A major insecticidal constituent of Ryania speciosa is isolated and characterized by n.m.r. and mass spectroscopy as the new alkaloid 9,21-didehydroryanodine (2); reduction of (2) with hydrogen (or tritium) gas yields both ryanodine (1) and 9-epiryanodine (3) (or their 9,21-3H analogues) in a 1:9 ratio.