4-hydroxy-3,9-dimethyl-2-oxo-9-(4-pentenyl)-6,7,8,9-tetrahydro-2H-pyrido<2,1-b><1,3>thiazinium hydroxide inner salt | 166535-56-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 4-hydroxy-3,9-dimethyl-2-oxo-9-(4-pentenyl)-6,7,8,9-tetrahydro-2H-pyrido<2,1-b><1,3>thiazinium hydroxide inner salt
• 英文别名: 4-hydroxy-3,9-dimethyl-2-oxo-9-(4-pentenyl)-6,7,8,9-tetrahydro-2H-pyrido[2,1-b][1,3]thiazinium hydroxide inner salt；3,9-dimethyl-2-oxo-9-pent-4-enyl-7,8-dihydro-6H-pyrido[2,1-b][1,3]thiazin-5-ium-4-olate
• CAS: 166535-56-4
• 化学式: C₁₅H₂₁NO₂S
• 分子量: 279.403
• InChiKey: NSLJQKBROIKYIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  68.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-hydroxy-3,9-dimethyl-2-oxo-9-(4-pentenyl)-6,7,8,9-tetrahydro-2H-pyrido<2,1-b><1,3>thiazinium hydroxide inner salt 以 甲苯 为溶剂， 反应 2.0h， 以80%的产率得到2,7a-dimethyl-1-thia-2,3,6,7,7a,8,9,10,10a,10b-decahydro-10b,2-epithiomethano-1H,5H-benzoquinolizine-3,12-dione
  参考文献：
  名称：

  8H-Anhydro-4-hydroxy-2-oxo-1,3-thiazinium Hydroxides as Mesoionic 1,4-Dipoles

  摘要：

  The previously unknown 8H-anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides (1) were prepared and their 1,4-dipolar cycloaddition behavior was examined. In most cases, elimination of the proton in the 8-position of the mesoionic ring was observed to occur unless extremely reactive dipolarophiles were used. The S,N-ketene acetals were converted to the corresponding alpha-diazo ketones for further study.

  DOI：

  10.3987/com-93-s(b)16
• 作为产物：
  描述：

  3-甲基哌啶-2-酮 在 劳森试剂 、 正丁基锂 作用下， 以 乙醚 、 苯 为溶剂， 生成 4-hydroxy-3,9-dimethyl-2-oxo-9-(4-pentenyl)-6,7,8,9-tetrahydro-2H-pyrido<2,1-b><1,3>thiazinium hydroxide inner salt
  参考文献：
  名称：

  Intramolecular 1,4-dipolar cycloaddition of cross-conjugated heterocyclic betaines. A new route to hexahydrojulolidines and related peri-fused ring systems

  摘要：

  Alkenyl-substituted bicyclic anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides prepared from 3,3-disubstituted thiolactams and 1,3-bielectrophiles formed thermally-induced intramolecular cycloadducts which underwent loss of carbonyl sulfide, followed by a 1,5-hydrogen shift, to hexahydrojulolidines and related ring systems.

  DOI：

  10.1021/jo00071a007

文献信息

• 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.