5-ethynyl-2-pyrrolidinone | 105457-63-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 5-ethynyl-2-pyrrolidinone
• 英文别名: 5-ethynylpyrrolidin-2-one
• CAS: 105457-63-4
• 化学式: C₆H₇NO
• mdl: MFCD19217960
• 分子量: 109.128
• InChiKey: ODCJSCFWGWZDMF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  5-ethynyl-2-pyrrolidinone 、 乙酰氯 、 三乙胺 以84%的产率得到
  参考文献：
  名称：

  LUNDKVIST, J. R. MICHAEL;RINGDAHL, BJORN;HACKSELL, ULI, J. MED. CHEM., 32,(1989) N, C. 863-869

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 4-(benzylideneamino)-6-(trimethylsilyl)-5-hexynoate 在 盐酸 、 potassium fluoride 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 1.17h， 生成 5-ethynyl-2-pyrrolidinone
  参考文献：
  名称：

  Conformationally restricted analogs of the muscarinic agent N-methyl-N-(1-methyl-4-pyrrolidino-2-butynyl)acetamide

  摘要：

  Conformationally restricted analogues of the selective partial muscarinic agonist N-methyl-N-(1-methyl-4-pyrrolidino-2-butynyl)acetamide (BM 5; 2) were synthesized. The compounds were tested for muscarinic and antimuscarinic activity in the isolated guinea pig ileum and in intact mice. They were found to be moderately potent muscarinic antagonists or weak partial agonists. The new compounds were less potent than 2 in inhibiting (-)-[3H]-N-methylscopolamine binding in the rate cerebral cortex. Thus, structural modifications of 2 in which part of the amide moiety has been connected with the methyl group in the butynyl chain to form a five-membered ring decrease affinity and in most cases abolish efficacy.

  DOI：

  10.1021/jm00124a022

文献信息

• Silylformylation catalyzed by Rh and Rh-Co mixed metal complexes and its application to the synthesis of pyrrolizidine alkaloids
  作者：Iwao Ojima、Robert J. Donovan、Masakatsu Eguchi、William R. Shay、Patrizia Ingallina、Anna Korda、Qingping Zeng

  DOI：10.1016/s0040-4020(01)87260-4

  日期：1993.1

  dialkyne, and an alkynyl nitrile proceed in high yields in which alkene and nitrile functionalities are inert for the reaction. Silylformylation is successfully applied to the syntheses of pyrrolizidine alkaloids, (±)-isoretronecanol and (±)-trachelanthamidine, from 5-ethynyl-2-pyrrolidinone (6) in combination with amidocarbonylation.

  Co 2 Rh 2（CO）12，Rh 4（CO）12，（t BuNC）4 RhCo（CO）4和Rh（acac）（CO）2在25°C和在大气压至一氧化碳的10个大气压下，得到（Z）-1-甲硅烷基-2-甲酰基-1-己烯（1），这是“甲硅烷基甲酰化”的产物，和/或（E）-1-甲硅烷基-1-己烯（2）。甲硅烷基甲酰化与氢化硅烷化产物的比例取决于所用氢化硅烷的电子性质，例如，PhMe 2 SiH几乎只给出1，而（MeO）3SiH赞成2的形成。当使用三烷基硅烷如Et 3 SiH和EtMe 2 SiH时，由Co 2 Rh 2（CO）12或（t BuNC）4 RhCo（CO）4催化的反应得到2,5-双（正丁基）-3 -甲硅烷基环戊-2-烯-1-酮（3）作为主要产物，是独特的甲硅烷基碳环化产物。形成机理3在氘标记实验的基础上进行了讨论。炔烃，二炔和炔基腈的化学选择性甲硅烷基甲酰化以高收率进行，其中烯烃和腈官
• Highly Robust Iron Catalyst System for Intramolecular C(sp ³ )−H Amidation Leading to γ‐Lactams
  作者：Jeonguk Kweon、Sukbok Chang

  DOI：10.1002/anie.202013499

  日期：2021.2.8

  Disclosed here is the use of an iron catalyst system for an intramolecular C−H amidation toward γ‐lactam synthesis from dioxazolone precursors. (Phthalocyanine)FeIIICl was found to catalyze this cyclization with extremely high turnover numbers of up to 47 000 under mild and aerobic conditions. On the basis of experimental and computational mechanistic studies, the reaction is suggested to proceed by

  本文公开了铁催化剂体系用于分子内CH酰胺化以从重氮恶唑酮前体合成γ-内酰胺的方法。发现（酞菁）Fe III Cl在温和有氧条件下以高达47 000的极高周转率催化这种环化反应。在实验和计算机理研究的基础上，建议该反应通过逐步的自由基途径进行，该途径涉及快速氢原子的提取和自由基的反弹。高周转率和空气相容性的合理来源也被合理化。
• Synthesis of pyrrolizidine alkaloids via rhodium-catalyzed silylformylation and amidocarbonylation
  作者：Masakatsu Eguchi、Qingping Zeng、Anna Korda、Iwao Ojima

  DOI：10.1016/s0040-4039(00)77453-3

  日期：1993.2

  Rhodium-catalyzed silylformylation and amidocarbonylation are applied to the syntheses of pyrrolizidine alkaloids, (±)-isoretronecanol and (±)-trachelanthamidine, from 5-ethynyl-2-pyrrolidinone.

  铑催化的甲硅烷基甲酰基化和酰胺基羰基化反应可用于由5-乙炔基-2-吡咯烷酮合成吡咯烷核生物碱，（±）-异戊烯醇和（±）-梯chel啶。
• Synthesis and evaluation of mono-, di-, and trifluoroethenyl-GABA derivatives as GABA-T inhibitors
  作者：Michael Kolb、Jacqueline Barth、Jean Georges Heydt、Michel J. Jung

  DOI：10.1021/jm00385a007

  日期：1987.2

  The syntheses of four derivatives of gamma-vinyl-GABA, in which vinylic hydrogen atoms were replaced by fluorine, are described. With use of 5-ethenyl-2-pyrrolidinone as starting material, the E and Z isomers of 4-amino-6-fluoro-5-hexenoic acid were prepared. The 6,6-difluoro and 5,6,6-trifluoro analogues could be synthesized from 4-oxobutanoic acid tert-butyl ester and (2,2-difluoroethenyl)- and

  描述了γ-乙烯基-GABA的四种衍生物的合成，其中乙烯基氢原子被氟取代。以5-乙烯基-2-吡咯烷酮为原料，制备了4-氨基-6-氟-5-己酸的E和Z异构体。6，6-二氟和5,6,6-三氟类似物可以分别由4-氧代丁酸叔丁酯和（2,2-二氟乙烯基）-和（三氟乙烯基）锂合成。测试了这些化合物作为GABA-T的抑制剂，并报道了其体外和体内生物化学。活性最高的衍生物是（Z）-4-氨基-6-氟-5-己酸。讨论了该系列中的构效关系。
• Process for preparing 4-amino-5-hexenoic acid
  申请人：MERRELL DOW FRANCE ET CIE

  公开号：EP0116257A1

  公开（公告）日：1984-08-22

  4-Amino-5-hexenoic acid is prepared by: (a) reacting 5-oxo-2-pyrrolidine-acetonitrile with hydrogen and dimethylamine in the presence of a palladium catalyst to form N,N-dimethyl-2-[5'-oxo-2'-pyrrolidine] ethylamine: (b) oxidizing N,N-dimethyl-2-[5'-oxo-2'-pyrrolidine]-ethylamine to produce the corresponding N-oxide derivative; (c) pyrolysis of the N-oxide derivative to form 5-vinyi-2-pyrrolidinone; optionally, separating, N,N-dimethyl-2-[5'-oxo-2'-pyrrolidine]ethylamine by-product from the 5-vinyl-2-pyrrolidinone product; and (d) hydrolyzing 5-vinyl-2-pyrrolidinone to form 4-amino-5-hexenoic acid.

  4- 氨基-5-己烯酸的制备方法如下 (a) 在钯催化剂存在下，5-氧代-2-吡咯烷乙腈与氢和二甲胺反应生成 N,N-二甲基-2-[5'-氧代-2'-吡咯烷]乙胺： (b) 氧化 N,N-二甲基-2-[5'-氧代-2'-吡咯烷]乙胺，生成相应的 N-氧化物衍生物； (c) 高温分解 N-氧化物衍生物，生成 5-乙烯基-2-吡咯烷酮； 选择性地从 5-乙烯基-2-吡咯烷酮产品中分离 N,N-二甲基-2-[5'-氧代-2'-吡咯烷]乙胺副产物；以及 (d) 水解 5-乙烯基-2-吡咯烷酮，生成 4-氨基-5-己烯酸。