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Author: Subject: Old methylamine synth request
FriendlyFinger
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[*] posted on 13-1-2006 at 18:08
Old methylamine synth request


Hi there,

I'm looking for details of am old methylamine synth that I saw once on the hive.

It claimed 1.2Kg MeNH2.HCl from 800g hexamine + H20 + HCl + 100g formaldehyde (paraformaldehyde or formalin?) with more water, refluxed at 104 deg C.

I find that yield hard to believe. An extra bit of formaldehyde, so what, how can that make any significant difference? Swim's yield without extra formaldehyde, or any added water besides the 23%HCl and refluxing 12 hrs @104 deg C was about 50%.

So what's the deal?
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joe_aldehyde
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[*] posted on 15-1-2006 at 23:27


Quote:


So what's the deal?


the deal is: hexamine is being cleaved into formaldehyde and ammonia, additional formaldehyde reacts with the ammonia which would usually be present as ammonium chloride to form methylamine.
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oneup
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[*] posted on 17-1-2006 at 09:51


would it be possible to turn methylamine into hexamine?
How can I do this?
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FriendlyFinger
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[*] posted on 18-1-2006 at 19:00


Can you really get 1.2kg from 800g hex simply from reflux at 104 - 105 deg C? or is it just bullshit?

[Edited on 19-1-2006 by FriendlyFinger]
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[*] posted on 20-1-2006 at 02:12


You're thinking of a post from Baal (baalchemist) where Jasium actually proposed those amounts and yields. Baal's post:
Quote:
Baals favorite Methylamine synth...

Since Baal has had so many recent inquiries lately on this subject, he would like to share a personal favorite. Back a few years ago when Baal Sumerian were still hangin, we made our MeAm as follows;
70g-Hexamine(fuel tablets) was added to 240ml-28%Hcl with magnetic stirring in a Vac-Reflux setup. Approx. 20"-22"Hg of Vac was applied and temp was raised to start it refluxing slowly. This was allowed to reflux for ~3hrs, then was rigged for vac distillation and the volume was reduced slowly over a few hours time. Continue til there is
a crystalline "mush" in the flask. This is your crude MeAm w/some impurities. 4-110ml 99%IPA boiling hot, portions were added to the mush, these were quickly swirled and decanted. The pooled extracts were then reduced in volume by vac. distillation til the flask contained a yellowish crystalline mush. The mush was then extracted with 6 50ml-99%IPA boiling hot portions, all were pooled together. As
alcohol extracts began to cool, large 5 sided crystals began to precipitate. This was then covered and placed in the freezer for 1 hour to finish crystallizing. Crystals were vac filtered, yield is typically 80-95% when done right. Extracting with hot IPA takes the place of washing with multiple solvents to purify the MeAm. This version keeps the obnoxious smells to a minimum, and the B.P.(refluxtemp) will easily stay below the 104c mark, thus reducing chances of add'l side reactions.

And Jasium's addition
Quote:
Re: Baals favorite Methylamine synth...

haven't done it exactly that way, but,using 800g of hex and throw another 100g of formaldehyde in the mix with h20 and hcl, do reg reflux a 104c, and cool and filter, then do vaccum reflux the rest of the way. yields were 1kg of meamhcl after alcohol (ipa) rextalization. bee sure to keep the reflux temp at 104c to insure no di or tri meam hcl
hope this helps
j


I can't comment on the reported yeilds directly. Chromic had this to say:
Quote:
MeAmCl from hex/HCl Bookmark

I don't believe that yields better than 50% (post-recrystallization) of pure scent-free flaky beautiful white snowflake-like crystals of methylamine hydrochloride can be acheived with this method or with the (para)formaldehyde/ammonium chloride method.

I'm very skeptical of anyone who claims otherwise. Notice how baalchemist never answered MaDMAx's question about the yields. 70g of hexamine (0.50mol) reacted with 200ml of 31.45% HCl (232g 31.45% HCl(aq), 72.96g HCl(g) ie 2.00mol of HCl) should in theory yield 101.1g of methylammonium chloride (ie 1.5mol of methylammonium chloride). So a 90% yield or whatever baal claims would be like 90g. I have SEVERE reservations on the validity of that yield. I'd be lucky to get 50g from that run (ie 50% yield).

I really should post that write-up...


BTW, Chromic did post his alternate writeup (with ~50% yeilds) in another thread. I can post that as well if you're interested.
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[*] posted on 31-1-2006 at 01:01


Yeh, I've read all of these before and actually I don't believe that "Jasium" did the synth himself unless he had a different user name on the hive because what he wrote was almost a direct copy of another post some time before that one. I think it was by "Icepick", I have it at home.

So can anyone say; NO! it's bulshit!!
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Baalchemist
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[*] posted on 3-3-2006 at 00:42


"I'm very skeptical of anyone who claims otherwise. Notice how baalchemist never answered MaDMAx's question about the yields. "

I believe I did answer his questions about yields, just because it did'nt fit 'your' criteria doesnt mean a thing. I never posted anything but truth, I stood nothing to gain by lying. My integrity is far superior to the majority that is why I had VIP status at the Hive and you did'nt. I had far too little time on my hands to 'reply' to the immense numbers of questions and PM's that accumulated for me at the Hive. Unlike some, I had a real life to attend to.




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[*] posted on 4-3-2006 at 03:21


Best results came from either the hexamine -> methylamine.HCl synthesis a la Baalchemist, say with vacuum applied (albeit such high yields as told were never reached)
and from the old Eleusis synthesis with addition of EtOH (hexamine/HCl/EtOH).

/ORG




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[*] posted on 23-3-2006 at 04:03


Now you got me TOTALLY confused:

Mr. Cool (in the MAN synth) says just mix hexa and muriatic and boil it down, claiming 96% yield. Doing it this way got me zero yield. I suspect the crystals were NH4Cl, as it was not hygroscopic, and did not melt easily, neither did it burn or char on further heating. Adding NaOH gave pure ammonia smell.

My guess: Instead of C6H12N4 + 4 HCl + 4 H2O --> 4 CH3NH2.HCl + 2 CO2
it went C6H12N4 + 4 HCl + 6 H2O --> 6 HCHO + 4 NH4Cl

Baal tells you to reflux. Fine so far.
Then Jason tells you to ADD (para)formaldehyde, to get more amine and avoid NH4Cl.
Eleusis tells you to let it sit, FILTER OUT the para that forms, THEN boil down.

Doing it ala Eleusis, this is what happened so far:

8g hexa, 8ml EtOH and 24ml 31.5% HCl gave 3.5g of (likely) paraformaldehyde precipitate overnight at RT. Half the filtrate on slow evap. gave 1.5g (when dry) of moist crystals that melted when driving the last water out. Boiling down the other half gave the same stuff. Is this now MeAmHCl? It lowers the mp of AN to 55C, just as MAN would. But with NaOH, I only smell ammonia again. Maybe my nose is wrong, as in not smelling the fish (I can't smell some things)?

I mean it's nice to know how to make para if I ever try the Bachmann, but what about the intended product? Why reflux at reduced pressure to keep at 104C instead of just heating? Add even more formaldehyde or remove some that forms?
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[*] posted on 25-3-2006 at 19:02


Baalchem was allways bosting his massive yields
before the hive went down i had been going there for atleast 6 to 7 years. I was there when he showed up
bosting his sick yields

I call BS

I dont know about hex for MeNH2 synth but i use
AmCl + 37% formaldehyde
2l of formaldehyde plus 1kg of Amcl IF done right (and I mean you watch the temp like a hawk,104 for 6 yours)

yields 850g of somewhat impure MeNH2
Onced washed with chloroform and recrystalized with abs EtOH then placed in a large Desicator under vac for a day or 2
I get 700g of pure white and DRY methylamine HCl.
Any Questions welcome. This is no joke and it took me at least 3 runs at that size and some inovation to get that yield.
I can see hex working that well.

Oh yeah and there is NO lost almost because the limiting reagent is the formaldehyde so the first precipitations are AmCl which are recuperated and used in future batches.

just my 2 cents
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[*] posted on 29-3-2006 at 03:58


Found out Eleusis was wrong here. In a text by Rhodium (from the Rhodiummirror on designerdrugs.com) it was cleared up. The precipitate is not paraformaldehyde but either AmCl or methylal (trimer of metylenimine) with too little water.

BTW the test above DID yield some MeNH2HCl, reacting with HNO3 (driving out the HCl) gave what MUST have been ~1g MAN (burns energetically after melting on Al foil, like HND).

I tried another run, using 28g (0.2 mol) hexamin, 100ml 31.5% HCl and 60ml water (to replace 80ml conc acid and water each). Boilled at reflux for 3 hours, temp rising from 102 to 113C (in the bath, not the reaction). Stopped when no more bubbles of CO2 were formed (easy to see if its gas or just boiling).

Boiling down in an oil bath, re-Xed from IPA, gave less than 9g yield and a butload of AmCl!

Some questions: NO loss? What about the boiled-away CH2O, methylal, CO2 from formic acid, methyl formate if the formaline was stabilized with MeOH ...
Is IPA ok instead of EtOH? Is 94% EtOH ok instead of anhydr. ?
Can you boil under reflux, then boil down, instead of distilling from the start? Do you NEED vacuum to boil it down?
Is there a difference in the smell of mono(!)methylamine and ammonia? I cant seem to smell it (I mean the difference :P )!
In short: how did you do it, other than what you already said, with vacuum pump or the stinky way?


On a side note, since hexa will be more or less completely hydrolized by the HCl, the yield should be the same per mol of N, if (!) enough CH2O is present (which it will be, hexa + 4 HCl --> 4 AmCl + 6 CH2O).

P.S. I bet what Mr Cool (or was that Aleng? The one that used lead nitrate) made was 80% AN instead of pure (M)MAN! He must have boiled most of the formaldehyde off before it could react...
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[*] posted on 23-4-2006 at 00:55


As quoted by Madchem "Baalchem was allways bosting his massive yields
before the hive went down i had been going there for atleast 6 to 7 years. I was there when he showed up bosting his sick yields"

I can tell you myself now that you are full of shit because I did not post the MeAm synth originally, it was posted by Sumerian. It was posted at a time when the Hive was'nt even 2 years old yet. So as you post this bullshit, how is it that you were there 6-7 years when that post wasnt even by whom you claim it was and far earlier than you claim? You are an embicile in its truest glory, another wannabee with a big sack of bullshit to mesmerize his minions......I was a VIP at the Hive and I dont recall you being invited to the VIP forum, ever. It was reserved only for those who werent full of shit......All my input at the Hive was all legit and if you can't handle it, then too fuckin bad. Once again, another big pussy, dickless wonder hiding behind the anonymity of cyberspace, talking shit.




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