Novel synthetic opioids (NSOs) are a class of opioid agonists that include analogs of fentanyl and structurally distinct non-fentanyl compounds normally used as standalone products, heroin adulterants, or constituents of counterfeit pain pills. Most NSOs are not currently scheduled in the U.S., are predominantly illegally synthesized, and sold on the Darknet. Among them, the cinnamylpiperazine derivatives such as bucinnazine (AP-237), AP-238, and 2-methyl-AP-237 and the arylcyclohexylamine derivatives, analogs of ketamine, such as 2-fluoro-deschloroketamine (2 F-DCK) have appeared in several monitoring systems. Two white powders purchased on the internet as bucinnazine were first analyzed with polarized light microscopy followed by direct analysis in real time-mass spectrometry (DART-MS) and gas chromatography-mass spectrometry (GC-MS). Both powders were white crystals with no other significant microscopic properties. The DART-MS analysis showed the presence of 2-fluorodeschloroketamine in powder #1, and AP-238 in powder #2. Identification was confirmed by GC-MS. The purity of each substance was 78.0% for powder #1, and 88.9% for powder #2, respectively. The toxicological risk associated with the misuse of NSOs still needs further study. The absence of bucinnazine and the presence of different active compounds in internet purchased samples raises public health and safety concerns. Display omitted •Powder samples advertised online as AP-237 were identified as 2 F-DCK and AP-238.•Found substances lack toxicity data increasing the risk of buying products online.•Lack of information on the identity of products can lead to toxicity and overdose.