Apart from the three articles/pages on this subject over at Rhodium's site, there is a paucity of information on this method of preparing morphine from OTC codeine (well OTC here at least). For instance, going off the known information to date, there was real doubt as to the recovery of realistic amounts of codeine and the "actual" yields. So that is where research comes in, to start with, let's go with the Pyridine.HCl route:
7-Desoxymorphine*
Henry Rapoport, Robert M. Bonner
J. Am. Chem. Soc., 1951, 73 (11), p 5485
DOI: 10.1021/ja01155a552
7-Desoxymorphine
A mixture of 2.0g of 7-desoxy-codeine and 6g of pyridine hydrochloride was placed in a bath at 220' and heated for six minutes in a nitrogen atmosphere, after which the reaction mixture was immediately cooled and treated with 25mL of water. Non-phenolic material was removed by ether extraction after the solution had been made alkaline with sodium hydroxide, and the ether extract was was washed with water, dried over magnesium sulfate, and evaporated to give 1.2g. (60%) of recovered 7-desoxycodeine. The aqueous phase was adjusted to pH 8 by addition of hydrochloric acid, and the mixture was extracted with methylene chloride. Evaporation of the methylene chloride left 0.7g (37% yield based on original 7-desoxycodeine or 92% yield based on unrecovered starting material) of phenolic material which was crystalized from benzene (0.1g in ca. 2mL of benzene). In order to free the compound from benzene which it retains tenaciously, it was slowly heated to 125' and sublimed at this temperature at 0.05mm. Pure 7-desoxymorphine (0.47g., 62%) was thus obtained, mp.143-144';[a]25D -67.2' (c 1.31, ethanol).
The Preparation of Morphine-N-methyl-C14[/u]**
Henry Rapoport, Calvin H. Lovell, Bert M. Tolbert
J. Am. Chem. Soc., 1951, 73 (12), p 5900
DOI: 10.1021/ja01156a543
Morphine-N-methyl-C14[/i]
Cleavage of 1.00g of codeine-N-methyl-C14 (specific activity 3.56uc/mg) was effected by heating with pyridine hydrochloride in the manner previously described for 7-desoxycodeine. The reaction mixture
was dissolved in 20 mL of water, basified with 10 mL of 4N sodium hydroxide, and the non-phenolic material was
removed by extraction with four 15Ml portions of chloroform. The combined chloroform extracts were washed with
10 mL of 0.5 N sodium hydroxide and 10 mL of water, and the aqueous phase, after adding the washings, was adjusted
to pH 9 and cooled thoroughly to precipitate phenolic material. After filtering and drying, this phenolic material was digested with 75 mL of methanol, the mixture was filtered hot, and the filtrate was chromatographed on an alumina (Merck and Co., Inc.) column (120 X 11 mm.) using 700 mL of methanol as eluent. The residue after
evaporation of the methanol was dissolved in 10 mL of 0.2N sodium hydroxide, filtered, and the filtrate was adjusted to pH 9, precipitating the crude morphine. After drying, this crude morphine was sublimed (180-190° (0.1 mm.)), and the sublimate was crystallized from absolute ethanol. There was thus obtained a total of 210 mg. (22%) of morphine-N-methyl-C14, m.p. 254-255', specific activity 3.75uc/mg.
(+)-Codeine and (+)-Morphine from Sinomenine***
Kakuji GOTO and Izuru YAMAMOTO
Proceedings of the Japan Academy
Vol. 30(
, 1954 pp.769-773
(+)-Morphine
A mixture of (+)-codeine (300 mg) and pyridine hydrochloride (3g) was heated in an oil bath at 175° (internal temperature of the test tube) for 10 min., under the current of dry C02. The isolation of (+)-morphine, a phenolic base, was carried out in an ordinary way. Recrystallized from methanol and ether, it formed prisms and melted at 247-248° (incorr.). Yield 45 mg (23% deducting unchanged (+)-codeine, which amounted to 120mg as hydrobromide).
NB Please note, the theoretical yield here is influenced by the fact that we are starting from codeine (299.4g/mol) and trying to form morphine (285.4g/mol), so the maximum yield is influenced by the fact that in order to do what we want we lose ~5% of the starting material in order to get a 100% theoretical yield, so in order to calculate yield, we must multiply the altered starting material x 0.95 to get the theoretical yield. We then divide the actual yield by the theoretical yield, then multiply by 100 to get the percentage yield.
* The actual yield is 62%
** The stated yield is 22%
*** The actual yield is 26.3%
Now, those yields look crappy, but it is still around 20% so 1/5 of the codeine purchased is converted to morphine. I have another couple of reference requests to come in, plus I wonder if anyone has tried the thermal decarboxylation of copper nicotinate to pyridine - I know Magpie (and someone else from memory) did carry out one of the ref's to pyridine quite successfully using the Copper chromite catalyst, but straight Cu nicotinate is supposed to degrade to it as well. Pyridine is soluble in most NP solvents IIRC, so just gassing it with dry HCl will give the salt. Run a tube from the rxn vessel into a solution of ammonia to trap the chloromethane (as methylamine) and the pyridine. The use of CO2 as the inert gas just made the route viable for mine.
a 96 pack of own-brand Ibuprofen/Codeine Phosphate tablets costs $11-15, and will yield about 1g of codeine (the dosage was designed to ensure that the pills contained the equivalent of 10mg of codeine base - the company originally involved found a loophole in the OTC rules). So between $100-150 (and 10 chemists, or a hour or two driving) will give enough for 10g of base. 10g of base, with 30g of Pyr.HCl should, with CO2 (from a soda bulb if necessary - it is only 6-10 minutes for fucks sake) should yield 2g of morphine. Given that morphine sulfate retails for between $0.50-$1.00/mg, $100-150/2g, or $0.05-$0.07/mg is looking rather more sustainable.
7-Desoxymorphine*
Henry Rapoport, Robert M. Bonner
J. Am. Chem. Soc., 1951, 73 (11), p 5485
DOI: 10.1021/ja01155a552
7-Desoxymorphine
A mixture of 2.0g of 7-desoxy-codeine and 6g of pyridine hydrochloride was placed in a bath at 220' and heated for six minutes in a nitrogen atmosphere, after which the reaction mixture was immediately cooled and treated with 25mL of water. Non-phenolic material was removed by ether extraction after the solution had been made alkaline with sodium hydroxide, and the ether extract was was washed with water, dried over magnesium sulfate, and evaporated to give 1.2g. (60%) of recovered 7-desoxycodeine. The aqueous phase was adjusted to pH 8 by addition of hydrochloric acid, and the mixture was extracted with methylene chloride. Evaporation of the methylene chloride left 0.7g (37% yield based on original 7-desoxycodeine or 92% yield based on unrecovered starting material) of phenolic material which was crystalized from benzene (0.1g in ca. 2mL of benzene). In order to free the compound from benzene which it retains tenaciously, it was slowly heated to 125' and sublimed at this temperature at 0.05mm. Pure 7-desoxymorphine (0.47g., 62%) was thus obtained, mp.143-144';[a]25D -67.2' (c 1.31, ethanol).
The Preparation of Morphine-N-methyl-C14[/u]**
Henry Rapoport, Calvin H. Lovell, Bert M. Tolbert
J. Am. Chem. Soc., 1951, 73 (12), p 5900
DOI: 10.1021/ja01156a543
Morphine-N-methyl-C14[/i]
Cleavage of 1.00g of codeine-N-methyl-C14 (specific activity 3.56uc/mg) was effected by heating with pyridine hydrochloride in the manner previously described for 7-desoxycodeine. The reaction mixture
was dissolved in 20 mL of water, basified with 10 mL of 4N sodium hydroxide, and the non-phenolic material was
removed by extraction with four 15Ml portions of chloroform. The combined chloroform extracts were washed with
10 mL of 0.5 N sodium hydroxide and 10 mL of water, and the aqueous phase, after adding the washings, was adjusted
to pH 9 and cooled thoroughly to precipitate phenolic material. After filtering and drying, this phenolic material was digested with 75 mL of methanol, the mixture was filtered hot, and the filtrate was chromatographed on an alumina (Merck and Co., Inc.) column (120 X 11 mm.) using 700 mL of methanol as eluent. The residue after
evaporation of the methanol was dissolved in 10 mL of 0.2N sodium hydroxide, filtered, and the filtrate was adjusted to pH 9, precipitating the crude morphine. After drying, this crude morphine was sublimed (180-190° (0.1 mm.)), and the sublimate was crystallized from absolute ethanol. There was thus obtained a total of 210 mg. (22%) of morphine-N-methyl-C14, m.p. 254-255', specific activity 3.75uc/mg.
(+)-Codeine and (+)-Morphine from Sinomenine***
Kakuji GOTO and Izuru YAMAMOTO
Proceedings of the Japan Academy
Vol. 30(
, 1954 pp.769-773 (+)-Morphine
A mixture of (+)-codeine (300 mg) and pyridine hydrochloride (3g) was heated in an oil bath at 175° (internal temperature of the test tube) for 10 min., under the current of dry C02. The isolation of (+)-morphine, a phenolic base, was carried out in an ordinary way. Recrystallized from methanol and ether, it formed prisms and melted at 247-248° (incorr.). Yield 45 mg (23% deducting unchanged (+)-codeine, which amounted to 120mg as hydrobromide).
NB Please note, the theoretical yield here is influenced by the fact that we are starting from codeine (299.4g/mol) and trying to form morphine (285.4g/mol), so the maximum yield is influenced by the fact that in order to do what we want we lose ~5% of the starting material in order to get a 100% theoretical yield, so in order to calculate yield, we must multiply the altered starting material x 0.95 to get the theoretical yield. We then divide the actual yield by the theoretical yield, then multiply by 100 to get the percentage yield.
* The actual yield is 62%
** The stated yield is 22%
*** The actual yield is 26.3%
Now, those yields look crappy, but it is still around 20% so 1/5 of the codeine purchased is converted to morphine. I have another couple of reference requests to come in, plus I wonder if anyone has tried the thermal decarboxylation of copper nicotinate to pyridine - I know Magpie (and someone else from memory) did carry out one of the ref's to pyridine quite successfully using the Copper chromite catalyst, but straight Cu nicotinate is supposed to degrade to it as well. Pyridine is soluble in most NP solvents IIRC, so just gassing it with dry HCl will give the salt. Run a tube from the rxn vessel into a solution of ammonia to trap the chloromethane (as methylamine) and the pyridine. The use of CO2 as the inert gas just made the route viable for mine.
a 96 pack of own-brand Ibuprofen/Codeine Phosphate tablets costs $11-15, and will yield about 1g of codeine (the dosage was designed to ensure that the pills contained the equivalent of 10mg of codeine base - the company originally involved found a loophole in the OTC rules). So between $100-150 (and 10 chemists, or a hour or two driving) will give enough for 10g of base. 10g of base, with 30g of Pyr.HCl should, with CO2 (from a soda bulb if necessary - it is only 6-10 minutes for fucks sake) should yield 2g of morphine. Given that morphine sulfate retails for between $0.50-$1.00/mg, $100-150/2g, or $0.05-$0.07/mg is looking rather more sustainable.
Rapoport.Bonner.7Desoxymorphine.pdf
i thought IIRC that synth at SM you mention used nicotinamide aka vitamin b1,),hey no1 have you found ANY other synths for pyrridine anywhere--its a handy little chem to have on hand 
(I might go request 