Kaumanns Oliver, Appel Roland, Lemek Tadeusz, Seeliger Florian, Mayr Herbert
Department Chemie und Biochemie, Ludwig-Maximilians-Universitat Munchen, Butenandtstr. 5-13 (Haus F), 81377 Munchen, Germany.
J Org Chem. 2009 Jan 2;74(1):75-81. doi: 10.1021/jo802241x.
The rates of the reactions of the colored para-substituted phenylacetonitrile anions 1a-c and the phenylpropionitrile anions 2a-c with Michael acceptors (3a-u) were determined by UV-vis spectroscopy in DMSO at 20 degrees C. The reactions follow second-order kinetics, and the corresponding rate constants k(2) obey the linear-free-energy relationship log k(2)(20 degrees C) = s(N + E), from which the nucleophile-specific parameters N and s of the carbanions 1a-c and 2a-c have been derived. With nucleophilicity parameters from 19 < N < 29, they are among the most reactive nucleophiles which we have so far parametrized. In DMSO, the nucleophilicity of the tert-butoxide anion is comparable to that of the p-cyanophenylacetonitrile anion 1b.
在20℃下于二甲基亚砜中，通过紫外 - 可见光谱法测定了有色对位取代苯乙腈阴离子1a - c和苯丙酸腈阴离子2a - c与迈克尔受体（3a - u）的反应速率。这些反应遵循二级动力学，相应的速率常数k(2)服从线性自由能关系log k(2)(20℃)= s(N + E)，由此得出了碳负离子1a - c和2a - c的亲核试剂特异性参数N和s。其亲核性参数为19 < N < 29，它们是我们迄今已参数化的反应活性最高的亲核试剂之一。在二甲基亚砜中，叔丁醇根阴离子的亲核性与对氰基苯乙腈阴离子1b相当。
