If you have a weird compound like diethyl ether or hexane, and you don’t want to risk setting your kitchen on fire (wise choice), use a chemical database. Websites like PubChem, NIST, or even Wikipedia (yes, really) list reliable boiling points. Just make sure the compound is anhydrous (no water) and at standard pressure.
For extra credit: look up the correlation with molecular weight. Heavier molecules usually boil higher, but not always. That’s the universe’s way of keeping you humble. Don’t overthink it—just trust the table.