m-Nitrobenzylidenemalonodialdehyde | 82700-46-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醛
• 英文名称: m-Nitrobenzylidenemalonodialdehyde
• 英文别名: 2-[(3-nitrophenyl)methylidene]propanedial
• CAS: 82700-46-7
• 化学式: C₁₀H₇NO₄
• 分子量: 205.17
• InChiKey: ZQBMISUCWLQKMW-UHFFFAOYSA-N

物化性质

• 熔点：
  91-93.5 °C
• 沸点：
  434.4±40.0 °C(Predicted)
• 密度：
  1.339±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  80
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  m-Nitrobenzylidenemalonodialdehyde 以 水 为溶剂， 生成 (Z)-3-Hydroxy-2-[hydroxy-(3-nitro-phenyl)-methyl]-propenal 、 (Z)-2-Formyl-3-hydroxy-3-(3-nitro-phenyl)-propen-1-ol anion
  参考文献：
  名称：

  Kinetics of the Reactions of Phenyl-Substituted Benzylidenemalonodialdehydes with Water and Hydroxide Ion

  摘要：

  A kinetic study of the reactions of substituted benzylidenemalonodialdehydes, ZC(6)H(4)CH=C(CHO)(2) with Z=p-NMe(2), p-OMe, m-OMe, p-Cl, p-Br, m-NO2, and p-NO2, with OH- and water in aqueous solution is reported. The reactions lead reversibly to the formation of adducts, ZC(6)H(4)CH(OH)C(CHO)(2)(-), although the kinetics are complex because of the formation of the enol form, ZC(6)H(4)CH(OH)C(CHO)=CHOH, and OH- addition to one of the carbonyl groups. Analysis of the pH-dependence of the rates allows a determination of the rate and equilibrium constants for water and OH- addition (k(1)(H2O), k(1)(OH), K-1(H2O), K-1(OH)) as well as, in some cases, of the pK(a) of the enol form and the equilibrium constant of OH- addition to a carbonyl group. Furthermore, at low pH, where the p-NMe(2) derivative is protonated, k(1)(H2O) and K-1(H2O) for this protonated form are also obtained. The rate and equilibrium constants correlate better with sigma(+) than with standard Hammet sigma-values, indicating that a substantial amount of resonance stabilization is lost in converting the olefin to the adduct. Bronsted-type plots of log k(1)(H2O) and log k(1)(OH) vs log K-1(H2O) show that the points for p-NMe(2) and p-OMe deviate negatively from the line defined by the other substituents. The observed deviations imply a reduced intrinsic rate constant (k(0)) for these compounds, due to a transition state in which the loss of resonance is ahead of bond formation. This behavior is reminiscent of that in the reactions of substituted benzylidene Meldrum's acids and benzylidenemalononitriles with nucleophiles, but opposite to that found with substituted beta-nitrostyrenes and other nitro-activated olefins.

  DOI：

  10.1021/jo00096a039
• 作为产物：
  描述：

  间硝基苯甲醛 、 1,3-bis-dimethylaminotrimethinium perchlorate 在 盐酸 、 高氯酸 作用下， 生成 m-Nitrobenzylidenemalonodialdehyde
  参考文献：
  名称：

  Arnold, Zdenek; Kral, Vladimir; Dvorak, Dalimil, Collection of Czechoslovak Chemical Communications, 1984, vol. 49, # 11, p. 2602 - 2612

  摘要：

  DOI：

文献信息

• Arylmethylenemalonaldehydes and their heterocyclic analogues: A novel group of organic lewis acids
  作者：Z. Arnold、V. Král、D. Dvořák

  DOI：10.1016/s0040-4039(00)87200-7

  日期：1982.1
• ARNOLD, Z.;KRAL, V.;DVORAK, D., COLLECT. CZECHOSL. CHEM. COMMUN., 1984, 49, N 11, 2602-2612
  作者：ARNOLD, Z.、KRAL, V.、DVORAK, D.

  DOI：——

  日期：——