AbstractDuring recent years, instead of concentrating on the detection of the intermediacy of new hetarynes, as they did between 1958 and 1964, workers in this field have been more concerned with the critical sifting and checking of the earlier work. Special interest has been shown in the relation between structure and reactivity in the hetarynes. It has been shown that in addition to the elimination‐addition mechanism (EA; hetaryne intermediate), other reaction paths (anomalous addition‐elimination mechanism [AEa] and “Reinecke mechanism”) are possible for nucleophilic cine‐substitutions on hetaryl halides. The use of deuterated hetaryl halides has proved very valuable for the elucidation of the mechanism of nucleophilic substitutions. Even where substitution mechanisms are superimposed on one another the occurrence of a hetaryne intermediate can be detected by a technique known as the “base competition method”. A five‐membered hetaryne (4,5‐didehydro‐1‐methylimidazole) has been detected for the first time by this method with a probability that borders on certainty. Selectivity determinations have shown that the replacement of a CH group in 1,2‐didehydrobenzene and in 1,2‐didehydronaphthalene by an N atom distinctly increases the reactivity to bases. According to EHT (Extended Hückel Theory) calculations, the as yet hypothetical 2,3‐didehydropyridine is richer in energy than 3,4‐didehydropyridine, this agrees more closely with the experimental findings than the opposite result obtained from simple MO calculations. Besides cine‐substitution (1,2 shift), tele‐substitution (1,3‐shift) has also been observed on reaction of hetaryl halides (pyridine, quinoline, and pyrimidine systems) with bases. An EA mechanism (via m‐didehydrohetarenes) and an AEamechanism are considered as