If you look at actually Golden Age comics, Hugo Strange and the Mad Monk are iirc the only somewhat important villains that pre date Robin.
Joker, Catwoman, Penguin, Scarecrow, Two Face and Clayface (but without any powers) are iirc the only ones that appeared reactively close after Robin in the early 40s. With Joker, Catwoman and Penguin the only ones that were appearing really frequently.
Mad Hatter and Riddler are from the late 40s.
And Ivy and Calendar Man are both Silver Age Villains and don't belong that early in Batman's history.
And Grundy isn't even an Batman villain.