For drugs in Twilight, two natural substances that would be of high value would be anything opium-based and cocaine.
Opiates are very useful for treating pain, though the problem is with the dosage, because you have to know the purity/potency of the said batch. Opiates cause, in high doses, cessation of breathing and unconsciousness, which is the thing that kills most junkies ODing on them. With potent enough stuff the guy can be out cold very quickly - I actually encountered one, while working as a paramedic, who had not even had managed to pull the needle out of the vein.
Cocaine, though mostly known for party usage by yuppies in the 80ies is a good local anesthetic, still used in nasal surgery for an instance. It does reduce the bleeding a bit as well as numbing (and it does cause excessive talkativeness and hilarity in the patient, if he is awake). It can be used to numb up the eyes as well, and pretty much anything else as well. Of course, in the Twilight timeline, the availability is not very high.
An interesting, potentially useful alternate is an aquatic centipede, found at least in the Mediterranean. While being bitten doesn't really feel that nice, the bite numbs the location bitten shortly after. I'm not completely familiar with what the said centipede secretes, but as far as I've heard, it is pretty effective.
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"Listen to me, nugget, and listen good. Don't go poppin' your head out like that, unless you want it shot off. And if you do get it shot off, make sure you're dead, because if you ain't, guess who's gotta drag your sorry ass off the field? Were short on everything, so the only painkiller I have comes in 9mm doses. Now get the hell out of my foxhole!" - an unknown medic somewhere, 2013.
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