The well-known N lone-pair orientation effect on (1)JCC spin-spin coupling constants (SSCCs) in oximes and their derivatives was used to study how negative hyperconjugative interactions of type LP1(O) → σ*CC depend on ortho interactions involving the OH group. This study demanded the following analyses: (i) a qualitative estimation of how (1)JCC SSCCs are affected by hyperconjugative interactions, (ii) a study of similar stereochemical effects to those in oximes, but in (1)JC1C2 and (1)JC1C6in a series of 2-substituted phenols, and (iii) a quantitative estimation, with the natural bond order approach, of some key electron delocalization interactions. A few unexpected results are quoted. LP1(O) → σ*CC interactions are affected by proximity interactions as follows: (a) they are enhanced by hydrogen bonds transferring charge into the (O-H)* antibonding orbital; (b) they are enhanced by proximity interactions of type LP1(O)···H-C; (c) they are inhibited by interactions of type LP(O1)···H-O. Consequences of these observations are discussed.