I've found Phenobarbital on the dark web for fairly cheap, 10g per box at roughly £55 (not including shipping, but it's very cheap at ~£1 per box) and I've ordered 2 just a couple of days ago. It's called Barbtial-100 and I've seen it on at least 2 different markets (both from the same vendor). Phenobarbital overdose can be fatal at 10g, but the highest I've ever heard someone surviving a Phenobarbital overdose is 16g, hence why I ordered 2 boxes to get 20g.
Phenobarbital should be as peaceful as Pentobarbital (Nembutal), the only problem with Pheno compared to Pento is that it's slower acting. You'll still go into a coma after about half an hour or 2 (providing you don't vomit beforehand), but it can take up to 3 days to make you CTB, so you have to make sure you can't be found for 3-4 days.
I've also found Isotonitazene which is supposed to be an incredibly powerful opioid (2.5 times more potent than hydromorphone and slightly more potent than fentanyl), but is a lot more expensive than the Barbital-100 I've previously mentioned. Cheapest I've found is 10g for ~£210. Opioids also have less bioavailability taken orally compared to having it injected, so I'm unsure if 10g will be enough. (I plan on ordering 20g once I can get more money converted to crypto.)
Etonitazene is twice as powerful as Isotonitazene but sadly I haven't been able to find it in any dark markets that I've checked.
I've also seen a few vendors selling Nembutal powder on one of the same markets that's also selling Barbital-100, but I dunno how legitimate they are since no orders have been made on any of them. Probably not that it matters to you since the cheapest I've found is ~£250 for 10g and you ideally want 20g.