ARRRRGGGHHH!

Chloroform is not used very much at all industrially. Previously it was used a fair amount as an "organic solvent" which means it was used to extract fats away from water based solutions. However, chloroform, like its heavier, much more toxic cousin, carbon tetrachloride, has been known to cause liver damage in some people and liver cancer in rats. Its industrial use involves significant safety equipment to ensure it is not inhaled by workers or released into the environment in significant amounts. Even the least toxic chlorinated hydrocarbon of the one-carbon series (methylene chloride, also known as dichloromethan) has come under tighter regulation.

Most of the things that used to be used for inhalation anesthesia (ether, chloroform) are either highly explosive or are associated with things that are nasty (liver and brain damage). You cannot buy the stuff that is currently used for without a federal license.

I would strongly advise against "putting people to sleep". They have a bad tendency, not generally discussed in BDSM fiction. They have a tendency not to wake up. Auto-erotic asphyxia (AEA) kills several people each year. And AEA is probably relatively safe compared to attempts to induce anesthesia for erotic purposes.

In the old days, after about eight years of post college education some of us got to use very fancy drugs to put people to sleep and then wake them up again. There was someone with five to six years training than you standing directly behind you. And it was still very scary. When I think about all the things that can go wrong! It is probably the reason why so many physicians undergo surgery under local anesthesia (or regional blocks) rather than general anesthesia.

THIS IS A BIG "DO NOT TRY THIS AT HOME".