The original Grunwald-Winstein equation (1948) involved the development of a scale of solvent ionizing power (Y). Subsequent work has refined this scale and involved the development of scales of solvent nucleophilicity (N) and a term to correct for deviations when aromatic rings are present, governed by the aromatic ring parameter (I). These three scales, and the sensitivities towards each, can be related to specific rates of solvolysis through linear free energy relationships (LFERs).One important area of application of LFERs has been to the solvolyses of tert-alkyl halides. It has been proposed that the solvolysis of tert-butyl chloride involves a nucleophilic component, although other workers have suggested that the effects observed are related to electrophilic not nucleophilic influences. Takeuchi (1997) studied a compound with two of the methyl groups of tert-butyl chloride replaced by neopentyl groups. For this highly-hindered substrate there was no evidence for nucleophilic participation. Liu (1998) and Takeuchi (2001) have reported concerning the solvolyses of additional significantly-hindered tertiary alkyl chlorides. Liu (2009) has presented a parallel study of bromides. Martins (2008) has considered hindered tertiary alkyl halides, mainly with carbon-carbon multiple bonds as substituents. It was proposed that the hI term was of importance, with the sensitivities (h) sometimes positive and sometimes negative. To explain negative values, it was suggested that the I scale might contain a nucleophilicity component. In this review, we bring together, with analysis and commentary, the work of Takeuchi, Liu, Martins and others concerning the solvolyses of tertiary alkyl halides, with emphasis on the relevance of the three scales that have been developed for use in Grunwald-Winstein correlations.

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使用简单和扩展 Grunwald-Winstein 方程关联高位阻叔烷基衍生物的溶剂分解速率

最初的 Grunwald-Winstein 方程 (1948) 涉及溶剂电离能力 (Y) 尺度的发展。随后的工作改进了这个尺度，并涉及溶剂亲核性 (N) 尺度的发展，以及当存在芳环时校正偏差的术语，由芳环参数 (I) 控制。这三个尺度以及对每个尺度的敏感性可以通过线性自由能关系 (LFER) 与特定的溶剂分解速率相关。LFER 的一个重要应用领域是叔烷基卤化物的溶剂分解。有人提出叔丁基氯的溶剂分解涉及亲核成分，尽管其他工作人员认为观察到的影响与亲电而非亲核影响有关。Takeuchi (1997) 研究了一种化合物，其中叔丁基氯的两个甲基被新戊基取代。对于这种高度受阻的底物，没有亲核参与的证据。Liu (1998) 和 Takeuchi (2001) 报道了其他显着受阻叔烷基氯的溶剂分解。Liu (2009) 提出了一项关于溴化物的平行研究。Martins (2008) 考虑了受阻叔烷基卤化物，主要以碳-碳多重键作为取代基。有人提议 hI 项很重要，敏感度 (h) 有时为正，有时为负。为了解释负值，有人建议 I 标度可能包含亲核性成分。在这篇评论中，我们结合分析和评论汇集了 Takeuchi, Liu,