α-Tritiotoluol | 6683-73-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: α-Tritiotoluol
• 英文别名: α-T-toluene；[α-³H]toluene；(α-³H oder ²H)Toluol；<α-3H> Toluol；<α-3H>-Toluol；(α-³H)Toluol；Toluene, [3H]；tritiomethylbenzene
• CAS: 6683-73-4
• 化学式: C₇H₈
• 分子量: 94.1326
• InChiKey: YXFVVABEGXRONW-CNRUNOGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  α-Tritiotoluol 在 氨-d3 、 potassium amide 作用下， 生成 deuteriomethyl-benzene
  参考文献：
  名称：

  摘要：

  Specific features of the stepwise hydrogen exchange mechanism and transition state structure in the systems acetophenone-liquid ammonia in the absence of foreign compounds and in the presence of bases and toluene-liquid ammonia in the presence of potassium amide were studied in terms of an approach based primary and secondary kinetic isotope effects of the substrate and the solvent. The mechanisms of reactions involving acetophenone and toluene were compared. In the first case, an elementary act of CH-acid ionization is contributed to a small extent by diffusion-controlled separation of the carbanion and ammonia molecule. hydrogen exchange in toluene is characterized by complete absence of the internal ion pair return effect. The ratio k(D)(NH3)/k(T)(NH3) for hydrooen exchange in acetophenone tends to decrease on addition of bases (with simultaneous increase in its rate), which may be explained by formation of an adduct via interaction between the unshared electron pair on the heteroatom in the base molecule and the carbonyl carbon atom. The anomalous temperature dependence of k(D)(NH3)/k(T)(NH3) for hydrogen exchange in toluene is interpreted as a result of contribution of side metalation of the C-H bond by potassium amide. The change in the solvent protophilicity due to replacement of the "light" solvent by deuterated one differently affects the kinetics and mechanism of hydrogen exchange in acetophenone and toluene. Measurements of the alpha-deuterium effect gave information on the mode of angular deformation of C-D bonds in the methyl group of toluene in the hydrogen exchange transition state.

  DOI：

  10.1023/a:1024997601298
• 作为产物：
  描述：

  苄基氯化镁 在 HTO 作用下， 以 乙醚 为溶剂， 生成 α-Tritiotoluol
  参考文献：
  名称：

  950 K处甲基吸收氢中某些碳氢键的相对反应性

  摘要：

  Relative reactivities of C-H bonds in alkylbenzenes in the hydrogen abstraction by methyl radicals at about 950 K were determined by means of labeled compounds. The following values normalized to the primary aliphatic C-H bond were obtained: r(Ph-H) = 0.7 +/- 0.1; r(Bz-H) = 4.6 +/- 0.5; r(sec,benzyl) = 8.7 +/- 1.0; r(tert,benzyl) = 9.0 +/- 1.0. The combination of these high-temperature values with low-temperature kinetic data from the literature reveals the absence of a straight connection between strength and reactivity of C-H bonds.

  DOI：

  10.1021/j100055a021

文献信息

• Heterogeneous palladium-catalyzed exchange labelling of representative organic compounds with tritium gas
  作者：Philip G. Williams、Chit Than、Sadegh Rabbani、Mervyn A. Long、John L. Garnett

  DOI：10.1002/jlcr.2580360102

  日期：1995.1

  alkanes and the alkyl chains of alkylbenzenes were rapidly and evenly labelled. Some aromatic compounds showed general ring exchange while others showed high specificity. These results for bulk palladium catalyst are strikingly different from those obtained with bulk platinum and supported palladium catalysts. The results are discussed in terms of currently accepted mechanisms of heterogeneous metal catalyzed

  使用 NaBH4 还原的氧化钯或氯化物作为催化剂，一系列有机底物成功地与氚气交换。交换条件包括反应温度为 100 °C，反应时间为 3 天，并通过放射性气相色谱和 3 H NMR 光谱分析产物。芳香族和脂肪族化合物都进行了交换，22 种底物中的 18 种结合了 > 35% 的可用氚，并且大多数产品显示出高放射化学纯度。3 H NMR 分析表明，烷烃和烷基苯的烷基链均被快速且均匀地标记。一些芳香族化合物表现出一般的环交换，而另一些则表现出高特异性。本体钯催化剂的这些结果与使用本体铂和负载钯催化剂获得的结果截然不同。
• Long, Mervyn A.; Garnett, John L.; Williams, Philip G., Australian Journal of Chemistry, 1982, vol. 35, # 5, p. 1057 - 1059
  作者：Long, Mervyn A.、Garnett, John L.、Williams, Philip G.

  DOI：——

  日期：——
• Koltai,E. et al., Chemische Berichte, 1971, vol. 104, p. 290 - 300
  作者：Koltai,E. et al.

  DOI：——

  日期：——
• ANGELINI G.; CPARAPANI C.; SPERANZA M., GAZZ. CHIM. ITAL., 116,(1986) N 9, 479-484
  作者：ANGELINI G.、 CPARAPANI C.、 SPERANZA M.

  DOI：——

  日期：——
• ——
  作者：I. F. Tupitsyn、N. N. Zatsepina

  DOI：10.1023/a:1024997601298

  日期：——

  Specific features of the stepwise hydrogen exchange mechanism and transition state structure in the systems acetophenone-liquid ammonia in the absence of foreign compounds and in the presence of bases and toluene-liquid ammonia in the presence of potassium amide were studied in terms of an approach based primary and secondary kinetic isotope effects of the substrate and the solvent. The mechanisms of reactions involving acetophenone and toluene were compared. In the first case, an elementary act of CH-acid ionization is contributed to a small extent by diffusion-controlled separation of the carbanion and ammonia molecule. hydrogen exchange in toluene is characterized by complete absence of the internal ion pair return effect. The ratio k(D)(NH3)/k(T)(NH3) for hydrooen exchange in acetophenone tends to decrease on addition of bases (with simultaneous increase in its rate), which may be explained by formation of an adduct via interaction between the unshared electron pair on the heteroatom in the base molecule and the carbonyl carbon atom. The anomalous temperature dependence of k(D)(NH3)/k(T)(NH3) for hydrogen exchange in toluene is interpreted as a result of contribution of side metalation of the C-H bond by potassium amide. The change in the solvent protophilicity due to replacement of the "light" solvent by deuterated one differently affects the kinetics and mechanism of hydrogen exchange in acetophenone and toluene. Measurements of the alpha-deuterium effect gave information on the mode of angular deformation of C-D bonds in the methyl group of toluene in the hydrogen exchange transition state.