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See, what I really want to know about castoreum is, who's the person that went around rimming wildlife until they found an animal whose butthole tasted good? And was this part of their job, somehow, or just a... personal hobby? So many questions, none of them answered by the Wikipedia article.
Most likely it was discovered during the butchering of beavers.
Beaver pelt was a highly valued product on the American frontier for hundreds of years. A whole trade was built around it. And given the circumstances of the first ~200 years of Europeans colonising Northern America, they wouldn't have wasted the rest of the animal just for the pelt - what little meat every beaver had would've been used.
So you're out there, butchering a beaver, grabbing it by the pu... anus, and you notice that even though you washed the carcass, there's some oily residue on your gloves/hand after pressing around the area. It's not something you've seen before, but you know very well how valuable all sorts of animal oils (tallow, pig fat, especially whale blubber) are, so you check it out. First thing you do is smell it... and damn, it smells GOOD. Maybe you've even had a bit of vanilla before as a treat, and recognise the scent being similar. Then you taste it, just a lick... and it's just like that piece of cake you had at the fancy cake shop ages ago as a kid. Or not recognise it but realise it's tasting good.
Either way, you just found a potentially usable resource. Spices and seasonings are still a luxury, so you tell others about it, after all, who wouldn't want to make some extra money on the work they're already doing?
And suddenly people want it. Vanilla is scarce and expensive, people like the flavour, and beavers are plentiful. You extract some oil, take it to the town chemist who checks it, deems it safe to use, and BAM, you have a new revenue stream, all you have to do is 30 minutes of extra work on the beavers you caught - wash the ass, express the anal glands for their oils, collect it up, and sell it by vials.
Most discoveries happen like that. Yes, to us it sounds weird, who the hell goes around licking asses of animals for hidden secrets? But in reality you were just making use of something, and found an extra resource.
People used to eat anything and everything out of desperation. They weren't out to taste anuses specifically. Well, most people weren't. They get to the last part, are still hungry, grimace and put it in their mouth and there's an unexpectedly pleasant (given the circumstances) surprise.
We also have dogs. After enough time with enough people and enough dogs, eventually someone's going to notice their dog being especially excited about eating the part that they'd normally give to it to eat, and so sniff, if not actually taste. Same surprised reaction.
There's also the fact that no person (or dog) must have died from doing this, so other people were less afraid to try it.
Animal Anuses Georg is an outlier and should not be counted