dicyanomethyl | 58821-77-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: dicyanomethyl
• CAS: 58821-77-5
• 化学式: C₃HN₂
• 分子量: 65.0543
• InChiKey: PCLXMHCHLVZVRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  异己烯 、 dicyanomethyl 生成
  参考文献：
  名称：

  Free radical additions. Part II. Kinetics of free radical additions of bromomalononitrile to alkenes and PMO treatment of the reactivity and regioselectivity

  摘要：

  DOI：

  10.1021/jo00378a009
• 作为产物：
  描述：

  丙二腈 在 二叔丁基过氧化物 作用下， 以 苯 为溶剂， 生成 dicyanomethyl
  参考文献：
  名称：

  Estimation of Bond Dissociation Energies and Radical Stabilization Energies by ESR Spectroscopy

  摘要：

  Correlations of various indices of the stability and reactivity of carbon-centered radicals with ESR hyperfine splitting constants have been examined. For a large number of mono-and disubstituted radicals there is a moderately good linear correlation of alpha-proton hyperfine splitting constants (a(H-alpha) with radical stabilization enthalpies (RSE) and with BDE(C-H), the C-H bond-dissociation energies for the corresponding parent compounds determined from thermodynamic and kinetic studies of C-C homolysis reactions. There is a similarly satisfactory linear correlation of a(H-alpha) with BDE(C-H) determined by Bordwell's electrochemical and acidity function method. In all cases the correlations fail for nonplanar radicals. As expected, beta-proton hyperfine splitting constants (a(HbetaMe)) for radicals with a freely rotating methyl substituent are less sensitive to deviations from planarity and give better linear correlations with RSE and BDE(C-H). The correlations cover a range of more than 20 kcal/mol and are reliable predictors of RSE and BDE(C-H) for a variety of radicals including captodative species. However, the correlations fail for significantly nonplanar radicals and for radicals with cyclic delocalized systems, e.g., cyclopentadienyl. The ratio a(HbetaMe)/a(H-alpha for suitably substituted radicals provides an index of pyramidalization and allows one to decide for which compounds values of RSE and BDE(C-H) can be confidently estimated.

  DOI：

  10.1021/jo971940d

文献信息

• Transition states of electrophilic radical additions to alkenes
  作者：Hendrik Zipse、Jianing He、K. N. Houk、Bernd Giese

  DOI：10.1021/ja00011a041

  日期：1991.5

  (S2CO-i-Pr) (C02) (PMe3)2. In conclusion, our results indicate that in the system under investigation there are small energy differences among the isomeric structures A, B, and C , so that both types of acyl coordination, B and C, are kinetically and thermodynamically accessible from their isomeric alkyl-xrbonyl structure A. Since most of the acyl complexes of molybdenum known to date have q2 structures while

  与钼结合的甲基。(ii) 甲基质子和 31P 核之间的耦合常数从 20 OC 时的 1.8 Hz（在较低温度下相应的信号未解析）增加到 20°C 时的 3.0 Hz。为了进行比较，在结构表征的甲基钨配合物 ~ ~ ~ + ~ W (CH3)(LL) (CO),-(PMe3)2 (LL = acac, S2CNR2, S2COR) 这种耦合范围从 3.5 到 8 Hz。(iii) 4 的溶液红外光谱(20"C) 比 1-3 的更复杂，除了由于 agostic 和 q2-酰基异构体中的羰基官能团产生的谱带外，还显示了在大约 100 处的两个吸收。191 2 和 1836 cm-I 可以暂时归属于甲基二羰基物种 Mo(CHJ (S2CO-i-Pr) (CO2) (PMe3)2 中的末端羰基配体。总而言之，我们的结果表明，在所研究的系统中，异构结构 A、B 和 C 之间的能量差异很小，因此两种类型的酰基配位
• Free radical additions. Part II. Kinetics of free radical additions of bromomalononitrile to alkenes and PMO treatment of the reactivity and regioselectivity
  作者：K. Riemenschneider、H. M. Bartels、R. Dornow、E. Drechsel-Grau、W. Eichel、H. Luthe、Y. M. Matter、W. Michaelis、P. Boldt

  DOI：10.1021/jo00378a009

  日期：1987.1
• Estimation of Bond Dissociation Energies and Radical Stabilization Energies by ESR Spectroscopy
  作者：Jochen J. Brocks、Hans-Dieter Beckhaus、Athelstan L. J. Beckwith、Christoph Rüchardt

  DOI：10.1021/jo971940d

  日期：1998.3.1

  Correlations of various indices of the stability and reactivity of carbon-centered radicals with ESR hyperfine splitting constants have been examined. For a large number of mono-and disubstituted radicals there is a moderately good linear correlation of alpha-proton hyperfine splitting constants (a(H-alpha) with radical stabilization enthalpies (RSE) and with BDE(C-H), the C-H bond-dissociation energies for the corresponding parent compounds determined from thermodynamic and kinetic studies of C-C homolysis reactions. There is a similarly satisfactory linear correlation of a(H-alpha) with BDE(C-H) determined by Bordwell's electrochemical and acidity function method. In all cases the correlations fail for nonplanar radicals. As expected, beta-proton hyperfine splitting constants (a(HbetaMe)) for radicals with a freely rotating methyl substituent are less sensitive to deviations from planarity and give better linear correlations with RSE and BDE(C-H). The correlations cover a range of more than 20 kcal/mol and are reliable predictors of RSE and BDE(C-H) for a variety of radicals including captodative species. However, the correlations fail for significantly nonplanar radicals and for radicals with cyclic delocalized systems, e.g., cyclopentadienyl. The ratio a(HbetaMe)/a(H-alpha for suitably substituted radicals provides an index of pyramidalization and allows one to decide for which compounds values of RSE and BDE(C-H) can be confidently estimated.