3-Methyl-3-(penten-5-yl)-2(1H)-piperidinethione | 144396-96-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3-Methyl-3-(penten-5-yl)-2(1H)-piperidinethione
• 英文别名: 3-(pent-4-enyl)-3-methyl-piperidin-2-thione；3-Methyl-3-(penten-5-yl)-2-valerothiolactam；3-methyl-3-(4-pentenyl)-piperidine-2-thione；2-Piperidinethione, 3-methyl-3-(4-pentenyl)-；3-methyl-3-pent-4-enylpiperidine-2-thione
• CAS: 144396-96-3
• 化学式: C₁₁H₁₉NS
• 分子量: 197.345
• InChiKey: IXMSSPWOKXXBGS-UHFFFAOYSA-N

物化性质

• 沸点：
  262.1±23.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 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：
  44.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-Methyl-3-(penten-5-yl)-2(1H)-piperidinethione 以 甲苯 、 苯 为溶剂， 反应 20.0h， 生成 (1R,11R,12S)-7-methyl-1-phenyl-13-thia-3-azatetracyclo[9.3.1.03,12.07,12]pentadecane-2,14-dione
  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
• 作为产物：
  描述：

  3-甲基哌啶-2-酮 在 劳森试剂 作用下， 以 四氢呋喃 、 正己烷 、 xylene 为溶剂， 反应 1.75h， 生成 3-Methyl-3-(penten-5-yl)-2(1H)-piperidinethione
  参考文献：
  名称：

  Cycloaddition Chemistry of Anhydro-4-hydroxy-1,3-thiazolium Hydroxides (Thioisomünchnones) for the Synthesis of Heterocycles

  摘要：

  一系列的α,α-二取代硫代异肟酮通过在三乙胺存在下，用溴乙酰氯处理非环状或环状硫代酰胺来制备。结果发现，这些介离子偶极体会发生双分子1,3-偶极环加成反应与多种不同的偶极体分子。当硫代酰胺的α-位上有氢原子时，最初形成的N-酰基亚胺离子会快速失去质子，产生S,N-酮烯醇缩醛，比形成硫代异肟酮的速度更快。还研究了几种带有附加烯烃的取代硫代异肟酮的环加成行为。内向环加成反应是邻近的π键跨过瞬态硫代异肟酮偶极子的结果，这是分子内反应的立体化学产物的成因。分子力学计算表明，内向非对映异构体的能量比相应的向外构体显著更低。尝试将硫代异肟酮偶极子环加成到附加的吲哚环上未能成功。相反，高产率地形成通过吲哚环以亲核方式环化到硫代N-酰基亚胺离子上的产物。

  DOI：

  10.1055/s-1994-25621

文献信息

• Intramolecular cycloaddition of isomünchnones derived from the rhodium(II) catalyzed cyclization of diazoimides
  作者：Donald L. Hertzog、David J. Austin、William R. Nadler、Albert Padwa

  DOI：10.1016/s0040-4039(00)61271-6

  日期：1992.8

  Rhodium(II) catalysis of various diazoimides containing tethered π-systems results in isomünchnone dipole formation followed by intramolecular dipolar-cycloaddition.

  铑（II）催化的各种含有束缚的π系统的重氮酰亚胺会导致异噻吩酮偶极形成，随后发生分子内偶极环加成反应。
• 8H-Anhydro-4-hydroxy-2-oxo-1,3-thiazinium Hydroxides as Mesoionic 1,4-Dipoles
  作者：Albert Padwa、Steven J. Coats、Lazaros Hadjarapoglou

  DOI：10.3987/com-93-s(b)16

  日期：——

  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.
• 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.
• Generation and cycloaddition reactions of transient alkyl-substituted anhydro-4-hydroxythiazolium hydroxides
  作者：Donald L. Hertzog、William R. Nadler、Zhijia J. Zhang、Albert Padwa

  DOI：10.1016/s0040-4039(00)61077-8

  日期：1992.9

  Transient alkyl-substituted anhydro-4-hydroxythiazolium hydroxides undergo efficient inter- and intramolecular cycloaddition to provide the corresponding 1,3-dipolar cycloadducts in high yield.