1-[1-(4-甲氧基苯基)-2-硝基乙基]哌啶 | 138783-47-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 1-[1-(4-甲氧基苯基)-2-硝基乙基]哌啶
• 英文名称: 1-[1-(4-Methoxy-phenyl)-2-nitro-ethyl]-piperidine
• 英文别名: 1-[1-(4-Methoxyphenyl)-2-nitroethyl]piperidine；1-[1-(4-methoxyphenyl)-2-nitroethyl]piperidine
• CAS: 138783-47-8
• 化学式: C₁₄H₂₀N₂O₃
• 分子量: 264.324
• InChiKey: AKNYLLXZWBJOEF-UHFFFAOYSA-N

物化性质

• 沸点：
  393.5±42.0 °C(Predicted)
• 密度：
  1.149±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  58.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  哌啶 、 1-(4-甲氧苯基)-2-硝基乙烯 以 乙腈 为溶剂， 生成 1-[1-(4-甲氧基苯基)-2-硝基乙基]哌啶
  参考文献：
  名称：

  Kinetic Study on Michael-Type Reactions of β-Nitrostyrenes with Cyclic Secondary Amines in Acetonitrile: Transition-State Structures and Reaction Mechanism Deduced from Negative Enthalpy of Activation and Analyses of LFERs

  摘要：

  A kinetic study is reported for the Michael-type reactions of X-substituted beta-nitrostyrenes (1a-j) with a series of cyclic secondary amines in MeCN. The plots of pseudo-first-order rate constant k(obsd) vs [amine] curve upward, indicating that the reactions proceed through catalyzed and uncatalyzed routes. The dissection of k(obsd) into Kk(2) and Kk(3) (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) revealed that Kk(3) is much larger than Kk(2), implying that the reactions proceed mainly through the catalyzed route when [amine] > 0.01 M. Strikingly, the reactivity of beta-nitrostyrene (1g) toward piperidine decreases as the reaction temperature increases. Consequently, a negative enthalpy of activation is obtained, indicating that the reaction proceeds through a relatively stable intermediate. The Bronsted-type plots for the reactions of 1g are linear with beta(nuc) = 0.51 and 0.61, and the Hammett plots for the reactions of 1a-j are also linear with pX = 0.84 and 2.10 for the uncatalyzed and catalyzed routes, respectively. The reactions are concluded to proceed through six-membered cyclic transition states for both the catalyzed and uncatalyzed routes. The effects of the substituent X on reactivity and factors influencing beta(nuc) and pX obtained in this study are discussed.

  DOI：

  10.1021/jo4007442

文献信息

• Nucleophilic addition to olefins. 16. Unusual substituent effects in the reaction of amines with .beta.-nitrostyrenes. Solvent effect on intrinsic rate constants
  作者：Claude F. Bernasconi、Richard A. Renfrow、Paul R. Tia

  DOI：10.1021/ja00275a047

  日期：1986.7
• Kinetic Study on Michael-Type Reactions of β-Nitrostyrenes with Cyclic Secondary Amines in Acetonitrile: Transition-State Structures and Reaction Mechanism Deduced from Negative Enthalpy of Activation and Analyses of LFERs
  作者：Ik-Hwan Um、Ji-Sun Kang、Jong-Yoon Park

  DOI：10.1021/jo4007442

  日期：2013.6.7

  A kinetic study is reported for the Michael-type reactions of X-substituted beta-nitrostyrenes (1a-j) with a series of cyclic secondary amines in MeCN. The plots of pseudo-first-order rate constant k(obsd) vs [amine] curve upward, indicating that the reactions proceed through catalyzed and uncatalyzed routes. The dissection of k(obsd) into Kk(2) and Kk(3) (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) revealed that Kk(3) is much larger than Kk(2), implying that the reactions proceed mainly through the catalyzed route when [amine] > 0.01 M. Strikingly, the reactivity of beta-nitrostyrene (1g) toward piperidine decreases as the reaction temperature increases. Consequently, a negative enthalpy of activation is obtained, indicating that the reaction proceeds through a relatively stable intermediate. The Bronsted-type plots for the reactions of 1g are linear with beta(nuc) = 0.51 and 0.61, and the Hammett plots for the reactions of 1a-j are also linear with pX = 0.84 and 2.10 for the uncatalyzed and catalyzed routes, respectively. The reactions are concluded to proceed through six-membered cyclic transition states for both the catalyzed and uncatalyzed routes. The effects of the substituent X on reactivity and factors influencing beta(nuc) and pX obtained in this study are discussed.