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首页> 外文期刊>Journal of Physical Organic Chemistry >Do general nucleophilicity scales exist?
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Do general nucleophilicity scales exist?

机译:是否存在一般的亲核量表?

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摘要

Comprehensive nucleophilicity scales including pi-, n- and sigma-nucleophiles have been constructed using benzhydrylium ions and structurally related quinone methides as reference electrophiles. It is shown how the correlation (Eqn (1)) log k(20 degrees C) = s(E + N), where s and N are nucleophile-specific parameters and E is an electrophile-specific parameter, has recently been employed to characterize further classes of nucleophiles (phosphines, amines, isonitriles, trifluoromethanesulfonyl-substituted carbanions) and electrophiles (2-benzylideneindan-1,3-diones and benzylidenebarbituric acids). Practical applications of the reactivity parameters E, N and s for developing Friedel-Crafts alkylations in neutral alcoholic or aqueous solution and for characterizing nucleophilic organocatalysts will be discussed. Eventually, a new correlation equation will be presented, which includes Eqn (1), the Ritchie equation (nucleophilic additions to stabilized carbocations), and the Swain-Scott equation (nucleophilic substitutions of methyl halides) as special cases.
机译:已使用苯甲鎓离子和结构相关的醌甲基化物作为参比亲电试剂,建立了包括pi-,n-和sigma-亲核试剂的综合亲核试剂规模。显示了最近如何使用相关性(Eqn(1))log k(20摄氏度)= s(E + N),其中s和N是亲核试剂特定的参数,E是亲电试剂特定的参数,表征其他类别的亲核试剂(膦,胺,异腈,三氟甲磺酰基取代的碳负离子)和亲电试剂(2-苄叉二氢-1,3-二酮和苄叉巴比妥酸)。将讨论反应性参数E,N和s在中性醇或水溶液中发展Friedel-Crafts烷基化反应以及表征亲核有机催化剂的实际应用。最终,将提出一个新的相关方程,其中包括Eqn(1),Ritchie方程(对稳定碳正离子的亲核加成)和Swain-Scott方程(甲基卤化物的亲核取代)。

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