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I've always been fond of hot food - hot in the sense that chillies are hot -  so I thought I'd list all the hot spices and vegetables I could think of, and see what was in them that made them hot. I was expecting some degree of overlap, but it was more than I had thought.

Essentially there are just two sort of "hot" food substance. The first shares a family of active ingredients that are chemically related

All the other "hot' things I thought of (Horseradish, Mustard, Radish, Wasabi) belong to the cabbage family and what makes them hot is Allyl isothiocyanate (aka mustard oil). Here's a model of the molecule, from Wikipedia:

Grey atoms are Oxygen Hydrogen, the black Carbon the blue Nitrogen, and the yellow Sulphur.