Abstract: | The thermal conversion of 4‐isoxazolines to 4‐oxazolines involves the transposition of two ring members. The ring‐contraction and ring‐expansion sequence in the reaction 2 → 5 has been previously clarified. The low N?N bond energy should favor an analogous conversion of 3‐pyrazolines 6 to 4‐imidazolines 7 ; the first example of such a transformation is reported here. In the yellow 16 , the 3‐pyrazoline is part of a pyrazolo5,1‐a]isoquinoline system. Daylight induces a ring contraction, which affords the 2‐isoquinolylaziridine derivative 21 . The latter is converted at 65° to the tricyclic 4‐imidazoline 26 by a sequence of electrocyclic aziridine ring‐opening and 1,5‐electrocyclization of a C=N‐conjugated azomethine ylide 25 . |