Bulldog44 (Stranger)
01-26-02 02:44
No 261069
      Hydrogenation without H2 gas  Bookmark   

Hey bees !!

Reading some of the great techniques at Rho's site I came across this hydrogenation process. A friend of my friends fish is trying a Codeine-oxycodone conversion and the last step is to put the converted Dihydro in a solution of 8% Gaa in Methanol and throw in some 5% PD/C. hook up a h2 cylinder @ 35 psi and shake a few hours.

Would this work instead of using the H2 gas ?? Why/Why not

The temp would have to be 80/90 c

This looks like a very promising road to explore for reseach. The chemicals
involved are just 5% or 10% Pd/C and ammonium formate. How would polymer
supported Pd work? The reaction conditions are mild [reflux at 100 C.] The
ammonium formate acts as a hydrogen donor (sodium formate works too).


Thanks


Leave the gun..........take the Canoli.
 
 
 
 
    hest
(Hive Bee)
01-26-02 04:36
No 261082
      Re: Hydrogenation without H2 gas  Bookmark   

I guess, but sometimes you need the presure to get the reacton going.
But 35psi ain't much so ill give it a tru, use plenty off Amform.
 
 
 
 
    Bulldog44
(Stranger)
01-27-02 06:04
No 261488
      Re: Hydrogenation without H2 gas  Bookmark   

For educational proposes only.............


Here are some other reports of hydrogenation without the addition of H2 gas. If you took one of these RX's and added the Ammonium Formate also, might that be all the better ?? would it increase yields ??
And by the way.............say your not going on to the next step to Oxy. Is dihydrocodeinone a stronger version of Codeine >> or just a precurser for something stronger ??


Procedure for the Production of Dihydromorphinones
==================================================

It is well known that morphine and its ethers, through treatment
with hydrogen gas in the presence of large amounts of noble metal catalysts
through heating the acid soln., can be transformed to the dihydrated keto
derivatives.
Surprisingly, it was now found that for this transformation to take
place, hydrogen is completely unnecessary, and that just heating the
acidified alkaloid solution with a larger amount of finely divided platinum
row metals, will suffice to affect the simultaneous dehydration/hydration
in good yields.
This success is particularly unexpected because it was not to be
foreseen that platinum metal not saturated with hydrogen is capable to use
the hydrogen originating from the dehydrogenation [of the 6-position]
almost quantitatively for the hydrogenation of the double bond [in the 7-8
position] of morphine or its analogs without in addition of excess
hydrogen from an external source.

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.

So say your went through with the standard (LOL) procedure for converting Codeine Freebase to dihydrocodeinone and you don't have a readily available source of H2 gas could you disolve the dihydrocodeinone in Gaa/methanol........add an excess of PD/C add ammonium formate, stirr and get a great yield ?? would the Gaa cause a problem with the ammonium Formate ?? In the procedure below I don't see where they use an acid.

" A mixture of 1 mole of azide, 4 moles of anhydrous ammonium formate and 5%
Pd-C (6-15% of the azide by weight) in 100 mL of methanol is stirred for
3-4 hours at ambient temperature. The catalyst is removed by filtration and
the product is isolated by standard procedures. Yield 74-93%."





Thanks in advance...............dream on


Leave the gun..........take the Canoli.
 
 
 
 
    LaBTop
(Daddy)
01-27-02 17:17
No 261590
      Re: Hydrogenation without H2 gas  Bookmark   

What source (reference) did you get this from? We always mention that, if we want a solid response. LT/

WISDOMwillWIN
 
 
 
 
    Bulldog44
(Stranger)
01-28-02 15:50
No 261998
      Re: Hydrogenation without H2 gas  Bookmark   

Sorry LabTop, Your right of course. All references for Rho's website

The hydorgenation method without H2gas is

../rhodium/chemistry /cth.txt

Some of the Codeine / oxycodone conversion RX's

../rhodium/chemistry /hydrocodone.html

My fishes friend is looking at a RX found @ poopies.org


<http://rhodium.lycaeum.org/chemistry/oxycodone2.txt>;

Its basically the same as the one @ Rho's site but sightly modified for the home Chemist. I'll copy the thread link but I'm not sure it will transfer you. I'll paste the RX

Link...............http://www.poppies.org/forum/DCForumID16/167.html

RE: Simpler Oxycodone from Codine(ala Rhodium)"
 
   LAST EDITED ON 09-13-01 AT 00:35 AM (EST)
 
Hey you fuck heads: CODEINE --> OXYCODONE
Dissolve your codeine base in the acid solution (acetic, we're following the method given at the begining of this thread somewhat 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.

BUYING Pd/C IS NOT ANY BIG DEAL BESIDES JOE BLOW IS ONLY GOING TO USE IT FOR LEGITIMATE PURPOSES SO HE HAS NOTHING TO WORRY ABOUT!!!!

Next is to reduce that double bond which is VERY EASY if you have a source of hydrogen. As far as other equipment, you need two syringes with the plunger removed and needles attached. To each you attach a balloon the the plunger end. Then, you need some sort of thick rubber to cover the mouth of your flask, but can be penetrated (air tight) by your needles. Ok, so you throw in like 3 molar %(of initial moles of codeine) of Pd/C (either 10% or 5% Pd on Carbon) into your flask which contains your goodies in a fairly concentrated solution of ~8% acetic acid in MeOH (Not super concentrated, but definately not super dilute) with STIRRING. Then you fill your ballons through the needles, purge your flask air space with hydrogen by inserting both needles through the rubber diaphram and insert a third needle to allow an out flow. After it has purged for a while pull out the purge needle and make sure that the hole it created is now sealed. Refill your balloons and reinsert them. Let it stir overnight. I have done this on a few gram scale so there wasn't a lot of hydrogen absorbed. If you were doing a tens of grams scale, you would need to refill the balloons several times during the reaction or you may still need to do this if you have bad leaks. Ok, so filter your solution. It's about the same color, maybe a little bit lighter, but don't worry cuz it worked. Again, basify, shake with chloroform and extract 3x. Evaporate, disolve in acetone and gas or drip in HCl to crystalize. Your crystals may turn to goo when exposed to air during filtration if you use wet HCl. Don't worry about it, just realize you are gonna have to drip an aqueous oxy solution into your nose instead of getting to snort bumps to get high. Do not over acidify during crystalization! When your solution turns from brown to clear, stop adding acid and filter. If you overacidify, your crystals will turn to brown goo balls in your flask. They won't be destroyed but if you dried and snorted 'em the leftover HCl's might burn your nose a bit.

This procedure is very easy and the whole shebang except for the work-up could be done in a day no sweat. The yields of both steps are very high yielding. I have taken an H-nMR of the compounds at each step of the way and found them to be highly pure with no observable starting material in their spectrums. So get to work! Next time I'll go over the conversion of oxycodone to oxymorphone which is super potent and this is even more simple of a reaction. None of the reagents in either synthesis are suspicious so fuckin' chill.

Realize that codeine can in many wayz be the gateway to your dreamz!!!
(hydro, oxy, oxymorph, morph, H, etc.)




(Guru is no guru of mine. Shit there goes my ratings......)


 
hope that helps..............

Love your work LabTop !!!!

Thanks in advance.

Leave the gun..........take the Canoli.