RFC: OTC small-scale MDMA synth overview v1.3

[MistaMiyagi]

OK bees, please bee gentle.  I have perused Shulgin, Zubrick, Rhodium, and Zwitterion.  I've even UTFSE.  What I am asking is for confirmation that this collection of independent steps could actually result in a pleasant dream.

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Purification of Safrole from Oil
Main Credits: Chromic, baalchemist
  Obtain safrole-containing oil.  Attempt purification via fractional crystallization.  In the absence of satisfactory purification, attempt purification via fractional vacuum distillation.  Target purity should be >95%.  All supernatants and waste fractions can be recycled to be repurified later.

Isomerization of Safrole to Isosafrole
Main Credits: Chromic
Expected yield: 80-95%
  Add KOH_(s) (1-2% by weight) to safrole.  Reflux for at least 4 hours.  Vacuum distill contents to yield isosafrole.  Target yield should be >85%.  Waste fractions may be recycled with waste fractions from safrole distillation.

Oxone oxidation of Isosafrole to Glycol/Epoxide
Main Credits: Chromic
Expected yield: 60%
  Combine 16.2g isosafrole, 200mL OTC MeOH, and 500mL dH₂O.  Under continuous stirring, add 85.5g OTC Oxone (85% potassium monopersulfate, 15% pH buffer).  Let reaction continue, under agitation, for at least 5 hours.  Cease agitation, allow solution to separate, and decant.  Save the supernatant.  Wash sediment with 4x50mL MeOH and combine washes with supernatant.  Add enough dH₂O to dissolve any remaining precipitate in supernatant.  Extract glycol/epoxide from supernatant with 4x60mL DCM washes.  Distill DCM from washes to recover DCM and leave a viscous glycol/epoxide oil.

MDP2P via hydrolysis of glycol/epoxide
Main Credits: Chromic
Expected yield: 95%
  Combine 15g glycol/epoxide, 25mL MeOH, and 120mL 15% H₂SO_4(aq).  Reflux mixture for 3 hours.  Allow mixture to separate.  Retain the dense bottom layer, which should be MDP2P.  Wash aqueous layer with 3x40mL DCM and combine washes with the (ketone) MDP2P.  Wash ketone mixture with 3x80mL 5% NaOH_(aq) and discard washes.  Distill DCM off for reuse.  Add 50mL safflower oil to ketone oil and vacuum distill.  Waste fractions may be recycled with other waste ketone fractions.

MDMA from MDP2P via Amination with Al/Hg/MeNO₂
Main Credits: Methyl Man, Dr. Drool, Osmium
Expected yield: >78%
  Dissolve 500mg Hg in 50mL 3% tincture of iodine.  Wait for color to turn from black/brown to clear (may take up to a week!).  Set HgI₂/MeOH mixture aside.  Combine 25g MDP2P and 50mL MeOH.  Use another 50mL MeOH to rinse MDP2P from source container and add to MDP2P/MeOH mixture.  Put 27.5g balled Al in reflux flask.  Assemble reflux still, start agitation, and pour the HgI₂/MeOH mixture into flask.  When amalgamation loses shiny silver color, add 20mL 99% MeNO₂.  Then, add MDP2P/MeOh solution portionwise, slow enough to prevent reaction runaway.  If amalgamation thickens up to the point of inefficient agitation, add up to 75mL MeOH into flask.  After addition is complete, allow mixture to reflux with no external heating for at least 3 hours.

MDMA freebase via extraction from amalgamation
Main Credits: Methyl Man, Dr. Drool, Osmium, lab_bitch
Expected yield: >90%
  Continue agitation and add 750mL 5% NaOH_(aq) portionwise.  Al/Hg sludge should coagulate and allow relatively easy filtration.  Vacuum filter the sludge, then follow with with 5x200mL xylene poured over the Al/Hg mass while still on vacuum.  This should extract the MDMA freebase.  Purify the freebase either by: washing with 4x500mL dH₂O, followed by 500mL saturated NaCl_(aq); and/or vacuum distilling freebase at approx 160o[/sub]C.

MDMA.HCl from MDMA freebase via gassing
Main Credits: Found via Grub's post, unknown author
Expected yield: >75%
Note: A better HCl generator can be found in

Argox's HCl Generation text.

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/hclgas.argox.html)
  Fill wash bottle 1/3 full with CaCl₂.  Add enough HCl_(aq) to cover 2/3 of CaCl₂.  Let sit for 2 minutes.  Submerge wash bottle spout in freebase/xylene mix.  Squeeze wash bottle slowly to introduce HCl_(g) into solution.  MDMA.HCl should precipitate from xylene.  Continue gassing until there is no further precipitate can be seen.  Vacuum filter the xylene/MDMA.HCl mix.  Repeat the gassing-filtering process until no more precipitate forms.  If crystals are not of desired purity, recrystallize.  Otherwise, enjoy.

(Optional) Recrystallization of MDMA.HCl
Main Credits: LaBToP
  Combine MDMA.HCl with enough hot 99% IPA to dissolve.  Cool the IPA at a controlled rate, bringing the MDMA.HCl out of solution.  Vacuum filter the MDMA.HCl crystals, but save the IPA supernatant.  Boil away approx. 75% of the IPA and recool the mixture to precipitate most of the remaining MDMA.HCl.  Vacuum filter these crystals, combine the MDMA.HCl aliquats, and store in an anhydrous container, perhaps even along with a silica gel (or other dessicant) packet.
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So, master bees, what is the consensus?  I throw myself upon your mercy.  Thank you for any feedback I receive, good or bad.
*** If this is simply an illusion, does that mean hallucinations are reality? ***

[ClearLight]

Please list the indicated yields for each step... also you didn't distill your mdma freebase prior to recrystallization

Infinite Radiant Light - THKRA

[pickler]

Looks like you chopped up a bucnh of other people's work and combined it all. It will work though. Only afew points to touch on.
1. allow mixture to reflux with no external heating for at least 3 hours.(MM al/hg)
After your addition is complete, your probably bot gonna get a three hour reflux . The synth says to stir for 3 hours after the addition is complete. It will reflux for a little while, but not three hours.



I went into the business for the money, and the art grew out of it.-Charlie Chaplin

[Rhodium]

Oh, wonderful. If everyone could research so well before trying to synthesizing something...

Add 50mL safflower oil to ketone oil and vacuum distill.

"Buffer oil" is superstition, and serves no purpose in organic chemistry. The source of the misinformation is Eleusis, interpreting the term "chaser solvent" in Zubrick all wrong. 

After reflux flask has cooled, continue agitation and add 3x250mL 5% NaOH(aq).

I have no idea about what you are trying to do here. Why not say "add 750ml 5% NaOH portionwise"?

(Optional) Recrystallization of MDMA.HCl

Very bad chemistry. Recrystallize from 7 times the weight of the MDMA.HCl in acetonitrile, or dissolve in the minimum necessary amount of boiling 99% isopropanol, then dilute with twice the amound of diethyl ether and let cool to 0°C for an hour or two, filter and wash the crystals on the vacuum buchner funnel with dry ether.


Do not use acetone with MDMA for washing, "crashing" or recrystallization. The acetone can condense with the amine, forming an enamine.

You are recycling your solvents, that is excellent. You are overestimating the importance of fractionating your precursors and collecting foreruns for re-processing (unless you are unusually cheap, have a real problems obtaining precursors, or have reason to believe that the step failed.

ClearLight is right, you should distill your MDMA freebase at ~160°C using an aspirator before crystallize the hydrochloride. Your HCl generator will probably work ok, but I think

https://www.thevespiary.org/rhodium/Rhodium/chemistry/hclgas.argox.html

is better. 

That way of performing a Nitromethane/MDP2P reductive methylamination is not reccommended. Instead add the nitromethane first, and when all of it has been reduced to methylamine, then add the MDP2P and continue the reduction.

Suggested reading:

Post 357309

(Osmium: "my preferred way", Chemistry Discourse)

Post 363298

(Osmium: "If your reaction is running so hot that it stinks ...", Methods Discourse)

[MistaMiyagi]

OK, I've incorporated the changes suggested by Rhodium, ClearLight, and the edit caught by pickler into the original post.

Rhodium, were you being sarcastic with the "Oh, wonderful."?  I knew there would be some mistakes in this, and I apologize for them.

The point of this post was twofold:
1.  Pique the experiences of others so that SWIM can avoid pitfalls that he hasn't found, and
2.  So that eventually, with everyone's error-checking and feedback incorporated into it, it could be a quick-and-dirty synopsis of a closest-to-complete OTC synth.

I am slightly afraid to use chem suppliers... I am trying to stick with chems that can be had for walking in with some cash.  The only one so far that will pose a problem is the HgCl₂... but I am sure it is in the Acquistion Forum somewhere...
*** If this is simply an illusion, does that mean hallucinations are reality? ***

[Rhodium]

No sarcasm, you have done your homework. This is so much better than all the people posting "what went wrong?" afterwards...

[goiterjoe]

HgCl2 is really easy to make from elemental mercury.  The procedure is documented on Rhodium's site.  A lot of bees around here praise making mercuric iodide, but I don't have any exerience with it personally.
All paths are the same: they lead nowhere

[humidbeing]

From personal experience HgI2 works great just as V-L
wrote about, with 2oz bottles and 500mg Hg. A few days
with occasional shaking and the solution will go from
mostly opaque to very clear light orange. Half will do for
 a standard MM 25gm reduction, with the fine tuning by ZJoe and others.
CG I miss you sweety, I really do.

[hCiLdOdUeDn]

That is exactly how swim does his complete synthesis. Instead of freezing (which takes some time to get right) try distilling it instead. With a stirbar it comes over fast.

Swim has experience with HgI2 and it works great. Swim just breaks a thermometer and empty the mercury into the tincture of iodine bottle.

Rhodium, what is the procedure to add the nitromethane first then ketone? Does the nitromethane alone cause it to reflux or addition of ketone?
To bee or not to bee, that IS the question.

[hCiLdOdUeDn]

Oh yeah and also a side note:

100% oxone is 42.8% potassium peroxymonosulfate(potassium monopersulfate) with 4.5% active oxygen.

Do not confuse 85% oxone as being 85% potassium monopersulfate.
To bee or not to bee, that IS the question.

[raffike]

Making HgCl2 from mercury is kinda easy too.For more info,check Rhodium's.
A friend with speed is a friend indeed

[photoman]

Above, Rhodium mentions using diethyl ether (twice the weight of MDMA) in the recrystallization. Usually it's just IPA and this is the first time SWIM sees ether incorporated too. Why is ether needed? Is it essential?

[Rhodium]

I's not essential, but as ether is an inert non-solvent for MDMA.HCl you will push more of your product out of solution.

[chem_123]

Oxone oxidation of Isosafrole to Glycol/Epoxide

can this step bee scaled? it says 60% yield...but the next step uses 93% yield weight?! can SWIM make a double batch for this step? or half the next steps ingredients in order to accomodate the yield loss?

this step also doesn't mention the baking soda...if it's used, will that slow the rxn? damage the desired product?

It tastes like burning!  

[a_mean_bee]

Do not use acetone with MDMA for washing, "crashing" or recrystallization. The acetone can condense with the amine, forming an enamine

Rhodium: I am curious about this statement because many of the posts that I've gone through for suggestions and procedure do recommend washing finished product with acetone. Mainly I'd like to know if enamine formation is a concern from the point of view of toxicity. Thanks.

[Rhodium]

I have never heard of anyone analyzing their product in that much detail as to be able to say if it presents an actual problem, but theoretically, acetone imine formation is fully possible.

Toxic? Who knows? It probably isn't, but if formed it will naturally degrade the purity of your product.

[a_mean_bee]

Ok. So, seemingly, not a matter of life and death then. Figured that I'd better check just in case. The 'contaminant' threads in the Stimulants forum have got me on contaminant alert. Which is good. Not to mention the normal concerns over preserving product integrity.

I've been surfing mercury disposal posts as well. Can anyone tell me if any one particular stage of the post Al/Hg cleanup is foremost in removing residual Hg. Assuming work up involves: basification, extraction with non-polar solvent, then washes of h2o and brine. Naturally the operator will pay fastidious attention to all phases of the procedure, but if she really wanted to focus on, or repeat, one of them with an eye to minimizing Hg ...

[Rhodium]

Can anyone tell me if any one particular stage of the post Al/Hg cleanup is foremost in removing residual Hg.

Proper, slow recrystallization of the final hydrochloride salt.

[SPISSHAK]

It contributes to the high, just kidding.
Rhodium, what do you base that assumption on?
The reason I ask is there are all kinds of theories about filtration, brine washes, Mercury/amine complexes, etc.
It's hard to see the forest thru the trees with all the disinfo out there.

[raffike]

Mercury falls to flask bottom as it's too heavy and mercury salts stay in water.No mercury comes thru a/b