this guy asked foaf a Q bout isolating compounds....

[cap]

hey gang feller foaf knows asked if she knew how to isolate the 4 primary active constituants contained within P. somniferum. foaf obviously had no idea. well, other than that its not easy.

has anybody come across any good literature or simplified techniques to isolate papervine, codeine, morphine, and thebaine? his main interest was in thebaine basically just a rough idea of the gear required, chemicals, knowledge of which procedures, and the like would be helpful. what would an a/b extraction on pods do?

really tho any help or guidance etc is greatly apprecated as foaf has no clue nor do i

the info will be relayed to my gfoaf and she will relay it back to this mysterious guy :crazy:

thanks

[cap]

weird this posted twice for some reason,mod note: plz delete duplicate thread

[Lefty]

Fractional distillation or silica based chromatography. I hope I mispelled or misthought something due to ethyl alcohol. Stuff your clausen adapter full of glass & let 'er rip. Merck index is a fuckin' golden place to start for compound isolation.

[cap]

awww no "oscar's thebaine isolation tek" ?

[Caljet666]

If you use Calcium Oxide or Calcium hydroxide to bring an aqueous opium solution to pH9 the morphine will become calcium morphenate which is still water soluble while the other alkaloids will be freebase and can be extracted with a non polar or filtered out.

Not sure about separating the other alkaloids. Swims got some info on opiates he's been collecting so he'll have a look through for ya.

[cap]

hey cal
curious if perhaps your info turned up anything insightful as of yet?
thanks for the response
there are patents all over google.
a search for thebaine brings up a superabundance o' patents on synthing,
as well as patents on isolating alkaloids out of raw opium. thing is--

foaf was hoping am organic chemist, or someone that knows someone who knows someone
who has experience with this sort of thing, could possibly enlighten us as to the following --

A. what level of skill is required. perhaps a list of procedures one must be proficient in?
eg: using a column, gasing, centrifuge, etc

B. most importantly, and im going to be blunt -- does he need real lab space/time,
at a multi-million-dollar fully equipt/state of the art facility,
or with the right knowledge, equiptment/setup, and sources, can it be done clandestinely

this woman bugged me again today for the info lol
so i apologize for hounding yall, but i know the answers are out there,
and fiigure ill remain vigilant a couple more days here....
....before telling him to fuck off and stop bugging my friend
for advice on how to make vicodin in his basement
thanks 'gain gang be well

[mjshroomer]

Papers on all of those extractions can be obtained in various journals in the chemical abstracts
.

However, I would like to note that producing such compounds can land you a 20 year to life prison sentence for manufacture of narcotics.

mjshroomer

[cap]

hey cal
curious if perhaps your info turned up anything insightful as of yet?
thanks for the response
there are patents all over google.
a search for thebaine brings up superabundant patents on synthin' up opiods,
as well as patents on isolating alkaloids out of raw opium. thing is--

foaf was hoping an organic-chemist type, hell,
even someone that knows someone who knows someone who has experience,
could possibly enlighten us as to the following --

A. what level of skill is required. perhaps a list of procedures one must be proficient in?
eg: using a column, gasing, centrifuge, etc

C. most importantly, and sorta in relation to "B", and im going to be blunt --
does he need real lab space/time at a multi-million-dollar fully equipt/state of the art facility?
or with the right diploma, knowledge, equiptment/setup, and sources, can it be done clandestinely

this woman bugged me again today for the info
so i apologize for hounding yall, but i know the answers are out there,
and fiigure ill remain vigilant a couple more days here....
....before telling him to fuck off and stop bugging my friend
for advice on how to make vicodin in his basement
thanks 'gain gang be well

[Caljet666]

Looking, Looking, Looking, but not much luck sorry. I did find this however. With this you could isolate codeine and morphine.



ROBERTSON-GREGORY PROCESS:
The opium is completely exhausted by five to ten times its weight of cold water; the solution obtained is evaporated to the consistency of a soft extract, and then the process is repeated with cold distilled water. This aqueous re-extraction causes impurities to precipitate, they are filtered off (this filtering step is difficult since the filter paper becomes clogged) and the solution obtained is evaporated until its density is 10 degrees Baume'(this is a specific gravity term). One hundred and twenty grammes(grams) of calcium chloride for each kilogram of opium are added to the boiling liquor which is then diluted with a quantity of cold water equal to its own volume. A precipitate of meconate and sulphate of calcium is thus formed and is filtered off. After filtering, the liquid is again concentrated, and this produces a new deposit which consists almost exclusively of calcium meconate. This deposit is filtered off and the solution is left standing. After a few days it becomes a crystalline mass composed of morphine hydrochloride and codeine hydrochloride: this is know as "Gregory's salt". The crystals obtained are drained and then placed in a cloth and squeezed out in the press. They are purified by successive crystallizations, the solutions being: decolorized each time with animal charcoal. When the crystals are sufficiently pure, they are dissolved in water and the morphine is precipitated with ammonia; the codeine remains in solution. (Note: whenever concentration of the mother liquid is required use a rotary evaporator under vacuum).

According to Barbier, the first drawback of this process is the 20 to 25 per cent of the morphine is left with the secondary alkaloids in the brown and viscous mother-liquids after filtration of "Gregory's salt." Schwyzer(Die Fabrikation der Alkaloide, 1927) separates and purifies this morphine by precipitating all the alkaloids, by dissolving the secondary alkaloids in acetone, by acetylating the impure morphine in order to purify it in the form of diacetylmorphine (Heroin), and then by saponifying(to hydrolyze with alkali eg. NaOH) the latter to re-convert it to morphine. This process is complicated and cannot be as good as the author claims, owing to the solubility of morphine in acetone which, although slight, is not negligible.

The second drawback is the hydrochloride of morphine and codeine crystallize in furry needles which retain the mother-liquids in which the crystallization occurred. Several successive crystallizations and subsequent recoveries are required for purification, and this is a time-consuming process.

Schwyzer(Die Fabrikation der Alkaloide, 1927) purifies the mixture of hydrochlorides by malaxation (meaning?), with a small quantity of ice-water and subsequent pressing; he repeats the process several times. This no doubt enables him to leave less morphine in the mother-liquids, but that fact does not make the process much more attractive.

This process is very attractive to one seeking Gregory's salt. Gregory's salt is a very effective pain killer and was used extensively as such by the British.


I was searching to find boiling points with no luck. I did find that morphine's was 250 and codeine's was 254. Thebaine, being paramorphine I believe would have a close boiling point which would make fractional distillation downright too hard. Almost impossible. If it were significantly different though you could separate the morphine first and then fractionate.

Chromatography can be done ghetto although swim has no experience in with it so he could only offer limited advice there. There would be a lot of trial and error before it would be perfected and swim thinks you could only run maximum of a few grams at a time. He is no expert on the matter though.

I have a DjVu file of Otto Snow's Oxy. PM me if you want a copy, there might be some helpful info in there.

[Caljet666]

Starting to close in on this. Just found this little snippet in OXY, plenty more to wade through yet. The lead acetate is a little scary, although swim's sure with a bit more research he'll find a substitute.

The separation of thebaine from opium extract usually takes place after morphine, codeine, narcotine and paperaverine have been removed. The alcoholic mother liquor from which narcotine and paperavine have crystallized is concentrated and taken up in acetic acid. Basic lead acetate is added to alkaline reaction, whereby narcotine and resinous materials are precipitated; the filtrate is freed from lead with sulphuric acid, and the crude thebaine precipitated with ammonia

Seems ya got swim a little obsessed with this now Cap. When the time comes (southern hemisphere) his FOAFOAF is gonna grow some and was looking at extracting the morphine to play with. Maybe hydromorphone or 6-monoacetylmorphine. Maybe he'll try to get the thebaine for oxycodone too.

[cap]

Originally Posted by Caljet666

Looking, Looking, Looking, but not much luck sorry. I did find this however. With this you could isolate codeine and morphine.



ROBERTSON-GREGORY PROCESS:
The opium is completely exhausted by five to ten times its weight of cold water; the solution obtained is evaporated to the consistency of a soft extract, and then the process is repeated with cold distilled water. This aqueous re-extraction causes impurities to precipitate, they are filtered off (this filtering step is difficult since the filter paper becomes clogged) and the solution obtained is evaporated until its density is 10 degrees Baume'(this is a specific gravity term). One hundred and twenty grammes(grams) of calcium chloride for each kilogram of opium are added to the boiling liquor which is then diluted with a quantity of cold water equal to its own volume. A precipitate of meconate and sulphate of calcium is thus formed and is filtered off. After filtering, the liquid is again concentrated, and this produces a new deposit which consists almost exclusively of calcium meconate. This deposit is filtered off and the solution is left standing. After a few days it becomes a crystalline mass composed of morphine hydrochloride and codeine hydrochloride: this is know as "Gregory's salt". The crystals obtained are drained and then placed in a cloth and squeezed out in the press. They are purified by successive crystallizations, the solutions being: decolorized each time with animal charcoal. When the crystals are sufficiently pure, they are dissolved in water and the morphine is precipitated with ammonia; the codeine remains in solution. (Note: whenever concentration of the mother liquid is required use a rotary evaporator under vacuum).

According to Barbier, the first drawback of this process is the 20 to 25 per cent of the morphine is left with the secondary alkaloids in the brown and viscous mother-liquids after filtration of "Gregory's salt." Schwyzer(Die Fabrikation der Alkaloide, 1927) separates and purifies this morphine by precipitating all the alkaloids, by dissolving the secondary alkaloids in acetone, by acetylating the impure morphine in order to purify it in the form of diacetylmorphine (Heroin), and then by saponifying(to hydrolyze with alkali eg. NaOH) the latter to re-convert it to morphine. This process is complicated and cannot be as good as the author claims, owing to the solubility of morphine in acetone which, although slight, is not negligible.

The second drawback is the hydrochloride of morphine and codeine crystallize in furry needles which retain the mother-liquids in which the crystallization occurred. Several successive crystallizations and subsequent recoveries are required for purification, and this is a time-consuming process.

Schwyzer(Die Fabrikation der Alkaloide, 1927) purifies the mixture of hydrochlorides by malaxation (meaning?), with a small quantity of ice-water and subsequent pressing; he repeats the process several times. This no doubt enables him to leave less morphine in the mother-liquids, but that fact does not make the process much more attractive.

This process is very attractive to one seeking Gregory's salt. Gregory's salt is a very effective pain killer and was used extensively as such by the British.


I was searching to find boiling points with no luck. I did find that morphine's was 250 and codeine's was 254. Thebaine, being paramorphine I believe would have a close boiling point which would make fractional distillation downright too hard. Almost impossible. If it were significantly different though you could separate the morphine first and then fractionate.

Chromatography can be done ghetto although swim has no experience in with it so he could only offer limited advice there. There would be a lot of trial and error before it would be perfected and swim thinks you could only run maximum of a few grams at a time. He is no expert on the matter though.

I have a DjVu file of Otto Snow's Oxy. PM me if you want a copy, there might be some helpful info in there.

Malax

\Ma"lax\, Malaxate \Ma*lax"ate\, v. t. [L. malaxare, malaxatum, cf. Gr. ?, fr. ? soft: cf. F. malaxer.] To soften by kneading or stirring with some thinner substance. [R.]
Webster's Revised Unabridged Dictionary, © 1996, 1998 MICRA, Inc.

pm'ing thanks cal

[Doctor D]

Cap, I stumbled upon this website while looking for something completely non-drug related. I immediately thought of you.

Method for Producing Oxycodone -- Poppies.org

The entire document was exceedingly long, so I just quoted a "small" portion of it. Also attached the document in its entirety. Hopefully this is somewhat along the lines of what you were looking for? There are other goodies on that website, too.

Thebaine, which also contains a morphinan-ring structure, differs from codeine in replacing the hydroxyl group of the morphinan C-ring with a methoxy group and the "C" ring has two double bonds--.DELTA..sup.6,7, .DELTA..sup.8,14.(i.e., thebaine differs from morphine in that both hydroxyl groups are methylated and the "C" ring has two double bonds --.DELTA..sup.6,7, .DELTA..sup.8,14). ##STR5##

The compound demonstrates the effect that minor modifications in structure of morphinan compounds may have in pharmacological effects, as thebaine lacks any substantial analgesic activity (Foye, Medicinal Chemistry, 256 (1975)).

While lacking medicinal usefulness in itself, thebaine is singularly important as a key intermediate in the synthesis of many useful opiate-derivatives (See, Barber et al., 18 J. Med. Chem. 1074-107, 1975), including oxycodone (Freund et al., 94 J. Prak. Chemie 135-178, 153, 1916; See Physician's Desk Reference, 2569, 54th Ed. 1999), naloxone, naltrexone and nalbuphine (See, U.S. Pat. No. 4,795,813 at Col. 1, lines 16-21). Thebaine is the only known .DELTA..sup.6,8 -diene compound among the naturally-ocurring morphine alkaloids (Seiki, 18 Chem. Pharm. Bull. 671-675, 1970).

Oxycodone may be prepared from thebaine by: dissolution of the thebaine in aqueous formic acid, oxidation treatment with 30% hydrogen peroxide (Seki, 18 Chem. Pharm. Bull. 671-676, 1970), neutralization with aqueous ammonia to yield 14-hydroxycodeinone and hydrogenation of the 14-hydroxycodeinone in acetic acid with the aid of a palladium-charcoal catalyst (Remington's Pharmaceutical Sciences 1041, 1975). Oxidation of thebaine may alternatively be performed using potassium dichromate in acetic acid (Freund et al., 94 J Prakt. Chem. 135, 1916) or performic acid (Iljima et al., 60 Helv. Chim. Acta 2135-2137, 1977). Improved yield, however, has been reported to be obtained by oxidizing with m-chloroperbenzoic acid in an acetic acid-trifluoroacetic acid mixture (Hauser et al., 17 J Med. Chem. 1117, 1974; See also, U.S. Pat. No. 4,795,813 to Schwartz, Col. 1, Lines 22-26). Yield may also be improved by hydrogenation of 14-hydroxycodeinone under a pressure of about 30 psi (Kra.beta.nig et al. 329 Arch. Pharm. Pharm. Med. Chem. 325-326, 1996).

Although particularly useful in the synthesis of numerous pharmaceutical preparations, thebaine is among the least abundant phenanthrene alkaloids in Papaver somniferum. Due to its scarcity, a number of investigators have proposed methods of obtaining this unique alkaloid using other more abundant opioid compounds as starting materials.

Seki (18 Chem. Pharm. Bull. 671-676, 1970) discloses a method for preparing .DELTA..sup.6,8 -diene compounds, such as thebaine, from .alpha.,.beta.-unsaturated ketones such as codeinone, which may be obtained from the natural alkaloid codeine. Codeinone was added to a mixture of p-toluenesulfonic acid (dehydrated prior to reaction), absolute methanol and dried benzene, the solution refluxed for 3 hours under azeotropic removal of water, and the reaction mixture purified by washing with diluted sodium hydroxide, to obtain thebaine. A reported maximum yield of 26.8% was reported when using 1.1-15 molar equivalents of p-toluenesulfonic acid to codeinone. Eppenberger et al. (51 Helv. Chim. Acta 381, 1968) report a four step method for converting dihydrocodeinone to thebaine which results in a similar yield of 27%. Schwartz et al. (97 J Am. Chem. Soc. 1239, 1975) demonstrate the total synthesis of thebaine in which the key step is the oxidative coupling of a reticuline derivative to a salutaridine derivative. The overall yield of dl-thebaine, however, was only in the 1-2% range based on isovanillin. Reaction of salutaridinol with an organic or inorganic acid halide or acid anhydride, followed by treatment with a strong base, is taught as a method of thebaine production in U.S. Pat. No. 3,894,026 to Sohar et al. A yield as high as 50.3% was reported (See, Col. 4, Line 29). Barber et al. (18 J Med. Chem. 1074-1077, 1975) report synthesizing thebaine (as well as oripavine) from codeine and morphine. Barber et al. teach methylation of the potassium salt of codeine to give codeine methyl ether followed by oxidation with .gamma.-MnO.sub.2 (See also, U.S. Pat. No. 4,045,440 to Rapoport et al., 1977). These authors claim a 67% yield of oxycodone from codeine. European Patent Application No. EP 0 889 045 A1 likewise teaches a process for the production of thebaine from the more readily available morphinans codeine and morphine. Such method provides for converting the starting material to an alkali metal or quaternary ammonium cation and reacting the same with a compound of the formula RX wherein R is an alkyl or acyl group and X is a leaving group.

While all of the above methods have been devised to increase the supply of thebaine by synthetic and semi-synthetic means, the fact remains that thebaine remains relatively costly as opposed to morphine and codeine.

The use of thebaine as a starting material to form other therapeutically useful opioids also suffers from a disadvantage unassociated with its relative scarcity--thebaine is a known convulsant, capable of causing (even in low doses) strychnine-like convulsions (Foye, Principles of Medicinal Chemistry 255, 1975; The Merck Index, 9203 (11th Edition), 1989). Employment of thebaine in any synthesis scheme, therefore, entails significant risks and requires the taking of a number of precautions. Considering the relatively high cost of, and the toxicity potential of, thebaine, it would be preferred if alternative synthesis methods were developed to manufacture the many opioid congeners currently synthesized from thebaine from cheaper and less toxic materials.

[cap]

Originally Posted by Doctor D

Cap, I stumbled upon this website while looking for something completely non-drug related. I immediately thought of you.

thanks