PNP's into amphetamines reduction on alu foil

icecool · Insistent Chemist

Is it also possible to use dichloromethane insted of diethyl ether.
To extract the amph oil out of the NaOH+Al+acetic acid etc slurry.
Just for everything in the synthesis where you use ether you will then use DCM since it is a lot cheaper and easier to get for SWIM.

IndoleAmine · Dreamreader Deluxe

DCM is heavier than water and will not float to the top like ether.
This makes separation very difficult, you would have to filter the Al sludge off to be able to separate the lower DCM layer (->big mess).

Better use toluene - it is cheap too, and floats to the top....

i_a

icecool · Insistent Chemist

But how does SWIM get rid of the toluene normally with ether SWIM evaporates it off by heating it.
And toluene boils at 110*c so doesn't the amph.freebase decompose?
SWIM doesn't have a vacuum distillation setup, neither steam distillation.
And when using mercury nitrate what would be better, Hg(I)NO3 or Hg(II)NO3?

P.S When wetting the filter on forhand I read to use cold anhydrous acetone.
Can this be replaced with ice cold anhydrous ether or ice cold anhydrous IPA?
It is ment for when filtrating amphetamine sulfate out of IPA.
So not that much will stick to the filter or go and sit inside of it.

IndoleAmine · Dreamreader Deluxe

No, the amine will not evaporate or decompose at 110°C at atmospherical pressure, but the IMO best way to remove toluene is by vacuum distillation.

Bonus: You can also recover all that precious solvent, instead of having to breathe its fumes and therefore effectively loosing it forever.... Very Happy

(saves alot of money, is healthier and better for the environment)

And sorry - but this are exactly the reasons why I won't give you any tips for evapping toluene at room temp. Wink

For wetting down the filter paper before filtering, every solvent that is a) anhydrous and b) inert to both filter paper and substance to be filtered can be used, IPA, acetone, toluene, ether, MEK, DCM - whatever you have at hand. The idea is to saturate the paper with something else than H2O or amph.sulfate salt so that these two can't go into the fibre structure of the filter paper anymore, and this is easily done by soaking the filter paper in something else but water or salt - afterwards, theres simply no room left, because all free spaces in the paper are already filled with IPA (or similar solvent).....

For Hg salts, I would choose the one with the best solubility in H2O. Think it are Hg(2) salts...

i_a

icecool · Insistent Chemist

I've done the distillation of toluene and ether on school many times at atmospherical pressure, so that will be fine.
But after all I did chose there anyway since my fumehood is working really well so there is no smell at all.
And ether well I'll distill it off and so I can check the boiling point of when it is all gone.
And then I'm sure I'm left with amphetamine freebase.

ps. At what temperatue does amphetamine.freebase decompose and at what temperature does the oil boil.

SWIM just added IPA+H2SO4 to the amph.freebase
It was out of 7g P2NP 7,6g of freebase oil.
Very dark red and at 80*C some drops came over at distillation probably IPA although that isn't miscible with ether right?

PPS: How long can P2NP be stored since it has been standing around for a while.
It has been standing for 4 weeks or so, could it be that I won't get any or very little amphetamine because it decomposed (although there are still the yellow crystals).
And why do you need to evaporate off all the solvent when you are going to add solvent again after all after you evaporated off all the solvent.
The mixture has been standing in the freezer now for 12 hours and there are still no crystals in there, only a very vague white mist.
And that is soooooo little, anyway is there any way to make amphetamine freebase again from the stuff I got now or what can I do with it, even when adding a drop of sulfuric acid in IPA there didn't form any crystals so I didn't add too much.

And another question about when adding the NaOH or KOH solution to the mixture to get rid of all the Al that didn't dissolve.
If you add it is it bad for the reaction when it gets really hot?
And if not all the aluminium will dissolve in the KOH or NaOH solution, well I took all the lumps out that where still in there, because they just wouldn't dissolve anymore.

IndoleAmine · Dreamreader Deluxe

Hm - ok, one thing after the other. Where should I begin? Maybe at the end of your post...

1) If not all remaining Al is eaten up by the NaOH, simply add more NaOH until everything has dissolved...
(if you have much Al left over, it maybe indicates that your rxn wasn't complete or that you used too much Al)

2) If the rxn gets too hot during basifying, product is lost. Before adding NaOH, conditions are strongly acidic and the amine stays in there even if it boils. Just remember that toxic Hg fumes will be evolved when things boil...

3) IPA is miscible with diethyl ether, in every proportion...

4) the reason to remove the solvent from the free base through distillation is because you would like to know how much amine you actually have, before adding H2SO4, right? Hard to measure out with all that solvent around, so it must be removed... Wink

5) if you added not too much H2SO4 to your amine (slightly less than 0.5x molar amount relative to amine), used enough IPA to dissolve both amine and H2SO4 in it, and if you used really dry solvents, you can be sure there will be crystals.
Since not even dilute acid dripped into excess amine did produce any crystals, I guess you used wet solvents, or your amine is no amine at all (then again, this is impossible when you do a proper acid/base extraction)...

6) your amine boils at 200-203°C at atmospherical pressure, and decomposes certainly above that temp., so it can be vacuum distilled without any losses (but it will probably char and decompose in the flask when you try distilling at atmos, I wouldn't try it)

7) Removing solvents doesn't mean checking the boiling point of the remainder! Very Happy

You are only meant to heat just enough to be able to remove the solvent, not until the remainder starts to distill too!! Thats the whole trick: don't let the goodies boil, but evap all solvent, fast and safe.... Wink

(be sure to let cool to room temp. before dimantling the dist. setup, or some product that still remains vaporized will be lost to the fume hood. If you let things cool down, everything condenses....)

8 ) when distilling ether, be extremely careful, always start the magnetic stirrer first before applying any heat, and don't let it stop before things have cooled down again! And a warm water bath (45-50°C) is absolutely enough heat for distilling ether at atmospherical pressure, don't use more! Before using redistilled ether, you have to free it from peroxides by shaking with aequous dilute ferrous sulfate (FeSO4) solution, and peroxide formation during storage can be avoided by adding a small piece of fresh, unoxidized copper wire/tubing to the flask containing your ether

If you still have no crystals and are sure you had amine freebase already, you might want to add some dilute NaOH solution to your crystallization attempt, distill away the low-boiling solvents, extract with ether or toluene several times, discard NaOH phase, combine nonpolar extracts and wash a couple of times with brine, then extract nonpolar phase several times with dilute HCl and discard nonpolar layer, wash combined aequous HCl phases with DCM until clean, then add NaOH to basify again and release the amine as oil floating to the top, which can then be extracted and worked up like common (but with anhydrous solvents and more care this time!)...

i_a

IndoleAmine · Dreamreader Deluxe

"Very dark red" - uh oh, doesn't sound like amph freebase, more like p2np destruction products...

It is said to be colorless to slightly yellow, not dark red! See brains posts, I think he included a pic of really nice waterwhite freebase...

i_a

Bumblebee · Wed Apr 20, 2005 6:37 am

in my case it was as folows:
I evapped away all solvents made strongly basic until all Al is dissolved...
extracted with toluene like IndoleAmine recommended.
Distilled all toluene off under reduced pressure (Aspirator), and i was left with a red oil at the bottom of the distilling flask (3-5ml from 7g P2nP).
distilled Amphetamine-smelling liqiud @ 110°C (1-2ml). some Amphetamine smell remained in the distilling flask so i think i didn´t get all out because of that small scale i did.
the white liquid was diluted with 30ml anhydrous IPA and crystallized with some drops of dil. H2SO4 in IPA, filtered with vacuum.
added some drops to the filtrate again, and some more crystals appeared. filtered.
after that last crystallisation no more crystals came out of the solution.
the remaining crystals in the Buchner were Washed with som cold IPA and dried.
it Yielded 1,8g of very fine product, as bioassay confirmed.
poor yield but success at all.
BB

IndoleAmine · Dreamreader Deluxe

Toluene doesn't mix as good with the aequous phase as ether would, so you need better/stronger mixing and probably one or two more extractions when working with toluene.

Although I usually get >95% within the first two extractions and almost all of the remainder with a third one, four toluene extractions is overkill and not necessary.

And I think I remember that ethereal extractions had to be done 4-5 times due to higher miscibility of ether with H2O and more solvent losses.

Bumblebee: Nice, you distilled your freebase! Although you may in fact loose one or two ml's to the glass walls, depending on the size of your setup, it is strongly recommended when the product is to be consumed. (Experience has shown that in various cases, similar undistilled substances, whose purities were supposed to be ">95% pure", proved as being in fact only 67 and 87.3 percent, respectively Shocked

(amine sulfate washed thoroughly to whiteness, and methylated amine hydrochloride recrystalized once to some hint of sparkliness.. - both without dist. of freebase!).

And this was with Al/Hg (nitropropene reduction and ketone/nitro red.amination, respectively).

Still waiting for further analysis of the other, minor compounds identified, rest assured I will report them as soon as I know it....

Cheers

i_a

IndoleAmine · Dreamreader Deluxe

For those of you owning a fume hood Laughing

: You can also distill away the alcohol, add more NaOH solution, crank up the heat and simply distill out the amine from the ugly Hg soup together with the water! This is called steam distillation, no vacuum needed here...

Small traces of Hg will be carried over into distillate maybe, so watch out and wash the toluene/ether/whatever properly with saturated NaCl solution.

Much less Hg mess to deal with, only clean water with amine floating on top.

Just add some HCl to the collected distillate, wash with DCM two or three times, add enough NaOH to bring pH up to >13, extract with whatever nonpolar you have at hand (naphta / pet.ether / DCM / toluene / ether / cyclohexane etc) at least two, better three times.
Small traces of Hg will be carried over into distillate maybe, so watch out and wash the toluene/ether/whatever properly with saturated NaCl solution, three times. Dry the combined, clean and Hg-free extractions over silica gel, Na2SO4, molecular sieves etc. (MgSO4 isn't good for drying amines!!), remove solvent through distillation (preferably under vacuum), and be left with the purest amine you can think of....
Wink

i_a

tetraedr · Wed Apr 20, 2005 9:17 am

How long it takes the distillation from Al/Hg after-reaction mixture of goal amine?

I thought about it.... But I am afraid, I can lost some product, at first. And, also, I takes a long time - about 2-3-4 h for (for example) 10 g starting material scale....

Also I am surprised, why the amine do not distill during rotary evaporator using? For example, SWIM use it for other similar process - methylamination on foil. For that procedure the alu residue was simple filtered off, then filtrate was concentrated on rotary evaporator under vacuum, then diluted with water and extracted....

icecool · Insistent Chemist

Hmm okay SWIM doesn't get why I keep having these trouble with this reaction.
But well SWIM used 10g Al foil for 7g P2NP.
SWIM would rather not discuss it further SWIM just think the reaction was not complete although some Al dissolved more then the time before.
But okay, just making some new and more P2NP then before and then SWIM can try again insted of keep thinking about what could have been the factor of which fucked it up.
And about the steam distillation you mean removing the methanol you used for the amalgamation and then when that is gone you add more NaOH to it.
And then simple the amine will come over with water and won't even be mixed in the water, and don't you need other glasswear then a normal distillation setup for steam distillation?
I guess this time SWIM had to distill it longer, but I was afraid that I would decompose the amine.
Anyway one little question about the basifying, you sayd (indole) :

2) If the rxn gets too hot during basifying, product is lost. Before adding NaOH, conditions are strongly acidic and the amine stays in there even if it boils. Just remember that toxic Hg fumes will be evolved when things boil...

So if SWIM gets you correctly the amine will not get lost in the acidic enviroment even if it boils but when you add NaOH and it boils the product IS lost.
And why won't the product decompose when steam distilling it will it also come over at 200*C or at 100 with water?

SWIM won't try to safe this batch it was only 7g P2NP and SWIM could better "waste" use his chemicals for another reduction.
And the acid/base method where the oil falls out isn't that a lot easier since you then know exactely how much amphetamine freebase you have...

IndoleAmine · Dreamreader Deluxe

The losses when boiling occurs during basification are due to steam distillation of some product - not due to decomposition!

For the ratios of Al and solvent/GAA, check the posts at the very beginning of this thread.

For steam distilling, a normal distillation setup is used, all amine vapors are condensed together with the water - no losses.

Just don't let it boil during basification, or else steam distillation will occur directly (at a vapor temp of below 100°C).

When you steam distill, you have the same situation like after acid/base extraction: amine sitting on top of aequous layer as oily drops/layer.

And if you add some HCl to this solution with amine on top, you can proceed directly to a/b (wash with solvent, basify, extract) and evaporate the solvent, either by wasting it to your room atmosphere or by distillation which is technically the same thing, and what you are left with is what you can measure out and calculate the molar amount of amine from its weight.

What do you mean with "And the acid/base method where the oil falls out isn't that a lot easier since you then know exactely how much amphetamine freebase you have..."? Question

icecool · Insistent Chemist

Well with the acid base method the oil is seperated from the water because it floats on top so when you don't disill off the rest you can also pour that into a seperatory funnel and then get rid of the crap and then you can weigh it.
And I know that the ratio's are in the beginning of this thread but that is for another chemical then P2NP so I was wondering if the ratio stays the same.
1,5g Al foil for 1,12g P2NP?
And when using bigger amounts should you also use more GAA or can the same be used since you use quite a lot of it.

icecool · Insistent Chemist

Okay now SWIM will be not so selfish as before and he will now try to not do everything too quick so that's why he is also first going to ask if this is correct what he is going to do insted of changing that factor the next time.

As follows:
5g P2NP will be reduced to amphetamine sulfate eventually.
5g Al foil will be grounded in the mixer to make nuggets and then add 200ml MeOH (is this too much or too less or good?).
Then 50mg HgCl2 will be added to this which is dissolved in a bit of water.
After approx 10minutes 5g P2NP will be added at once which is dissolved in 20ml GAA and 40ml IPA.
Then the reaction is left as long as it needs for all (or the most) aluminium to dissolve.
After that SWIM doesn't know what to do anymore he wants to try the steam distillation should he do that now? or first basify or do that after steam distillation.
What he will do further is steam distill it and if he gets it correctly then he will distill off the alcohol and together with the alcohol and water the amine will come over and float on top of the water.
Now basifies it with NaOH and he won't let it get over 60*C.
Then he will extract it with DCM or ether and combine the extracts and then add brine to it and then dry the extracts with anhydrous MgSO4.
Then he will distill of the solvents.

Could someone explain more (indole?) about steam distillation what is the advantage, since you still need to evaporate off the solvents after all.
And when exactely do you start the steam distillation, do you first distill over the alcohol and then the very little water that is in the reaction with the amine? or after basifying then there is more water of which the NaOH was dissolved in but then still isn't there pure amphetamine freebase oil floating on top of the water?
And can it then directly be reacted with H2SO4 in anhydrous IPA?

Okay SWIM couldn't wait since SWIM was quite sure about hisself this time.
So SWIM started doing a lab journal this time and writing down everything he noticed and used etc.
Now the reaction is done there is almost no aluminium sludge at the bottom and the extracts are very clean veeeeeeeeeery light yellow mostly transparant.
Insted of dark red

anyway now I'm laughing because of it but well...it still has to be washed with brine and then dried for 12 hours on MgSO4 and then tomorrow SWIM will distill of the solvents and get the temperature up to 120*C to make sure that there are not solvents left anymore.
then weigh it and dissolve it in 4x it's volume of MeOH (can ether also be used?), and then take that total volume and add to that the half molarity of what the amphetamine freebase is.
So for the people who don't know what SWIM means if SWIM has 5g freebase oil, that would represent (this isn't true!) 4 mols of amphetamine freebase then SWIM would calculate how many grams 2 mols of H2SO4 is and then dissolve that in the same volume as what the total volume of the MeOH+amph freebase oil is.
One weird thing, SWIM got MeOH from a supermarket and he just added MgSO4 to it which is anhydrous and it doesn't make clumps with the water in the MeOH Confused

Is this anhydrous methanol that they sell there :S I thought there would be at least a little bit of water in there but it just floats around (the MgSO4) it "snows".