I understand saccharin was discovered only because a chemist by the name of Constatin Fahlberg happen to notice a sweet taste on his fingers after a day in the lab working with new compounds.
That said, to answer your question, if you know a certain series of unstable nitrogen compounds like nitroglycerin is toxic, you can safely deduce that if you were to create another in that same series, it would be equally toxic.
My guess is, a good many compounds are just indicated as toxic, because it’s a reasonable conclusion, and not because someone tasted it to be sure.
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