Rhodium's riddle

[Bulldog44]

Alrighty then, I guess the Bees that could help are just too played out on the Codeine>Oxy synth to help. What are yeh gonna do ??.

That’s OK I figured it out all by myself. However it would have been nice if one of these learned Sages had taken the time to answer…………like I said what are yeh gonna do ??.

Lets see if a riddle interests the brain-trust.

OK

I have read/surfed and browsed my eyes out and came up with what appears to the untrained eye to be a double standard in some Synths that Rho has posted on his site. Here are the pertinent URL’s

https://www.thevespiary.org/rhodium/Rhodium/chemistry/hydrocodone.html
%3Bhttps%3A//www.rhodium.ws/chemistry/dihydromorphinones.html

The first link calls for 2 fairly elaborate steps to reach dihydrocodeinone.

The second link calls for 1 very easy step to reach dihydrocodeinone, IE: Codeine Freebase+ dil hcl+PD/C+1hr reflux= dihydrocodeinone

Dihydrocodeinone by definition is the active narcotic in Vicodin. Correct (1. See attachment below)

So learned ones my question to you is what is the best synth to use ?? Will the second one convert Codeine Freebase to dihydrocodeinone AKA Vicodin ??


Hows this laid out LabTop ??


Merck

Monograph number: 4826
Title: Hydrocodone
CAS Registry number: [125-29-1]
CA name(s): 4,5-Epoxy-3-methoxy-17-methylmorphinan-6-one;
Additional name(s): dihydrocodeinone;
Trade names(s): Bekadid; Dicodid (Knoll).
Molecular formula: C18H21NO3
Molecular weight: 299.37
Composition: C 72.22%, H 7.07%, N 4.68%, O 16.03%.
Literature references: Prepn by hydrogenation of codeinone: Mannich, Lowenheim, Arch. Pharm. 258, 295 (1920); by oxidation of dihydrocodeine, Ger. pat. 415,097 (1925 to E. Merck), Frdl. 15, 1518 (1925-1927); by catalytic rearrangement of codeine: Ger. pat. 623,821. Industrial prepn from dihydrocodeine: K. Pfister, M. Tishler, U.S. pat. 2,715,626 (1955 to Merck Co.). Pharmacology and toxicity data: N. B. Eddy, J. G. Reid, J. Pharmacol. Exp. Ther. 52, 468 (1934). Brief description: A. Stein, Pharmazie 10, 180 (1955). Review: Small, Lutz, "Chemistry of the Opium Alkaloids," Suppl. No. 103, Public Health Reports, Washington (1932).
Properties: Prisms from alcohol, mp 198 deg. Sol in alcohol, dil acids. Insol in water. uv max: 280 nm (.epsilon. 1310). LD50 s.c. in mice: 85.7 mg/kg (Eddy, Reid).
Melting point: 198
UV Maxima: 280
Caution: May be habit forming. This is a controlled substance (opiate) listed in the U.S. Code of Federal Regulations, Title 21 Parts 329.1 and 1308.12 (1995).

Derivative: Hydrochloride monohydrate
Molecular formula: C18H21NO3.HCl.H2O
Properties: crystals, mp 185-186 deg dec. [.alpha.]D27 -130 deg (c = 2.877). Very sol in water.
Melting point: 185-186
Rotation: -130

Derivative: Bitartrate hemipentahydrate
CAS Registry number: [34195-34-1]
Trade name(s): Calmodid, Codinovo, Duodin, Kolikodal, Orthoxycol, Mercodinone, Synkonin, Norgan, Hydrokon
Molecular formula: C18H21NO3.C4H6O6.2H2O
Properties: Needles, mp 118-128 deg. One gram dissolves in 16 ml water, in 150 g 95% ethanol. Almost insol in ether, chloroform. pH of a 2% aq soln about 3.6.
Melting point: 118-128

Derivative: Hydriodide
Molecular formula: C18H21NO3.HI
Properties: mp 219-220 deg.
Melting point: 219-220

Derivative: Methiodide
Molecular formula: C18H21NO3.CH3I
Properties: mp 250-255 deg.
Melting point: 250-255

THERAP CAT: Analgesic (narcotic); antitussive.





Thanks as always In advance for all your help

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

[blondie]

arrogant sob arent we?

how easy a synth is probably depends on how easy it is for bulldog to aquire pd/c or k t-butoxide benzene aso.

[Bulldog44]

Blondie, if you mis-understand my take on the hive's brain trust allow me to clarify. The inner core of the hive is the finest collection of clan chemists in the world. I think they get bored answering the same questions over and over...............just trying to make it different........

So I guess in an unclear way your take is one could use EITHER pd/c..............or k t-butoxide benzene ........right ?? so the synth in example 1 uses k t-butoxide benzene ...........the second uses pd/c both will work equally well.
Leave the gun..........take the Canoli.

[blondie]

well blondies certainly not the hives brains trust so she probably should not have responded. the thing with the simultaneous hydrogenation and dehydrogenation is that since its a patent it may well have ommited important details for commercial reasons. blondie thinks she read about about the pd/c thing being done - oxidation/reduction at poppies.org - but there was some experimentataion required to get it too work - ph was mildly acidic ph4? - iirc.

if your working with codeine then you need to reduce the 7-8?? double bond with pd/c irrespective of how you do the oxidation (with potassium butoxide) - so woulndt cost much to try it in one step. hope it helps.

[Bulldog44]

Thanks Blondie.........that helps.............I thought a single step was asking just tooooooooooooo much !! Sounds like it gets back close to the Cod>Oxy synth..........Na dichromate oxidation..............pd/c H2..re up...and yes all this takes place in Diluted HCL or GAA......It would be nice if the man.........the legend..........that translated these patents would jump in............Rho !!!!!!

I'm no patent expert but these are translated from the originals. I would think that in order to patent a process all steps need to be present.......

Example 5:

6 grams codeine freebase was dissolved in a solution of 4 grams of tartaric
acid in 50 ml of water, and 6 grams palladium black was added. The solution
was refluxed for 1 hour and worked up as in example 1. Yield 75% of theory.


Rhodium very concise in what he posts........if he thought there was a step or two left out of a synth he was posting I think he would have commented on that. Referencing the 2nd URL.
Leave the gun..........take the Canoli.

[blondie]

blondie had a really bad day at work yesterday and was in a filthy mood - she apologizes for missing the tone of your post.

blondie feels the lack of details and info regarding the method in the german text is due to thebaine, codeine, morphine being the expensive inputs in any transformation. doing the oxidation and reduction as seperate steps although more complex will give better yields - therefore these processes receive more attention from industry and commerce. since the goals of industry and the cland chemist are very different - yields are probably less important than simplicity - it still might make sense to check into patent method. i doubt that you will get a better answer than this. have a search through poppies.org since there are/were quite a few people at that site that were quite interested in the single step codeine --> hydrocodone - and i think that there was a reported success.

[Rhodium]

I am sure that I translated the german patents correct, and did not leave out any steps. However, patents are notiorious for not giving detailed enough procedures sometimes, this could be one of those instances. By doing that, the companies can BOTH patent a process, and stop their competitors from just copying their work.

The other two-step synthesis is wonderful, and they seem to have put down a lot of work to perfect the synthesis. I'd say go for the two-step reaction if you have the chemicals.

If someone finds that success story at poppies.org - please copy it to this thread.

[blondie]

Pheesees
Charter Member
96 posts, Rate this user 11-04-00, 05:16 PM (EST)
    
7. "RE: Synthesis of Analgesics"
 
   I've managed to do the acid/catalyst process to hydrogenate codeine, but am having trouble removing the impurities formed. I use 5% Pd/C catalyst. I have read that palladium gives slightly higher yeilds than platinum. The Pd on C catalyst is used by the ton in oil refining, so it's not too hard to get, just kind of expensive. However, it can be reused 20 or more times, so the cost per unit isn't too bad. Note that the acid process not only hydrogenates, but also converts the codein to codeinone as well. I tried a cold process with H2 gas, acid & catalyst, & it did not work. When I use the hot acid process, I get a brown sticky impurity which so far I have not been able to remove. Wonder if I could set up a fake company to buy a few pounds of thebaine.
Make a couple of pounds of pure oxy, and that should last me for awhile. By the way, platinum is used extensivly in jewellery making, so jewelers & pawnshops might be possible sources.
 
In dreamland I used 5% HCl refluxed with PdC, then basified with NaOH & extracted with chloroform. This left a light brown crunchy product. Attempts to recrystallize from ethanol did not remove the impurities. This process uses no metal except the Pd in the catalyst, which probably is nontoxic in whatever trace amounts left after extraction. Snorting the powdered product produced a moderate buzz & a real nasal burn. Treating product with juust enough HCL to allow it to dissolve in H2O & then drying produced a chloride salt highly souble in H2O which give a decent buzz when taken orally. The brown impurities are probably organic breakdown products because they stay through the freebase, extraction, & salt conversion. I don't know if any are toxic, so am leary of using too much of this product. I have also tried the ethanol/catalyst process, with similar results except the product was lighter in color & didn't seem anywhere near as strong. Have you actually attempted the dichromate process?

[spaz]

My puppy has been doing the one step hydrocodone conversion for quite some time now with moderately pleasing results.  But he is also getting brown Alpo as an end result.  It certainly seems to be narcotic as he drools a lot and lays on his back with paws in the air.  But also seems to be somewhat speedy.  Fido assumed that some caffeine was coming across in the initial NaOH/H2O/CHCl3 extraction (from Canadian OTCs, 325mg Aspirin, 15mg caffeine, 8mg codeine phosphate).  He also knows a little Aspirin is there cause he is always bitching about being able to smell and taste it.  And finally, when extracting 200 pills, he gets 1.8 - 2 grams codeine out.  He figured he was doing doggy math but perhaps not.

This was never a big issue though as he got his Alpo and felt really good about himself.  But then he got ambitious and decided to try the BBr3 conversion to Morphine Hydrate and then from there, to Haron HCL (being a wise little puppy, figured out how to make AA versus going to the fucking meetings).  Some dreamer posted a question along these lines just yesterday to the newbie forum.  Perhaps the wrong place as the newbie forum seems to contain all greyhounds versus the more layed back bloodhounds.  Fido will not repeat the dreamers post but essentially, it stated that the BBr3 conversion went just as advertised (after some trial and error) but yielded a product that was not correct (very soluble in cold H20 and completely in cold CHCl3).   The dreamer concluded that the shit coming across in the extract was spoiling things and Fido, being an expert on shit agrees.  Fido would love to get paws on 100% pure unadulterated codeine but that just ain't gonna happen.

So, if anyone has any wisdom for Fido, he would just love to hump your leg (or anything else) in exchange for it.

BTW:  If any interest, here is Fido's doghouse special for some tasty if funny looking hydrocodone.  H2SO4 has been found to work the best, in 5 - 10% concentration.  Also important to have the correct amount of liquid versus input, around 1 to 12 or so.  If to little liquid, not all input will react.  The unreacted input seems to crystalize out soon as cooled a little.  Not a disaster though as this can simply be collected and redone.  Then the remaining liquid can be basified and the good stuff will fall out.  But Fido has done too much liquid before and could not get anything to fall out regardless of how much base he added.  He has also found it helpful in getting a good end product to not use too much alcohol when recrystallizing.  And finally, Fido used palladium black (which is what the directions call for) versus pd/c.  Palladium black can be easily yanked from pdcl2 which is easily available as a photography product from non-chemical supply hounds.

[Bulldog44]

Blondie………….awesome post!! I have read all OP8 and Pheesees posts. He seems to have actually done this synth a few times. I don’t know if your asking the Dichromate question or if it was cut and pasted.

SpudBoy did the Na Dichromate reduction and PD/C H2 gas re-up last month but had limited success. He made some mistakes and started with to small of an amount of Codeine. I’m sure Spud is ready to go again. With one synth under his belt the second will be better.

 I’m convinced that the one step conversion of Codeine to Hydro does not work………..it can’t. What happens is that the Codeine is converted to codeinone. That can be hydrogenated in GAA and Methanol + PD/C to form something else. What it is I don’t know. Possibly Dihydrocodeine or Dihydrocodone………………….I don’t think it converts to 14-hydroxycodeinone or hydroxycodone there are just to many steps missing. I’m sure Spudboy is going to give it a whirl soon. I will post his results when he tells me.

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

[spaz]

Fido gonna clean up his act a little in the extraction process just to give it a try.  He thinks that perhaps raising the PH too high in the initial extract from OTC was ruining his Alpo.  Fido gonna try hed Bee's solution and using Ammonia versus NaOH to adjust PH and bee very careful to not exceed PH 12.  Perhaps that is why unwanted kibbles coming over in output from initial extraction.

And would not hurt he thinks, to re-extract the 1st extract output, keeping solubility data of all products in mind, and carefully going to PH 12.  Perhaps this is a good excersize for beginning Bee fido, an excersize in precision.  AT least fido could rule out contaminents coming over tweaking the acid/pd black reaction.  And fido has done the BBr3 process correctly before (and he certainly thinks output from this reaction much cooler to taste, and much more versatal such as input to Hair-on HCL, di-lau-did, etc).  He has learned to bee VERY careful and precise here due to a volcano forming first time he tried (15g BBr3 turned to vapor in 3 seconds).  Fido will not use homemade CHCl3 again that perhaps might contain some h20.  But even when done 100% correctly, twice, output ng as previously said.

But fido does note that if acid/pd black process ng for HydroC, then process probably ng for HydroM???

Fido don't fully understand the chemistry behind the reactions here, but can probably at least do some paw work as in beeing VERY careful about the quality of his input products.

[spaz]

Okie, Fido worked on a little empirical data centering around the question of HydroC or not to HydroC.  He cleaned up his extract act, carefully bringing the PH to 12 using 30% ammonium hydroxide.  He did not really like using the ammonia cause it took a shitload and with 400 OTCs, he already had 800ml of dh20 to extract.  Almost did not fit into his 1000ml extract funnel.  Also NaOH is cheap compared to the amounts of ammonia required (I know ammonia is cheap but shipping on reagent grade from a chem supply house is not).

After the extract, he did have slightly less then theoretical at around 2.8gs.  His scale sucks.  He then popped it into a RB flask, added 25ml 10% h2so4, and .5g Pd black.  Refluxed for an hour, sucked REALLY dry, then recrystallized from a minimal amount of etoh.  The crystals when seperating from the base, seems quite pasty.  But after the etoh, he gets a very light brown crystal (if too much etoh, very hard to dry.  Can actually end up with like an brown oil shit).  Fido duz have one question here though, perhaps answerable by a real chemist, "just what the hell do they mean by dilute"?

Fido laps up around 1/4g of this puppy chow.  He gets the usual pleseant mind release, and he was seen scratching his ass (and his nose) on the road but not too much.  He also does not go to sleep real early.  

Fido lucks out and scores 100mg generic hydoC from his local vet just two days later.  He laps this shit right down.  He gets the same mind release, and tiny bit of itching and takes two hours or so to fall asleep.

It seems to Fido that brown shit = HydroC (and what else, not so sure).  Fido does know that he can take incredible amounts for just a little doggy.  He is not sure what to make of that.  He suspects he has significant tolerance even though Fido stops regularly for 4 to 8 weeks at a time cause he does not want to run into bitch neighborhood lady Mrs Jones again.  Fido also notes that on cosmic doses, like 3/4g, he gets tremendous opiate effect but also starts to get truly unpleseant shit like not sleeping till the sun comes up, scratching at fleas all night long...  Just like the time he whoofed down 4 MScontins.  He could not pee for 12 hours to boot.

So Fido sez, eat the brown shit.  It do work.  And if one has a easy source, like OTCs, what the hell.  Just based on the little bit of emperical data, Fido thinks that he's getting some HydroC at least, and possibly some codiene or codiene tweak.  If the HydroC is in the majority, it would certainly mask any codiene products in final output.  But Fido still has loftier dreams, hence will be focusing his alpo-glo on the BBr3 reaction.

[Ritter]

SWIM has more experience than he cares to really admit to with pure hydrocodone, and I can tell you this-  if that stuff you were taking was pure hydrocodone, that 1/4 gram dose would have most likely dropped you dead.  Not to mention the 3/4 gram dose-- in a fairly non-opiate tolerant person such as yourself the only opiate you could have possibly embibed and lived at those dosages would be codeine.  Granted a small amount of the product may have been successfully converted to hydro, but I'm guessing its negligible.  Just so you know, codeine(the phosphate salt) has a ceiling on the therapeautic dosage of about 240mg which means  larger doses in non-tolerant individuals will not have any additional affects attributable to the opiate receptors(mu). 

Stop wasting your valuable Pd black, get yourself some chromate salts, learn how to use your Pd for catalytic hydrogenation and make oxycodone!!!

[cheeseboy]

Spaz:

   Why DO opiates like heroin and methadone leave you sleeping with your arms stretched in the air? (like a happy puppy)!LOL (seriously folks, why?)
Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.

[spaz]

Fido does not doubt Ritter's expertise in this matter.  But Fido still does not believe end product all or mostly codeine.  It has changed some, as it no longer tastes bitter.  Fido heard codeine is very bitter tasting, so much so he used it to enhance his doggy breath for the real hot bitch down the street. 

Geeze, some of you other smarter hounds around here need to help old Fido out and try the reaction and see what the hell you think pops out.  Fido just a silly old mutt.

Fido will yield to Ritter's advice though and move on.  Fido has tried the oxy conversion once but screwed the pooch.  Fido will probably bee working on the BBr3 reaction since he paid a shitload of Milk Bones for the BBr3 and even more for the shipping.

But Fido will look more at the oxyC conversion (then of course the oxyM icing).  Fido do have a question here though.  The conversion recipe uses for input 30 grams of codeine.  Will this procedure scale way down?  Like to 3 grams?  When scaling so far down, it does make some of the amounts of chemicals added tiny.  Fido no doggy guru on this subject but he thinks that scaling some reactions down to far makes them not work as predicted.

[Bulldog44]

What a great thread ! . OK so spudboy got geared up to do the cod>Oxy synth again and got to the last two steps. It was going very well ( except for the low yield from codiene extraction) when spudboy thought he would try a homemade shaker for the H2 re-up. He put a 18 inch blade on his variable speed sawz-all and duct taped his 250ml flask filled with the goodies 2 it. He then used clamps to hold saw to the table and taped the trigger at about 1/4 speed. It worked great for about 15 minutes. then the tape would stretch anf he would re adjust it. During one of re adjustments he accidentally taped the hold button and the saw went on HIGH SPEED and the flask broke and the goodies and PD/C and GAA went EVERYWHERE!! needless to say Spudbiy was VERY depressed for a week or two and has not tryed the synth since......................he is getting his chem legs back and will try it again probably sometime in May. Will keep you updated...............don't let this thread die !!! Keep posting

PS> spaz> nice job........I agree tho if you converted the COD to OXY and did 250mg you be nice and stiff. Even in a tolerant person 30 - 50 mg is alot of oxy. 15mg to a non tolerant person isa hellofa buzz. Keep trying.


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

[blondie]

US5847142

although the two step - 7-8 reduction followed by oppenhaurer oxidation is probably the only feasable route to hydrocodone/dilaudid from codeine and morphine for the cland chemist this patent is interesting. It is one step simultaneous hydrogenation/dehydrogenation similar to the one archived at rhodiums based on the German patent 

https://www.thevespiary.org/rhodium/Rhodium/chemistry/dihydromorphinones.html

. 
it is interesting that they also could not replicate the claimed yields with palladium black.

Catalytic rearrangement of morphine has been described using palladium black. It is not possible, however, to carry out this process on a large scale that would be suitable for manufacturing since the procedure affords 30-35% of the undesired o-desmethylthebainone along with the desired product. Isolation of the pure product is very tedious and requires extensive purification.

The present inventors have now found a new one-step route to hydrocodone and hydromorphone giving greater than 80% yield requiring minimal purification by simple methods.

the process uses organometallic complexes as catalyst. the rearrangement simultaneously oxidises the hydroxy to the keto group and also saturates the cyclohexene ring.

[Bulldog44]

Hi Blondie and Rho ! SpudBoy is back and rarin to go. I tried the link and it doesn't come up so I'll go to Rho's site and take a look. Spud can get Palladium Black but has PD/c 10% think that would be a OK sub for Palladium ?. I'm still dubious when it comes to anything thats a one step process.............in your dreams are you going to try this ??
Leave the gun..........take the Canoli.

[blondie]

Bulldog, listen to Rhodium and Ritter's advice since they are the experienced chemists here and do it in two steps.

here is the link for the two-step conversion

https://www.thevespiary.org/rhodium/Rhodium/chemistry/hydrocodone.html