Bache-Andreassen Lihn, Uggerud Einar
Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo, Norway.
Org Biomol Chem. 2003 Feb 21;1(4):705-13. doi: 10.1039/b209955c.
The reactivity of carbonyl substituted methyl oxonium ions (R1R2COCH3+) towards ammonia has been investigated using an FT-ICR mass spectrometer and ab initio calculations. The monosubstituted ions (R1 = H; R2 = H, CH3, C2H5 and i-C3H7) show different reaction patterns with variable degree of: (1) nucleophilic substitution, (2) addition-elimination and (3) proton transfer, when reacted with ammonia. In all cases addition-elimination dominates over nucleophilic substitution, and the observed reactions are slow. The trends in reactivity are consistent with the alkyl group's electronic properties, as expressed by a single parameter linear or slightly non-linear model.
使用傅里叶变换离子回旋共振质谱仪和从头算计算方法，研究了羰基取代的甲基氧鎓离子（R1R2COCH3+）与氨的反应活性。单取代离子（R1 = H；R2 = H、CH3、C2H5和i-C3H7）与氨反应时，表现出不同的反应模式，具有不同程度的：（1）亲核取代、（2）加成-消除和（3）质子转移。在所有情况下，加成-消除反应均比亲核取代反应占主导地位，且观察到的反应较慢。反应活性趋势与烷基的电子性质一致，可用单参数线性或略微非线性模型表示。
