From: smi@sch.tiac (Samson)
Subject: Heroin Manufacture
Date: 17 Oct 1997 18:02:34 GMT

The making of heroin

I wrote this piece a few months ago, but never got around to posting it.
Most of the information on synthesis comes from the DEA publication _Opium
and Heroin Cultivation in Southest Asia_. Recently, someone put the this
on the web at http://www.omnilex.com/public/ps.html, HTML'ed and
illustrated. Then they took it down (although the table of contents is
still there), and it remains down. Someone did post the text while it was
up, though, and it can be found on DejaNews. But I figured I'd post this
anyway, just to show how much idle time I have on my hands...

Corrections from people who know more about chemistry than I do (i.e,
pretty much anyone) are welcomed.

I._The Poppy_

Illicit cultivation of the opium poppy (Papaver somniferum) has
traditionally been an Asian business. More recently, production has
spread to the highlands of the tropical regions of the Western
Hemisphere, primarily Mexico and Colombia. The worldwide illicit opium
harvest in 1995 was estimated at 4,157 metric tons, the majority
accounted for by the estimated 2,561 tons produced in Southeast Asia
(primarily Myanmar (Burma), with significant crops also in Laos, Thailand,
China, Vietnam, and Cambodia) (1). Following Southeast Asia is Southwest
Asia, primarily Afghanistan (with smaller amounts growing in Pakistan,
Turkey, Iran, India, Lebanon and Khirgistan), these two regions
accounting for the vast majority of opium destined for conversion to
illicit heroin. Colombia was estimated to have produced 65.5 tons of
opium in 1996 (2), while Mexico was estimated to have grown 53 tons in
1995 (3). Heroin originating from these Western Hemisphere sources is
destined almost exclusively for the United States, while Southeast Asian
product enjoys worldwide distribution. Heroin of Southwest Asian origin
is mostly exported to Europe or consumed locally.

P. somniferum is an annual, flowering plant, believed to have evolved,
through centuries of breeding and cultivation, from a wild-growing
ancestor native to the northeastern Mediterranean coast (4).  It grows
best in dry, temperate climates, usually at altitudes of over 800 meters
(2500 ft) above sea-level. The optimal growing season is from September
to July depending on the regional climate. In Southeast Asia, planting
is completed by late October, in order to take advantage of the long
days of the Southern Hemisphere winter.  Growing plots are selected for
maximum sun exposure on slopes of gradients of 20 to 40 degrees for
optimal drainage. (Excessive moisture is damaging to the plant). About
one pound of seed is needed to sow one acre of land. By November, when
the young plant enters the cabbage or lettuce stage and has reached a
height of about one foot, some of the plants are removed in order to
leave room for the others to grow (about 1 to 2 feet between plants). A
typical opium poppy field has 60,000 to 120,000 plants per hectare (2.46
acres) (5). The mature plant reaches a height of about 2-5 feet by late
winter, beginning to flower after about 90 days of growth, 3 to 8
flowers per plant. Flowering continues for several weeks, reaching full
bloom by early spring (or later, depending on the region; later
development is typical in more western regions (4)). After full bloom,
the petals drop to reveal a small, round grayish-green fruit which
continues to develop into an oblate, elongated or globular capsule (
also called the seedpod, bulb or poppy head) about the size of a chicken
egg. The skin of the pod encloses the ovary, the walls of which secrete
the latex (opium) which collects in a network of vessels and tubes
throughout the pod.

About two weeks after the petals have fallen, the pods are fully mature,
as indicated by the aforementioned shape of the capsule, a change in
color from grayish-green to dark green; the points of the pods crown now
stand straight out or are curved upward. At this point the pods are
ready to be scored (or tapped, incised or lanced). Harvesters make the
incision with a a three- or four- bladed instrument (iron or glass
blades bound tightly on a wooden handle), designed to make an incision
of about one millimeter deep. (Too deep an incision may result in
excessive spilling either into the center of the pod or to the ground;
too shallow and the latex will not ooze as desired). The pods are scored
two to three times each in the afternoon, causing the white latex to
drip onto the surface of the pod. The opium oxidizes, darkens, and
thickens overnight, and in the morning is scraped from the surface with
a flat iron blade. This process is repeated over several days until each
pod is depleted of its opium. Each pod may yield from 10 to 100
milligrams of opium, with an average of 80 milligrams, which is set
aside in a container to dry in the sun. (Pods giving highest yields are
marked, cut from the plant, cut open and dried in the sun, their seeds
saved for the next planting).  Dried, raw opium is brown to black in
color; higher-quality product is brown and sticky. A typical farm will
produce 3 to 9 kilograms of opium per acre (5).

II._Opium: Some vital statistics_

Over 40 different alkaloids have been identified as present in opium
(4,6), mostly as salts of meconic acid (4). The most important of these,
of course, is morphine. Although Turkish opium (Druggists Opium) may
contain up to 21% morphine (4), the average morphine content of opium
tapped from P. somniferum is 9 to 14% by mass. Next most prominent is
codeine (3-methoxymorphine) which constitutes 0.5 to 2.5% of the dried
latex. Noscapine, comprising 4 to 8% of opium, has been used as an
over-the-counter, non-psychoactive cough suppressant (6). Papaverine,
present at 0.5 to 2.5%, is sold as a digestive antispasmodic.  Thebaine,
0.5 to 2%, is a convulsant in high doses; it is also similar in
structure to morphine is used in the licit manufacture of semisynthetic
opiates such as hydrocodone and oxycodone. (Other species of poppy,
notably _Papaver bracteatum_ , contain higher concentrations of thebaine
and are cultivated for the extraction of this alkaloid (7)). Other
alkaloids include narceine, protopine, laudanine (laudanosine),
codamine, cryptopine, lanthopine, and others.

Ideally, the above alkaloids should be removed in the purification of
opium for conversion to heroin. However,  clandestine chemistry is
rarely ideal, and some of these alkaloids are often not removed,
remaining as imupurities of origin. The most notable impurity of origin
results from the failure to remove codeine. The manufacture of heroin,
discussed in detail below, involves the acetylation of morphine to form
3,6-diacetylmorphine. Acetylated codeine (acetylcodeine) often
constitutes 10% of the narcotic content of street heroin, sometimes up
to 45% of this quantity (6).  Acetylcodeine is a key marker used in
signature analysis of heroin, as the heroin-to-acetylmorphine ratio of
seized batches has been found to vary among source countries (6,8-11).
Also, acetylcodeine has been found to be two times as toxic as
diacetylmorphine (heroin) in mice (6), and hence it may contribute to
street heroins toxicity. Unreacted morphine and codeine are also present
in some poorly processed heroin, which may bring about adverse reactions
in users, especially when the drug is injected intravenously. The
non-phenanthrene alkaloids (i.e, all alkaloids except morphine, codeine,
and thebaine) are more rarely found, probably decomposed in the
acetylation process (6). Noscapine, papaverine, laudanosine and/or
cryptopine are occasionally present but in such small amounts that
although toxic at higher doses, they are not thought to contribute to
the pharmacological effects of street heroin. Thebaine is decomposed by
acetylation, and although the decomposed product, acetylthebaol, is
sometimes present, it is not thought to have any harmful effect.

III._Heroin manufacture_

The complete conversion of raw opium to pure heroin hydrochloride
(diacetylmorphine HCl) may be summarized as follows:

1.) Purification of raw opium --> 2.) extraction/purification of
morphine from opium --> 3.) conversion of morphine to heroin base -->
4.) purification of heroin base and conversion to hydrochloride salt.

After step 4, diluents and adulterants may be added either by the
manufacturer or by parties further along the distribution chain. Also,
shortcuts may be taken at steps 2, 3 and 4, and steps 2 and 4 may be
eliminated altogether. The process delineated in this section is that
observed in Southeast Asia (5), designed to result in nearly pure
diacetylmorphine HCl. A brief discussion of how the aforementioned
shortcuts bear on the properties of heroin originating from other
regions and comments on diluents and adulterants commonly found in
seized samples will follow.

1.) Purification of opium.

Raw opium collected from the poppy as described above is placed in an
open cooking pot of boiling water. This should dissolve all of the
alkaloids in the opium, while solid plant material, soil, twigs, etc.
remain undissolved and float to the top of the solution. Solid
impurities are scooped out or filtered by straining the mixture though
cheesecloth or burlap. The liquid is then re-heated over a low flame,
evaporating the water to leave behind a thick, dark paste, which is then
dried in the sun. The opium left behind has a putty-like consistency and
is generally about 20% lighter (20% more pure) than the raw material. At
this point the product may be exported for smoking or eating or consumed
locally. This process may be carried out by farmers before shipping for
consumption or further processing, or the raw opium may be transported
to heroin manufacturing sites where the preparation is undertaken on a
larger scale.

2.) Extraction of morphine.

Processed opium is stirred in large drum of boiling water until it has
completely dissolved. Slaked lime (calium hydroxide), at about one-fifth
the mass of opium (8), (or a fertilzer with a high lime content) is
added to the solution. This has the effect of converting morphine,
insoluble in cool water, into the soluble salt, calcium morphenate. For
the most part, the other alkaloids do not react, and when the mixture is
cooled, the morphenate remains in solution, while the other chemicals
settle to form a brown sludge at the bottom of the container. (Codeine
is somewhat soluble in water and some amount is likely to remain in
solution). The calcium morphenate solution is scooped or poured from the
drum and filtered and pressed through burlap rice sacks or some other
makeshift filtration apparatus. The filtered solution is re-heated, but
not boiled, in cooking pots to which ammonium chloride is added at about
one-fourth the mass of opium processed (8). After the pH of the solution
reaches 8 or 9 it is cooled. Within a few hours, morphine base and any
remaining codeine precipitate out of solution and settle to the bottom
of the pot. The solution is then poured off through cloth filters,
leaving chunks of morphine base on the cloth, which are squeezed dry and
set aside to dry further in the sun. The dried crude morphine base is a
coffee-colored powder. (A more scrupulous chemist might use ether in the
filtration to dissolve any residual codeine out of the base mixture, but
this is not reported in accounts of illicit manufacture).

From this point, some manufacturers may proceed directly to step 3.
Ideally, however, the crude morphine base is purified by dissolution in
dilute hydrochloric (or sufuric) acid, forming a solution of morphine
hydrochloride (or sulfate). Activated charcoal is added, and the
solution is heated and filtered hot through a fine cloth. The filtration
 is repeated several times, removing the charcoal and colored impurities
with it. The filtrate may be dried in the sun to leave behind morphine
hydrochloride, a fine white powder if purification is complete, which
may be pressed into 1 kg bricks and transferred for further processing
at a remote site. Alternatively, ammonium hydroxide may be added to the
morphine HCl solution (or re-dissolved morphine HCl), precipitating
morphine base, filtered and dried to form a granular solid (8).

3.) Conversion of morphine to heroin base.

The key chemical used in the acetylation of morphine to form heroin is
acetic anhydride, a colorless, highly combustible liquid with a strong
pickle-like odor. Though internationally controlled as a heroin
precursor, acetic anhydride also used to synthesize aspirin and
chemicals for leather tanning and photography. Morphine hydrochloride or
morphine base is mixed with acetic anhydride at about three-times the
mass of the former in a stainless steel or enamel pot. The pot lid is
tied or clamped on with a damp towel for a gasket (a makeshift reflux
apparatus), and the mixture is heated at 85 degrees Celsius (185 degrees
F), avoiding boiling. The cooking proceeds for about 5 hours until all
the morphine has dissolved. The pot is opened, and the mixture -- now a
solution of water, acetic acid, and diacetylmorphine (heroin) -- is
allowed to cool. Water is added to the mixture at three-times the volume
of acetic anhydride, and the mixture is stirred. (Optionally, a small
amount of chloroform is added. The mixture is allowed to stand for 20
minutes. The chloroform dissolves colored impurities and settles to the
bottom of the pot as a red, greasy liquid, and the water layer is
carefully poured off.) Activated charcoal is added to the mixture,
absorbing solid impurities, which are filtered out repeatedly until the
solution is clear. Approximately 2.2 kilograms of sodium carbonate (soda
ash) per kilogram of morphine are dissolved in hot water and added
solwly to the mixture until effervescence stops, precipitating solid
heroin base. Heroin base is filtered with a fine cloth, set aside and
heated until dry. The heroin base should be a granular, white powder at
this point. If still colored (beige or light brown), the base may be
re-dissolved in dilute hydrochloric or citric acid (8), treated with
charcoal again, re-precipitated and dried. Alternatively, in some
manufacturing regions, the incompletely purified base may be packed and
transported for sale (a practice probably typical in Southwest Asia).
About 700 grams of heroin base will be produced from each kilogram of
morphine.

Optionally, killed heroin chemists may further purify the base by
dissolving it in twice its mass of boiling ethyl alcohol, filtering the
solution through a heated funnel into a heated flask. This removes
traces of sodium carbonate remaining in the base. The flask is submerged
in an ice bath, where it is transformed into a thick white cream. The
substance is placed in a pan in a refrigerator with a fan set to blow
across the pan to slowly evaporate the alcohol . The paste crystallizes
after several hours and is then vacuum filtered. The product, referred
to as alcohol morphine base, is re-crystallized heroin base.

4.) Conversion of heroin base to heroin hydrochloride.

For each kilogram of heroin base (or re-crystallized heroin base), 6.6
liters of of ethyl alcohol, 6.6 liters of ether, and 225 milliliters of
concentrated hydrochloric acid are measured out. The base is dissolved
by heating with one-third of the alcohol and one half of the acid.
Another one-third of the acid is stirred in. Next, the remaining acid is
added slowly, dropwise, until the product is completely converted to the
hydrochloride salt. This result may be confirmed either by observing
that a drop of solution evaporates on a glass plate leaving no cloudy
residue or by placing a drop of solution on Congo red paper, observing
it turn the paper blue. Once the conversion is complete, the remaining
alcohol is stirred in. Then half of the ether is added, and the mixture
is allowed to stand for 15 minutes. As soon as crystals begin to form in
the solution, the remaining ether is added at once, stirred, and the the
vessel is covered. The mixture becomes nearly solid after an hour. It is
then filtered, and the solids are collected on clean filter paper.
Wrapped in the paper, the solid is dried on a wooden tray, usually over
lime rock, and dried in the sun. The fully dried product, heroin
hydrochloride, is a fine white powder, ready for packing and shipping.





References:

1.) _The Supply of Illicit Drugs to the United States: National
Narcotics Intelligence Consumers Committee 1995_ . Drug Enforcement
Administration, August 1996.

2.) _Report of the International Narcotics Control Board for 1996_.
International Narcotics Control Board, E/INCB/1996/1,  United Nations
Publication, 1996

3.) Constantine, Thomas A. The Threat of Heroin to the United States.
Statement Before the House Subcommittee on National Security,
International Affairs and Criminal Justice Committee on Government
Reform and Oversight, September 19, 1996.

4.) Claus, E.P., Tyler, E.T., Brady, L.R. _Pharmacognosy (6th ed.)_,
1970. (Lea & Febiger: Philadelphia).

5.) _Opium Poppy and Heroin Cultivation in Southeast Asia_. Drug
Enforcement Administration, Intelligence Division, Sept, 1993. (DEA -
92004)

6.) Soine, W.H. Clandestine drug synthesis. _Medicinal Research
Reviews_. 6:1 (1986), pp. 41-74.

7.) Sharghi, N. & Lalezari, I. _Papaver bracteatum_ Lindl., a highly
rich source of thebaine. Nature, (March 25, 1967), p. 1244

8.) Narayanaswami, K. "Parameters for determining the origin of illicit
heroin samples". _Bulletin on Narcotics_, 37:1 (1985), pp. 49-62

9.) ONeil, P.J., Baker, P.B. & Gough, T.A. Illicitly imported heroin
products: Some physical and chemical features indicative of their
origin. _Journal of Forensic Sciences_, 29:3 (1984), pp. 889-902.

10.) ONeil, P.J. & Pitts, J.E. Illicitly imported heroin products
(1984-1989): Some physical and chemical features indicative of their
origin.  _Journal of Pharmacy and Pharmacology_, 44 (1992), pp. 1-6

11.) Baker, P.B. & Gough, T.A. The separation and quantitation of the
narcotic components of illicit heroin using reverse-phase high
performance liquid chromatography, _Journal of Chromatographic Science_
