(E)-2-butenediazoic acid

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (E)-2-butenediazoic acid
• 英文别名: (E)-2-butanediazoate；N-butan-2-ylnitrous amide
• 化学式: C₄H₁₀N₂O
• 分子量: 102.136
• InChiKey: XLZNUVFGVGNMAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  41.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-2-butenediazoic acid 在 sodium perchlorate 作用下， 以 异丙醇 为溶剂， 生成 Butan-2-diazotat
  参考文献：
  名称：

  Rate-Limiting Formation of Diazonium Ions in the Aqueous Decomposition of Primary Alkanediazoates

  摘要：

  Rate constants, k(0), for the buffer-independent decomposition of four primary (E)-alkanediazoates and one primary (Z)-alkanediazoate in aqueous media at 25 degrees C, ionic strength 1 M (NaClO4) are reported. Between pH 4 and 12 the plot of log k(0) against pH is biphasic with a hydrogen ion-dependent reaction at the high-pH end changing to a pH-independent region at lower pH. The change in absorbance at 235 nm of the relatively stable (E)-trifluoroethanediazoate as a function of pH gives a good fit to a simple titration curve for a monofunctional acid with pK(a) = 7.00 +/- 0.04 that is in good agreement with the kinetic pK(a) determined from the pH-rate profile between pH 4 and 12. The plot of log k(1), the pH-independent rate constant, against sigma* for the primary (E)-alkanediazoates, and (E)-methane- and (E)-2-butanediazoates previously reported, yields a common line with a slope rho* = -4.4. Of the 1-butanol formed from the decomposition of (E)-1-butanediazoate in D2O at pH(obs),b, = 10.50, 6% contains deuterium, while, of the 1-butanol formed in the presence of 1 M NaOD in D2O, 25% contains deuterium. A total of 96% of the iodotrifluoroethane formed upon decomposition of (E)-trifluoroethanediazoate in a D2O solution that is 1 M in NaI contains at least a single deuterium atom. These data combined with small negative values of Delta S#, normal solvent deuterium isotope effects, and the decreases in k(1) of between 500- and 1000-fold on change of solvent to ethanol are consistent with a mechanism that involves the rate-limiting unassisted heterolytic bond fission of the diazoic acid to yield the diazonium ion. The decomposition of [O-16]-(E)-1-butanediazoate in water containing 47 +/- 2% O-18 yields 1-butanol of which 49 +/- 2% contains O-18. This observation, in combination with the observed pH-dependent deuterium incorporation into 1-butanol during decomposition of (E)-1-butanediazoate, above, indicates that the 1-butanediazonium ion is a diffusionally equilibrated intermediate. The rate constant for the pH-independent decomposition of the (Z)-trifluoroethanediazoate is 2600 times greater than that for the corresponding (E) isomer. The decomposition of the (Z)-trifluoroethanediazoate, but not its (E) isomer, is catalyzed by buffer acids, and the catalysis by carboxylic acids is characterized by a Bronsted plot with a slope alpha = 0.41. Catalysis by methoxylammonium ion is comparatively weak, the rate constant falling a log unit below the aforementioned Bronsted line. The solvent deuterium isotope effect for formic acid catalysis is k(HA)/k(DA) = 3.1 +/- 0.2 It is concluded that the mechanism for general acid catalysis of the decomposition of the (Z)-diazoic acid entails proton transfer to oxygen that is concerted with N-O bond heterolysis to yield the diazonium ion.

  DOI：

  10.1021/ja00094a016
• 作为产物：
  描述：

  仲丁胺 在 三氧化二氮 作用下， 生成 (E)-2-butenediazoic acid
  参考文献：
  名称：

  Kinetic studies on the formation ofN-nitroso compounds VI. The reactivity of N2O3 as a nitrosating agent

  摘要：

  DOI：

  10.1007/bf01134177

文献信息

• Garcia-Rio, Luis; Iglesias, Emilia; Leis, J. Ramon, Journal of the Chemical Society. Perkin transactions II, 1993, # 1, p. 29 - 37
  作者：Garcia-Rio, Luis、Iglesias, Emilia、Leis, J. Ramon、Pena, M. Elena、Rios, Ana

  DOI：——

  日期：——
• (E)-2-Butanediazoic acid decomposes via a diazonium ion intermediate
  作者：Jari I. Finneman、Jian Ho、James C. Fishbein

  DOI：10.1021/ja00060a076

  日期：1993.4
• Kinetic studies on the formation ofN-nitroso compounds VI. The reactivity of N2O3 as a nitrosating agent
  作者：Julio Casado、Albino Castro、J. Ram�n Leis、M. Arturo L�pez Quintela、Manuel Mosquera

  DOI：10.1007/bf01134177

  日期：——
• Rate-Limiting Formation of Diazonium Ions in the Aqueous Decomposition of Primary Alkanediazoates
  作者：Jian Ho、James C. Fishbein

  DOI：10.1021/ja00094a016

  日期：1994.7

  Rate constants, k(0), for the buffer-independent decomposition of four primary (E)-alkanediazoates and one primary (Z)-alkanediazoate in aqueous media at 25 degrees C, ionic strength 1 M (NaClO4) are reported. Between pH 4 and 12 the plot of log k(0) against pH is biphasic with a hydrogen ion-dependent reaction at the high-pH end changing to a pH-independent region at lower pH. The change in absorbance at 235 nm of the relatively stable (E)-trifluoroethanediazoate as a function of pH gives a good fit to a simple titration curve for a monofunctional acid with pK(a) = 7.00 +/- 0.04 that is in good agreement with the kinetic pK(a) determined from the pH-rate profile between pH 4 and 12. The plot of log k(1), the pH-independent rate constant, against sigma* for the primary (E)-alkanediazoates, and (E)-methane- and (E)-2-butanediazoates previously reported, yields a common line with a slope rho* = -4.4. Of the 1-butanol formed from the decomposition of (E)-1-butanediazoate in D2O at pH(obs),b, = 10.50, 6% contains deuterium, while, of the 1-butanol formed in the presence of 1 M NaOD in D2O, 25% contains deuterium. A total of 96% of the iodotrifluoroethane formed upon decomposition of (E)-trifluoroethanediazoate in a D2O solution that is 1 M in NaI contains at least a single deuterium atom. These data combined with small negative values of Delta S#, normal solvent deuterium isotope effects, and the decreases in k(1) of between 500- and 1000-fold on change of solvent to ethanol are consistent with a mechanism that involves the rate-limiting unassisted heterolytic bond fission of the diazoic acid to yield the diazonium ion. The decomposition of [O-16]-(E)-1-butanediazoate in water containing 47 +/- 2% O-18 yields 1-butanol of which 49 +/- 2% contains O-18. This observation, in combination with the observed pH-dependent deuterium incorporation into 1-butanol during decomposition of (E)-1-butanediazoate, above, indicates that the 1-butanediazonium ion is a diffusionally equilibrated intermediate. The rate constant for the pH-independent decomposition of the (Z)-trifluoroethanediazoate is 2600 times greater than that for the corresponding (E) isomer. The decomposition of the (Z)-trifluoroethanediazoate, but not its (E) isomer, is catalyzed by buffer acids, and the catalysis by carboxylic acids is characterized by a Bronsted plot with a slope alpha = 0.41. Catalysis by methoxylammonium ion is comparatively weak, the rate constant falling a log unit below the aforementioned Bronsted line. The solvent deuterium isotope effect for formic acid catalysis is k(HA)/k(DA) = 3.1 +/- 0.2 It is concluded that the mechanism for general acid catalysis of the decomposition of the (Z)-diazoic acid entails proton transfer to oxygen that is concerted with N-O bond heterolysis to yield the diazonium ion.