Codeine

Codeine was first isolated from opium in 1832 by Robiquet (1). It is present in the latex only in small amounts -- around 0.5% to 1.5%. Codeine on the pharmaceutical market is not extracted from opium but prepared via the methylation of morphine. Codeine is the most widely consumed (licit) opiate. The International Narcotics Board estimated that some 180 metric tons of codeine were consumed worldwide in 1995, against a total morphine-derivative consumption level of 236 metric tons for the same year . While codeine is present only in small amounts in opium latex as a whole, since it comprises some 5% to 15% of the narcotic alkaloid content of the gum, it may be present as a contaminant in illicit opiate products. The narcotic content of street heroin typically includes about 10% acetylcodeine, and Soine  has suggested that this may account for some toxic reactions to street heroin: [acetylcodeine is] two times more toxic and three times more active as a convulsant than diacetylmorphine [heroin]. He speculates that, "based on the common occurence of acetylcodeine in heroin at relatively high concentrations it could contribute to its toxicity.                                   By Jason Taylor

>Known methods of converting codeine to morphine by demethylation (codeine is morphine 3-methyl ether). Cleavage of aromatic ethers are commonly effected by reflux with concentrated HBr or HI. This relatively simple method can unfortunately not be used on codeine, as the oxygen bridge at the 9,10 position on the morphinan carbon skeleton would also rupture, causing the rearrangement of the molecule to the very potent emetic apomorphine, completely devoid of opiate-like effects. The author takes no responsibility whatsoever of whatever the reader might do with the information contained in this document. Keep in mind that the procedures described herein are probably illegal to carry out in all civilized parts of the world. Suggestions of alternative demethylation methods or anecdotal reports of the use of the syntheses below are welcomed.

The Demethylation of Codeine to Morphine