Hexane works just fine for extracting, with about 5 or 6 thorough pulls you can get 1+% from good bark, and if you freeze precipitate you'll get white and yellow crystalss (which can be recrystallized if you want but should be fine to vaporize as is, if you dried them well).. Its good for first extractions I would say, and yeah as snozz said its pretty similar to naphtha (naphtha is usually a mix with the likes of pentane, hexane, heptane).
Toluene and xylene will pull DMT easier, as well as some plant oils and inactive impurities, and also small amounts of other alkaloids (NMT and 2-MTHBC) which might or might not affect the trip considering they are in so small amounts (around 3%).
The thing with toluene and xylene is that they smell really nasty, toxic, xylene specially (toluene is "sweeter" but yuck imo like "sweet" cancer

). Work in well ventilated area.
Considering you do an evap test and these solvents you are using evap clean, yeah its safe to smoke the product from their extraction, but I recommend redissolving the product in non-denatured ethanol/acetone and re-evaporating to remove traces of those solvents trapped in the goo/crystals (do the same for naphtha/hexane stuff imo)
Eventually you might want to check out into salting instead of evaporating the xylene/toluene (or limonene! ). It adds a couple of steps to extraction but you can reuse solvents and get a good yield (and working with limonene is so much nicer than with petrochems imo). Check out BLAB tek in the wiki for detailed instructions
Whatever way you extract, I would say that another just-as-essential factor to take in account is smoking method. Or rather, vaporization method, ideally... Look into the GVG if you have a bit to spend, its IMO (and of many here) the ultimate DMT vaporization method. Otherwise the normal VG. Some people have had success with The Key or similar improvised vaporizers, but I havent tried. The Machine was too harsh for me, and so were any normal pipes. Before, I had mild success with bong and dmt sandwhiched between thick layer of ashes, and going very easy on the lighter. But if you can get the GVG (and a good torch lighter), you wont regret!