Amphetamine Sulfate

icecool · Insistent Chemist

Okay well the acetone fucked the crystalization up yesterday since there was probably water present.
The crystal cake was shrinking when drying and the remaining liquid was subjected to an acid/base extraction.
But there remained crystals in the mixture, and they made a gel when HCl was added.
Probably too concentrated HCl was added and the amine was destroyed or something went wrong since at the end there wasn't any oil anymore.
And the ehter extract while the amine was dissolved as a salt was yellow/orange.
Normally that is the amine but now it should be the crap in there.
But well next time SWIM will take more care and start with more pure P2NP and not so old P2NP I guess that makes bad yields too when the P2NP has aged for a week or 2 weeks at room temperature.

hAzzBEEn · Fri May 13, 2005 12:01 am

If you are worried about your P2NP degrading over time, you could try storing it in a sealed container in the freezer or deep freezer. Once upon a time I read the Large Scale Methedrine Synth by "Louis Freeh" posted on Rhodiums website and it recommended storing P2NP in the freezer. It even went on to say that P2NP keeps for long periods of time (years??) in the freezer. The file isn't available in the Synthetikal - Rhodium archive, but if you look through the list it is the one that says "zipped word document" next to it. It was referred to in this post on the hive:

http://12.162.180.114:90/synthetika/hiveboard/crystal/000388453.html

I know the later versions of Rhodiums site (archive on my hard drive at home) had this article as an HTML file.
It has a nice writeup (with pictures) about doing a 20+ mole synth of P2NP for someone with big dreams.
If you want, ICECOOL, I will try to dig it up for you.
I thought you might appreciate it, as I followed SWII's success with PNP via n-butylamine condensation in this thread:

https://www.synthetikal.com/synthforum/about492.html

BTW... Good work!!

icecool · Insistent Chemist

Yeah I would really appreciate it.
I don't know how fast it degrades.
But well next experiments will be done on smaller scale like 5-10g P2NP reductions.
And with much more care etc so a much higher yield will be achieved.
Now a lot of factors could be the problem and I need to eleminate those factors which can be easily avoided.
- Use more Al now I used for 5g P2NP 5g Al foil next time I'll use 7,5g Al.
- Use clean P2NP it might reduce yield a lot when it is dirty?
- Stirr better
- ?

hAzzBEEn · Fri May 13, 2005 6:22 pm

About the storage of nitropropene crystals, here is the quote from the "Louis Freeh" Large Scale Methedrine Synthesis from Rhodium's page:

IndoleAmine · Dreamreader Deluxe

This isn't the nitropropene degradation thread, guys! Very Happy

(you know where to discuss this..)

HCl cannot be used here, since the product HCl salt would be very hygroscopic and nearly impossible to make even with anyhdrous HCl unless the freebase is distilled several times (it forms a liquid hydrated HCl salt variation, and you end up with a puddle instead a pile of powder if using a nonplar, or nothing when using alcoholic solvent/acetone..)

The solution: use H2SO4 99% and make the sulfate; and soak up the tiny one percent H2O with anhydrous acetone..

IndoleAmine · Dreamreader Deluxe

For better yield:

- Use cleaner starting materials, especially nitropropene

- stir vigorously, to ensure that the Al is distributed evenly in the liquid reaction mxture

- use more solvent, especially more acetic

- add the Al in preamalgamated, small portions

- alternatively, add the nitropropene in portions

- let run longer while heating to slight reflux, until the color is a very light grey (not dark blueish/grey!)

Whatever you do, keep in mind that the evolving hydrogen has to do its work; so if you let things become too vigorous all hydrogen will simply bubble away and you will see just alot of foam on top for several minutes, then the reaction is over - and not much has been reduced. Better let it run as slow/cold as necesary to ensure even hydrogen uptake during all the time.

i_a

Sandmeyer · Fri May 13, 2005 8:23 pm

icecool · Insistent Chemist

When there is foam it doesn't really matter if the bubbles are big or small most of the time they are big.
and will be evolved at the top of the reaction mixture and thus not getting suspended threw the liquid thus not reducing the nitropropene.
Anyway when using dirty P2NP will you actually get a bad yield or just dirty amphetamine?
Is it possible to dry H2SO4 in an exiscator with MgSO4 in it?
Or how should you dry it?
Next time SWIM will use 1,5 times as much Al as P2NP to make sure there is enough Al and will use super pure P2NP which has been recrystalised several times.
Also use a head stirrer which stirrs vigourisly.
And also not make much P2NP anymore since SWIM can't use it up all at once anyway.
And for SWIM acetic acid is quite hard to get, so is there also another acid which can be used insted of GAA?
HCl for example, or would that be too strong with too much water?
Or 37% H2SO4 or another concentration?
Now SWIM uses 33ml GAA and 66ml EtOH and 20g P2NP when making the solution.
Any comments on that ratio?

icecool · Insistent Chemist

When there is foam it doesn't really matter if the bubbles are big or small most of the time they are big.
and will be evolved at the top of the reaction mixture and thus not getting suspended threw the liquid thus not reducing the nitropropene.
Anyway when using dirty P2NP will you actually get a bad yield or just dirty amphetamine?
Is it possible to dry H2SO4 in an exiscator with MgSO4 in it?
Or how should you dry it?
Next time SWIM will use 1,5 times as much Al as P2NP to make sure there is enough Al and will use super pure P2NP which has been recrystalised several times.
Also use a head stirrer which stirrs vigourisly.
And also not make much P2NP anymore since SWIM can't use it up all at once anyway.
And for SWIM acetic acid is quite hard to get, so is there also another acid which can be used insted of GAA?
HCl for example, or would that be too strong with too much water?
Or 37% H2SO4 or another concentration?
Now SWIM uses 33ml GAA and 66ml EtOH and 20g P2NP when making the solution.
Any comments on that ratio?

IndoleAmine · Dreamreader Deluxe

Icecool: You can also use aequous acetic acid, 60% concetration was found to work nicely. HCl is probably too strong, but sulfuric is of use in this context since you can concentrate acetic acid by forming sodium acetate from vinegar (25% acetic) and sodium hydroxide, which can be dried by heating and then be turned into Na2SO4 and GAA with addition of 98% sulfuric - then simply distill the GAA out, redistill, and ready...
(My advice: look around; there are lots of OTC sources for 60% acetic where you live, I guess Wink

)
For drying H2SO4/alcohol solutions, you could use Na2SO4 or MgSO4 - just make sure to filter off completely. But since it is for crystal formation, why not use 98% H2SO4, and later bind the water by adding lots of acetone? Easier and recommended for purity reasons anyway...

Sandmeyer: depends on what you do. Go figure.

Bumblebee · Tue May 17, 2005 6:12 am

i read everything i can about crystallizing my DOOphetamine sulfate, and tried a lot...

but i only got crystals of my product when i dissolved it in 4xamount of ether. From IPA no Precipitate could be isolated, from acetone the same... Crying or Very sad

May it be that the diethylether is the only thing i have that is almost waterfree??
In ether it snows funny to the bottom and can be filtered off, in for example my IPA it stays dissolved. when i neutralized with H2SO4 and the IPA is evaporated there are yellow brownish dirty chrytals....

And i didn´t understand correctly how to figure out how much H2SO4 is needed to make the sulfate.
for example i have there 5ml of freebase (0,913 g/ml) this is 4,56g Freebase
4,56g Freebase is 33,7mmol.

will i have to stir in 33,7mmol Sulfuric?

I read that it is a diaminesulfate. Does this mean the are 2mol of amine to 1 mole of H2SO4?

the calculation on the first side of this thread seemed to use the double molar amount of H2SO4 compared to the Freebase....
idid it with that calc and as i added just a fourth of the acid it was too much and the crystals dissolved again and it led to a ph of 2,4!

what is right??

java · Consumer

Here is what others have tried in solving the problem......java

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abc123
(Stranger)
07-14-01 03:23
No 190479
sulfate salt? Bookmark

instead of gassing ...32%HCl can be dripped onto a product but the water will dissolve it and it will take forever for crystals to form
but is it possible to take a few drops of 96% H2SO4 and dilute with DCM and pour that directly onto your oil and make a sulfate...would this work?

b159510
(Hive Bee)
07-14-01 07:28
No 190494
Re: sulfate salt? Bookmark

I think that for sulfuric acid to fully dissociate, it
should be diluted w/ water to a max concentration of
~ 10%. Some sulfate salts of amines are soluble in DCM.

AMINATOR
(Stranger)
07-14-01 07:34
No 190496
Re: sulfate salt? Bookmark

I heard the best way to do that is to disolve your freebase in acetone and drip in your 95-99% sulphuric and the salt precipitates. the acetone and any water will form a solution but the acetone will still maintain a good solubility barrier especially scince there hardly any water in the acid. after you filter you product placing the tone in the freezer should get you any that did dissolve but it won't be much if any. happy cookin!

b159510
(Hive Bee)
07-14-01 08:58
No 190505
Re: sulfate salt? Bookmark

Has any bee used this acetone/conc.sulfuric acid method
to form the sulfate salt of an amine? I have not heard
of this, and it seems the reaction between acetone and
conc. sulfuric acid would be undesirable.

Rhodium
(Chief Bee)
07-14-01 16:13
No 190541
Re: sulfate salt? Bookmark

Yes, better use diethyl ether instead of acetone when doing this. The acid could catalyze imine formation between the amine and acetone.

https://www.rhodium.ws

Osmium
(Stoni's sexual toy)
07-15-01 01:27
No 190624
Re: sulfate salt? Bookmark

I don't like such "shortcuts" at all. When done correctly this even might be a good way to crystallize, but my experience tells me that most bees using this route will end up with an unstable dirty product. Same goes for that "add HCl to freebase and let evaporate" method. Bad chemistry IMHO.
What is wrong with gassing? Works every time. If your product doesn't crystallize then it's very impure and you obviously didn't do an A/B, in which case you deserve to end up with peanut butter anyway, for being too lazy to do this easy and highly efficient step.

AMINATOR
(Newbee)
07-15-01 02:21
No 190633
Re: sulfate salt? Bookmark

yeah, Ive always just gassed it myself, that method is from pugsleys pseudonitrsite text on rhodiums site...I assumed it was legit. gassing is easy. if you don't want to do a reaction. you can also just bubble air though it and dry the gas with calcium chloride or something...or maybe a reaction is better. Ive had good results with gas by this method but have never used a Nacl+H2so4 reaction yet.

Scooby_Doo
(Newbee)
07-15-01 15:07
No 190736
Re: sulfate salt? Bookmark

Sulfuric acid is insoluble in DCM. Making good crystals with H2SO4 is just as much work as gassing with HCl like Os hinted. However there was a post on the old board who crystalized MDA in ethanol using sulfuric acid which worked well. I can't remember if it was conic or diluted a little.

AMINATOR
(Newbee)
07-17-01 01:57
No 191035
Re: sulfate salt? Bookmark

I would probably dilute to at least half probly less. Just safer to judge dropwise. also I guess the product will decompose if excess acid is left on it.recystalisation from a miniumum amount of hot methanol is recomended after making the sulphate.put it in the freezer.

endo1
(Stranger)
06-18-02 07:13
No 322635
Sulfate w IPA
(Rated as: excellent) Bookmark

SW likes to turn MDA in to MDA sulfate when his batches are 1/2 kg+. SW has been diluting 99% H2SO4 w 99% IPA to make a 10% H2SO4 solution (No water). Not sure why boiling the H2SO4 solution or adding water was suggested earlier in this thread but he does not do that. He uses IPA (7x volume of base) w base disolved in it then SLOWLY adds dilute H2SO4 solution with lots of stirring. He watches PH with a hydroponic PH pen. He is very carefull not to go below 8. SW is not sure what exactly happens when filtered while PH is below 8 but he has heard some nasty rumors about product turning color/ turning to mush. Best thing to do if PH < 8 is to add more base so always hold back a bit of base. SW thinks that many other solvents could replace the IPA in the above procedure.

SW thinks that the sulfate anion is divalent so 1 sulfate anion attaches to two MDA molecules to make one molecule. That would mean MDA sulfate has a molecular weight of 454.5 and is twice as strong as 1 HCl salt molecule (weight = 215.6 Cool

. 1g of MDA base should make 1.2680017g of MDA sulfate(or 1.2034438g of MDA Hcl). If SW's above calculations are correct then a slight adjustment to dosage is in order if you were using the HCl salt before. For instance if you considered 1 dose of MDA HCl to be 80mg then 1 dose of the sulfate would be about 84.2mg.

SW's sulfate product seems to be whiter, friendlier to the nose, less hygroscopic and it seems to have much less smell than his HCl salt product. (Note: he does use hardware store toluene when he makea his HCl product.)

endo1
(Newbee)
07-19-02 21:53
No 334676
Uh oh, when using the above procedure SW has ... Bookmark

Uh oh, when using the above procedure SW has noticed only 80-90% of product recovered (SOME of the missing product IS recovered as base if 2x volume of water added to remaing solvent and another A/B is done). Could this be from the 1 or 2% water in the IPA or H2SO4? 99% lab grade IPA and 98% lab grade H2SO4 were used. He has also tried brining the Ph down to 7 while filtering lots through out the procedure(this seemed to get the best yield but still only <90%. Also a little more product does ppt going from Ph 8 to 7). After the first patty is filtered product DOES show signs of water present (sticks to filter paper and plugs it up, slow flowing solvent thru product etc.) SW also noted that 10 to 15% more H2SO4 was required to bring the PH to the desired level than was calculated by the mol math. (pure distilled MDA base was used) Is MDA sulfate a little bit soluble in IPA? Is H2O created during this method of crystalization? If not where does the H2 go? Can MgSO4 be used to dry IPA/Base and or IPA/H2SO4 before procedure is started? (and would this help?) Should he try using toly or ether instead of IPA?

Osmium
(Stoni's sexual toy)
07-19-02 23:23
No 334737
The reason is that you add H2SO4 until you reach ... Bookmark

The reason is that you add H2SO4 until you reach pH 8. That is clearly not enough H2SO4
I'm not fat just horizontally disproportionate.

endo1
(Newbee)
07-26-02 00:36
No 337081
Thanks O Bookmark

Thanks O but I did mention SW went to pH7 and didn't get much more pcpt. He did find his missing product after distilling the solvent away he was left with a significant mass of brown crud. A small sample of this brown crud disolved in IPA! A sample of his original filtrate (MDA-SO4) did not. SW thinks some MDA bisulfate compound was formed by acdident. bisulfate was reacted with naoh solution to give back base and product recrystalized via HCl. SW thinks he needs to add the H2SO4 solution way fucking slower. Any other hints on preventing the bisulfate from forming? cooling perhaps?

neuromodulator
(Hive Bee)
07-27-02 20:10
No 337766
Crystallization. Bookmark

There are 1001 ways to skin a cat. Also, it depends on the cat in question.

icecool · Insistent Chemist

Indole you sayd HCl would be too strong, but if you would use dilute HCl?
Or insted of distilling H2SO4 with sodiumacetate and all this work just use insted plain H2SO4.
That would be a lot quicker then distilling sodiumacetate etc.
And besides HCl costs per liter 1 euro and a little bottle of acetic acid 60% of 250ml costs like 6 euro or so.
And what is the purpose in this reaction of the acid, to make H+?

DrugPhreak · Working Bee

SWIDP was wondering about the amine/acetone/acid condensation. SWIDP guesses they will use anhydrous EtOH then. Confused

Bumblebee · Wed May 18, 2005 8:34 am

Thx a lot.
What I learned for sure is, that water is our major enemy in this stage of proceeding...

I will try it this way:
distill off the nonpolar....
and measure the remaining amine...
dissolve it in (virgin) IPA (6xvolume)....
than i add drying agent (MgSo4 will do i think)....

i will mix 1part 95-98% H2SO4 with 3parts IPA
add MgSO4 to this too and let stand both for at least 10 hours with occasionally swirling...

after drying i remove the MgSO4 via vacuum filtration from both...
stopper both flasks and set them in the freezer until they are colder than -5°C.

when everything is cold enough, i take that Amine/IPA mix and equip it with a Ph electrode (it should be possible to measure the ph with it in IPA...?!?or not?) and drip in H2SO4/IPA solution until PH is 8.
a lot of crystals should fall directly out!
after filtering them off with vacuum, i think it will be a good idea to concentrate the filtrate a bit via destillation, cool again and crystallize the remaining amine in solution.
this way there won´t remain 10-20% Freebase in the Alcohol. its more likely that you will get nearly 95%of the amine crystallized, due to the decreased amount of IPA in the end.

that was meant for plain amphy btw...
i wonder how the other amines are crystallised correctly (for example MDA/MDE/MDMA/MET*/2CB/). thats of interest too!
think in the case of MDMA or its related M*th it can be done simly by bubbling with dry HCl-gas in toluene...

in PIHKAL A. Shulgin uses some crystallisation techniques i don´t understand completely:

MDA: