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Just because something is a good design or would be extremely useful doesn't mean it will appear due to evolution. But if a large mammal DID just suddenly develop a useful form of toxic that wouldn't poison itself somehow and could be easily used as a weapon, then yeah it would probably be useful. Actually most large animals that use toxins to hunt will do something much more biologically efficient; they'll go over to something in the environment that's poisonous and rub up against it to make themselves poison. That way they don't need to make it themselves.
