As I continue my massive research project, here’s a few tidbits about heroin’s chemical make-up, history and the golden triangle.
Chemistry: (Via Wiki)
Heroin (INN: diacetylmorphine, BAN: diamorphine) is a semi-synthetic opioid synthesized from morphine, a derivative of the opium poppy. It is the 3,6-diacetyl ester of morphine (hence diacetylmorphine). The white crystalline form is commonly the hydrochloride salt diacetylmorphine hydrochloride, however heroin freebase may also appear as a white powder.
As with other opiates, heroin is used both as a pain-killer and a recreational drug. Frequent administration quickly leads to tolerance and dependence and has a very high potential for addiction. If sustained use of heroin for as little as three days is stopped abruptly, withdrawal symptoms can appear. This is much quicker than other common opioids such as oxycodone and hydrocodone.
One of the most common methods of heroin use is via intravenous injection (colloquially termed “shooting up”). When taken orally, heroin undergoes extensive first-pass metabolism via deacetylation, making it a prodrug for the systemic delivery of morphine. When the drug is injected, however, it avoids this first-pass effect, very rapidly crossing the blood-brain barrier due to the presence of the acetyl groups, which render it much more lipid-soluble than morphine itself. Once in the brain, it is deacetylated into 3- and 6-monoacetylmorphine and morphine which bind to μ-opioid receptors, resulting in intense euphoria, decreased pain perception and anxiolytic effects (relief of anxiety).
Internationally, heroin is controlled under Schedules I and IV of the Single Convention on Narcotic Drugs. It is illegal to manufacture, possess, or sell heroin in Belgium, Denmark, Germany, India, the Netherlands, the United States, Australia, Canada, Ireland, United Kingdom and Swaziland. However, under the name diamorphine, heroin is a legal prescription drug in the United Kingdom. In the Netherlands, heroin is available for prescription as the generic drug diacetylmorphine to long-term heroin addicts. Popular street names for heroin include black tar, junk, skag, horse, chiva, “H”, “Boy”, and others.
The opium poppy was cultivated in lower Mesopotamia as long ago as 3400 BC. The chemical analysis of opium in the 19th century revealed that most of its activity could be ascribed to two ingredients, codeine and morphine.
Heroin was first synthesized in 1874 by C. R. Alder Wright, an English chemist working at St. Mary’s Hospital Medical School in London, England. He had been experimenting with combining morphine with various acids. He boiled anhydrous morphine alkaloid with acetic anhydride over a stove for several hours and produced a more potent, acetylated form of morphine, now called diacetylmorphine. The compound was sent to F. M. Pierce of Owens College in Manchester for analysis, who reported the following to Wright:
- Doses … were subcutaneously injected into young dogs and rabbits … with the following general results … great prostration, fear, and sleepiness speedily following the administration, the eyes being sensitive, and pupils constrict, considerable salivation being produced in dogs, and slight tendency to vomiting in some cases, but no actual emesis. Respiration was at first quickened, but subsequently reduced, and the heart’s action was diminished, and rendered irregular. Marked want of coordinating power over the muscular movements, and loss of power in the pelvis and hind limbs, together with a diminution of temperature in the rectum of about 4° (rectal failure).
Wright’s invention, however, did not lead to any further developments, and heroin only became popular after it was independently re-synthesized 23 years later by another chemist, Felix Hoffmann. Hoffmann, working at the Bayer pharmaceutical company in Elberfeld, Germany, was instructed by his supervisor Heinrich Dreser to acetylate morphine with the objective of producing codeine, a constituent of the opium poppy, similar to morphine pharmacologically but less potent and less addictive. But instead of producing codeine, the experiment produced an acetylated form of morphine that was actually 1.5-2 times more potent than morphine itself. Bayer would name the substance “heroin”, probably from the word heroisch, German for heroic, because in field studies people using the medicine felt “heroic”.
From 1898 through to 1910 heroin was marketed as a non-addictive morphine substitute and cough suppressant. Bayer marketed heroin as a cure for morphine addiction before it was discovered that heroin is rapidly metabolized into morphine, and as such, “heroin” was basically only a quicker acting form of morphine. The company was somewhat embarrassed by this new finding and it became a historical blunder for Bayer.
As with aspirin, Bayer lost some of its trademark rights to heroin under the 1919 Treaty of Versailles following the German defeat in World War I.
In the U.S.A the Harrison Narcotics Tax Act was passed in 1914 to control the sale and distribution of heroin and other opiates. The law did allow heroin to be prescribed and sold for medical purposes. In particular, recreational users could often still be legally supplied with heroin and use it. In 1924, the United States Congress passed additional legislation banning the sale, importation or manufacture of heroin in the United States. It is now a Schedule I substance, and is thus illegal in the United States.
Production and trafficking:
Heroin is produced for the black market by refining opium. The first step of this process involves isolation of morphine from opium. This crude morphine is then acetylated by heating with acetic anhydride. Purification of the obtained crude heroin and conversion to the hydrochloride salt results in a water-soluble form of the drug that is a white or yellowish powder.
Crude opium is carefully dissolved in hot water but the resulting hot soup is not boiled. Mechanical impurities – twigs – are scooped together with the foam. The mixture is then made alkaline by gradual addition of lime. Lime causes a number of unwelcome components present in opium to precipitate out of the solution. (The impurities include inactive alkaloids, resins, proteins). The precipitate is removed by filtration through a cloth, washed with additional water and discarded. The filtrates containing the water-soluble calcium salt of morphine (calcium morphinate) are then acidified by careful addition of ammonium chloride. This causes freebase morphine to precipitate. The morphine precipitate is collected by filtration and dried before the next step. The crude morphine (which makes only about 10% of the weight of opium) is then heated together with acetic anhydride at 85 °C (185 °F) for six hours. The reaction mixture is then cooled, diluted with water, made alkaline with sodium carbonate, and the precipitated crude heroin is filtered and washed with water. This crude water-insoluble freebase product (which by itself is usable, for smoking) is further purified and decolourised by dissolution in hot alcohol, filtration with activated charcoal and concentration of the filtrates. The concentrated solution is then acidified with hydrochloric acid, diluted with ether, and the precipitated heroin hydrochloride is collected by filtration. This precipitate is the so-called “no. 4 heroin”, commonly known as “china white”. Heroin freebase cut with a small amount of caffeine (to help vaporise it more efficiently), typically brown in appearance, is known as called “no. 3 heroin”. These two forms of heroin are the standard products exported to the Western market. Heroin no. 3 predominates on the European market, where heroin no. 4 is relatively uncommon. Another form of heroin is “black tar” which is common in the western United States and is produced in Mexico.
The initial stage of opium refining—the isolation of morphine—is relatively easy to perform in rudimentary settings – even by substituting suitable fertilizers for pure chemical reagents. However, the later steps (acetylation, purification, and conversion to the hydrochloride salt) are more involved—they use large quantities of chemicals and solvents and they require both skill and patience. The final step is particularly tricky as the highly flammable ether can easily ignite during positive-pressure filtration (the explosion of vapor-air mixture can obliterate the refinery). If the ether does ignite, the result is a catastrophic explosion.