The initially formed cycloadducts which retained the carbonyl sulfide bridge could be induced to lose COS on further heating. Julolidine-type derivatives were obtained principally via a nonconcerted process. Variation in lactam ring size, coupled with tether length and substituent in the 1,3-bielectrophile , enabled control of ring size, substituents, and whether an ortho- or peri-fused tricyclic system resulted from the overall cycloaddition. In contrast to the lactam system, the thiolactams require disubstitution in the 3-position to avoid proton loss in the intermediate betaine with formation of a 1,3-thiaioline-4,6-dione.

  DOI：

  10.1021/jo00117a035

文献信息

• Olefinic-Amide and Olefinic-Lactam Cyclizations
  作者：Jie Zhou、Jon D. Rainier

  DOI：10.1021/ol901448n

  日期：2009.8.20

  Olefinic-amide and olefinic-lactam cyclization reactions that result in the generation of cyclic enamides are described.
• Intramolecular 1,4-Dipolar Cycloadditions of Cross-Conjugated Heteroaromatic Betaines. Synthesis of Hexahydrojulolidines and Related Peri- and Ortho-Fused Ring Systems
  作者：Kevin T. Potts、Thevarak Rochanapruk、Albert Padwa、Steven J. Coats、Lazaros Hadjiarapoglou

  DOI：10.1021/jo00117a035

  日期：1995.6

  3-Alkenyl 2-lactams react with (chlorocarbonyl)phenylketene to give nonisolable anhydro-4-hydroxy-2-oxo-1,3-oxazinium hydroxides which undergo regio- and stereospecific 1,4-dipolar cycloaddition in moderate yields to produce cycloadducts containing a carbon dioxide bridge. Thermolysis of the cycloadduct led to extrusion of carbon dioxide via a nonconcerted 1,5-hydrogen shift to give julolidine-type derivatives. Two of the cycloadducts were characterized by single-crystal X-ray determinations. A significant enhancement in the overall yield of the cycloaddition occurred in related reactions using anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides obtained from 3-alkenyl-3-ethyl(or methyl) 2-thiolactams and a variety of 1,3-bielectrophiles such as (chlorocarbonyl)phenylketene, carbon suboxide, substituted malonyl dichlorides, and ethyl (chlorocarbonyl)acetate. The thiazinium betaines were often isolable, and in one instance, a single-crystal X-ray characterization was possible. Cycloaddition of the thiazinium betaines occurred in a regiospecific manner. The initially formed cycloadducts which retained the carbonyl sulfide bridge could be induced to lose COS on further heating. Julolidine-type derivatives were obtained principally via a nonconcerted process. Variation in lactam ring size, coupled with tether length and substituent in the 1,3-bielectrophile , enabled control of ring size, substituents, and whether an ortho- or peri-fused tricyclic system resulted from the overall cycloaddition. In contrast to the lactam system, the thiolactams require disubstitution in the 3-position to avoid proton loss in the intermediate betaine with formation of a 1,3-thiaioline-4,6-dione.