Sciencemadness Discussion Board

puzzling extraction

mfilip62 - 25-3-2010 at 17:04

There is an interesting chemical puzzle that you may like...

In one pill you have;

Codeine phosphate hemihidrate
caffeine
propyphenazone
acetaminophen
some forms of starch

Hoy you get any of these chemical 99% pure!?

OK,it is fairly easy to get acetaminophen and starch because they don't dissolve in cold water very well.
Then you use some kind of organic solvent to extract acetaminophen
(which one!?)

Most of the caffeine and codeine will be dissolved in water.
Now comes the tricky part; How to separate them!?

Can't find any info on chemical properties of propyphenazone either...

What fascinated me in the first place is that pharmaceutical company added starch and caffeine into mix to prevent codeine abuse,anyone guessing why starch!?(Hint:Hot water extraction...:D )



Notice;
I don't won't to abuse codeine nor do I need it.
I gone trough long morphine pain treatment in hospital,
and opiates are not something you want to mess with!
I strongly advice not to take them without medical reasons and prescription.There is no "one night stand" with opiates,they
are the essence of satisfaction in brain and WILL TAKE OVER your life!

DJF90 - 25-3-2010 at 17:13

Quote:
What fascinated me in the first place is that pharmaceutical company added starch and caffeine into mix to prevent codeine abuse,anyone guessing why starch!?


Ever heard of tablet binder..? Caffiene also has properties that supplement the medicinal effects of the active compounds.


not_important - 25-3-2010 at 17:42

Quote: Originally posted by mfilip62  
...
Can't find any info on chemical properties of propyphenazone either...


Must have tried too hard

http://www.avignapharma.com/pdf/PROPYPHENAZONE%20BP.pdf

http://www.springerlink.com/content/g788722456700532/

https://info.ngwa.org/GWOL/pdf/042579851.pdf



propyphenazone_solubility.png - 15kB

JohnWW - 25-3-2010 at 18:26

The pills are obviously intended to be an analgesic. The propyphenazone (see Wiki) is another analgesic, without the sedative and addictive properties of codeine, which it is obviously intended to partly substitute for. The caffeine is very probably added to overcome the sedative effect of the codeine.

180px-Propyphenazone.svg.png - 5kB

mfilip62 - 26-3-2010 at 06:59

Thanks for info!
So it means its pretty insoluble in water,and you need
to get it out of paracetamol/starch/cellulose leftover.
Quote: Originally posted by DJF90  
Quote:
What fascinated me in the first place is that pharmaceutical company added starch and caffeine into mix to prevent codeine abuse,anyone guessing why starch!?


Ever heard of tablet binder..? Caffiene also has properties that supplement the medicinal effects of the active compounds.




No,they use micro-crystalline cellulose for that in the same tablet.
They use starch to prevent extraction via hot water/ice method,
because starch gets swollen and acts as jelly ruining extraction.
(don't know exact term for that in English,but it acts as pudding.)

Caffeine is used for two reasons;to improve speed of codeine absorption and to counter sedative effects.

And of course it is analgesic medicine,but people use it to counter
alcohol hangover,not sure if this is any good...


Now what method would you use to separate caffeine and codeine salt!?

Picric-A - 26-3-2010 at 07:47

Maybe try extracting the freebase caffeine from codeine phosphate with something like DCM or ethyl acetate?

bquirky - 26-3-2010 at 08:34

Pardon my ignorance But how dose starch inhibot Seperaation of codine from paracetamole ?

mfilip62 - 26-3-2010 at 10:39

Its simple.

Most efficient method of extracting codeine by dissolving medicine containing acetaminophen/codeine (I think they are named Tylenol or something like that in US) in almost boiling water shortly and than freezing it.All of codeine is still dissolved but most of acetaminophen participates,so you can remove it.

But,if medicine also contains starch o other gelling agent,you get useless thick slime.

@ Picric-A

I am not familiar with that method,please explain.

Is it caffeine freebase or not in its "original" form in those pills
I don't know.

Notice that I don't have very much of fancy chemicals,so method needs to be as simple as possible.

Codeine and caffeine probably have very different boiling points,
does any of these sublimates!?

rrkss - 26-3-2010 at 11:17

Couldn't you use an enzyme to break the starch down and then do the extraction with the hot water/ice method eliminating the gelling problem?

mfilip62 - 26-3-2010 at 11:39

Of course,but starch is added to make it hard for average junkies,
not chemist.

It's not point there,you can do it with cold water,this step
is easy but I am asking how to separate codeine salt and
caffeine!?

Picric-A - 26-3-2010 at 11:41

Quote: Originally posted by mfilip62  
Its simple.

Most efficient method of extracting codeine by dissolving medicine containing acetaminophen/codeine (I think they are named Tylenol or something like that in US) in almost boiling water shortly and than freezing it.All of codeine is still dissolved but most of acetaminophen participates,so you can remove it.

But,if medicine also contains starch o other gelling agent,you get useless thick slime.

@ Picric-A

I am not familiar with that method,please explain.

Is it caffeine freebase or not in its "original" form in those pills
I don't know.

Notice that I don't have very much of fancy chemicals,so method needs to be as simple as possible.

Codeine and caffeine probably have very different boiling points,
does any of these sublimates!?


So long as your pills are the same as mine the caffeine is present as the anhydrous freebase. This is fairly soluble in DCM and (less so) ethyl acetate. The Codeine posphate, being very polar, is not and so the caffeine should go to the DCM layer and the Codeine stay in aqueous layer.

Simply seperate the two layers then evaorate the DCM which should provide you with fairly pure caffeine. Evaporate the water to give rather crude codeine. This can be purified by recrystalisation to get rid of traces of paracetamol and other impurities.

The DCM can be found in paint brush cleaner and the ethyl acetate in nail polish remover.




ps. I have had this problem before, when trying to extract the codeine using hot water the other binding agents makes the water form a gel which is almost impossible to filter.
Anybody know how to counter this?

[Edited on 26-3-2010 by Picric-A]

un0me2 - 27-3-2010 at 22:35

And here is a journal article, funnily enough, from the very first page of google search results using "propyphenazone" as the search term, in PDF format too...:o Strangely enough, it discusses separating PRECISELY the mixture you ask about by TLC...

MIGHT I SUGGEST YOU UTFSE? (Not the one on this site, but Google would be kind of a no-brainer surely?)

Attachment: Dimitrovska.Determination.of.Propyphenazone.Paracetamol.Caffeine.and.Codeine.Phosphate.with.TLC.pdf (1.8MB)
This file has been downloaded 3072 times

DJF90 - 28-3-2010 at 08:29

Microcrystalline cellulose is not a binder but a filling/bulking agent. Try mixing it with a little water and a powdery substance (take caffeine for example) and make a little ball... when it dries, it will quite readily fall apart;the same, mixture with starch however will stay firm, due to the "gelling" of the starch which binds everything together.

mfilip62 - 28-3-2010 at 11:04

Can't argue with that,but there is no doubt that starch's gelling properties have abuse preventive role in medicine like this one.

Thanks unome2,but in this report they use ethanol and water to separate propyphenazone/paracetamol/caffeine from codeine salt,and I need pure caffeine for now,pure codeine salt is just bonus if it is easy to get.

If I dissolve tablet in ethanol/methanol mix what will dissolve and what
would be left over!?

I am not sure will codeine salt dissolve in ethanol while everything else
stays undissolved.
After all,methanol/ethanol is just slightly less polar than water,but
will it dissolve codeine salt without disolving caffeine?! I doubt.
So conclusion is simple:
If caffeine is more saluble in more readily available non-polar solvent that does not dissoles codeine salt use that,and if codeine salt is more saluble in more readily available polar solvent that does not dissoles
caffeine use that!

What do you guys think about that!?

Any chart on codeine salt/solvent/temperature salubility or same for caffeine to put an end on this!?


DJF90 - 28-3-2010 at 11:11

My conclusion is that if you are after caffeine, start with ProPlus or teabags...

mfilip62 - 28-3-2010 at 11:34

I tried with coffee,but with poor results.Tea even worse.
In my country,anything else that contains caffeine but Coca-Cola,coffee and these tablets is blatantly expansive and hard to find.
Better variation of tabs have around 100mg of caffeine per 8mg of codeine salt,but they are getting withdrawn,while others have only 15 to 10 ration.

Any response on my previous post about solubility!?

rrkss - 28-3-2010 at 11:39

Use teabags and make a really concentrated tea solution by boiling the teabags in water. Then do an extraction using dichloromethane or ethyl acetate; dichloromethane being the better solvent. Evaporate off the organic solvent giving you crude caffeine. You can then purify the caffeine by sublimation onto a cold finger.

mfilip62 - 28-3-2010 at 11:58

Will try,thanks!

For now this is the most cheapest method,because packing of pills
costs around $2, containing far more caffeine.

@Picric-A

As long as I remember you can't make jelly out of papaya and some other exotic fruits without some special additives,and I am pretty sure that grapefruit juice has synergistic effect with codeine,as used in war
here when morphine was scarce.(Again,I am not sure if this is purely placebo,but I think not.)

ergo

They contain some kind of jelly killer proteins,so just use
juice(not sure which one,search for it) instead of water and some grapefruit in mix,but make sure kids don't get hold of it :cool:

chemrox - 28-3-2010 at 19:37

caffeine potentiates codeine.

mfilip62 - 29-3-2010 at 04:04

Yep,that's true,actually it speeds up absorption.
but I am not sure is it because it speeds up whole metabolism
or just some receptors/barriers.

As pain relief there is no use AT ALL of 8-20mg codeine,although
it serves well as antitussic (caught-suppressant) in that doses.
(30mg seems to be best for that.)
Not sure if there is any good of caffeine when using it "for fun"?

Only reason why they put it in such small quantities is to get addicted.
You don't have any noticeable effect,but it surely grows
number of opiate receptors,making you an addict over prolonged treatment so they can make more money.

I think that codeine based OTC medicines will b soon banned for that.

DJF90 - 29-3-2010 at 06:24

1-2 Codeine triphosphate 15mg really helps when I have a migraine, so I disagree that 8-20mg is good only as an antitussic.

mfilip62 - 29-3-2010 at 09:00

Just saying what I heard and how it effects me.
I didn't meade research!
But I see no point on researching something that would
destroy sale,so its probably sloppy gowermentall research.

For me,these combo tablets work's great for lighter pain,
and that is probably becouse I use them a lot(cca. 3)
being 200+ lbs and 6ft high.:D

Everyones metabolises medicines differently,so its difficult topic.

For example I really feel effects of caffeine that helps me study,
but codeine sucks comparing with tramadol in pain relief.

Maybe it's off topic but for me,tramadol is greatest discovery since aspirin!Some say it's opiate,but can't really compare it with mofrine .It does kinda remind,but deffinitely not much...
After all,chemicaly its something differnt...
Does wonders with pain,acts as great antidepressant,and doesn't make's you confused and "don't give a damn,I live in wonderland!" type of feeling like other painkillers.I think it actually helps you work and think better,acting allmost like some kind of stimulant,it is unbeliveable that you can go nod and than work in instant if you want.Best of all is that you don't get addicted if ou don't use brutally big doses very often.
Even if you are that stupid,diazepam is OD antidote.

Nothing helped me more to get off morfine and postoperative pain after surery!

mr.crow - 29-3-2010 at 10:34

Maybe a doctor could help you out getting the right pain relief. I am not sure why you need to do an extraction other then for fun.

EDIT: I am not trying to imply or accuse the OP of anything. This is just what I found when I was looking up codeine on google.


A quick search revealed some pretty sketchy websites where people talk about extracting codeine.

Apparently demethylating codeine was really popular in New Zealand to make morphine. Also in Russia they react it with iodine to add to the double bond, then add red P to make HI. This demethylates it and reduces the double bond and OH to make crude desomorphine or 'the crocodile'.

Yeah that was off topic to this thread and not appropriate for the forum, but I thought it was interesting.

[Edited on 30-3-2010 by mr.crow]

mfilip62 - 29-3-2010 at 16:47

This is ridiculous,why don't we stick to the subject!?
Maybe I didn't say it clearly enough,but I am;
1.)Clean for more than a year,not even Tramadol!
2.)Not interested in effect of codeine when I can get medicine
10 times better from my doctor ASAP, IF I need it.
3)Need extraction of caffeine,don't give damn if codeine gets destroyed.
(that is why i suggested some kind of distillation in he first place,
read my posts!)

Luckily,pain is mostly gone,ibuprofen handling it 99%.
It was blast injury from PROM-1 bouncing mine.
Still have enough shrapnels to be suspicious at
airport and one particularly nasty pierce me all
the way trough scapula and lungs.

While in traumatic state and some time postoperative I
received morphine.
When morphine wasn't longer needed,they tried to detox with tramadol,which was new stuff at the time,last shot before going to methadone therapy.
Fortunately tramadol did wonder for me,so there was no need for methadone.
Doctor prescribed codeine once as caught suppressant in other operation where pneumonia became
extremely dangerous(I got it day after the eardrum reconstruction,
if you know basics of anatomy this is quite terrifying combo),but it doesn't do much good to me,unlike pholcodine(which gives no "feeling",but binds ONLY to the cough receptors.)

Using opiates just for "fun" is plain idiocy,they will ruin your life that way and someday you may need them and they won't work!

Wan't me to publish me medical char!?

I believe your intentions are purely good,but
some of you are extreme hypocrites!
when I,or some rag-head,ask for advice how to make state of the art new HE that can go past most modern detectors to shot plane form the sky,no problem!

But when someone asks something related to drugs,
even if its just theoretical,its taboo,IT'S ILLEGAL!

Hope I cleared things up a bit!
Can we please stick back to the topic!?

OK;

Russians will ferment shit to got drunk,and isn't HI also used to make crystal meth out of some sort of flu medicine(ephedrin?!)!?
I heard they just dissolve codeine containing medicine(along with barbs
and other things) and IV that shit. That's pretty fucked up!

[Edited on 30-3-2010 by mfilip62]

mr.crow - 29-3-2010 at 17:56

I'm sorry, I wasn't trying to imply or accuse you of anything. Reading my post again I can see how it could be considered negative. I just thought it was interesting :(

I don't know if they sell caffeine pills where you are, but you could use that and not worry about the codeine.

Ouch, a mine?? eardrum reconstruction? :o :o

mfilip62 - 31-3-2010 at 07:36

No problem my friend,I bolted that I am not being mad at you,
but general hypocrisy and lack of attention when someone reads posts.

Yep,just search form PROM-1 mine,I am lucky to be alive!
If mine was rotated few mm in different direction it could
hit me in the head,hart or somewhere even worse.
Tympanoplastica(eardrum reconstruction) is not big problem nor pain,
but pneumonia that followed was.
Smashed scapula and pierced lungs are FAR worse,crippling and painful.

Anyway,what was that Russian method you were talking about!?
Any details!?
Basically,it is meth-cooking but using codeine instead of ephedrine?

Anyone knows anything on original topic?:D

watson.fawkes - 31-3-2010 at 11:13

Quote: Originally posted by mfilip62  
Anyone knows anything on original topic?:D
Not exactly the original topic, but in the USA, at least, you can buy caffeine in bulk off the web and it's dirt cheap. Here's a source I found with just a bit of web-searching. Unless there's some subsidy I don't know about for the tablets you have, I would expect bulk to be cheaper.

mr.crow - 31-3-2010 at 18:23

Well it was an anecdotal comment on some druggie forum so I don't really want to link it

Apparently desomorphine is a huge problem in Russia and they make it the same way as meth in North America.

http://english.pravda.ru/society/stories/04-05-2009/107494-d...

Another way to ruin home chemistry :(