Pharmacology - Experiment- Heroin from Codeine

[On The Nod]

[top]Experimental Details

In this section the procedure followed in homebake laboratories is fully described. Additional comments on the method, based on studies carried out in this laboratory on the reactions involved, are included in the discussion section.
1. Extraction of codeine
Several packets of tablets, sufficient to yield about 2 g of codeine, are crushed and mixed with water. The mixture is filtered using a filter pump, Buchner funnel and side-arm flask, to remove tablet binding agents, diluents and other excipients. The aqueous filtrate is poured into a separating funnel and sodium hydroxide solution added to make the solution strongly alkaline. This is then extracted with chloroform (about 50 ml). The chloroform layer is drained off and evaporated to dryness using gentle heating (often on a domestic stove). The aqueous layer containing aspirin and paracetamol is discarded. The codeine base is recovered as a white crystalline solid for use in Step 3.
2. Preparation of pyridine hydrochloride
In a beaker pyridine (20 ml) and concentrated hydrochloric acid (25 ml) are strongly heated (to about 190°C) to drive off water. The product is cooled rapidly to form a waxy white solid which is stored in a sealed container in a freezer to minimise exposure to moisture and avoid decomposition.
3. Reaction of codeine and pyridine hydrochloride
The reaction is carried out using a boiling tube which is flame-dried before use. Pyridine hydrochloride (3.5 g) as prepared in Step 2 is then heated in the tube until it melts and any residual moisture is driven off. Any resulting condensation on the inside walls of the tube is wiped off. Codeine base (1.5 g) is added to the tube which is then stoppered with a rubber bung covered with filter paper and heated until the mixture starts to fume. Heating is continued until a reddish-orange colour develops in the reaction melt, which becomes noticeably more viscous (6-12 min). The contents of the boiling tube are then poured into a 500 ml separating funnel and the volume made up to 100 ml with water. Sodium hydroxide solution (10%) is added until the contents of the separating funnel are strongly basic. As the sodium hydroxide is added the contents turn milky-brown before becoming clear brown again. Chloroform (20 ml) is added. After extraction the greyish-brown chloroform layer is either discarded or put aside for later recovery of the codeine contained in it. The aqueous layer is poured into a 400 ml beaker and the pH is carefully adjusted to pH 9 using hydrochloric acid and narrow-range indicator paper. The solution is rapidly filtered under suction, using a Buchner funnel and 2 filter papers, to remove a fine, dark brown residue containing unwanted by-products. The filtered solution is then poured into a clean beaker and precipitation is induced by vigorously rubbing the side of the beaker with a 'seeding stick' as the pH is carefully lowered to 8.5 with additional hydrochloric acid. (In homebake laboratories a split wooden clothes peg is often used as the 'seeding stick'.) The product is allowed to settle for at least 5 min before being filtered off under vacuum. The morphine product is recovered as a powder, ranging in colour from beige to dark brown.
4. Conversion of morphine to heroin
Morphine powder as prepared in Step 3 is placed in a spoon. A small amount of acetic anhydride is added and the mixture ignited. Addition of acetic anhydride may be repeated. A brown or black tar-like residue remains.

On The Nod added 2 Minutes and 1 Seconds later...

[top]Results and Discussion

1. Procedural details
The procedure outlined in the experimental section has been followed many times in this laboratory. The glassware and other equipment required for the reaction are remarkably simple and readily available from scientific supply companies. The main items include several beakers, a separating funnel, a filter pump and tap attachments, a Buchner flask and funnel, a boiling tube with a rubber bung or cork and an evaporating basin. The chemicals necessary include hydrochloric acid, pyridine, chloroform and sodium hydroxide. Acetic anhydride is also necessary if the final step to heroin is intended. Hydrochloric acid and sodium hydroxide are widely available. Chloroform, pyridine and acetic anhydride are available from chemical supply companies. Recent awareness among supply companies of the significance of a request for small amounts of these chemicals has led to stricter monitoring of orders. In a number of laboratories pyridine has been replaced by a crude mixture of picolines (methylpyridine isomers) and other substituted pyridines. In at least two cases the mixture also contained an intense purple dye indicating that it had been obtained from a chemical distributor where the mixture of pyridines and dye is added to ethanol in the course of preparing 'methylated spirits' (denatured alcohol).
The most common source of heat found in these laboratories has been small methylated spirits burners. These give a cooler flame than do laboratory bunsen burners and enable better control of the reaction between codeine and pyridine hydrochloride. In a few laboratories investigated, heating had been carried out using cooking oil on a domestic stove element. Under laboratory conditions the reaction has been carried out using a heated sand bath.
The use of a rubber hung in the boiling tube to produce a sealed reaction vessel is a simple solution to the problems of morphine oxidation and decomposition on heating and the need to minimise access of moisture to the reaction mixture.
2. Product yields
Homebake laboratory operators have claimed yields of morphine equivalent to 50% conversion from codeine but the reaction also forms a complex mixture of by-products, whose structures are now being studied by us. In our laboratory using these procedures nett yields have not exceeded 30%. Indeed, in the light of Rapoport and Bonner's work this appears to be the maximum that could be expected. Morphine having a purity of 92% calculated as the anhydrous free base and determined by HPLC has been prepared, although purities in the 80% region are more typical. Negligible codeine is present with the morphine, indicating that the chloroform extraction step is efficient in removing this. This high purity, with little or no codeine contamination, is characteristic of 'homebake' morphine.
The crude method used to acetylate the resultant morphine can result in up to 60% conversion to heroin. The brown or black tar-like residue is used either by heating it strongly on a piece of aluminium foil and inhaling the fumes or by injection. If the injection route is used, water is added to the spoon, a small amount of acid may be added to assist dissolution, and the mixture warmed. The syringe is filled using a cigarette filter to remove insoluble by-products of the reaction. A distinctive feature of the product is that it contains unusually high levels of 3-O-monoacetylmorphine, clearly present because of incomplete acetylation of morphine (Fig. 3). ln complete contrast to the usual situation with illicit heroin, the 3-O-monoacetylmorphine level exceeds that of 6-O-monoacetylmorphine. Recent studies have elucidated the requirements for the formation of 3-O-monoacetylmorphine and also its decomposition, since it is readily hydrolysed. In homebake heroin the initial high 3-O-monoacetylmorphine level is rapidly reduced by this hydrolysis, particularly as the product is frequently dissolved in a small amount of water containing acid, in preparation for injection.
One completed synthesis, based on an initial quantity of approx. 2 g of codeine, yields an acetylated product which is dissolved in 4-5 ml of water. The concentration of heroin in this solution is typically between 10 and 40 mg/ml, depending on the skill of the operator. Obviously the solution also contains morphine and 3-O-monoacetylmorphine. This should provide enough for several 'fixes' or allow for a small surplus to be sold, depending on the level of addiction of the user.

Reputation Comments on this post:

	This has been covered a million times before, this adds ZERO new information, and involves the use of toxic chemicals
	Nice Write Up

[gmeziscool2354]

bump.

this thread is brilliant!!!!

but highly dangerous information.

Reputation Comments on this post:

for bringing up the 'highly dangerous' part

[anonuser30500]

Very clear explanation of how to get from the frying pan into the fire!

Should be in the heroin forum really.

Swim would have been doing this if Swim was addicted to the gear.

Must be a few a level chemistry students who have their little labs on the go.

[SkipRipper]

Anyone know of OTC methods to procure pyridine? SWIM came across a thread on another forum describing the decarboxylation of niacin and some people replying verified it. SWIM can't remember where he saw that post though.