N-Benzoylconiine | 51874-06-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-Benzoylconiine
• 英文别名: 1-benzoyl-2-propyl-piperidine；1-Benzoyl-2-propyl-piperidin；Phenyl-(2-propylpiperidin-1-yl)methanone
• CAS: 51874-06-7
• 化学式: C₁₅H₂₁NO
• mdl: MFCD08693035
• 分子量: 231.338
• InChiKey: ZTVDXUDRHVAAGS-UHFFFAOYSA-N

物化性质

• 沸点：
  356.4±11.0 °C(Predicted)
• 密度：
  1.011±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.533
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-Benzoylconiine 、 五溴化磷 生成 辛烷,1,5-二溴-
  参考文献：
  名称：

  v. Braun; Schmitz, Chemische Berichte, 1906, vol. 39, p. 4366

  摘要：

  DOI：
• 作为产物：
  描述：

  N-amino>-6-propyl-2-piperidinone 在 sodium hydroxide 、 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 N-Benzoylconiine
  参考文献：
  名称：

  Asymmetric Total Synthesis of (R)-(-)-Cryptopleurine and (R)-(-)-Julandine via Highly Enantioselective Amidoalkylations with N-Acylhydrazonium Salts

  摘要：

  The first enantioselective total syntheses of the phenanthroquinolizidine alkaloid(-)-cryptopleurine (1) and its seco base (-)-julandine [(R)-3] are described. The synthesis of(R)-3 allowed the 9aS configuration to be assigned to natural dextrorotatory julandine as shown by structure (S)-3. Both synthetic approaches are based on the high degree of 1,3-asymmetric induction achieved using an N-acylhydrazonium salt, which belongs to a new structural class of activated azomethines. Upon exposure of methoxy lactam 9, with a chiral 2-substituted pyrrolidine auxiliary, to BF3 . Et(2)O and a silyl enol ether the in situ generated N-acylhydrazonium intermediate 10 underwent asymmetric nucleophilic addition to give the (GR)-keto lactams 13 and 14 with complete diastereoselectivity. On the other hand, nucleophilic addition to the N-acylhydrazonium ion 25, with an acyclic chiral auxiliary, showed poor diastereoselectivity. From these results, the high degree of diastereoselection observed for the N-acylhydrazonium ion 10 can be rationalized in terms of the pyramidal stability of the trivalent nitrogen in the chiral pyrrolidine auxiliary. Removal of the chiral auxiliary from 13 and 14 was achieved by reductive N-N bond cleavage using BH3 . THF, affording (BS)-piperidine derivatives 15 and 31, respectively, which were transformed into quinolizidinones 30 and 35, respectively, via intramolecular aldol condensation. Reduction of 30 with alane provided (-)julandine [(R)-3]. In addition, 35 was converted to (-)-cryptopleurine (1) in two steps, by radical cyclization with Bu(3)SnH and AIBN, followed by LiAlH4 reduction.

  DOI：

  10.1021/jo00124a025

文献信息

• Mechanism of the von Braun amide degradations with carbonyl bromide or phosphorus pentabromide
  作者：B.A. Phillips、G. Fodor、J. Gal、F. Letourneau、J.J. Ryan

  DOI：10.1016/s0040-4020(01)93483-0

  日期：1973.1

  isolation of crystalline n-alkylene-α-bromoiminium bromides, and their smooth thermal decomposition, which makes the von Pechmann-von Braun type of degradation competitive to the Hofmann methylation; (2) new procedure was found for preparing ammonium tribromides and iododibromides using carbonyl bromide; (3) a number of the heterofore unknown imidoyl bromides have been prepared and characterized, and their

  先前已宣布分离出α-溴代六氟锑酸六氟锑酸6，这是羰基溴酰胺降解酰胺的第一个中间体。目前的研究表明，使用COBr 2或PBr 5时，第一个中间体是三溴化亚胺（7）。结晶的三溴化物与环己烷的反应几乎定量地以结晶形式得到一溴化物8。将环状一溴化亚胺8加热到120°可以高产率地产生α，ω-二卤代烷烃（13型）和苄腈，而在溴苯中加热到100°可以分离ω-溴烷基苯甲酰亚胺基溴（9或10）。详细说明了该和其他酰亚胺基溴化物的独立合成。通过溶解在液态二氧化硫中或与氟代硫酸甲酯反应，可以使酰亚胺基溴化物与N-烷基硝化氮（11）的平衡向硝化盐方向移动。所有这些步骤均已通过NMR监测。在120°时，ω-溴代烷基亚氨基溴化物经腈离子裂解成α，ω-二溴代烷烃和苄腈。除了获得机理信息外（1），我们还分离了结晶的n-亚烷基-α-溴亚胺鎓溴化物，并实现了平稳的热分解，这使得von Pechmann-von Braun类型
• Schotten; Baum, Chemische Berichte, 1884, vol. 17, p. 2549
  作者：Schotten、Baum

  DOI：——

  日期：——
• Schotten; Baum, Chemische Berichte, 1886, vol. 19, p. 500
  作者：Schotten、Baum

  DOI：——

  日期：——
• Asymmetric Total Synthesis of (R)-(-)-Cryptopleurine and (R)-(-)-Julandine via Highly Enantioselective Amidoalkylations with N-Acylhydrazonium Salts
  作者：Hideaki Suzuki、Sakae Aoyagi、Chihiro Kibayashi

  DOI：10.1021/jo00124a025

  日期：1995.9

  The first enantioselective total syntheses of the phenanthroquinolizidine alkaloid(-)-cryptopleurine (1) and its seco base (-)-julandine [(R)-3] are described. The synthesis of(R)-3 allowed the 9aS configuration to be assigned to natural dextrorotatory julandine as shown by structure (S)-3. Both synthetic approaches are based on the high degree of 1,3-asymmetric induction achieved using an N-acylhydrazonium salt, which belongs to a new structural class of activated azomethines. Upon exposure of methoxy lactam 9, with a chiral 2-substituted pyrrolidine auxiliary, to BF3 . Et(2)O and a silyl enol ether the in situ generated N-acylhydrazonium intermediate 10 underwent asymmetric nucleophilic addition to give the (GR)-keto lactams 13 and 14 with complete diastereoselectivity. On the other hand, nucleophilic addition to the N-acylhydrazonium ion 25, with an acyclic chiral auxiliary, showed poor diastereoselectivity. From these results, the high degree of diastereoselection observed for the N-acylhydrazonium ion 10 can be rationalized in terms of the pyramidal stability of the trivalent nitrogen in the chiral pyrrolidine auxiliary. Removal of the chiral auxiliary from 13 and 14 was achieved by reductive N-N bond cleavage using BH3 . THF, affording (BS)-piperidine derivatives 15 and 31, respectively, which were transformed into quinolizidinones 30 and 35, respectively, via intramolecular aldol condensation. Reduction of 30 with alane provided (-)julandine [(R)-3]. In addition, 35 was converted to (-)-cryptopleurine (1) in two steps, by radical cyclization with Bu(3)SnH and AIBN, followed by LiAlH4 reduction.
• v. Braun; Schmitz, Chemische Berichte, 1906, vol. 39, p. 4366
  作者：v. Braun、Schmitz

  DOI：——

  日期：——