Stereoelectronic effects in cyclohexanones, methylenecyclohexanes, spiro, and epoxy compounds of cyclohexanes and further derivatives were investigated by measuring ¹J_C,H coupling constants and by identification of Perlin effects, that is, of differences in the coupling constants for equatorial and axial CH bonds in the methylene groups of six‐membered rings. The Perlin effects were correlated with results from natural bond orbital analyses. NMR experiments and calculations were performed with conformationally restricted 4‐tert‐butyl‐substituted derivatives. It turned out that the coupling constants are strongly influenced not only by stereoelectronic interactions with CC, CO, and CN π bonds, or with the π‐type CC or CO bonds of the three‐membered rings, but also by the s character of the respective CH bonds' carbon orbital. Reliable correlations of measured and calculated coupling constants were achieved with B3LYP/6‐311++G(d,p) and BP86/aug‐cc‐pVTZ‐J functionals.

中文翻译：

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立体电子效应：环己烷衍生化合物中的Perlin效应

通过测量在环己酮，methylenecyclohexanes，螺环和环己烷和进一步的衍生物的环氧化合物立体电子效应进行了研究¹ Ĵ _C，H耦合常数和由鉴定Perlin的效果，也就是在对赤道和轴向C中的耦合常数的差异，六元环亚甲基中的H键。Perlin效应与自然键轨道分析的结果相关。NMR实验和计算是使用构象受限的4-叔丁基取代的衍生物进行的。原来，耦合常数不仅通过与CC，CO和CNπ键，或与π-C型立体电子相互作用强烈影响三元环的C或CO键，但也取决于各自CH键的碳轨道的特征。使用B3LYP / 6-311 ++ G（d，p）和BP86 / aug-cc-pVTZ-J功能可实现测量和计算的耦合常数的可靠相关性。