From Primetime to Daytime: Fred Flintstone as Superstone (1965)
Fred Flintstone (Alan Reed) will do anything to 1) make a few extra bucks and 2) impress his daughter, Pebbles. In this 5th season episode of The Flintstones, Fred steps in when the star of the TV show, Superstone, quits, right before a scheduled personal appearance in Bedrock. This leaves Barney (Mel Blanc) to mind Pebbles, as well as his own adopted son, Bamm-Bamm.
Superstone, of course, was a parody of Superman, who would be licensed to Hanna-Barbera 8 years after this episode aired, with the launch of Super Friends.