Controlled Substances

1.4.1 herion

Whenever one thinks about drugs of abuse and addiction, heroin is one of the most recognized drugs. Heroin is a synthetic drug, produced from the morphine contained in the sap of the opium poppy. The abuse of this particular controlled substance has been known for many years. The correct chemical nomenclature for heroin is O3, O6 -diacetylmorphine. Heroin is synthesized from morphine in a relatively simple process. The first synthesis of diacetylmorphine reported in the literature was in 1875 by two English chemists, G.H. Beckett and C.P. Alder Wright. 1 In 1898 in Eberfield, Germany, the Farbenfarbriken vorm Friedrich Bayer and Company produced the drug commercially. An employee of the company, H. Dresser, named the morphine product "Heroin".2 There is no definitive documentation as to where the name "heroin" originated. However, it probably had its origin in the "heroic remedies" class of drugs of the day.

Heroin was used in place of codeine and morphine for patients suffering from lung diseases such as tuberculosis. Additonally, the Bayer Company advertised heroin as a cure for morphine addiction. The analgesic properties of the drug were very effective. However, the addictive properties were quite devastating. In 1924, Congress amended the Narcotic Drug Import and Export Act to prohibit the importation of opium for the manufacture of heroin. However, stockpiles were still available and could be legally prescribed by physicians. The 1925 International Opium Convention imposed drug controls that began to limit the supply of heroin from Europe. Shortly thereafter, the clandestine manufacture of heroin was reported in China. The supplies of opium in the Far East provided a ready source of morphine—the starting material for the synthesis. The medical use of heroin in the U.S. was not banned until July 19, 1956 with the passage of Public Law 728, which required all inventories to be surrendered to the federal government by November 19, 1956.

In the past 50 or so years, the source countries for opium used in clandestine heroin production have increased dramatically. Political and ecomomic instability in many areas of the world account for much of the increased production of heroin. The opium that is used to produce the heroin that enters the U.S. today has four principal sources. Geographically all of these regions are characterized by a temperate climate with appropriate rainfall and proper soil conditions. However, there are differences in the quality of opium, the morphine content, and the number of harvests from each of these areas. Labor costs are minimal and the profit margins are extremely high for those in the upper echelons of heroin distribution networks. Heroin Sources by Region

The "Golden Triangle" areas of Burma, China, and Laos are the three major source countries in this part of the world for the production of illicit opium. Of these three countries, 60 to 80% of the total world supply of heorin comes from Burma. Heroin destined for the U.S. transits a number of countries including Thailand, Hong Kong, Japan, Korea, the Philippines, Singapore, and Taiwan. Southeast Asian heroin is usually shipped to the U.S. in significant quantities by bulk cargo carriers. The techniques for hiding the heroin in the cargo are quite ingenious. The shipment of Southeast Asian (SEA) Heroin in relatively small quantities is also commonplace. Criminal organizations in Nigeria have been deeply involved in the small quanitity smuggling of SEA heroin into the U.S. The "body carry" technique and ingestion are two of the better known methods of concealment by the Nigerians. SEA heroin is high quality and recognized by its white crystalline appearance. Though the cutting agents are numerous, caffeine and acetaminophen appear quite frequently.

Southwest Asia—Turkey, Iraq, Iran, Afghanistan, Pakistan, India, Lebanon, and the Newly Independent States of the former Soviet Union (NIS) are recognized as source countries in this part of the world. Trafficking of Southwest Asian heroin has been on the decline in the U.S. since the end of 1994. Southwest Asian heroin usage is more predominant in Europe than in the U.S. The Southwest Asian heroin that does arrive in the U.S. is normally transhipped through Europe, Africa, and the NIS. The political and economic conditions of the NIS and topography of the land make these countries ideal as transit countries for heroin smuggling. The rugged mountainous terrain and the absence of significant enforcement efforts enable traffickers to proceed unabated. Most Southwest Asian heroin trafficking groups in the originating countries, the transitting countries, and the U.S. are highly cohesive ethnic groups. These groups rely less on the bulk shipment and more on smaller quantity commercial cargo smuggling techniques. Southwest Asian heroin is characterized by its off-white to tan powdery appearance as compared to the white SEA heroin. The purity of Southwest Asian heroin is only slightly lower than that of SEA heroin. The cutting agents are many. Phenobarbital, caffeine, acetaminophen, and calcium carbonate appear quite frequently.

Central America—Mexico and Guatemala are the primary source countries for heroin in Central America. Mexico's long border with the U.S. provides easy access for smuggling and distribution networks. Smuggling is usually small scale and often involves illegal immigrants and migrant workers crossing into the U.S. Heroin distribution in the U.S. is primarily the work of Mexican immigrants from the States of Durango, Michoacan, Nuevo Leon, and Sinaloa. Concealment in motor vehicles, public transportation, external body carries, and commercial package express are common. This heroin usually ranges from a dark brown powder to a black tar. The most commonly encountered adulterants are amorphous (formless and indeterminate) materials and sugars. The dark color of Mexican heroin is attributed to processing by-products. The purity of Mexican heroin varies greatly from seizure to seizure.

South America—Heroin production in this part of the world is a relatively new phenomenon. Cultivation of opium has been documented along the Andean mountain range within Colombia in the areas of Cauca, Huila, Tolima, and Santaner. There have been a number of morphine base and heroin processing facilities seized in Colombia in the past few years. Smuggling of South American heroin into the U.S. increased dramatically in 1994 and 1995. The primary method of smuggling has been by Colombian couriers aboard commercial airliners using false-sided briefcases and luggage, hollowed out shoes, or by ingestion. Miami and New York are the primary ports of entry into the U.S. One advantage which the traffickers from South America have is the importation networks that are already in place for the distribution of cocaine into the U.S. Transhipment of this heroin through other South American countries and the Caribbean is also a common practice. South American heroin has many of the same physical characteristics of Southwest Asian heroin. However, the purity of South American heroin is higher with fewer adulterants than Southwest Asian heroin. Cocaine in small quantities is oftentimes encountered in South American heroin exhibits. In such cases, it is not always clear whether the cocaine is present as a contaminant introduced due to common packaging locations of cocaine and heroin, or whether it has been added as an adulterant. Isolation of Morphine and Heroin Production

There are some very specific methods for producing heroin. However, all involve the 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°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 re-crystallized 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. One of these procedures is referred to as "homebake" and was described in the literature by Rapoport et al.6 This particular procedure has been reported only in New Zealand and Australia.

Acetylation of Morphine to Diacetylmorphine (Heroin)—This process involves placing dried morphine into a reaction vessel and adding excess acetic anhydride (Figure Sometimes a co-solvent is also used. The mixture is heated to boiling and stirred for varying periods of time ranging from 30 min up to 3 or 4 h. The vessel and contents are cooled and diluted in cold water. A sodium carbonate solution is then added until precipitation of the

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