1-(2-Pyridinyl)-3-butyltriazene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1-(2-Pyridinyl)-3-butyltriazene
• 英文别名: N-(butyldiazenyl)pyridin-2-amine
• 化学式: C₉H₁₄N₄
• 分子量: 178.237
• InChiKey: BLMVRWBBASVATD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  49.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(2-Pyridinyl)-3-butyltriazene 以97%的产率得到
  参考文献：
  名称：

  Farnsworth David W., Wink David A., Roscher Nina M., Michejda Christopher+, J. Org. Chem., 59 (1994) N 20, S 5942-5950

  摘要：

  DOI：
• 作为产物：
  描述：

  2-溴吡啶 、 n-butylazide 在 正丁基锂 作用下， 以54.5%的产率得到1-(2-Pyridinyl)-3-butyltriazene
  参考文献：
  名称：

  Decomposition of Pyridinyltriazenes in Aqueous Buffer: A Kinetic and Mechanistic Investigation

  摘要：

  1-(X-pyridinyl)-3-butyltriazenes (X-PBT), where X = 2, 3, or 4, were prepared as prototypes of new chemotherapeutic agents. The acid-catalyzed decomposition of the 1-(X-pyridinyl)-3-butyltriazenes leads to the formation ofthe corresponding aminopyridines and butyl alcohols. pH-rate profiles, determined over a pH range of 3.5-12.00, show sigmoidal curves with slopes asymptotically approaching 0 at the extremes. The transitions have slopes where rate is inversely proportional to pH, indicating regions of acid catalysis. The solvent kinetic isotope effect, k(H2O)/k(D2O), for each reaction is <1.0. The determination ofthe kinetics ofthe decomposition in amino buffers, ranging in pK(a) from 8.95 to 10.4 and concentrations from 0.03 to 0.15 M, indicates negligible variation in the rate constant. These data strongly support the conclusion that the decomposition is specific acid catalyzed (A1) for each X-PBT isomer. This implies that the reactions involve fast, reversible protonation followed by the rate-determining heterolysis of the protonated species to the n-butyldiazonium ion and X-aminopyridine. Near neutral pH, the half-lives ofthe 2- and 4-isomers are similar to 100-fold shorter than that of the 3-isomer. This difference can be explained by protonation of the pyridinyl N, which leads to direct dissociation only for the 2- and 4-isomers. Experimental pK(a')'s were obtained for each isomer: 2-PBT, 5.19 +/- 0.19; 3-PBT, 4.89 +/- 0.12; 4-PBT, 7.77 +/- 0.16. These values are lower than, but follow the same order as, the pK(a) values for the analogous isomers of aminopyridine.

  DOI：

  10.1021/jo00099a024

文献信息

• Farnsworth David W., Wink David A., Roscher Nina M., Michejda Christopher+, J. Org. Chem., 59 (1994) N 20, S 5942-5950
  作者：Farnsworth David W., Wink David A., Roscher Nina M., Michejda Christopher+

  DOI：——

  日期：——
• Decomposition of Pyridinyltriazenes in Aqueous Buffer: A Kinetic and Mechanistic Investigation
  作者：David W. Farnsworth、David A. Wink、Nina M. Roscher、Christopher J. Michejda、Richard H. Smith

  DOI：10.1021/jo00099a024

  日期：1994.10

  1-(X-pyridinyl)-3-butyltriazenes (X-PBT), where X = 2, 3, or 4, were prepared as prototypes of new chemotherapeutic agents. The acid-catalyzed decomposition of the 1-(X-pyridinyl)-3-butyltriazenes leads to the formation ofthe corresponding aminopyridines and butyl alcohols. pH-rate profiles, determined over a pH range of 3.5-12.00, show sigmoidal curves with slopes asymptotically approaching 0 at the extremes. The transitions have slopes where rate is inversely proportional to pH, indicating regions of acid catalysis. The solvent kinetic isotope effect, k(H2O)/k(D2O), for each reaction is <1.0. The determination ofthe kinetics ofthe decomposition in amino buffers, ranging in pK(a) from 8.95 to 10.4 and concentrations from 0.03 to 0.15 M, indicates negligible variation in the rate constant. These data strongly support the conclusion that the decomposition is specific acid catalyzed (A1) for each X-PBT isomer. This implies that the reactions involve fast, reversible protonation followed by the rate-determining heterolysis of the protonated species to the n-butyldiazonium ion and X-aminopyridine. Near neutral pH, the half-lives ofthe 2- and 4-isomers are similar to 100-fold shorter than that of the 3-isomer. This difference can be explained by protonation of the pyridinyl N, which leads to direct dissociation only for the 2- and 4-isomers. Experimental pK(a')'s were obtained for each isomer: 2-PBT, 5.19 +/- 0.19; 3-PBT, 4.89 +/- 0.12; 4-PBT, 7.77 +/- 0.16. These values are lower than, but follow the same order as, the pK(a) values for the analogous isomers of aminopyridine.