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首页> 美国卫生研究院文献>Proceedings of the National Academy of Sciences of the United States of America >Structural effects in solvolytic reactions; carbon-13 NMR studies of carbocations†: Effect of increasing electron demand on the carbon-13 NMR shifts in substituted tert-cumyl and 1-aryl-1-cyclopentyl carbocations—correlation of the data by a new set of substituent constants σC+
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Structural effects in solvolytic reactions; carbon-13 NMR studies of carbocations†: Effect of increasing electron demand on the carbon-13 NMR shifts in substituted tert-cumyl and 1-aryl-1-cyclopentyl carbocations—correlation of the data by a new set of substituent constants σC+

机译：溶剂分解反应中的结构效应；碳正离子的碳13 NMR研究†：电子需求增加对取代的叔枯基和1-芳基-1-环戊基碳正离子中碳13 NMR位移的影响-数据与一组新的取代基常数σC+的相关性

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The cationic carbon substituent chemical shifts (ΔδC+) for nine representative meta-substituted tert-cumyl carbocations are correlated satisfactorily by the σm+ substituent constants (slope ρ+ = -18.18, correlation coefficient r = 0.990). However, the substituent chemical shifts (ΔδC+) for the corresponding para derivatives are not correlated by the σp+ substituent constants. The possibility of developing a set of substituent constants capable of correlating such 13C NMR shifts was examined. The slope of the line defined by the meta substituents (ρ+ = -18.18) was utilized to calculate σC+ constants for both meta and para substituents. The utility of these constants was then tested by their ability to correlate the 13C NMR shifts in the cations for a different system, the 1-aryl-1-cyclopentyl cations. Indeed, these σC+ values correlate very well with the ΔδC+ values, yielding ρC+ = -16.84, r = 0.999.
机译：9个代表性的间位取代的叔枯基碳正离子的阳离子碳取代基化学位移（ΔδC + ）与σm + 取代基常数（坡度ρ+ = -18.18）令人满意地相关。 ，相关系数r = 0.990）。但是，相应对位衍生物的取代基化学位移（ΔδC + ）与σp + 取代基常数无关。研究了开发一组能够与这样的 13 C NMR位移相关的取代基常数的可能性。用间位取代基定义的直线的斜率（ρ+ = -18.18）计算间位和对位取代基的σ C + 常数。这些常数的效用随后通过它们将不同系统阳离子的1-sup-1-环戊基阳离子的 13 C NMR位移相关联的能力进行了测试。实际上，这些σ C + 值与ΔδC + 值具有很好的相关性，得出ρ C + = -16.84，r = 0.999。

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