Isolation of Morphine and Heroin Production

same four steps: (1) The opium poppy (Papaver Somniferum L.) is cultivated; (2) the poppy head is scored and the opium latex is collected; (3) the morphine is the isolated from the latex; and (4) the morphine is treated with an acetylating agent. Isolation of the morphine in Step 3 is accomplished using a rendition of one of the following five methods:

1. The Thiboumery and Mohr Process (TMP)—This is the most well known of the reported methods for isolating morphine followed by the acetylation to heroin. Dried opium latex is dissolved in three times its weight of hot water. The solution is filtered hot which removes undissolved botanical substances. These undissolved botanicals are washed with hot water and filtered. This is done to ensure a maximized yield of morphine in the final product. The filtrate is reduced to half its volume by boiling off the water. The laboratory operator then adds to the filtrate a boiling solution of calcium hydroxide which forms the water soluble calcium morphinate. The precipitates, which include the insoluble alkaloids from the opium, and the insoluble materials from this step are filtered. These insolubles are then washed three more times with water and filtered. The resulting filtrate, which contains calcium morphinate still in solution, is then evaporated to a weight of approximately twice the weight of the original weight of the opium and then filtered. This results in a concentrated calcium morphinate solution which is heated to a boil. Ammonium chloride is then added to reduce the pH below 9.85. When this solution cools, morphine base precipitates and is collected by filtration. The morphine base is dissolved in a minimum volume of warm hydrochloric acid. When this solution cools the morphine hydrochloride precipitates. The precipitated morphine hydrochloride is then isolated by filtration.

2. The Robertson and Gregory Process (RGP)—This method is similar to the Thiboumery and Mohr Process. The laboratory operator washes the opium with five to ten times its weight of cold water. The solution is then evaporated to a syrup which is then re-extracted with cold water and filtered. The filtrate is evaporated until the specific gravity of the solution is 1.075. The solution is boiled and calcium chloride is added. Cold water is added to the calcium morphinate solution which is then filtered. The solution is concentrated and the calcium morphinate then precipitates out of solution as the liquid evaporates. The calcium morphinate is then redissolved in water and filtered. To the filtrate is added ammonia which allows the morphine base to precipitate. This morphine base can then be further treated to produce the pharmaceutical quality morphine.

The Thiboumery and Mohr Process and the Robertson and Gregory Process are used by commercial suppliers for the initial isolation of morphine from opium. In clandestine laboratories, the same methodologies and rudimentary steps are followed. However, since the operators are using “bucket chemistry”, there are modifications to hasten and shortcut the processes.

Three other methods can then be utilized to convert the relatively crude morphine base through purification processes to high quality morphine base or morphine hydrochloride crystals. Modifications of these purifications are used by clandestine laboratory operators.

3. The Barbier Purification—The morphine base is dissolved in 80ｰC water. Tartaric acid is added until the solution becomes acidic to methyl orange. As the solution cools, morphine bitartrate precipitates, is filtered, washed with cold water, and dried. The morphine bitartrate is then dissolved in hot water and ammonia is added to pH 6. This results in a solution of morphine monotartrate. The laboratory operator then adds activated carbon black, sodium bisulfite, sodium acetate, and ammonium oxalate. This process results in a decolorization of the morphine. When this decolorization process is complete, ammonia is added to the solution which results in white crystals of morphine base. These purified morphine base crystals are then filtered and dried. This high quality morphine base is converted to morphine hydrochloride by adding 30% ethanolic HCl to a warm solution of morphine in ethanol. The morphine hydrochloride crystallizes from solution as the solution cools.

4. The Schwyzer Purification—The acetone insoluble morphine base (from either the TMB or RGP) is washed in with acetone. The morphine base is then recrystallized from hot ethyl alcohol.

5. The Heumann Purification—The laboratory operator washes the morphine base from either the TMB or RGP) with trichloroethylene, followed by a cold 40% ethanol wash. This is subsequently followed by an aqueous acetone wash. The quality of the clandestine product is usually evaluated by the color and texture of the morphine from one of these processes. If the clandestine laboratory operator is producing morphine as his end product, with the intention of selling the morphine for conversion by a second laboratory, the morphine will usually be very pure. However, if he continues with the acetylation of the morphine to heroin, the “intermediate” morphine will frequently be relatively impure.

Heroin can be produced synthetically, but requires a 10-step process and extensive expertise in synthetic organic chemistry. The total synthesis of morphine has been reported by Gates and Tschudi in 1952 and by Elad and Ginsburg in 1954.3,4 A more recent synthesis was reported by Rice in 1980.5 All of these methods require considerable forensic expertise and result in low yield. There are also methods reported in the literature for converting codeine to morphine using an O-demethylation. The morphine can then be acetylated to heroin.