Modern, Improved MDMA synthesis

[Euler-Mascheroni]

A modern, high yielding synthesis of MDMA using available cheap starting materials. Derived by an experienced clandestine chemist, written down by a noob.
As I did not try out this synthesis and am quite inexperienced, I would like to know you guys thoughts. Give it a shot and try it:
(I did not come up with this rout, I dont take either credit nor responsibility)

This synthesis was derived from Hamilton Morris' podcast in the episode "studying chemistry in prison".
If you are not familiar with Hamiltons work, I can do nothing but recommend him.
As the title says, the clandestine chemist interviewed, spend over a decade in prison, where he studied and refined his synthesis of MDMA, 2C-B and Mescaline. After he got out of jail he tested his methods with great success.
This was a free flowing interview, so he didnt mention all the details but this is what I scraped together.


Synthesis:

The starting material is helional: cheap, available and unwatched.
Overview: Helional —> carb. acid —> imide —(Hoffman)—> MDMA

1): Oxidation to form the carb. acid
(helional is unreactive, typical oxidants wont work)
oxidation with dimethoxydixoyrane made from oxone (potassium peroxymonosulfate), H2O, acetone

2): Formation of the imide
using urea at 160deg (75%)
byproduct: ammonia and starting material => recovery (90% yield)
difficult without acid catalyst (10%): HCl too strong (50%), Phosphoric acid is good, 1 drop/2 g carboxylic acid
(this apparently is a patented method)

3): Hoffman rearrangement with bleach
1: chlorination of the amide: delicately, bleach is fragile —> low temp, excess base, drip bleach over 1h.
amide will dissolve, if cold enough: precipitate will form
2: temperature 60deg. 4h
Neutralize base after 1h, isocyanate forms the imine


Are there any problems with this rout?
What do you think? Please correct me if I made some stupid beginner mistake somewhere (very likely)
He also talked about making mescaline and 2C-B. I can write them down too, if thats something of interest.

 

[WillD]

Helional is available? If it is made from the piperonal, then I would choose the paths easier.

 

[TotalSynthesis]

i would be interested in this route too if anybody knows more.
Helional is freely available at about 60€/Liter

 

[MadHatter]

Freely available from where?

 

[TotalSynthesis]

there are tons of sources, like Keten, Silu, org.chem.poland, also german companies, dutch companies, UK, US etc....
simply google for it

 

[MadHatter]

Ok. Apparently also sold as an ingredient for soap-making and perfumery, which is even more accessible.

So here's a great resource: https://www.thevespiary.org/talk/index.php?topic=19177.0
The experimental part of that post is here:

Spoiler: EXPERIMENTAL HELIONAL --> MDP2P

Helional (6.72g, 35mmol) was dissolved in 130ml of benzene. A catalytic amount of p-TSA was added (20-25mg), morpholine (3.5g, 40.25 mmol, 1.15 mol eq.) was added and the mixture was flushed with argon. A Dean-Stark attachment was fitted in and the contents were mildly refluxed until no more water could be seen coalescing on the bottom of the trap (theoretical: 0.63ml H2O). This took around 30-40 min. and the mixture was refluxed for the next 20 minutes afterwards. The contents were left to cool down, flushed with argon once again and poured into a pressure-equalized addition funnel.

In the same flask (or a bigger one, whatever you prefer) sodium dichromate dihydrate (20.86g, 70mmol, 2 mol. eq.) was dissolved in around 80-90ml GAA. That mixture seized up when cooled down, but after adding 30-50ml of benzene and stirring it became a fully mobile liquid again. The mixture was cooled down once again to 5C. The enamine solution was then dripped in slowly over an hour. After the entirety was added, the mixture was stirred for 2 hours. During all these steps the temperature didn't get over 10-15C.

The reaction mixture was then diluted with water (~100ml) and poured into a separatory funnel. It was washed with water and then dilute sodium hydroxide solution to remove any excess acetic acid. The benzene layer was then washed with brine to remove any remaining water and concentrated by distillation. Obtained oil was flushed continuously with argon and warmed up on a water bath to remove any remaining benzene and then subjected to vacuum distillation (~10mbar). A fraction of neon-yellow, mobile oil came over at 130-150C and was collected. Yield: 2.81g, 44.9% based on helional.

This yield can surely be improved with optimization. Maybe an even larger excess of amine is called for, maybe the total volume of solvents should be cut down to reduce losses. I can't say much, this requires experimentation and that's why I need you guys.

Analysis:
A drop or two were dissolved in 5ml methanol and analyzed by GC-MS (even more diluted, of course).
The column had to be overloaded for any impurities to be found. The GC peaks are streaked and fin-like because of that overloading. The peaks are characteristic for MDP2P and those for helional are very tiny or absent at all. All the spectra are attached as a pdf. Library search based on peak surface area yielded purity of >99%.

The continued route from MDP2P to MDMA is assumed general knowledge.

A very interesting route indeed. Especially if GAA + dichromate can be used instead of the pretty non-OTC Oxone.
In that great post, the poster made an excellent comparison between different oxidizers for the initial reaction:

Spoiler: COMPARISON OF OXIDIZERS

Review of oxidizing agents

Sodium dichromate dihydrate in GAA/benzene
Pros:

Spoiler: COMPARISON OF OXIDIZERS

-Cheap
-Simple workup
-Visual aid as it's reduced to chromium(III)
-No smell, easy to work with
Cons:
-An environmental and health hazard if not dealt with properly
-The oxidation requires 2 mol eq. which translates to as much as 3.10g of dichromate per 1g of helional
-No compatibility with toluene

Sodium metaperiodate (NaIO4) in THF/water
Pros:
-Green
-Recyclable
-Relatively simple workup
Cons:
-Expensive
-Due to the large molar mass it suffers from the same problem as dichromate
-The solvent system makes hydrolysis possible

Dichromate in dilute sulfuric acid/diethyl ether system
Pros:
-Relatively high yields
-No worries of overoxidation (not a problem with a ketone, but eh I guess it's an advantage)
-Possibly could be done one-pot too, but no other solvents than diethyl ether are described in the original paper
-Cheap
Cons:
-26ml of the aq. solution per 1g of helional (sic!)
-The same environmental and health hazard as in #1.

Copper(I or II)/oxygen or any other singlet oxygen initiator (methylene blue etc.)/oxygen
Pros:
-Very cheap
-Possibly high yields
Cons:
-Side products
-Smelly (you'd need to cool down the enamine solution a lot not to allow any solvent to escape with excess oxygen)
-Requires an oxygen tank or an oxygen bottle
-Heterogeneous
-Would require the solvent to be changed (to DMF or acetonitrile, they dissolve oxygen much better than hydrocarbons)

I wonder if potassium permanganate could work?

 

[MadHatter]

But in this detailed and comprehensive write-up they use morpholine in the first reaction. Now that's not exactly OTC. According to the comments, piperidine could work as well.

But to OP: can you link the sources of your write-up? There seem to be something missing ...

 

[TotalSynthesis]

have a look for Caroat, thats also Potassiumperoxymonosulfate and can be found OTC.
found it in a brew supply shop for disinfection and in a camping shop for cleaning watertanks.

Will get through your post later once i have some more time. thx

 

[ASheSChem]

??

 

[TotalSynthesis]

you're trying to sell recipes?
That's poor !!

maybe you should register at clickworkers.com if you'd like to earn with copy&paste

 

[TotalSynthesis]

well, a community is for sharing and exchanging information.
Since your first post was "you can buy....." without contributing anything of value here, that does not make you a trustworthy member who seems knows his shit.

Maybe try with ebay. read my tutorial about fake ids, get a bankaccount and sell it there

 

[btcboss2022]

I'm curious about the price you would ask for this recipe hahah If don't works I guess money is returned back no?hahaah(joking of course)

 

[btcboss2022]

But price of your recipe?;-)

 

[ASheSChem]

not the same idea ?

http://bbzzzsvqcrqtki6umym6itiixfhni37ybtt7mkbjyxn2pgllzxf2qgyd.onion/threads/mdp2p-from-helional.2874/

 

[Thorsp3]

my new account. can call no particular

 

[Thorsp3]

my new account. can call no private