The well-known N lone-pair orientation effect on (1)J(CC) spin-spin coupling constants (SSCCs) in oximes and their derivatives was used to study how negative hyperconjugative interactions of type LP1(O) -> sigma* CC depend on ortho interactions involving the OH group. This study demanded the following analyses: (i) a qualitative estimation of how (1)J(CC) SSCCs are affected by hyperconjugative interactions, ( ii) a study of similar stereochemical effects to those in oximes, but in (1)J(C1C2) and (1)J(C1C6) in 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) -> sigma* 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)center dot center dot center dot H-C; (c) they are inhibited by interactions of type LP(O-1)center dot center dot center dot H-O. Consequences of these observations are discussed.3412841294