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Benzimidazole opioids are a class of synthetic opioids that contain a benzimidazole core structure. The pain-relieving properties of these substances were discovered in the mid-1950s by the Swiss company Ciba AG. The most important subgroup are the nitazene opioids, which since 2019 have become increasingly widespread as narcotics in North America and Europe, as well as West Africa. Some other benzimidazole-containing opioids are classified separately under the orphine subgroup. There is currently no medical usage due to the high potencies of certain analogs.^[1]

In 1957, the pharmaceutical research department of Ciba AG published the discovery of the (low) analgesic effect of 1-(β-diethylaminoethyl)-2-benzylbenzimidazole (desnitazene).^[2] Shortly afterwards, the nitazenes were discovered in structure-activity relationship studies.^[3][4]

The class of nitazene opioids is defined chemically by the presence of the benzimidazole core structure and pharmacologically by mu opioid agonist activity. The compounds are derived from the historical prototype 1-(β-diethylaminoethyl)-2-benzylbenzimidazole (desnitazene). The replacement of the N,N-dialkylamino unit by pyrrolidinyl or piperidinyl, which is found in nitazepyne and nitazepipne compounds, falls into the spectrum of designer drugs. Substitution of the benzyl for thienylmethyl, pyridylmethyl, α-napthylmethyl or styryl has a potency-reducing effect.^[5][6] Substitution in position 4 of the benzyl affects analgesic potency in the following order: ethoxy > isopropyloxy > n-propyloxy > methoxy > methylthio > H/Cl/F > hydroxy. The most potent of the known compounds contain a nitro group in position 5.^[6] The replacement of benzimidazole with an indole has been known from studies conducted by Ciba AG since 1963.^[7]