Subject:      Homebake: Codeine to Morphine
From:         [dmurphy 3] at [aol.com] (DMurphy3)
Date:         1995/10/26
Newsgroups:   alt.drugs.chemistry

This came from Forensic Science International, K. Bedford, S. Nolan, R.
Onrust, and J. Siegers, v34, 1987, pp 197-204. Title is "The Illicit
Preparation of Morphine and Heroin from Pharmaceutical Products Containing
Codeine: 'Homebake' Laboratories in New Zealand". 

"The O-demethylation of codeine to yield morphine has been accomplished
using a very simple method based on pyridine hydrochloride. This reagent
was introduced to opiate chemistry by Rapoport and Bonner (J. Amer. Chem.
Soc., v73, 1951, p5485) and was first applied to the conversion of codeine
to morphine by Rapoport, et al. (J. Am. Chem. Soc., v73, 1951, p5900). The
reaction was carried out under nitrogen at 220 C because morphine is prone
to decomposition or oxidation reactions at elevated temperatures and the
nitrogen atmosphere prevents or reduces these. It also limits the access
of moisture which reduces the yield."

Following is the method used, with some elaboration: 
1. Crush sufficient pills to yield 2 g of codeine and mix with distilled
water. Filter with a vacuum funnel to remove insolubles and add to a
separatory funnel. Add NaOH solution to make the solution pH 12. Extract
twice with chlorofrom (2x25 mL). This will be the bottom layer. Discard
the water layer, which contains the aspirin or acetominophen) and
evaporate the chloroform layer to dryness under gentle heat. The result is
codeine base, a white crystalline powder.

2. Combine 20 mL pyridine and 25 mL conc. HCl in a beaker and heat
strongly to 190 C to drive off any water. Cover and cool rapidly to obtain
a white waxy material. This should be stored in a sealed container in the
freezer if not to be used immediately.

3. The reaction is carried out in a glass boiling tube (here one could use
a large ignition type test tube) which is sealed on one end. This should
be oven dried before use. Then 3.5 g of the pyridine salt is added to the
tube and this is then heated until it melts and for a few minutes more to
drive off any moisture. Add 1.5 g of the base and seal the tube with a
rubber stopper covered with a filter paper. Heat until the mixture begins
to fume and continue until the mixture develops a reddish-orange color and
becomes noticeably more viscous, typically 6-12 minutes. 

Pour this into a 500 mL sep funnel and make the volume up to 100 mL with
distilled water. Add 10% NaOH until strongly basic. The contents will
become milky brown and then  clear brown as the solution is made basic.
When this point is reached, extract with 20 mL chloroform. This will
contain any unreacted codeine (up to 70%) and may be saved for recovery if
desired. The morphine is in the water layer. 

Put the water layer in a beaker and carefully adjust the pH with HCl to pH
9 using a narrow range pHydronium paper. This is critical. Rapidly filter
using two layers of paper (here one could use a paper designed for very
fine crystals) and a vacuum flask/funnel as in step 1. A very fine brown
powder will collect on the paper. This is unwanted byproducts and should
be discarded. 

Pour the filtrate into a clean beaker and, while carefully adjusting the
pH to 8.5, vigorously rubbing the inside of the beaker with a "seeding
stick" (here the authors mention that a split wooden peg is sometimes used
in the home labs in NZ; a glass stirring rod would be preferable).
Crystals should begin to form. These are allowed to settle for at least 5
minutes and then are recovered by vacuum filtering to recover the morphine
as a beige to dark brown product.

The authors report some perp's claims of 50% conversion from the codeine,
but say they obtained 30% typically, and further state that this is about
what one would expect from Rapoport's paper. Purity of up to 92% with a
more typical purity in the 80% range was reported by the authors using
this method.

TI   The illicit preparation of morphine and heroin from pharmaceutical
     products containing codeine:  'homebake' laboratories in New Zealand
AU   Bedford, Keith R.; Nolan, Susan L.; Onrust, Rene; Siegers, Jan D.
CS   Chem. Div., Dep. Sci. Ind. Res., Auckland, N. Z.
SO   Forensic Sci. Int. (1987), 34(3), 197-204
     CODEN: FSINDR; ISSN: 0379-0738
DT   Journal
LA   English
CC   4-2 (Toxicology)
     Section cross-reference(s): 1
AB   Since 1983, a large no. of small-scale illicit labs. producing
     morphine and heroin from com. available, codeine-based
     pharmaceutical products have been encountered in New Zealand.  The
     ***codeine***     ***demethylation***   procedure is based on the
     use of pyridine-HCl.  Very simple lab. equipment and reagents are
     required and these can be utilized by people with little or no chem.
     background, following a recipe-like procedure.  The process yields a
     characteristic product known as homebake.  This process is fully
     described.
ST   forensic morphine heroin prepn
IT   Legal chemistry and medicine
        (heroin and morphine prepn. in illicit labs. in)
IT   57-27-2P, Morphine, biological studies   561-27-3P, Heroin
        (illicit lab. prepn. of)

Subject:      Any synthesis, Any time, Any where - Anacharsis
From:         <[102232 2645] at [compuserve.com] (Anacharsis)>
Date:         1995/10/27
Message-Id:   <46rkg4$[fk 6] at [dub-news-svc-4.compuserve.com]>
Newsgroups:   alt.drugs.chemistry

And also for all the people out 
there who are constantly asking how to convert codeine to 
morphine, there are numerous articles that specify *exactly* 
how to do this, e.g., (the simplest one I’ve seen) A rapid, high-yield 
conversion of codeine to morphine. Rice, Kenner C. Journal of 
Medicinal Chemistry (1977), 20(1), 164-5. (And check out page 
166, too. A comparable item.)