One-pot Amphetamine Synthesis From P2NP With NaBH4/CuCl2 (1kg scale)

[Loki12]

@ImOutAlso
I do exactly like you said in step 1, first water, then IPA, turn on stirring, make sure it is going nicely and then add all NaBH4. Temp rise is +1-2C.
I did see your setup, quite nice, I was also impressed by the equipment choice you described, definitely wish I had went the more budget route also.

The next time I finish salting out, I will vacuum filter off the IPA in the buchner and after stripping 99% of IPA, I will pour acetone on the moist cake, give it a stir and turn the vacuum on again, correct?

As for the color, I had read about oxidation of this compound years ago and your description confirmed it for me, it was in fact just oxidation

@UWe9o12jkied91d
Thank you as well, next time I will try cooling with cold water when it reaches 50C, I now believe I previously overcooled and way too early too, not letting the reaction reach the needed temperature. I add cucl2 dropwise dissolved in the least amount of water possible after adding the rest of P2NP and letting it stir for a minute or two.

When I apply the heat at 80C for 30 minutes, I am left with two layers, clear on top and blackish copper with nabh4 it seems like on bottom, but the reaction seems to still be going (bubbling) even after stirring is turned off and temperature is allowed to fall down to about 40C. I tried to solve this by heating for longer (50 minutes, it stopped refluxing at this point), but quite strong bubbling still persisted.
I read about this method and some people have mentioned this can be caused by unreacted NABH4 which is apparently added in excess in this synthesis, I believe they described adding acetic acid to "neutralize" the NABH4 and stop the mixture from bubbling, is this something that should be considered at all? Or is it fine if I run the reaction mixture through a vacuum filtration at 30-40C to get rid of boro and copper then proceed to base it with cold NaOH? I don't see any borate crystals forming when separating the layers, so I should be good, right?

 

[WinterDust]

Yes,

When you wash with acetone, you don't need to stir, just keep the vacuum on and pour the acetone directly.

 

[chicaloca]

I don"t understand how you can use IPA to extract a aqueouse phase with IPA, because IPA is miscible with water... I'm lost here:!

 

[UWe9o12jkied91d]

Let me show you the way then.
Adding base fills in the spaces essentially with hydroxide and sodium ions so that any bits of oil or ipa stuck in solution have no choice but to float up.Now, you can look up salting out alcoholes from aq. sol. BUT this is especially true for IPA, it likes to separate off really easily upon salting ou with NaCl or alkalizing with NaOH, if you try this with ethanole which has a greater affinity for water than IPA or methanol you will see it does seaparate but not as clean, the interface will be messier.
In any case while IPA extraction is fine I would for sure use some organic solvent aswell to decrease polarity of what alcohol i am using

 

[chicaloca]

Thanks but I don't understand well and so anyway I plane to extract with DCM

 

[Melv99]

DCM will work just fine. So to most other NP solvents

 

[41Dxflatline]

Any reason this synth doesn't use the much cheaper, less suspicious and widely available copper sulphate pentahydrate?

 

[UWe9o12jkied91d]

CuSO4 is what one of the first few reports of this reaction used, 80%+ yields reported, just like with CuCl.

 

[blackburn]

Hi after adding acid it turns Little blue and very strange,

What can this be?

@G.Patton

Spoiler: pic

 

[blackburn]

And its not getting thick like cream, everything sinks to the bottom.

 

[G.Patton]

Can you tell me, what is it and what have you done?

 

[blackburn]

Its the the amphetamine base after RM, and i just added the sulfuric acid to it and its getting Little blue/green color and sinks to the bottom @G.Patton

 

[UWe9o12jkied91d]

Unreacted copper salts + p2np

 

[blackburn]

Hmm ok what should i do different after i put in all p2np i put in copper and then after copper reacts i leave it for 30min at 80c

thanks

 

[G.Patton]

You've added too much CuCl2. As, @UWe9o12jkied91d said, it is polluted amphetamine. You can filter it and wash.

 

[Pervitin]

Had the same problem, like you can read above. Washed it several times with Ipa.

 

[CasualChemist]

I tried the synthesis for a second time, wirteup of my first attempt is here: comment

This time I followed advice from @UWe9o12jkied91d and kept temperatures higher throughout the process. For the context my reaction is scaled down to 5 grams of P2NP.

First I pre-heated IPA+water mixture to 40 °C before adding NaBH4 (single batch). I omitted the ice/water bath completely and instead prepared a 120 mm computer fan pointed at the reaction flask. I added a spoon of fine grinded P2NP, temperature started rising and I turned the fan on when it reached 55 °C. I added next batch when temperature dropped to around 48 °C. I continued this procedure with temperature oscillating more or less in this range.

I waited for a minute and started adding CuCl2 solution.

On a side note, this time I made solution a bit more concentrated because I took into account that the original recipe mentioned 105 grams of CuCl2 in H2O and CuCl2x2H2O has ~27% bigger molar mass due to presence of water molecules, hence I used equivalent of 133 grams of CuCl2x2H2O in 200 ml of water.

With each addition of CuCl2 solution mixture foamed a lot and released brown precipitate which then turned into black flakes, like in the previous run. Temperature didn't rise too much so I placed the reaction flask in an oil bath and applied heating. With simultaneous heating and addition of CuCl2 temperature reached 72-74 °C, I was careful not to exceed 80 °C and used air cooling from time to time. Then I let it reflux at 75-78 °C for 30 minutes.

Unlike the previous run, after the reflux no layer separation occurred in the RM and I noticed distinct presence of an oily substance mixed with the RM. I tried filtering off the black dust with a filter paper but the mixture was so oily/thick it would barely go through filter paper so I just decanted the clear part and discarded the rest. I looked closer at the black residue and noticed two interesting things: tiny copper particles and oil patches floating on the surface.

Then I continued with NaOH, layer separation, phosphoric acid and so on.

This time again, my supposedly IPA+A-oil mixture didn't have a slightest yellow tint to it, it was colorless and a bit murky. Why in most of user reports A-oil is distinctly yellow? Most illustrations I found online including the Wikipedia page shows amphetamine freebase as a colorless liquid looking pretty much like what I've got. Does that depend on quality of P2NP crystals? I have a fairly fresh batch from nitrochemis.com and I keep in a fridge, crystals have very light yellow color.

Final product looks exactly like my previous batch, I didn't test it yet because I still have to do a wash.

Also I can't find any reference on how the final product should feel like when snorted. A ~100% pure product shouldn't burn at all? Does it make a difference if it's a phosphate or a sulfate? I'd be grateful if someone could describe actual sensation with high purity product.

 

[UWe9o12jkied91d]

Pure sulphate at least should not burn, i don't know about phosphate.There is discomfort due to fine particles irritating and tickling the mucosa, but after the fact it should not chemically burn.

 

[CasualChemist]

So I must've f'd something up again, because it burns like hell. It's also very salty in taste, some sodium salts must be present I guess.

Product also looks a bit different this time. First batch looks more like ground chalk and likes to form small lumps. Second one is a very fine powder. Both are snow white and very soluble in water.

Any ideas what could have gone wrong this time?

 

[UWe9o12jkied91d]

No idea tbh, did you do anything different? It would be an idea to extract the water layer with a portion or two of non polar solvent and ensure mass is sufficiently basic and dry the final product in solvent with a drying agent.You can purify your product obtained by a/b or recrystalization or both.

 

[41Dxflatline]

Recrystallised nitrochemis p2np is lovely, before then though it REEKS of benzaldehyde and is a luminous canary yellow, A-Oil is 'yellow' because p2np is yellow and sometimes it doesn't all react

 

[KokosDreams]

Hey guys,

We've finally succeeded in the lab with this synthesis.

First of all I have to say that we are no chemists, have no background in chemistry and have never synthesized any synthetic drug before. This is the first synthesis route we are trying.

We have had several tries so far that we kept to ourselves without sharing too much here. We quickly found out in what ways the lab needed to be improved to proceed with a successful synthesis.
We then took time to improve the cooling system, temperature control, ventilation and more aspects of the lab and got back to work just recently.

Just so that you know, the target product is purified freebase, not sulphate.

Synthesis report:

At this point unfotunately an issue occured as our vacuum pump can not be adjusted for the evaporation of water to be able to provide an accurate pressure.
We tried bringing water to boil at 0.04 MPa + 71.5 °C and played with the temperature in the levels between 71.5 - 90 °C but had to stop when it wouldn't boil.
The freebase:water (1:5) mixture is now sitting in a seperatory funnel until we have found a solution to this issue.

Current results (warning: pornographic content):

To be able to estimate the potency of the organic phases, that we have seperated and combined, we proceeded with carrying out two different crystalization processes.

First of all, we have so far produced 14L of organic phase from 800g of P2NP which we consider a big success after comparing this yield with fellow chemists from this forum. We are now storing this organic solution to carry out several experiments to learn more about the process.

Note: difference in colour comes from different mixing ratios of extracted aeqeous layer and firstly collected organic layer

1. 210ml freebase/ipa solution + 50ml anhydrous acetone + 99.99% sulphuric acid
Result: 7.2g of dried freebase (we messed up a little and spilled some product, yield should have been higher)

2. 200ml freebase/ipa solution + 99.99% sulphuric acid
Result: 7.3 of dried freebase

(this picture is not a picture of the dried sulphate)

The assumption here is that we are yielding Sulphate with around 60% - 61%.

Our goal is to find out how the addition of acetone is influencing the yield and also purity of the product.
So far we can say that the yield is not too much affected, we can not say too much about the purity yet as we haven't sent it to the lab yet. We will send it to the lab along a sample fo purified freebase once we got there. The sulphate that was crystalized without the use of acetone looks a little less white than the other but that's just an assumption..a quantitative lab test will tell more.

Freebase purification:

We were curious and wanted to find out how much purified freebase we could yield from the organic phase, per our estimations it should be approx 5% of the freebase/ipa solution which means that we should get approx 100ml actual freebase from 2L freebase/ipa solution.

We have carried out the evaporation of IPA in our rotovap. Here comes the tricky part, we did this step already in the past and it lead to us receiving a gooish, geelish honey like cream after the IPA was fully evaporated. Our assumption back then was that we have let it stay in the rotovap for too long, that's why we were more careful this time.

At the end of the evaporation process we could start seeing oily solid parts sticking to the distillation flask and assumed this might be our product + impurities:

We decanted the oily liquid into a beaker to view the results:

Strangely we have received 200ml instead of the estimated 100ml, we think this difference might come from impurities and us not drying the solution beforehand.

We then proceeded with adding water (on the picture you see 1:1 freebase:water ratio, we later stepped it up to 1:5) and shaking the solution in the flask to clean the flask and catch all solids/oil leftovers:

If you look closely, you can see oily parts floating in the water.
In the past we have had the same results and were able to produce a slightly milky freebase from this via a regular steam distillation.
We now wanted to put this to our rotovap when the above described issue occured.

We are right now stuck at this step and have stored the solution in a separatory funnel over night at room temperature (17 °C):

So far so good, we are curious to see what you guys think of our results and maybe what you would improve.
We are kinda happy with the so far produced results but need to find a way to make the distillation process of water work.

We are trying to get our hands on a very precise vacuum gauge for our vacuum pump to be able to provide a lower vacuum to manipulate the boiling point of water to lower levels around 28 - 40 °C. Another idea of ours is to further cool the water inside of the chiller as it reached 24.5 °C during the process as our chiller is not capable of holding it below 15 °C by himself.

As for the production of sulphate we are very happy as we are hitting (or even slightly exceeding) the yield from video tutorial and we are confident that we can achieve the same for the freebase production but we first need to get there, somehow.

Question:

1. When adding the IPA/Freebase solution to the rotovap we didn't had any issues with evaporating the IPA but when adding the freebase/water solution the pressure in the rotovap could not be held at the same level, although we have added the same volume of liquid for each process (1L each).
What could be the reason for this and how can we prevent this from happening?

2. What is your best and favourite way to go from impure freebase (after evaporating IPA) to a purified freebase (via steam distillation/ vacuum distillation/rotovap)

3. What ways do you prefer to remove IPA from the IPA/Freebase solution?
We think that it is not normal that we result in this honey like compound and assume that it should be more liquid.

4. It was recommended that we switch to a NaHCO3/Water wash instead of carrying out a distillation of the freebase:water solution to seperate the layers (followed by DCM extraction of water layer), what is your experience with this?

At this point I want to thank the professionals on this forum along other forum members that helped us to get to this point.

@G.Patton thanks for your amazing advice and help so far at all times of the day
@HEISENBERG thanks for providing this platform for beginners like myself to learn and meet like-minded people
@GhostChemist Thanks for providing more insight on the process and also for sharing your experience with us
@ImOutAlso Thanks for sharing your experience with us
@madmoney69 Thanks for the emotional support
@UWe9o12jkied91d Thanks for helping me with the steam distillation some weeks ago

That's it from me today, I wish you all an amazing start into the weekend.

Cincerly,

Koko

 

[UWe9o12jkied91d]

It’s hard to tell, in some of the pictures it looks like unreacted p2np, have you tried regular gravity filtration to isolate that solid?

on the other hand in some of the pictures it does have an oily look, it might be p2np turned oil with solvent due to heat that partially crystalized

Or it might be your pure amine that is degrading to this omega-fine white dust as freebase amines dr still freebase amine that gels up in the presence of water,so might be good to dry before

What I can add is that you do not use a rotovap as a faux steam distiller, you need to set up an apparatus either 1 flask or 2.Ideally for you based on what I have read would be to integrate a steam distillation in the process, distilling straight from reaction flask after naoh sol addition, skipping filtering of the solids, cutting back on manipulations and time.I would suggest you finally buy a mantle, it will make the difference compared to a plate for steam distill, especially for 20L.And I hear you barking, you have 1 neck only, just 2 way adaptor, center stirrer side condenser of choice, or just buy a stirred mantle if youre buying rotovaps

 

[KokosDreams]

Hey man, thanks for the extended feedback.

I did had it sitting in a beaker for a while and I could see two different layers forming, I assumed the upper (more liquid) layer was probably water as I didn't dried it before or maybe even isopropyl that I haven't fully removed in the evaporation process of IPA

Does this makes sense?

Picture:

I hope we are talking about the above described compound (picture) when you are talking about 'solids'
It's consistency is actually like yummy honey, don't know how else to describe it
I will definitely apply drying once I step into mass production, for this I will get a new batch of anhydrous sodium sulphate
I just left it out to prevent any complications to accure, which probably doesn't even makes sense
Interesting, I have seen videos online of 'essential oil extraction' with a rotovap ad figured it would make sense for me too, I also got it to work now and will post another report below my original comment in a few minutes
That is very interesting, I do believe in your experience and am always amazed when you do recommend me things I have never heard before elsewhere.
If I do distill straight from my 20L rbf I would need to skip on a second extraction of the sludge+aeqeous layer, correct?
I actually have a 20L heating mantle in my lab for my 20L 3-Neck RBF, I just never thought of using this for an actual steam distillation as I only use this flask for the main reaction (NaBH4, P2NP, CuCL2) - very interesting
I feared a stirred mantle might cause issues when carrying out this very route as the sludge tends to get hard quickly, even when still in touch with fluids.
But I think there was a misunderstanding here as I do have 3 necks in my 20L RBF, or are you talking about my distillation set-up? This has a 2L RBF with 1 neck

I will post my updated results now.

 

[KokosDreams]

Update on the above posted synthesis report:

We got the rotovap to work to distill of the water by removing 50% of the solution that was put into the distillation flask, I have learned that high volumes of liquid might cause gases to build inside of the rotovap system that prevent a consistant application of vacuum.

I am now removing water (and hopefully freebase ) from the distillation flask at 40 °C

After a while a milky distllate started to collect inside of the receiving flask.
What was interesting is, that I could see crystal clear bubbles floating on top of the distillate, aswell as in the tap of the receiving flask. I firstly assumed that the crystal clear liquid was IPA, that wasn't fully removed before, but after removing it and smelling it, I do now think that it is my product. Another fact that might proof this theory is that it wasn't solluble in water.

Here a few pictures to further explain the current situation:

You can clearly see a liquid floating on top and also one being pushed into the tap at the bottom that is not solluble in water.
I assume that the water became milky as there might be freebase inside, that could now be removed with a DCM extraction.

Another interesting discovery I made was the look of the freebase/water sollution close to the end of the evaporation process:

I again assume that the oily/gooish liquid floating in the yellow/orange solution is our product, amphetamine freebase
When I had the same solution in a beaker and left a little of it in the beaker after decanting the whole solution into the distillation flask, it looked like this:

I now wonder if I massively failed or if I am on a good way receive amphetamine freebase from this
I honestly do have a good feeling and would proceed with a DCM extraction, then DCM evaporation to hopefully receive my product.

What do you guys think?

@UWe9o12jkied91d @G.Patton What do you guys think?

 

[41Dxflatline]

Funny you should post this, mine just finished refluxing. Is it supposed to be in layers? The black copper is in its own a small layer at the bottom of the flask

 

[KokosDreams]

After what step exactly?
After the addition of the CuCL2/DH2O solution it is normla for the RM to seperate into layers.
Lower layer: dark/brown/red sludge with solids from the copper reaction
Top layer: yellowish/greenish colour depending on how the reaction worked out containing your product

In this case you continue with the upper layer, the lower layer can be used for an extraction with the aeqeous phase (+IPA) collected after adding 25%NaOH to the RM