So this is basically a complete rip of an old german patent thats been on the rhodium archive for a very long time, for anyone who hasn't seen it already, its a method of heading from codeine to dihydrocodeinone. This initially put me off, thinking a person would then have to go from dihydrocodeinone to dihydrocodeine or hydrocodone, until stupid me realised that dihydrocodinone handily enough is hydrocodone.

http://en.wikipedia.org/wiki/Dihydrocodeinone

See wikipedia, specifically, the first line for a source on that claim.

All it takes, quite literally, is to reflux codeine (or morphine) in alcohol, in the presence of either palladium, palladium black, platinum, or platina black. This is obviously a hydrogenation catalyst, which I imagine can be reused simply by filtering it off at the end of the reaction. The reaction yields either hydrocodone or hydromorphone in 60 - 95% yields.

This, to me, seems to be a stupidly easy way of making an easily available, cheap and weak opiate into a comparatively much more powerful opiate.

The only problem lies in the acquisition of palladium or palladium black, it is doubtless that it is easily available, but sadly, the price is very high. Saying that, only a very very small amount is required, for example in the ref, 10g of codeine freebase is converted to hydrocodone with just 0.5g of palladium black.

Anyway, I've blathered enough, below are two of the more interesting examples within the patent;

300g codeine freebase was dissolved in 2000ml dilute HCl, and was heated with 25g of finely powdered palladium, and boiled under reflux for an hour. The palladium was filtered off, and the filtrate basified with NaOH solution. The precipitated base was recrystallized from alcohol. Yield 85-95% of dihydrocodeinone, mp 195°C.

Obviously that's a huge amount, and I imagine people would have difficulty getting their hands on 300g of codeine freebase, but that's not to say it could not be easily scaled down.


10 grams of codeine was dissolved in 100ml alcohol, and after the addition of 0.5 grams palladium black the solution was refluxed for 4 hours. Workup as in Example 1. Yield 7 grams of dihydrocodeinone.

I chose this example simply becuase it exemplifies the fact that it is such a stupidly simple reaction. The workup mentioned is simple a case of filtering off the catalyst, and concentrating the alcohol until hydrocodone delightfully crystallises.

http://psychedelichosting.info/Ionium/Rhodium/chemistry/dihydromorphinones.html

That is the ref I've been blathering on about.

Anyway, what does the might of LT think about this?

I say, although old and been discussed to death from what I can see on the hive archive, it still looks a viable and easy method of heading straight to a stronger opiate if codeine is OTC where you live.

Thoughts? Any other references on this procedure? Handy unheard of supercheap source of OTC palladium?

Credit has to to go to StateofHack, me and him were discussing the procedure just before I wrote this.

Palladium black

Palladium Black (Precipitated Pd metal)

Dissolve 5 g palladium chloride in 30 ml concentrated hydrochloric acid and dilute with 80 ml water; cool in an ice-salt bath and add 35 ml 40% formaldehyde solution (or equimolar amount of 37% formaldehyde). Add a cold solution of 35 g potassium hydroxide in 35 ml water dropwise during 30 min to the vigorously stirred palladium solution. Warm to 60°C for 30 minutes and the wash the palladium precipitate six times by decantation with water. Filter on a sintered crucible, wash with 1 liter water and suck dry (approx 3.1 g yield) and transfer to a dessicator charged with silica gel for storage.

Alternate procedure [3]

Heat a mixture of palladium chloride (0.50 g) and water (100 ml) to 80°C and carefully neutralise the suspension, to wide-range indicator paper, with 20% sodium hydroxide solution (if the end point is overshot, palladium hydroxide precipitates). Add 2.6% formic acid (2.5 ml) and, after about 2 min make the solution strongly alkaline with 20% sodium hydroxide solution (5 ml). Add more of the formic acid (5 ml) and make sure that the solution is still alkaline. Heat the mixture on a steam bath for 2 hours. Filter off the precipitate with a small ('Hirsch') funnel (Whatman filter paper No. 541), wash it free from alkali and dry it over calcium chloride in a vacuum desiccator.

Palladium black from PdCl2 and NaBH4, by Rocketdoc

Magnetically stir PdCl2 in water (100-200ml per gram PdCl2). If it does not dissolve, add conc. HCl until complete dissolution. The solution should now look like tea. Now add a pinch of sodium borohydride to the solution. The water immediately turns black. Add a little more sodium borohydride and then stop the stirring. Once the Pd black has settled, the water should be clear, and not tan colored anymore. If the color is still present, this means all of the PdCl2 has not been reduced, so then add some more sodium borohydride with stirring. The final color of the water should be clear. Filter off the precipitate and wash it with dH20.

Ref [3] [3] H. Wieland, Chem. Ber., 45, 484 (1912)

Yes palladium chloride is not cheap but it is still very easy to get and the lowest price i could find is 5g for 120 USD :(

But still with codeine being OTC in Europe (and for the US it can be bought from off-shore pharmacies ;) ) it gives a pretty good way to some nice opiate.

Its nice because there is no need for high pressures or anything "too hard" (depends from location i know) to get :)

edit: It has been noted at the hive that it is/can be a bitch to prepare palladium black! So keep this in your head!

I was actually looking at this a few days ago. Also, I lol'd at the "jewish conspiracies" tag.

[QUOTE=Von Bass;10294937]This initially put me off, thinking a person would then have to go from dihydrocodeinone to dihydrocodeine or hydrocodone, until stupid me realised that dihydrocodinone handily enough is hydrocodone.

I had a charge involving this, and it was a small pill of Vicodin from what I know, and the lab results from the cops and on the papers called it dihydrocodeinone.

I had a charge involving this, and it was a small pill of Vicodin from what I know, and the lab results from the cops and on the papers called it dihydrocodeinone.

Excellent good. That at least shows that wikipedia is right.


Palladium black from PdCl2 and NaBH4, by Rocketdoc

Magnetically stir PdCl2 in water (100-200ml per gram PdCl2). If it does not dissolve, add conc. HCl until complete dissolution. The solution should now look like tea. Now add a pinch of sodium borohydride to the solution. The water immediately turns black. Add a little more sodium borohydride and then stop the stirring. Once the Pd black has settled, the water should be clear, and not tan colored anymore. If the color is still present, this means all of the PdCl2 has not been reduced, so then add some more sodium borohydride with stirring. The final color of the water should be clear. Filter off the precipitate and wash it with dH20.

Ref [3] [3] H. Wieland, Chem. Ber., 45, 484 (1912)


That method, to me at least, looks fairly easy, mainly seen as though it has all the handy indicators (e.g. if its not black by now, add moar NaBH4)

I personally think though, the chaps in the patents managed to yield very high amounts with straight palladium, so currently I would look into sources of raw palladium, its being sold fairly easily as purified metal and ingots, becuase of its precious-metal status. Sadly its still not cheap, and I can't yet find a source selling it in anything like gram quantities.

I was actually looking at this a few days ago. Also, I lol'd at the "jewish conspiracies" tag.

If you don't mind, did anything put you off it?

Oh, and about the jewish conspiracies;

America apparently uses 99% of the world supply of hydrocodone as vicodin.
Abbott laboratories is the trademark holder and manufacturer of vicodin.
Abbott laboratories was founded by a Dr. Wallace C. Abbott, and later partnered with Dr. Alfred S. Burdick
If you ask me, these people, not least their jewish sounding names, bear enormous similarities to the famous jews Bud Abbott and Benjamin D. Burdick...

Okay so that was entirely pulled outta my ass and google. :(

That method, to me at least, looks fairly easy, mainly seen as though it has all the handy indicators (e.g. if its not black by now, add moar NaBH4)

I personally think though, the chaps in the patents managed to yield very high amounts with straight palladium, so currently I would look into sources of raw palladium, its being sold fairly easily as purified metal and ingots, becuase of its precious-metal status. Sadly its still not cheap, and I can't yet find a source selling it in anything like gram quantities.


Dissolve 5 g palladium chloride in 30 ml concentrated hydrochloric acid and dilute with 80 ml water; cool in an ice-salt bath and add 35 ml 40% formaldehyde solution (or equimolar amount of 37% formaldehyde). Add a cold solution of 35 g potassium hydroxide in 35 ml water dropwise during 30 min to the vigorously stirred palladium solution. Warm to 60°C for 30 minutes and the wash the palladium precipitate six times by decantation with water. Filter on a sintered crucible, wash with 1 liter water and suck dry (approx 3.1 g yield) and transfer to a dessicator charged with silica gel for storage.

This one is better, i am not using my NaBH4 for that seriously!Look around you can buy palladium in small quantities, hit me up on msn if you need help :)

If you don't mind, did anything put you off it?
My lack of codeine, Pd, and (mostly) time. A month ago it would have been money, but now that I have a job, I have enough money but no time. :(

Oh, and about the jewish conspiracies;

America apparently uses 99% of the world supply of hydrocodone as vicodin.
Abbott laboratories is the trademark holder and manufacturer of vicodin.
Abbott laboratories was founded by a Dr. Wallace C. Abbott, and later partnered with Dr. Alfred S. Burdick
If you ask me, these people, not least their jewish sounding names, bear enormous similarities to the famous jews Bud Abbott and Benjamin D. Burdick...

Okay so that was entirely pulled outta my ass and google. :(

I thought you knew what you were talking about at first... :(:mad:

Edit: This might be a good time to find a doc on how to clean cat converters.

I imagine the Pd will be the problem for most people, its either stupidly expensive or just not damn available. Palladium chloride can be found, which is one thing to look into.

I believe I may have an available source of cheap platinum without stealing it off catalytic converters, it remains to be seen whether or not Pt would be a good enough hydrogenation catalyst - there are refs for it being used with 'platina black', which I would guess to be Platinum black, which is simply finely powdered platinum.

5 grams of codeine hydrochloride was dissolved in 30 ml water, and acidified with a little HCl, and after the addition of 4 grams platina black, the solution was refluxed for 5 hours. After workup as in Example 1, the yield was 65-75% of theory

Interestingly enough, there is another procedure in which 'colloidal platinum' is used;

To a solution of codeine hydrochloride, slightly acidified with HCl, 50 ml of a 10% solution of colloidal platinum was added, and the solution was refluxed for 3 hours. Workup as in example 1. Yield 3 g dihydrocodeinone.

A quick google for 'colloidal platinum' yields some people selling this stuff, in incredibly weak solns as some sort of health drink -

http://wvw.purestcolloids.com/mesoplatinum.htm

This is only a 10ppm solution, you'd have to buy a hellofa lot and concentrate it to get up to 10%, e.g. concentrating the solution 10,000 times...

Edit ; My cat found 100mg of platinum just lying around in some spare electrodes...

http://i37.tinypic.com/1zn9c81.jpg

I imagine the Pd will be the problem for most people, its either stupidly expensive or just not damn available. Palladium chloride can be found, which is one thing to look into.

I believe I may have an available source of cheap platinum without stealing it off catalytic converters, it remains to be seen whether or not Pt would be a good enough hydrogenation catalyst - there are refs for it being used with 'platina black', which I would guess to be Platinum black, which is simply finely powdered platinum.



Interestingly enough, there is another procedure in which 'colloidal platinum' is used;



A quick google for 'colloidal platinum' yields some people selling this stuff, in incredibly weak solns as some sort of health drink -

http://wvw.purestcolloids.com/mesoplatinum.htm


This is only a 10ppm solution, you'd have to buy a hellofa lot and concentrate it to get up to 10%, e.g. concentrating the solution 10,000 times...

Edit ; My cat found 100mg of platinum just lying around in some spare electrodes...

http://i37.tinypic.com/1zn9c81.jpg

That is great but to me honest for the "first time" anyone doing this should stick to what is being said in the paper. Also Pd/Cl can be sourced with not much trouble from chem supplies (wont go into how to intelligently source it but yeah, if your not stupid than you should know).
As for the drink that does not sound like the best idea, who knows what else is in there :(

That is great but to me honest for the "first time" anyone doing this should stick to what is being said in the paper.

Entirely agreed, although I imagine an experimenter would alter the quantities rather a lot, staying within ratios of course.

Also Pd/Cl can be sourced with not much trouble from chem supplies (wont go into how to intelligently source it but yeah, if your not stupid than you should know).

Definitely easy enough yeah, my only complaint with that, as I believe we discussed was the whole connotations of PdCl and the wacker.

As for the drink that does not sound like the best idea, who knows what else is in there :(

Fair point, it was more just added in by me as a thinking out loud point, almost as a definition for what colloidal platinum actually is. Its not as though it would even be economically viable to acquire colloidal platinum that way. I wouldn't worry what else would be in there - in the link it specifically states;

"The only other ingredient [apart from Pt] is pure pharmaceutical grade deionized water."

Although, amusingly enough, it then goes on to claim;

"Colloidal platinum does not combine with any substances in the body"

So its not actually absorbed, changed or 'combined'? E.g., it does nothing and just either passes straight through, or simply accumulates in your body?

Strange what some people will buy :p

Entirely agreed, although I imagine an experimenter would alter the quantities rather a lot, staying within ratios of course.

Of course, that is taken for granted



Definitely easy enough yeah, my only complaint with that, as I believe we discussed was the whole connotations of PdCl and the wacker.

Ah yes true, but ordering this and maybe some chemical developing formulation would not be suspicious, you got to pay a little more but what the heck, under the radar!
Either way, point remains: This is easy and can be scaled up!

This fascinates and intrigues me, but I'm too much of a noob to really understand how to do it. If someone wrote up a step-by-step my friend would try it for sure.

This fascinates and intrigues me, but I'm too much of a noob to really understand how to do it. If someone wrote up a step-by-step my friend would try it for sure.

Well it is step-by step by you do not want to be doing this sort of thing (pyrophoric materials) without knowing exactly wtf is going on :)

Edit ; My cat found 100mg of platinum just lying around in some spare electrodes...

http://i37.tinypic.com/1zn9c81.jpg

The article mentions several successful trials using "finely divided" palladium, so wouldn't finely divided platinum work as well? Those electrodes are relatively easy to get, so couldn't one break an electrode into tiny pieces and use that as a catalyst?

The article mentions several successful trials using "finely divided" palladium, so wouldn't finely divided platinum work as well? Those electrodes are relatively easy to get, so couldn't one break an electrode into tiny pieces and use that as a catalyst?

possibly, but i would rather no waste precursors and start straight from palladium black (made from pd/cl)

The article mentions several successful trials using "finely divided" palladium, so wouldn't finely divided platinum work as well? Those electrodes are relatively easy to get, so couldn't one break an electrode into tiny pieces and use that as a catalyst?

That's two electrodes there, 50mg a piece I'm sure. By 'finely divided', I wouldn't be surprised if they meant '400 mesh', which would make powdering that smaller amount of metal down very difficult. If a person can get them for free, I suppose there's no harm in trying, its not the actual reaction wastes much in the way of chemicals. Half a gram or a gram of codeine can be had very cheap for a quick test run.

That's two electrodes there, 50mg a piece I'm sure. By 'finely divided', I wouldn't be surprised if they meant '400 mesh', which would make powdering that smaller amount of metal down very difficult. If a person can get them for free, I suppose there's no harm in trying, its not the actual reaction wastes much in the way of chemicals. Half a gram or a gram of codeine can be had very cheap for a quick test run.

Hmm, guess you could powder those two down, not very fine but with some coffee grinding and a bit of muscle :) Its true actually 500 mg of codeine can be gotten with a little walking not too hard...hmmm....

Damn euro's and your codeine. :mad: Since we're on the subject of sourcing (kinda), how risky is ordering codeine online for us Americans? A prepaid visa gift card (works as credit/debit) and an empty house in another neighborhood would be enough, I doubt there would be a partyvan for anything less than a few kilos of codeine.

Damn euro's and your codeine. :mad: Since we're on the subject of sourcing (kinda), how risky is ordering codeine online for us Americans? A prepaid visa gift card (works as credit/debit) and an empty house in another neighborhood would be enough, I doubt there would be a partyvan for anything less than a few kilos of codeine.

;) I love opiates! How risky? Well its a yes and no, i mean most people who have been "caught" just got love letters (warning bullshit) so along as you do not push your luck your good. Its a russian rullet, but with paintballs ;)

US 3,214,385 and US3210152 are relevant to this (regenerating catalyst :) )

;) I love opiates!

Who doesn't? ;)

How risky? Well its a yes and no, i mean most people who have been "caught" just got love letters (warning bullshit) so along as you do not push your luck your good. Its a russian rullet, but with paintballs ;)

Sounds good, nothing like a love letter from teh feds. Not like they can really prove you ordered them, especially if they send a love letter. Just as long as there's no party van...:eek:

Who doesn't? ;)



Sounds good, nothing like a love letter from teh feds. Not like they can really prove you ordered them, especially if they send a love letter. Just as long as there's no party van...:eek:

;) Indeed who doesn't ?

Well, if they really wanted to they could, i guess its just case individual. Being codeine bulk pills online is the way to go on about this (dirt cheap) or OTC (if your in EU).

So who will dream about this? I would love some proof before wasting my pd/cl --> pd black :)

;) Indeed who doesn't ?

Well, if they really wanted to they could, i guess its just case individual. Being codeine bulk pills online is the way to go on about this (dirt cheap) or OTC (if your in EU).

So who will dream about this? I would love some proof before wasting my pd/cl --> pd black :)

I would, but I think I'm going to be spending too much time dreaming about college :( Not sure how good of an idea it would be to order codeine to a dorm...

I would, but I think I'm going to be spending too much time dreaming about college :( Not sure how good of an idea it would be to order codeine to a dorm...

Not a good one, you should value your tuition > personal chemistry

bumb

This an an OTC method for oxycodone, however it may only be otc to some as the starting material is codiene. This is a collaboration of works NOT my own work, i've only taken the bits and ptu them together in one place.

You will need:

Potassium/Sodium Dichromate
Sodium Dithionite (sodium hydrosulfite)
Codiene
Chloroform/DCM

Step 1

This step is accreditted to dopamine.

Dissolve your codeine base in the acid solution (acetic, we're following the method given in Lone Ranger's procedure above, so use those amounts) in a rb flask and set it in an ice water bath with stirring. Now that it's nice and cool, slowly pipette in the dichromate solution. The solution immediately turns a milky orange/yellow. Now remove the ice and set it in your oil bath on a hotplate and throw your water cooled condenser on top. I used a temperature controlled hotplate so I just dialed the temp in to ~83 and made sure it stayed there for ~20 min. If you stick a thermometer in your oil bath you should be able to do about the same. Heat is bad for opiates, but I have not found that letting it cook at 80-90 for 30 min to be terribly detrimental. Anywayz, you can tell that the reaction is complete when there is no more color change. The new color should be a dark brown/red. Pipette pour your solution into a sep. funnel, wash your flask with a bit of water and pour that in too. There will be some black insoluble crap left in the flask. Don't worry about that shit. Now basify with ammonia. You don't have to be exact, just make sure the pH is taken to above 10 and then extract three times with chloroform. If you get an emulsion, just deal with it by adding a butload of chloroform and only taking the unemulsified chloroform with each separation. Take your chloroform solutions and back extract with water twice to make sure you didn't bring nasty Cr with your product. The product is yellow when disolved in a large amount of solvent and dark brown/red when concentrated. You just converted codeine's hydroxy group to a ketone and put a hydroxy under the nitrogen bridge. Evaporate off your solvent.

So now you have to first step done only 1 step to go till you get Oxycodone.

Step 2

From Oxy, by Otto Snow

10 grams of 14-hydroxucodienone is heated with 20grams of sodium hydrosulfite (dithionite) in 60mL of water. After a short while complete solution takes place. (at this point i think its probably good to leave it for say an hr) This is saturated with soda or ammonia and Oxycodone precipatates and is filtered off. This cna be recrystalised or titrated to form HCl salt.

There you go completly OTC for some bee's anyway. Dithionite can be made from the action of zinc powder on a sodium bisulphite solution, which is filtered to yield dithionite in solution. Alternatly it may be in some houselhold products for removing rust.

Not mine, buy ergot, though it would be relevant to this thread ;)