Codeine Homebake

[Nuke]

Hey, this is a post I left on a drug chemistry newsgroup and I thought I'd leave it here too incase anyone is interested in cooking up there own dope. Its basically a method to convert Codeine to morphine it was origionally from a chemist called rapoport.

This is what swin had been dreaming after having multiple failures with the
Kiwi Homebake.
Swins List:
-2 grams of Codeine Base
-muriatic acid (HCL)
-Pyridine
-Chloroform
-Methylene Chloride
-Caustic potash
-Ammonium Chloride
-Phosphoric Acid
-pyrex ignition Tube or small boiling flask
-Sep Funnel
-Buchner Funnel and flask with side arm.
-Alcohol Burner
-Rubber bung with thermometer in the center


-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.


-Add 6 grams Pyridine HCL and heat untill it melts and continue
untill it is Anhydrous (Circa 190°). Wipe the inside of the flask if
there is any condensation.


-add 2.5 grams Anhydrous codeine base and flush out the vessel with Nitrogen
quickly seal with your bung/thermometer.


-Heat up to 210°-220° for 6-8 minutes. After heating Cool rapidly in
Ice water and dissolve with 30 mL of water. Add Phosphoric acid
dropwise until you hit pH 5.


-add to a Smallish sep funnel and Extract 3 times with 20 mL portions
of methylene Chloride. (remember to get any last bit out of the tube
using a little bit of phosphoric solution. Also, it may be necessary
to re-adjust the pH after each extraction).


-Add dilute Caustic potash untill the solution is highly basic
(12+ is good).


-Now having a "cleaner" solution with both your unreacted codeine and
your newly cleaved morphine you can once again extract with the
methylene chloride twice at say 20 mL a piece. (this contains
your codeine which you can re-cover and re-use By washing with a small
ammount of phosphoric solution ,basifying and then extracting back
into the DCM or the chloroform and evaping).


-now you should vacuum filter this highly basic solution containing
the soluble morphinate which will get rid of all the solid shit that
was created in the reaction.


-Add Ammonium chloride untill about pH 9.1, at this point just set her down
in a sink of cool water turn off the lights in the room wait for a few hours.
Come back, filter the morphia, wash with tiny little bits of water and let
her dry out.

Every yield is different plus this way takes quite a bit of time.


P.s. Swin has a nitrogen tank from a paint ball gun that works great, you
could use an old burnt out light bulb I reckon as a source for a small
amount of nitrogen. Im not quite sure exactly how pure this morphine is but
Im betting its pretty damn pure. Subliming it should clean it up or
rapoport also recommends chromatography on an alumina adsorbent column and
further with cellulose powder chromatography. Also dont use the Kiwi method
for acetylating (Unless you like monoacetylmorphine?!) . The final product
is the 3-0-mono-acetylmorphine with small amounts of diacetylmorphine.

[Nuke]

Here is a better method for the same O-demethylation of codeine --> morphine, Only this one is alot more efficient (50-90% yield!) using BBr3 as the cleaving agent. It leaves a cleaner product and is easy to preform given the right equiptment. The draw back would be BBr3 is highly volatile and HBr gas is incredibly rotten shit so you would need to either use a fume hood , glove box, outdoors with a mask on etc etc. I personally have not tried this method yet But when I do I'll post a write up about what some of the problems are so on and so forth. I'll also annotate this procedure with any usefull info I may find.



Procedure:

1. Dissolve 2.99 g of anhydrous codeine in 25 ml of CHCL3 (Chloroform).

2. Create a solution of 15 g of BBR3 (Boron Tribromide) in 175 ml of
CHCL3. Be sure that this solution is kept well stirred for step 3.

3. Add solution 1 to solution 2 over a 2 minute period, maintained in
the range of 23-26 degrees C.

4. The reaction mixture will consist of a suspension of white solid in
the chloroform. This should then be poured into a well-stirred mixture of
80 g of ice and 20 ml of concentrated (28-30%) NH4OH. The two-phase
system should be kept at -5 to 0 degrees C for 30 minutes with
continuous stirring, then filtered. (Yes, by vacuum.)

5. The resulting crystals should be washed thoroughly with small
amounts of cold chloroform and H2O, and dried. This should yield about 2.67 g
(88.1%) of tan crystals. Now for those that are happy with a bird in the hand, voila, that's
it. For those high achievers who want to go the extra step, read on.

6. To gain additional yield, take the aqueous phase from the filtrate,
and saturate with NACL. Extract with 4 X 50 ml of CHCL3-EtOH (3:1).

7. Evaporate this, which will leave a remaining residue (approximately
151 mg).

8. Dissolve this residue in 2 ml of H2O containing 1 drop of 37% HCL.
After addition of .5 ml of chloroform, the pH should be adjusted to 9.0

with concentrated NH4OH while stirring. The crystalline material which
separates should be filtered, washed with cold H2O and chloroform, and
then dried. This will produce an additional 86 mg, giving a total yield
of 2.76 g, which is 91%. Additional product could be produced by
additional extractions of the aqueous phase. (Although I doubt more than one
additional extraction would be worth the effort.)

[nonnie7781]

ok i know you may think i am stupid, but i dont know where to get all these chemicals from, is the result the same as heroin?

[bogumil]

The chemicals are all pretty easy to get. But I for myself keep my fingers from this synthesis because my chemical skills are not good enough and I dont really want to mess with HBr ... poisonouss stuff ...

But the procedures work (I heard. Would be great if someone who did it, could report and give advice, then I would give it a try).

And: No, the product is not like heroin. It is one step before heroin. Heroin is acetylated morphine (=diacetylmorphine is the chemical name for heroin). Its very easy (much much easier than the demethylation of codeine to morphine) to make heroine from morphine, when you get acetic anhydride. This are the common ways to get H:

opium - codeine - morphine - heroin
opium - morphine - heroin

[kramorph]

Thanks, swim posted a thread asking for alternate demethylation methods as swim cannot obtain pyridine although I suspect BBr3 would also be hard to get. Where would one get it and what is a good reason to need it(other than to make your own smack!). Swim isnt very computer literate and Is still getting the hang of this site. If anyone knows where to get pyridine and/or BBR3 in Aust. swim would greatly appreciate it. Swim would like to try both methods and post his results for everyone else to share.:)

[kramorph]

Penty of chemicals avail from o/seas but no bastard ships to Oz.Cant get fuckall here without health dept approval, police clearances etc etc.Looks like I'll have to get the balaclava and gloves out again and pretend to be a cat, oh well stuck with poxy methadone and expensive sugar with a sprinkle of H in it.

[Nuke]

And: No, the product is not like heroin. It is one step before heroin. Heroin is acetylated morphine (=diacetylmorphine is the chemical name for heroin). Its very easy (much much easier than the demethylation of codeine to morphine) to make heroine from morphine, when you get acetic anhydride. This are the common ways to get H:



You'd be suprised, the boron bromide syth really is pretty simple, I was wrong about the need for a fume hood or glove box . Even know hydrogen bromide is pretty nasty it's no more nasty than hydrogen iodide. All you need to do is bubble it through water after having added the codeine in chloroform. People make it sound as if its like prussic acid where when you open the bottle it immediatly forms gas because of the air, i've found this simply isn't the case, the only thing to be carfull around it water, because it is extremely reactive with water. Also the actual cook is pretty easy stuff to since the entire synth is done at ambiet or below ambient temps, where as the AA morphine cook, is at elevated temps and is very sensetive to heat that is to high, plus it takes a long bloody time, maybe if you had the DMAP catayst it may be easier but without it the process can be some what strenuous.

[bogumil]

You'd be suprised, the boron bromide syth really is pretty simple, I was wrong about the need for a fume hood or glove box .
So you did this process? Ok, that makes me interested in the whole procedure again, now that you say it is relatively easy. Ill check if I have the chemicals .


I have some questions:



4. The reaction mixture will consist of a suspension of white solid in
the chloroform. This should then be poured into a well-stirred mixture of
80 g of ice and 20 ml of concentrated (28-30%) NH4OH. The two-phase
system should be kept at -5 to 0 degrees C for 30 minutes with
continuous stirring, then filtered. (Yes, by vacuum.)

Do I really take 80 gram of frozen water, crush it, and then add the NH4OH to it?



5. The resulting crystals should be washed thoroughly with small
amounts of cold chloroform and H2O, and dried.
How exactly do I wash crystals with chloroform?



Thank you!

[kramorph]

could some nice person send me some BBr3,no one will sell it here too toxic they reckon and no o/seas supplier will send it here not even Indians or Chinese.Can I make it with boric acid and Br compounds? Pyridine method too much messing around for poxy dirty yeild!

[shinobi]

if your gona get someone to send you chemicals i sugest you get a mail box in the name of someone else. Customs open EVERYTHING and your gona be mighty f*cked if they find people sending you chemicals as private mail.

[Nuke]

Do I really take 80 gram of frozen water, crush it, and then add the NH4OH to it?


Yes








How exactly do I wash crystals with chloroform?


Take the aqueous put it in a sep funnel with an equal amount of the chloroform, shake the shit out of it and then seperate the layers.


You don't even have to do that though, just spraying small amounts while it on a failter works fine.

[Buckshot]

So did Bogumil pull it off?

[red26]

So did Bogumil pull it off?
Honestly I havent seen any of these guys around in a really long time. Hopefully Bog did it tho. Man this thread brings back mems.;)

[OxyContinuously]

Nuke, are you a chemist like me? Only reason I ask is because I am liking your synthesis, and it will definitely work you sound like you know what you are talkin about (don't take offense to that; take it as a compliment ;-); you put in all the essential steps and the reactions are pretty standard across the board. Hey, it's cool to have another chemically minded person around. Theres a few of us here on the 'phile. PM me anytime if you wanna bullshit about chemistry or have any questions regarding reactions, etc. I'd be happy to contribute/help out whatever.


Note to people who have to ask why certain steps are being performed: Do not attempt this if you are unsure, and use the exact chems Nuke specified; don't add or eliminate anything. ANyway, talk to you guys later. (I couldn't resist posting a reply--anything relating to the synthesis aspect of chemistry is music to my ears--well, eyes in this case)

OxyC

[Papa Verine]

Hey, this is a post I left on a drug chemistry newsgroup and I thought I'd leave it here too incase anyone is interested in cooking up there own dope. Its basically a method to convert Codeine to morphine it was origionally from a chemist called rapoport.

This is what swin had been dreaming after having multiple failures with the
Kiwi Homebake.
Swins List:
-2 grams of Codeine Base
-muriatic acid (HCL)
-Pyridine
-Chloroform
-Methylene Chloride
-Caustic potash
-Ammonium Chloride
-Phosphoric Acid
-pyrex ignition Tube or small boiling flask
-Sep Funnel
-Buchner Funnel and flask with side arm.
-Alcohol Burner
-Rubber bung with thermometer in the center


-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.


-Add 6 grams Pyridine HCL and heat untill it melts and continue
untill it is Anhydrous (Circa 190°). Wipe the inside of the flask if
there is any condensation.


-add 2.5 grams Anhydrous codeine base and flush out the vessel with Nitrogen
quickly seal with your bung/thermometer.


-Heat up to 210°-220° for 6-8 minutes. After heating Cool rapidly in
Ice water and dissolve with 30 mL of water. Add Phosphoric acid
dropwise until you hit pH 5.


-add to a Smallish sep funnel and Extract 3 times with 20 mL portions
of methylene Chloride. (remember to get any last bit out of the tube
using a little bit of phosphoric solution. Also, it may be necessary
to re-adjust the pH after each extraction).


-Add dilute Caustic potash untill the solution is highly basic
(12+ is good).


-Now having a "cleaner" solution with both your unreacted codeine and
your newly cleaved morphine you can once again extract with the
methylene chloride twice at say 20 mL a piece. (this contains
your codeine which you can re-cover and re-use By washing with a small
ammount of phosphoric solution ,basifying and then extracting back
into the DCM or the chloroform and evaping).


-now you should vacuum filter this highly basic solution containing
the soluble morphinate which will get rid of all the solid shit that
was created in the reaction.


-Add Ammonium chloride untill about pH 9.1, at this point just set her down
in a sink of cool water turn off the lights in the room wait for a few hours.
Come back, filter the morphia, wash with tiny little bits of water and let
her dry out.

Every yield is different plus this way takes quite a bit of time.


P.s. Swin has a nitrogen tank from a paint ball gun that works great, you
could use an old burnt out light bulb I reckon as a source for a small
amount of nitrogen. Im not quite sure exactly how pure this morphine is but
Im betting its pretty damn pure. Subliming it should clean it up or
rapoport also recommends chromatography on an alumina adsorbent column and
further with cellulose powder chromatography. Also dont use the Kiwi method
for acetylating (Unless you like monoacetylmorphine?!) . The final product
is the 3-0-mono-acetylmorphine with small amounts of diacetylmorphine.

How did you go from muriatic acid to conc. Hydrochloric in the first step?

[OxyContinuously]

How did you go from muriatic acid to conc. Hydrochloric in the first step?


Papa Ver. A lot of times, depending on the maker, muriatic acid is 12% hydrochloric acid. In some rare cases, there is a scent mixed in, but for the most part the 12 percent means that the rest is diluted with water. The strongest HCl so to speak (or concentrated) is 12 M (molar). To answer your question, Papa V, you could gently heat off the water to obtain a more concentrated product. That would make the most sense and would probably be the safest.

OxyC

[Buckshot]

Oxy I'm glad your into chemistry.

But any good chemist knows the value of asking questions...specificly on a msg board like this.
For you to imply "blindly follow the steps, and if you need to ask anything, you're not ready" Seems more like a crank cook, then a decent chemist.


And by the way Mr.Wizard, some of us were members of The Hive from when it opened till it closed.

Hailz to Rhodium

Buckshot aka Curbshot

[Papa Verine]

Oxy I'm glad your into chemistry.

But any good chemist knows the value of asking questions...specificly on a msg board like this.
For you to imply "blindly follow the steps, and if you need to ask anything, you're not ready" Seems more like a crank cook, then a decent chemist.


And by the way Mr.Wizard, some of us were members of The Hive from when it opened till it closed.

Hailz to Rhodium

Buckshot aka Curbshot

Hey Buckey, Oxy was just making the point that you should know what you're doing before you find yourself in the middle of a synth and then asking questions. I don't think your implying he's not a decent chemist is fair. He's erring on the side of caution because he knows there are a bunch of smart-ass kids like yourself visiting these threads. You know?

[Ickyuck]

School time. I love it.

[nick]

I'm not a chemist but I'm with Papa.I think what Oxy C says is eminently sensible.I don't think making M for human consumption is to be undertaken unless you're sure what you're doing.

[poonwhalla]

absolutly nickI am there with you but let us know You the progress weather you burn your self under your skin or find a good way to do things in laymens terms that is or just keep acting like a+b+Hero2 jesus you don't know that mang what a fucking retard

[Buckshot]

It is the night before Christmas Eve and maybe I'm a prick/grinch.

But many discoveries were stumpled upon by accident.

Try things. Ask questions.

Merry Christmas Oxy

[robojunkie]

Oxy I'm glad your into chemistry.

But any good chemist knows the value of asking questions...specificly on a msg board like this.
For you to imply "blindly follow the steps, and if you need to ask anything, you're not ready" Seems more like a crank cook, then a decent chemist.


And by the way Mr.Wizard, some of us were members of The Hive from when it opened till it closed.

Hailz to Rhodium

Buckshot aka Curbshot

Hey Buckey, Oxy was just making the point that you should know what you're doing before you find yourself in the middle of a synth and then asking questions. I don't think your implying he's not a decent chemist is fair. He's erring on the side of caution because he knows there are a bunch of smart-ass kids like yourself visiting these threads. You know?

I know this last part of the thread is a little old but I gotta drop my 2 pennies...It's always good to ask questions before undertaking any synthetic procedure, but not during, especiallly on line or somewhere you gotta wait for a response. There are plenty of problems that can arise unexpectedly in any given method. If one is just being a "cookbook chemist" stick with vick's inhalers and CWE's. What would you have done if there was NO precipitate to filter? Give Up? Yeah these amounts given are important but if you don't know why your chances for success are really dropped. Morphine isn't some easily A/B extracted material, at least in this (small pH range) environment...too much BBr3, not enough ammonia equals soluble stuff. Around ph~9 the resulting boric acid is now a borate salt. If not ph~9 you'll have boric acid, ie protonated morphine, ie water soluble. If someone got to this point and said "oh shit, better basify with some carbonate", now you got the sodium/calcium morphinate salt, also water soluble. Not to mention all the ammonium bromide and boric acid/borate. These are all soluble in water and if the ph aint right you'll be looking very disappointingly at an empty filter paper wondering what the fuck? Reactions are easy, its the work up and purification that require more than just a manual.

And yeah dude Rhodium and Strike (at least until he opened that company:() knew what they were doing but that doesn't mean anyone who was ever on the hive is some expert. Go read some of the old guys new site and you'll see countless arguments and debates, some reasonable some base on nothing but hunch. Unexpected shit always comes up in even simple conversions. Also, BTW, the original paper isn't an underground write up; it's taken essentially verbatim from a literature article from 1978, I believe. Always best to know at least enough to answer your own questions before and especially during any conversion, regardless of what to what.

[jacky]

so which "old guys new site" are we talking about?

I loved the hive of course....so is there something similiar?

[robojunkie]

Sort of....called "wet dreams" I can usually tell when someone from there shows up and instead of all that swim crap they talk about "a dream I had where...". Forget the actual URL, I never post there. A lot of the same people from what I can gather. Focuses way more on the phenethylamines of course.