N-phenyl-2-trimethylsilylheptanamide | 1027938-07-3

• 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-phenyl-2-trimethylsilylheptanamide
• CAS: 1027938-07-3
• 化学式: C₁₆H₂₇NOSi
• 分子量: 277.482
• InChiKey: VYKITWAHRYRQPR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  N-phenyl-2-trimethylsilylheptanamide 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 0.42h， 生成 N-苯基庚酰胺
  参考文献：
  名称：

  Charge-directed conjugate addition reactions of silylated .alpha.,.beta.-unsaturated amidate anions

  摘要：

  A variety of N-substituted alpha-silylated-alpha,beta-unsaturated amidate anions (2) have been found to be excellent Michael acceptors in charge-directed conjugate addition reactions with Grignard and organolithium reagents. The effects of olefin substitution, Si-substitution, N-substitution, and amidate counterion have been studied. Anionic acceptors may be prepared in situ by the addition of silylated vinyllithium reagents to isocyanates and then allowed to undergo conjugate addition reactions with subsequently added nucleophiles, but it was found to be more efficient to isolate neutral acceptors and regenerate the acceptor anion through the use of excess nucleophile. Beta-Substituted acceptors were found to react only with reactive organolithium reagents while a beta,beta-disubstituted acceptor failed to undergo conjugate addition reactions. A primary amide acceptor (14d) also undergoes addition reactions with larger quantitites of nucleophiles suggesting that dianionic amidate acceptors (31) are involved. Diene acceptor 24 was found to undergo a 1,6-addition reaction with n-BuLi. Sodium and potassium amidate salts were found to be inferior to lithium and magnesium salts in addition reactions in keeping with the expectation that an increase in carbonyl-group charge burden retards conjugate reactions. Triphenylsilyl-containing acceptor 16 was found to be more reactive in reactions with n-BuMgCl but less reactive with bulkier tert-BuMgCl. Adduct dianions can be monoalkylated with alkyl iodides and used in Peterson olefination reactions.

  DOI：

  10.1021/jo00078a028
• 作为产物：
  描述：

  [1-(trimethylsilyl)vinyl]magnesium bromide 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.25h， 生成 N-phenyl-2-trimethylsilylheptanamide
  参考文献：
  名称：

  Charge-directed conjugate addition reactions of silylated .alpha.,.beta.-unsaturated amidate anions

  摘要：

  A variety of N-substituted alpha-silylated-alpha,beta-unsaturated amidate anions (2) have been found to be excellent Michael acceptors in charge-directed conjugate addition reactions with Grignard and organolithium reagents. The effects of olefin substitution, Si-substitution, N-substitution, and amidate counterion have been studied. Anionic acceptors may be prepared in situ by the addition of silylated vinyllithium reagents to isocyanates and then allowed to undergo conjugate addition reactions with subsequently added nucleophiles, but it was found to be more efficient to isolate neutral acceptors and regenerate the acceptor anion through the use of excess nucleophile. Beta-Substituted acceptors were found to react only with reactive organolithium reagents while a beta,beta-disubstituted acceptor failed to undergo conjugate addition reactions. A primary amide acceptor (14d) also undergoes addition reactions with larger quantitites of nucleophiles suggesting that dianionic amidate acceptors (31) are involved. Diene acceptor 24 was found to undergo a 1,6-addition reaction with n-BuLi. Sodium and potassium amidate salts were found to be inferior to lithium and magnesium salts in addition reactions in keeping with the expectation that an increase in carbonyl-group charge burden retards conjugate reactions. Triphenylsilyl-containing acceptor 16 was found to be more reactive in reactions with n-BuMgCl but less reactive with bulkier tert-BuMgCl. Adduct dianions can be monoalkylated with alkyl iodides and used in Peterson olefination reactions.

  DOI：

  10.1021/jo00078a028

文献信息

• Charge-directed conjugate addition reactions of silylated .alpha.,.beta.-unsaturated amidate anions
  作者：Manning P. Cooke、Charles M. Pollock

  DOI：10.1021/jo00078a028

  日期：1993.12

  A variety of N-substituted alpha-silylated-alpha,beta-unsaturated amidate anions (2) have been found to be excellent Michael acceptors in charge-directed conjugate addition reactions with Grignard and organolithium reagents. The effects of olefin substitution, Si-substitution, N-substitution, and amidate counterion have been studied. Anionic acceptors may be prepared in situ by the addition of silylated vinyllithium reagents to isocyanates and then allowed to undergo conjugate addition reactions with subsequently added nucleophiles, but it was found to be more efficient to isolate neutral acceptors and regenerate the acceptor anion through the use of excess nucleophile. Beta-Substituted acceptors were found to react only with reactive organolithium reagents while a beta,beta-disubstituted acceptor failed to undergo conjugate addition reactions. A primary amide acceptor (14d) also undergoes addition reactions with larger quantitites of nucleophiles suggesting that dianionic amidate acceptors (31) are involved. Diene acceptor 24 was found to undergo a 1,6-addition reaction with n-BuLi. Sodium and potassium amidate salts were found to be inferior to lithium and magnesium salts in addition reactions in keeping with the expectation that an increase in carbonyl-group charge burden retards conjugate reactions. Triphenylsilyl-containing acceptor 16 was found to be more reactive in reactions with n-BuMgCl but less reactive with bulkier tert-BuMgCl. Adduct dianions can be monoalkylated with alkyl iodides and used in Peterson olefination reactions.