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Boron tribromide demethylation of codeine

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- Mon, 10 Oct 2016 14:55:50 EST 9Opqdgsf No.78280
File: 1476125750712.png -(19996B / 19.53KB, 593x246) Thumbnail displayed, click image for full size. Boron tribromide demethylation of codeine
I am having trouble with this synthesis. I take 15ml DCM with 200mg codeine base dissolved and make sure its really dry with sieves. Then add something like 500mg of boron tribromide. Immediately the codeine drops out of the DCM solution... no doubt my homemade BBr3 contains a small amount of HBr and Br2. This stuff is unbelievably reactive with air, i've never seen anything fume like it in my life. So i waited/stirred 30mins then added ice/ammonia. No precipitate, i assume the codeine hbr simply dissolved in the aqueous. So next i tried the same thing but added 200mg DIPEA to soak up the acid. Still no morphine precipitate. I worked up both layers both times and verified there was no morphine, i thought it might be dissolved in the high PH aqueous layer but that's only possible with NaOH i believe, morphine should always be insoluble in ammonia hydroxide. I don't know what the problem is.

My boron tribromide is a bit red, i don't have enough to distill. I started from Br2 and Al to make aluminum bromide, anhydrous. Unfortunately i couldn't distill this either but i did leave it under vacuum to hopeful get the free bromine out. I melted it and poured it into another flask with potassium tetrafluoroborate and ended up with only a few ml of BBr3 distilling over. Next time i will use liquid tetrafluoroborate. All 3 of these things really fume like hell. I'm not looking forward to doing it again. I will try to use a vacuum next time, my joints weren't greased and it was pulling in more air then it was worth. I have to make sure i don't get the aluminum bromide on the ground joints as well, god damn what a mess. A propane torch wouldn't even get them apart i had to soak in WD40 then use a propane torch.
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trypto - Mon, 10 Oct 2016 20:38:44 EST nMwxstEB No.78281 Reply
>>78280
I worked with BBr3 once in a fully stocked lab (not drug stuff), and it still made me nervous. That shit's nasty and extremely reactive with water. It comes in one of those sealed bottles you extract with a syringe under N2. Burns paper.

I don't really understand the BBr3 synth completely, but if you're only getting a few mils, I imagine it would be especially hard to keep dry in atmospheric conditions. An N2 setup would be optimal, but lacking that I'd do the reaction with BBr3 synthed on the same day.

IIRC, I demethylated in an ice bath. If you're just throwing 500mg of BBr3 right in there, it's probably be getting too hot and producing some byproducts [INSERT THERMODYNAMIC EXPLANATION HERE].
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Betsy Pittwill - Mon, 10 Oct 2016 23:35:34 EST yvh9Qry5 No.78284 Reply
If you went through the trouble of making aluminum tribromide, why not use that directly for demethylating? From the efforts made at the hive on eugenol to safrole chemistry, aluminum halides and anhydrous pyridinium salts should both work for breaking aryl methyl ethers.
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Phoebe Fuckingwell - Tue, 11 Oct 2016 16:17:54 EST 9Opqdgsf No.78286 Reply
>>78284
Not sure if aluminum bromide would work, not sure what solvent to use either. I think in dcm a halide exchange would take place making dibromomethane.
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Phoebe Fuckingwell - Tue, 11 Oct 2016 16:30:53 EST 9Opqdgsf No.78287 Reply
>>78282
Boron tribromide + water = lots of heat. If you drop a drop in water you can hear it hiss and fizzle as it boils. Morphine gets chewed up very quickly in hot acidic or basic conditions. And ya cold would help precipitate out the goods as well.
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Phoebe Fuckingwell - Tue, 11 Oct 2016 16:33:42 EST 9Opqdgsf No.78288 Reply
>>78281
Ya, the first time i tried i could hear the BBr3 sizzle as it hit the DCM solvent. Next time i put the codeine and dcm in the freezer first, i also gave it a few hours over 4a sieves to make sure it was dry.
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Bombastus !uYErosQbLM!!Mybq1UbK - Tue, 11 Oct 2016 21:03:30 EST Req4jw5M No.78289 Reply
1476234210582.png -(15099B / 14.75KB, 593x150) Thumbnail displayed, click image for full size.
Sounds to me like you may not have pure / enough BBr3. Certainly when you drop it in the DCM, it just goes away :(

>>78282
As a base. Remember when you learned about "tetrahedral" and hybridization shit in high school? You also learned that BrX3 groups can bond with NH3 in order to create a complex. You didn't learn the properties of the complex but it is more stable than simple BBr3 since it forms an "adduct". The adduct is more stable and as a solid, it is less reactive and non-volatile but does effervesce (gives off BBr3 so it doesn't technically "effervesce").

BF3 forms an adduct with etherates and that's how we used those in the lab. I've never worked with pure BBr3 but have handled BCl3 but only when it's in the solid form giving off ammonia.

Get some HBr in Acetic Acid. That shit is non-reactive and a simple reflux away to demethylate most things in good quantity.
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trypto - Tue, 11 Oct 2016 22:11:27 EST igoqGrTk No.78290 Reply
>>78288
How fast do you add the BBr3? It should be dropwise to help dissipate heat.

>>78289
>Get some HBr in Acetic Acid. That shit is non-reactive and a simple reflux away to demethylate most things in good quantity.
OP says morphine gets chewed up in hot acid conditions... in which case HBr is no good.

Is that true? Hydrolysis maybe?
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Bombastus !uYErosQbLM!!Mybq1UbK - Wed, 12 Oct 2016 00:29:11 EST Req4jw5M No.78291 Reply
Dropwise would be the only way to add something extremely hydropyrophoric like BBr3. Solid or not.

>>78290
So don't heat it up. There're are a lot of papers on morphinans demethylated using HBr:AcOH without ether or tert-amine cleavage. It doesn't even need that much heat, if I remember the papers correctly.

Not home so not sure about papers. Also really fucking high.
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Lillian Fellykudge - Wed, 12 Oct 2016 01:34:19 EST zsw9I8fO No.78292 Reply
It's too bad I couldn't find BBr3 online for sale anywhere besides big wholesalers.

It might be easier to do the Codeine -> Hydrocodone >>>78225
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Betsy Chemmlefut - Wed, 12 Oct 2016 22:54:07 EST 9Opqdgsf No.78295 Reply
>>78292
I've tried that and it didn't work either, likely due to the catalyst being poisoned by caffeine or something. Maybe i will try again. A guy on the long gone forum zoklet said codeine must be quite pure or your hydrogenation won't work. I've hbr in acetic acid as well without success, its hard to generate clean dry hbr. Apparently acetic acid/hbr demethylation of hydrocodone yeilds desomorphine.
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Bombastus !uYErosQbLM!!Mybq1UbK - Thu, 13 Oct 2016 11:27:48 EST Req4jw5M No.78296 Reply
>>78295
This part is true. You'd want nothing in your reaction vessel but codeine, distiled water, sulfuric acid, and palladium black) (even other opioids can interfere with the proton exchange).
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Alice Blackstone - Thu, 13 Oct 2016 23:07:27 EST 9Opqdgsf No.78298 Reply
>>78296
Would you suggest methanol or water to be the best solvent for hydrogenation? I do have some good clean lab grade H2SO4, and acetic acid. My HCl is from the hardware store, although it looks clean it probably isn't. I will try water and sulfuric tonight. Think 1% w/w H2SO4 is good?

I have about 250mg of 10% PD/C left, i always use new for my experiments. Is there any way to clean up used contaminated catalyst? Wash it with methanol then dry it, maybe heat it. I could just order another gram i guess. I tried to make raney nickle once as well maybe i will try again. I took some quarters (made of nickle) and aluminum and melted it together and quenched it in watch. Seemed to alloy. I guess i should perfect my use of PD/C first haha.
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Bombastus !uYErosQbLM!!Mybq1UbK - Fri, 14 Oct 2016 02:30:34 EST 6N1t5rKu No.78299 Reply
1476426634844.jpg -(6266B / 6.12KB, 261x166) Thumbnail displayed, click image for full size.
>>78298
Distilled water. 20% sulfuric acid solution. Just pretend it's 100% concentrated sulfuric to make your life easier. Also don't forget to use half to dissolve the codeine and the other half in order to react it.

Clean it up by running acetone over it 3 times and water over it 3 times. You can overkill by running an acid, a base, acetone, methanol, dcm, acetone, then water over it. This shit's pretty inert. You can even heat it up to around 300C in order to drive off everything and THEN wash it with inorganic and organic
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Rebecca Nipperpod - Sat, 15 Oct 2016 00:19:21 EST 9Opqdgsf No.78300 Reply
I tried yesterday with 2% and today with 20% sulfuric. No success. I will have to add more purification steps to get rid of the caffeine or whatever else is causing problems. Oh well. Still i don't think the impure codeine could have interfered with the BBr3 demethylation. I guess the answer is higher purity all around.
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Rebecca Nipperpod - Sat, 15 Oct 2016 00:20:40 EST 9Opqdgsf No.78301 Reply
By the way thanks for your help Bombastus. I'll get there, someday.
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Bombastus !uYErosQbLM!!Mybq1UbK - Mon, 17 Oct 2016 12:13:20 EST Req4jw5M No.78304 Reply
>>78300
What's your source of codeine?
If it's any pharmaceutical, you should maybe invest in a burette and some silica gel. This method of purification is top notch and can even purify black tar heroin to china white. In the long run, it'll save you a shit load of money.

The other benefit is that you can only purify 500mg MAX of anything at a given time. (downside to a few individuals) Why would you need anything over a g, anyway?
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Sophie Wishwater - Mon, 17 Oct 2016 20:42:48 EST 2Hc2eoG6 No.78305 Reply
>>78304
What is that process called? I'd like to try it.
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Bombastus !uYErosQbLM!!Mybq1UbK - Mon, 17 Oct 2016 22:39:15 EST 6N1t5rKu No.78306 Reply
1476758355149.jpg -(45693B / 44.62KB, 480x480) Thumbnail displayed, click image for full size.
>>78305
Column Chromatography.
Cost of burette - $50
Cost of stand - build your own
Cost of silica gel - $40
Cost of solvent - $30
The only issue is you'll need a UV lamp and maybe TLC plates (google how to make them from small pieces of glass). But this is a literally a /chem/ board so I'm giving this as the best option to purify codeine from caffeine.

It also takes some time to perfect but is how most chemistry people purify shit.
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Bombastus !uYErosQbLM!!Mybq1UbK - Mon, 17 Oct 2016 22:39:58 EST Req4jw5M No.78307 Reply
>>78305
Column Chromatography.
Cost of burette - $50
Cost of stand - build your own
Cost of silica gel - $40
Cost of solvent - $30
The only issue is you'll need a UV lamp and maybe TLC plates (google how to make them from small pieces of glass). But this is a literally a /chem/ board so I'm giving this as the best option to purify codeine from caffeine.

It also takes some time to perfect but is how most chemistry people purify shit.
>>
Bombastus !uYErosQbLM!!Mybq1UbK - Mon, 17 Oct 2016 22:40:40 EST /sas5Pn/ No.78308 Reply
>>78305
Column Chromatography.
Cost of burette - $50
Cost of stand - build your own
Cost of silica gel - $40
Cost of solvent - $30
The only issue is you'll need a UV lamp and maybe TLC plates (google how to make them from small pieces of glass). But this is a literally a /chem/ board so I'm giving this as the best option to purify codeine from caffeine.

It also takes some time to perfect but is how most chemistry people purify shit.
>>
Bombastus !uYErosQbLM!!Mybq1UbK - Tue, 18 Oct 2016 00:15:43 EST Req4jw5M No.78310 Reply
>>78309
Column Chromatography.

I said it three times fam (due to 420chan's spam filter fails, lol).
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Bombastus !uYErosQbLM!!Mybq1UbK - Wed, 19 Oct 2016 17:27:26 EST 6N1t5rKu No.78313 Reply
>>78312
Yeah I don't know what the fuck happened with the triplicate messages but eh. I get that happen a lot which is stupid.

I hope that image gave you more pain relief than the opioids in the hospie, fam.

nb
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press !QUHukXEvkY - Wed, 19 Oct 2016 19:19:16 EST B3jdPBiB No.78314 Reply
1476919156962.png -(53691B / 52.43KB, 861x606) Thumbnail displayed, click image for full size.
>>78313
at first glance it actually i actually thought it to be a column

hospitals in my country arent very easy when it comes to opioids.
all i got was IV ketamine four times during the flight to the hospital. not like i actually needed the last three shots, but whod turn down free drugs. i did order 3 grams of ketamine once i had my phone back with me, its always nice to have something waiting for you when youre coming back home. so in between drinking poppy tea, snorting ket and harvesting tons of mushrooms id actually call it a paid vaccation. but enough advertisment for my blog

i reckon you could use a much cheaper DIY column if its only gravity chromatography. maybe even some transparent PE-HD tubes with a proper hose fitting unless youre using DCM. id eyeball the costs at 30 bucks max

couldnt you just use an A/B extraction since caffeine is a weaker base than codeine?
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Bombastus !uYErosQbLM!!Mybq1UbK - Thu, 20 Oct 2016 01:19:23 EST 6N1t5rKu No.78315 Reply
>>78314
That is a column
Treat /chem/ as your blog. Who cares. Start a "stop the Presses" thread and rant about your life. Hell it might actually attract some more traffic than what exists right now.

Not to the extent of removing down to the 5% of caffeine from the solution. I don't think you'll be able to purify them without the use of a column or vacuum sublimator.

that isn't a column
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press !QUHukXEvkY - Fri, 21 Oct 2016 14:50:08 EST B3jdPBiB No.78320 Reply
1477075808223.jpg -(72727B / 71.02KB, 711x720) Thumbnail displayed, click image for full size.
>>78315
while im already derailing a thread; do you have any ideas on muhsroom extraction?
havent attempted it yet since the hooch is still in the mail but i was going to go with the very crude method of soaking the raw material in ethanol w=0,7 and then letting the filtrate evaporate in order to get material that i might recrystallize.
i suspect that simply soaking the material in dilute acetic acid and then basifying it with a subsequent non polar extraction (maybe DCM, maybe EtOAc)
but the zwitter ionic nature of psilocin bugs me to no end

i have to salute OP's resources
i might be able to contribute on the matter once i stop being this high lol

its pretty sad how little happens on /chem/, sciencemadness is ice but theyre all very catious (rightfully so) eventhough i saw several of their mods in the hive or the successors of it
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Charlotte Fuckingville - Sat, 22 Oct 2016 00:27:23 EST 9Opqdgsf No.78322 Reply
The codeine was is from 8mg tablets, 15mg caffeine, 200mg aspirin. Lots of other filler and shit on the ingredient list. I was thinking the caffeine should have been washed away by my DCM wash (while the codeine was still in phosphate form). So idk. Yes chromatography is likely the answer, i've never run a column but i suppose i can figure it out.

I have a UV bulb but i need to find a power supply and ballast, i forget what is required now. Something like 20 volts and a 100 ohm resistor. Its one of those really small uvc germicidal bulbs off ebay, screws into something like a Christmas light socket. Obviously 120ac would blow it though, even 12 volts ended up blowing it because once the mercury heats up and vaporizes it causes a huge current spike which must be limited by some kind of ballast.
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Charlotte Fuckingville - Sat, 22 Oct 2016 00:48:34 EST 9Opqdgsf No.78323 Reply
>>78320
I used to grow shrooms i thought about extraction but never attempted it. I was planning to use methanol only because its cheap and available at the hardware store. Evaporate with minimal heat (enough to keep condensation from making a wet goop mess) and a fan. Then try to wash with petroleum ether, maybe recrystallize from methanol in the freezer. Maybe add a little dcm to lower the solubility in the mixture.

Your way would probably be cleaner and higher yielding, but who knows. According to this somthing like that should work. https://erowid.org/archive/rhodium/chemistry/psilocin.extraction.html

I hate water in these situations though, so hard to evaporate without heat or time.
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Esther Donderkare - Mon, 24 Oct 2016 19:43:12 EST 2Hc2eoG6 No.78327 Reply
Would it be easier to just buy some CYP2D6...
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Albert Henkinbanks - Wed, 26 Oct 2016 15:27:19 EST 9Opqdgsf No.78328 Reply
>>78327
I don't think it would be feasible to create an artificial liver, but i really don't know. I do know scientists have modified e.coli to produce thebaine. 2mg from 20grams of sugar isn't too good though, and i expect the modified bacteria would be incredibly fragile. So unfortunately we won't be growing morphine in mason jars like magic mushrooms anytime soon.

Countries like Canada are lucky just to have codeine. If you don't have an opiate to start from you are pretty much forced to grow poppies.

I've found my mercury, i'm going to shake the small amount of bbr3 i have left with it then try the reaction again.
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fromNepal - Tue, 02 Mar 2021 13:56:20 EST T37piBU8 No.79999 Reply
Has anyone succeded in demethylating codeine ?
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Charlotte Bardfield - Mon, 12 Jul 2021 14:40:35 EST SEVIfr/l No.80049 Reply
>>78280
if i put pyridine and codeine in a frying pan and bake it for a while, can i get 10% morphine?
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Ebenezer Pickwell - Fri, 15 Oct 2021 18:43:39 EST vEdeBfXv No.80072 Reply
>>80049
you would get mostly tar, and maybe some morphine.
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Bombastus !uYErosQbLM!!Mybq1UbK - Sat, 13 Nov 2021 21:11:32 EST vPbGdL3X No.80091 Reply
>>80049
Just do it in the oven like a normal person. $20 toaster oven I bought used from Craigslist and put it outside was the best results and doesn't build up the toxic chemicals in your house.
You can get some dirty 80% morphine that you can clean up using one of those silica frit / diatom earth things you get on ebay.

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