Cyanates are pretty harmless. We would often leave the Kipps Apparatus on at school thinking how funny the rotten eggs smell was. Only found out years later that hydrogen sulphide is nearly as toxic as hydrogen cyanide. We also used benzene to clean up glassware after organic chemistry, and handled mercury (literally) when making a barometer. It was handed out in open beakers.
I knocked myself out once with home-made chloroform (carbon tetrachloride solvent + bleach I think).
The best schoolboy explosive was nitrogen triiodide - easy to make, unbelievably sensitive and a nice purple cloud when it goes off.