3-methyl-3-(4-pentenyl)-piperidin-2-one | 166535-82-6

• 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-(4-pentenyl)-piperidin-2-one
• 英文别名: 3-Methyl-3-pent-4-enylpiperidin-2-one
• CAS: 166535-82-6
• 化学式: C₁₁H₁₉NO
• 分子量: 181.278
• InChiKey: IGEIHOBTZRAZHC-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-methyl-3-(4-pentenyl)-piperidin-2-one 在 sodium periodate 作用下， 以 甲醇 、 水 、 苯 为溶剂， 反应 15.0h， 生成 1-ethanesulfinylacetyl-3-methyl-3-pent-4-enylpiperidin-2-one
  参考文献：
  名称：

  通过亚氨基亚砜的Pummerer环化-去质子化-环加成级联反应合成取代的2-吡啶酮。

  摘要：

  由δ-戊内酰胺分两步通过与乙基亚磺酰基乙酰氯一起加热然后高碘酸钠氧化来制备1-乙亚磺酰基乙酰基哌啶-2-酮。将亚氨基亚砜缓慢添加到甲苯，乙酸酐（10当量）和对甲苯磺酸（1摩尔％）的回流混合物中导致形成异丁香酮偶极，该偶极偶极子以高收率进行了双分子捕集。环加合物的立体化学归属是根据X射线晶体学确定的，这是相对于偶极的内环加成的结果。环加成的区域化学与HOMO-偶极子控制过程一致。制备了几种含有链烯基的相关亚氨基亚砜，并使其经受了Pummerer反应条件。由环化-去质子化序列形成的所得介电偶极子经过整个悬垂烯烃进行偶极环加成，从而以高收率提供分子内环加合物。在痕量对甲苯磺酸的存在下将这些环加合物暴露于乙酸酐会导致开环，从而产生5-乙酰氧基取代的2-吡啶酮。酰胺氮上的孤对电子有助于打开氧桥以产生瞬态N-酰基亚胺离子，随后失去质子。在某些情况下，带有氧桥的酰胺电子对从反平面排列部分扭曲，并且发生竞

  DOI：

  10.1021/jo982315r
• 作为产物：
  描述：

  3-甲基哌啶-2-酮 、 5-溴-1-戊烯 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.75h， 以80%的产率得到3-methyl-3-(4-pentenyl)-piperidin-2-one
  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

• 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 cycloaddition of cross-conjugated heterocyclic betaines. A new route to hexahydrojulolidines and related peri-fused ring systems
  作者：Kevin T. Potts、Thevarak Rochanapruk、Steven J. Coats、Lazaros Hadjiarapoglou、Albert Padwa

  DOI：10.1021/jo00071a007

  日期：1993.9

  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.
• 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.