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Preparation of MDMA by reductive amination with sodium borohydride

by Labtop

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Introduction

Until recently reductive amination with NaBH4, for the production of MDMA, was assumed to be inferior to the well-known NaCNBH4 route (that has been popularized by Alexander Shulgin for the production of MDA) and other synthetic routes, like aluminum amalgam. The following method proves that the NaBH4 reduction actually is superior to all other common routes used in clandestine chemistry.

The method is relatively simple, it doesn't require complicated equipment. The work-up on the reaction mixture is simple and efficient. The method is very usefull for big scale production of MDMA and gives high yields (+90%!).

There is a relatively rapid formation of the imine and the imine is reduced relatively rapidly. There's no reduction of the ketone to the secundary alcohol, as one might expect(2). In similar reactions, the water that is produced during the forming of the imine (Schiff Base) is removed (with drying salt, or molsieves, or by using toluene as the solvent, so the water and the toluene form an azeotrope) from the reaction before the imine is reduced. Because of the stability of the imine, this is not necessary for the production of MDMA.

This reaction is an improvement of a known synthesis (1), a similar reduction in an aqueous sollution of ethanol was performed, but the yields were only 31%.

Synthesis

MDP-2-P + methylamine-> intermediate imine + H2O-> MDMA

Ingredients

  • MDP-2-P 1000 g
  • Methanol 3000 g (>99%)
  • MeNH2 (gas) 300 g (99,9%) (Be very carefull with MeNH2-gas: it is toxic and carcinogen, but when handled with care, no problems. I advice to not use a gasmask, because when you smell it you can avoid it, but with mask you are not warned and it can be uptaken through your skin! Use wet towels to avoid problems at ev. leaking points!)
  • NaBH4 100 g (NaBH4 is a common reducing agent. Do not spill NaBH4 on hands or face without noticing it(e.g. whiping sweat off your face), or you will be punished with red spots there which will never go away! It takes minutes before you feel the pain, and then its too late. So wash face and hands with water, frequently.)
  • filtered clean H2O
  • 33% HCl
  • conc.NaOH solution
  • DCM (DiChloroMethane)
  • Acetone >98%

Equipment

There are several options for the reaction vessel. One could think of a 500 to 1500 L stainless steel milk cooling tank, that is modified to ones needs. But a fermentation tank (plastic or stainlees steel, from 20 to 8000L), with small modifications will do just as fine. Or one could buy a 1m3 (=1000 L.) plastic tank everywhere at second hand tank and cans stores. Have a handy manhole to clean, are totally airtight and as a bonus, have a nice tap-valve at the bottom. They ship NaOH ,33% HCl etc. all over the world with them.

Add 200 mL DCM to the reactionvessel and mix for 10 min. Stop the mixer and wait 30 minutes. The DCM with the rest of the freebase will sink to the bottom. Tap off. Combine the two. There will be app. 1750 mL of base fluid + DCM.

A solid diaphragm vac.pump is recommended for the vac. distillation. For example a Vacuubrand Type MD 4C, 3.0 m3/h. It sucks from 1.7 to 11.2 m3/hour, ask for Chemistry Design(PTFE) series.

MeNH2-gas is made by reacting MeNH2.HCl with conc.NaOH. (An other option is to react 40% MeNH2 with dry KOH.)

Step by step

1) Preparation

Dissolve 300g methylaminegas in chilled 3000g methanol (-20C). Cool the mixture to +5. Start the mixer (anticlockwise so no air is mixed in) and add the1000g MDP-2-P.

Notes: Make 300g MeNH2-gas by reacting MeNH2.HCl with NaOH. Or dissolve the methylaminegas in methanol, using an upside down laying (45 degree's) gastank with (fluid) methylaminegas in it, no pressure regulator on it. Attach a thick black synthetic rubber hose to the valve, open that valve slowly ,while the hose is down at the bottom of your first jerrycan with icecold Methanol,which stands on a big flat digital balance. Surround the hose with a wet towel. Add slowly 300g gas in the jerrycan. Be aware of a popping sound when the gas implodes when it enters the Methanol. Don't let suck back, close the valve everytime suddenly.

2) Reaction

Start adding NaBH4, one teaspoon ca. every 5 minutes, H2-gas bubbling has to disappear before adding again, temp. should be between 8-10 deg. (Wash down with methanol). Adding of the NaBH4 will take 2-7 hours. With mixer on let it sit for 2 days. (4 hours will do for people that are in a hurry,loss 10-20%).

NOTES: When the reaction vessel is opened it should be covered by a wet towel, so the methylamine-gas can be absorped by the water. (1 L water absorps 1000 L NH3.) An airlock might be sufficient for that goal too. Do not airtight the flask, let a thin tubing out the window,wrapped at the end with a WET towel!.

3) Work-up I

Leave the mixer on. Add 8 L clean H2O with 8 mL 33% HCl. Liquid will be greenish brown, pH=10,5 (11 is better than 10). !!When green soap starts to form: you added far too much HCl. Freebase will sink to the bottom of the vessel. Tap of, till clear water is coming out of the valve.

Add 200 mL DCM to the reactionvessel and mix for 10 min. Stop the mixer and wait 30 minutes. The DCM with the rest of the freebase will sink to the bottom. Tap off. Combine the two There will be app. 1750 mL of base fluid + DCM.

Notes:You can again basify the water with conc NaOH sol. to pH =13-14 and tap off the last oil.

The 8 mL 33% HCL (1%) is added to the water to make sure any unreacted NaBH4 is neutralised.

4) Work-up II

A vac.distillation setup is prepared. First the methanol, DCM, water and other lowboiloing stuff are removed, then at 165 C the clean freebase comes over. App. 1.0 L.

Notes: Step 1. The water and other lowboiling stuff comes over at 130 C. Remove when nothing more comes! Step2. Set on 165 C. At first around 140-145C you see the first little drops of oil condensate and at 160-165 C and 20-18 mbar it starts Running!.

To distill of the water, methanol and other low boiling stuff from the reaction mixture, the use of an aspirator is sufficient! To get the freebase out the use of a decent vacuum pump is recommended.

5) Crystallization

Mix the base 1:4 with clean,cold(-10 to -20 C) acetone and bubble through with a Stainless steel pipe 8 mm x 1 meter with HCl-gas 99%. SLOWLY! After ca. 5 min a thick, white crystal mass will form. Check frequently with pH-meter or paper,until pH=7 -6,5. If the mix get to hot, place back in big freezer to cool and proceed with next cold batch. Be very carefull not to go under pH=7 to 6,5, because then your powder will solute again and you must add base again until pH comes up again to 7. So keep always at least 200 mL base ready in case of mistakes ! Dry the acetone/powder mix in a Buechner-funnel with aspirator vacuum. Dry again on glassplates on the floor under airconditioner or slow blowing fan's in a dry room.

Epilogue

There are reasons to believe that the salt form of the amine can be used, but the gas method is by far preferrible. Ethylamine can be used to produce MDEA. Ammonium acetate or NH3 gas to produce MDA is another possibility, yet to be researched further.

The same method was tried with P-2-P, with unsatisfactory results when no water was removed, because the imine that's formed here isn't as stable. When you remove the water while forming,with a drying agent, this also works.

References

  1. Noggle, F. T.. Jr., DeRuiter, J., and Long, M. J.. "Spectrophotometric and Liquid Chromatographic identification of 3,4-Methylenedioxyphenylisopropylamine and its N-Methyl and N-Ethyl Homologs." Journal of the Association of Official Analytical Chemists, Vol. 69. No. 4. 1986, pp. 681-686.
  2. Shellenberg. K. A.. "The Synthesis of Secondary and Tertiary Amines by Borohydride Reduction." Journal of Organic Chemistry, Vol. 28, Nov. 1963 pp. 3259-3261.
  3. J. Weichet, J. Hodorova and L. Blaha, "Reductive amination of phenylacetylcarbinols by sodium borohydride." Coll. Czech. Chem. Commun. 26, 2040-2044 - CA 56, 5864c (1962)

Discussion


Gyrogearloose:

Saga of the elves... One morning at dawn, a magic hour for elves and fairies, I awoke, unable to sleep further. I heard some noise outside my window and dicided to see what it was. There in a toadstool ring, was a small group of elves unloading some lab equiptment. Wee little pieces of glass hardly big enough to see. I was fascinated and decided to watch from my position.

I got myself a pillow and setteled in. One jolly little fellow was setting up a flask with some methylamine HCL in it, fitted with a cork and a thisle funnel for addition. In the flask was some water gathered from the morning dew. He emptyed in the solid Methylamine HCL and added a little water. He hooked up a tube of dririte to the out flow of the flask and then taking a precooled flask from under a large mushroom filled with MeOH. He then gleefully stuck the end of the tube from the Flask (with the dryrite in it) into the container of MeOH. Another elve then started to open the flow from the thisle funnel which held some Concentrated NaOH in H20. Glorybee, the gas started to flow as if from the mouth of the wind Gods.

Since the elves had finite amounts (500 grams Methylamine HCL) to begin with there was no need to weigh the container or collect the gas as a liquid and then weigh and proceed. When they were finished with this task they began to move a wagon into place that had a large stainless steel container with a copper coil silver soldered around it, elves are very good with metal you know , especially silver. (moon metal and elves are creatures of the moon.) they hooked the ends of the copper pipes up to a nearby Icecold stream thru a pump system they devised and the container began to grow cool (5 degrees C). Well they then added the MeOH solution with the Methylamine gas in it to the container. One of the elves kept dipping his finger into the solution to see if it was cold enough (elves can do things like that without harm because of Magic) when he could tell that it was about 5 degrees C. they added some MDP2P (one liter), it all turned yellow and began to grow even colder as drops of condensation formed on the vessal. Quickly they erected a platform and started to pour in a white powder (150 grams, NaBH4) it said in runes on the bottle. Slowly they added the magic powder for at each addition (oh say a spoon size dose) of it there was great bubbling and a strange gas evolved from the solution. The color got lighter as they went(of the solution dummy)

When they finally got it all in they shut down the pump for the cooling and let it all stir for hours (6) After a fine elve party they began preparations to stop the reaction.

In a huge cauldron the added (8000 ml of H20 with 80 ml of HCL) in it and poured in the contents of the cooling vessal. first it turned white and then a freebase oil fell out on the vat. upon checking with some PH paper the solution was Base, the paper turned purple.

From a tap in the bottom they collected the oil and did a standard acid base workup on it and then added it to some dry IPA and added the HCL slowly to obtain a load of what must have been moon crystals. Each elve revently took a dose from the pile and a great party ensued. it was only after this I awoke to write this down before forgetting like a dream the events of the night before. When I looked out in the morning I saw on a upside down toadstool, that the elves had left me some moon crystals.


r2d3:

Gyro: What formula do you use to calculate the weight of MeAm gas generated? Do you simply drop the HCl part of the MeAm.HCl, and assume the balance will be generated as gas?


ReFlux:

Gyro - over what period of time (how long) did you add the NaBH4 to the sol'n? Did you record the temp. of the fluid after the addition was over (for the course of the reaction?)


Gyrogearloose:

Formula, formula, have you ever been around elves? Full of themselves you know, just a dash of this a pinch of that, a twinkle of the eye. But I did notice that they began with 500 grams of methylamine HCL in the soild form, and they bubbled all of it into the Cold MeOH. In answer to your question r23d, er excuse me, anyway yes.

Reflux, yes they did watch the temp closely as a matter of fact.

It was at 3 degrees C when the addition was started and within one spoon full it went to 16 C. sooo the elves waited inbetween spoons for the cooling to effect the 6 or 7 degree level again before next addition, also before you ask the color change was as follows when the spoon went into the mix, first white foam stirring seems to be slowed down and then it goes to brown color, after next addition same thing throughout. Just like the game instructions say at the end add to the HCL H20 mix and like magic (the elves like this part sisnce it includes magic) the brownish oil falls out in a few min, but they found out that if you wait for 30 min, it all falls out for you. It then cleans up quite nicly with acid base workup, oil bath distill then They now have tried all the mentioned crystals methods posted here, but seem to prefer the acatone, acid method .


LabTop:

Now to celebrate the resurrection of the UBB,here's my present:

To simplify life for you all, here's the ULTIMATE FOOLPROOF EASIEST WAY to make: MDMA, MDA, MDEA (use ethylamine instead of methylamine) if you have the chems available!

A practical way to make Honey's is as follows:

Reactant Ratios
MDA MDMA
MDP2P 0.5 1.0
Methanol 3.0 3.0
NH4OAc 1.0
MeNH2 0.3
NaBH4 0.1 0.1

These quantities are in weight! (So: gram or kg).

Following starting quantity is 25 kg P:

Prepare 6x20 L yerrycans in wich you can fill each 12,5 L cooled (-20 C) MeOH. In each yerrycan you dissolve 1,25 kg methylamine in the cooled MeOH.

Let the MethylAmine dissolve in the -20 C cooled MeOH wich you already put in the freezer one night before! Use a upside down laying gastank with MA (30-45' angle)and fill with a thick synthetic black rubber hose the liquid-MA as deep as possible in the MeOH. SLOWLY! It takes ca. 10 min., per yerrycan.

The yerrycan stands on a digital balance, so you know the weight added. Surround the hose with a wet towel at the filling opening of the yerrycan for the unhealthy smell.

When ready fill all the yerrycans in the reactiontank.

[Add in case of (MDA) now the AAcetate( in methanol) instead of the MeNH2 !].

Cool now the reactiontank to +5 C and start the mixer anticlockwise, so the fluid circulates from bottom to top. This way no air is mixed in, so less oxidation. Add at +5 C the 25 L. MDP2P .(pre-cooled).

Start then directly (because a slow reaction starts already), every ca. 5 min, adding the NaBH4, ca. 3 soupspoons per time. Use a funnel and wash every time with a little methanol. Keep all holes closed inbetween or it stinks!

Because of the excessive cooling the temp. will not rise much, only to +15 C. Wait again till ca. +7 C to add again. Are you impatient and add to quick, then the mix will start heating,evenso boiling! This may never occur,then your product will be lost !

This process takes ca. 7 hours. Ending temp. will be ca. 25 C. Stop after 7 hrs. the cooling and let react with mixer on for 36 hours.

After this time, you prepare 200 L clean water, which you mix with 2 liter 33% HCl solution.

This mix you add to the cooling tank (fast), then you messure the pH, should be between 11,5 and 12. (If you add coincidently too much acid,you will see greenish fat form in and on the fluid. Stop after 10 min. the mixer and let the raw brown base precipitate 30 min to the bottom and tap off the base through the valve at the bottom. Stop tapping when you see lighter color (water) coming.

Add now 3 liter methylenechloride (dichloromethane=CH2Cl2) to the tank, mix 10 min., stop the mixer, wait again 30 min. and tap off the rest of the base, now diluted in the CH2Cl2.This gives totally ca. 43 L raw base.

Now we remove the CH2Cl2, Methanol and the water in a simple distillation setup, without vacuum, with magnetic mixer/heater, mixerpin teflon, glassware with NS29 connections ( 20 L 2-neck flatbottom flask PYREX!, thermometer, cooler 60 cm, glas-alonge and 10 L collecting flat-bottom erlenmeyer flask).

Start at 35->55 C for CH2Cl2, then 55->85 C for methanol and 130 C for all the water. Re-use the CH2Cl2 and the methanol! Now you are left with ca 28 L half-clean base.(light brown).

Now we will clean the raw base by 2 times recrystallisation with acetone 98%, (m)ethanol 98%, and after that washing min. 3 times with acetone 98%. Use 20 L P.P. plastic buckets to do this.

Mix 5 L base (cold) and 10 L icecold acetone. Leaf inductionmotor-mixer on. Bubble HCl-gas 99% through with 1 meter StainlessSteel pipe, (inner diameter min 5mm) until white crystals form. Stop when pH= 7,3 and start with the next 5 L base. The first one will rise again to ca. pH=8,0. Later you can bubble again a littlebit HCl-gas through until again pH=7.0 . Let the crystals precipitate and pour the upper acetone off.

Re-dissolve the wet crystals now in the minimum quantity of HOT(nearly boiling) (m)ethanol in a metal bucket (because its hot !) until you see no more crystals, so you have a saturated solution in (m)ethanol!

Pour 5 L of this solution back in the plastic bucket, and add 5 L -15 C Acetone. When cooling down, you will see crystals form again,in a dirty solution. Wait until no more crystals come, pour off again and dissolve again in hot (m)ethanol. Do this as many times until you have snowwhite crystals. Dry on glasplates on the floor with blower.

You now have H(M)ONEY in the Bank.


Gyrogearloose:

Well guys From 360 ml of MDP2P to begin with the elves got 108 grams of the crystals, using the method for them of adding HCL to the freebase oil then adding the cold acetone, boom fun to watch the crystals comeinto chunks then .The elves love it....

PS I must mention here that those 108 grams were the most potent ever felt by the elves, by the way.......


LaBTop:

Gyro, I'm a bit worried here. This is about MDA? Did your Elfes use 33% HCl or bubbled 99% HCl gas?Did they NOT pass the pH 7 border? If they used 33%, there will be another substantial part of their product dissolved in the 66% water part! Do'nt throw it away... Boil it dry, and look, next present...

Before ,you mentioned me they get 342 gram out of 400 gram MDP2P. What was that? MDA I thought. When Billy does this, he always get min. 90 gram to max. 122 gram out of 100 gram MDP2P (MDMA !).with 99% HCl-gas!Like you make toothpaste instead of crystals...At the end its heavy to mix around!

So again, distill your SUSPECTED TO BE MDP2P always one time, to get min 95% and check eventually with any possible means if you really have MDP2P.

I got the impression that many people here do'nt work with real min 95 % MDP2P, but contaminated product. Billy works with for sure 98% MDP2P ! Checked,Checked and Checked!

I wait with the Pressure stuff until I have the feeling that the one's who work on this, do'nt need anymore help, otherwise everybody runs to the pressure Pots.

Hey, how about the P2P to Meth stuff? ANYBODY any NEWS? Get famous,post it!

Billy looks now at a solution of P2P,5A Molsieves,MeOH+10%MeNH2, which stood for a week.It turned slowly to a dark GREEN fluid. With a bit white precipitate between the molsieves (Alu-salt?) Can the Alu ions in the molsieves do that in a week?

Should he filter and add then the NaBH4 or should the Alu already have reduced (part of) it? INPUT please. MUCH MORE INPUT!


Gyrogearloose:

e gads, sir you were right on, it was hiding in the water........I was thinking it was small but powerful in a new way. This is high octaaane stuff. Its by far the best yet for the elves. Additional 232 grams were recovered thanks to your highness sir laBtop.

Sorry for making you look bad sir, it was the elves fault as you can see. Pointed ears somehow miss things round ones hear... Same goes for heads...as for the crystalization method they just neutralized the oil with 38% HCL and then added cold acetone and the boulders rolled on into being, minimum cleaning needed.


Sunlight:

When I dreamt with the methyl nitrite, I noticed a possible little work of cocatalyst, sometimes the Pd turnover arrived to 25 or so instead the usual 15-18 %, like in Ritter' rxn. Never 150 as in the patent. So finally I decided to use plenty catalyst. About Gyro's work, I've never dreamt with isopropyl nitrite, but I can speak about my recent test-dream about the LabTop's NaBH4 procedure, and I've got a similar success to Gyro using am. acetate (unfortunately I made a stupid mistake and I lost some product but I got a near 55 % of a healthy amine), and 56 % with aq. MeNH2, so don't be suspicious with these bees. I must recognize that I was when I saw in a previous test react NaBH4 with water and methanol , how the hell it can reduce anything if it reacts with the solvent ? But I go beyond my doubts and I discover it works. Reflux didn't got product with NaBH4 but I did, may be he failed with his ketone. I can not assure the procedure yields so much as LabTop says, but why not ? And about nitrites, it seems that some strange variable can be involved that makes the CuCl2 not work. I don't doubt about the Japanese researchers, but ...