N-n-butyl-2,3-bis(trimethylsilyl)-4-oxobut-3-enamide | 233268-97-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-n-butyl-2,3-bis(trimethylsilyl)-4-oxobut-3-enamide
• CAS: 233268-97-8
• 化学式: C₁₄H₂₉NO₂Si₂
• 分子量: 299.561
• InChiKey: YXPJLWRDZZUYLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  正丁胺 、 N-n-butyl-2,3-bis(trimethylsilyl)-4-oxobut-3-enamide 以 乙腈 为溶剂， 生成 N,N'-di-n-butyl-2,3-bis(trimethylsilyl)succinamide
  参考文献：
  名称：

  Amination of Bis(trimethylsilyl)-1,2-bisketene to Ketenyl Amides, Succinamides, and Polyamides:  Preparative and Kinetic Studies

  摘要：

  The reaction of the bisketene (Me3SiC=C=O)(2) (1) with amines is facile and proceeds by two distinct steps forming first ketenylcarboxamides 3 and then succinamides 5. Successive reaction of 1 with two different amines gives mixed succinamides, while phenylhydrazine gives succinimide 7. The reactions of 1.8 equiv of 1 with 1,4-(H2NCH2)(2)C6H4 gives alpha,omega-bisketenyldiamide 13, while equivalent amounts of 1 and diamines gave polymeric amides. Mixed ester amides 8 are formed by sequential reaction of 1 with an alcohol, followed by an amine, or vice versa. Kinetic studies of the amination reaction of 1 with excess amines in CH3CN gave rate constants k(obs) for the formation of ketenylcarboxamides that were fit by the relationship k(obs) = k(a)[amine](2) + k(b)[amine](3). Further reaction of the n-butyl ketenylcarboxamide 3b with n-BuNH2 to give the succinamide 5b was first order in [n-BuNH2], while the further reaction of the CF3CH2 ketenylcarboxyamide 3c with CF3CH2NH2 to form 5c was fit by the equation k(obs) = k(c)[amine](2)/(k(d)[amine] + 1). The reaction of 3b with CH3OH to form the ester amide 8a is strongly accelerated compared to CH3OH addition to the corresponding ketenyl ester and gives significant stereoselectivity for formation of erythro product, and both these effects, as well as the absence of higher order kinetic terms in the reaction of 3b with n-BuNH2 may arise from coordination by the carboxamido group to the nucleophile.

  DOI：

  10.1021/jo9825052
• 作为产物：
  描述：

  bis(trimethylsilyl)-1,2-bisketene 、 正丁胺 以 二氯甲烷 为溶剂， 反应 0.08h， 生成 N-n-butyl-2,3-bis(trimethylsilyl)-4-oxobut-3-enamide
  参考文献：
  名称：

  Amination of Bis(trimethylsilyl)-1,2-bisketene to Ketenyl Amides, Succinamides, and Polyamides:  Preparative and Kinetic Studies

  摘要：

  The reaction of the bisketene (Me3SiC=C=O)(2) (1) with amines is facile and proceeds by two distinct steps forming first ketenylcarboxamides 3 and then succinamides 5. Successive reaction of 1 with two different amines gives mixed succinamides, while phenylhydrazine gives succinimide 7. The reactions of 1.8 equiv of 1 with 1,4-(H2NCH2)(2)C6H4 gives alpha,omega-bisketenyldiamide 13, while equivalent amounts of 1 and diamines gave polymeric amides. Mixed ester amides 8 are formed by sequential reaction of 1 with an alcohol, followed by an amine, or vice versa. Kinetic studies of the amination reaction of 1 with excess amines in CH3CN gave rate constants k(obs) for the formation of ketenylcarboxamides that were fit by the relationship k(obs) = k(a)[amine](2) + k(b)[amine](3). Further reaction of the n-butyl ketenylcarboxamide 3b with n-BuNH2 to give the succinamide 5b was first order in [n-BuNH2], while the further reaction of the CF3CH2 ketenylcarboxyamide 3c with CF3CH2NH2 to form 5c was fit by the equation k(obs) = k(c)[amine](2)/(k(d)[amine] + 1). The reaction of 3b with CH3OH to form the ester amide 8a is strongly accelerated compared to CH3OH addition to the corresponding ketenyl ester and gives significant stereoselectivity for formation of erythro product, and both these effects, as well as the absence of higher order kinetic terms in the reaction of 3b with n-BuNH2 may arise from coordination by the carboxamido group to the nucleophile.

  DOI：

  10.1021/jo9825052

文献信息

• Amination of Bis(trimethylsilyl)-1,2-bisketene to Ketenyl Amides, Succinamides, and Polyamides:  Preparative and Kinetic Studies
  作者：Annette D. Allen、Patrick A. Moore、Sharif Missiha、Thomas T. Tidwell

  DOI：10.1021/jo9825052

  日期：1999.6.1

  The reaction of the bisketene (Me3SiC=C=O)(2) (1) with amines is facile and proceeds by two distinct steps forming first ketenylcarboxamides 3 and then succinamides 5. Successive reaction of 1 with two different amines gives mixed succinamides, while phenylhydrazine gives succinimide 7. The reactions of 1.8 equiv of 1 with 1,4-(H2NCH2)(2)C6H4 gives alpha,omega-bisketenyldiamide 13, while equivalent amounts of 1 and diamines gave polymeric amides. Mixed ester amides 8 are formed by sequential reaction of 1 with an alcohol, followed by an amine, or vice versa. Kinetic studies of the amination reaction of 1 with excess amines in CH3CN gave rate constants k(obs) for the formation of ketenylcarboxamides that were fit by the relationship k(obs) = k(a)[amine](2) + k(b)[amine](3). Further reaction of the n-butyl ketenylcarboxamide 3b with n-BuNH2 to give the succinamide 5b was first order in [n-BuNH2], while the further reaction of the CF3CH2 ketenylcarboxyamide 3c with CF3CH2NH2 to form 5c was fit by the equation k(obs) = k(c)[amine](2)/(k(d)[amine] + 1). The reaction of 3b with CH3OH to form the ester amide 8a is strongly accelerated compared to CH3OH addition to the corresponding ketenyl ester and gives significant stereoselectivity for formation of erythro product, and both these effects, as well as the absence of higher order kinetic terms in the reaction of 3b with n-BuNH2 may arise from coordination by the carboxamido group to the nucleophile.