Baals favorite Methylamine synth...

[baalchemist]

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.
GODISNOWHERE

[baalchemist]

The notes I transcribed that reaction from are from 4 years ago, and I didnt write down the actual gram count. If my memory serves me right, that creates 1M of MeAm. So it would be 80-95% of that amount. Most of the runs were
90%-95% in yields. I'm still hunting for some add'l notes that have some large scale details of the same reaction. Will be sure to post ASAP for those interested.
GODISNOWHERE

[sunlight]

Did you check the melting point, baal ?
I beleive to remeber that I asked it to you and your answer was afirmative and correct, but I'm not sure now.

[baalchemist]

You are correct Sunlight, I had a Chemist friend back then
analyze said product and M.P. was right on the money. 
GODISNOWHERE

[cilliersb]

Baal

I also use the NH4OH + Formaldehyde -> Hexamine
then Hexamine + HCl -> MeAM.HCL

Works very well for me, but I'm considering buying my Hexamine pure. Just stir at RT for like 16 hours after mixing Hexamine into HCl (muriatic) and then evap water. This works fine for me every time!! recryst from IPA may be an option, but acetone washes work fine too.

ps: surprize surprize baal, I may be an evil chemist, but at least I've figured out that GodIsEverywhere!!

[sunlight]

Cilliersb, that procedure was first published by Eleusis-Zwiterion (my best wishes for him), but I'm not sure it works so easy. Have checked mp or wathever to see if you have the good stuff and not a mixture of ammonium, methylamine and dimethylamine chloride ?

[sparks]

If my memory serves me right extraction and recrystalising from methanol worked just fine for me.

[zooligan]

MeOH works but IpOH works mucha betta.  Nearly makes it a pleasure.  Very little AmCl carries over with the IpOH, and the crystals that drop from the IpOH are *distinctly* different than the left-behind AmCl (in all the right ways).  I understand that larger alcohols perform even better...

Now, about that left-behind AmCl that's produced when using purchased hex... could you add some (para)formaldehyde to the pot of stirring hex/HCl and force the rxn towards more MeAm (by concurrent AmCl+formaldehyde rxn)

z
"And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"

[Rhodium]

zoo: Yes, that should work, but I believe it would be better if you collected the ammonium chloride from after the reaction, and saved that for another run with paraformaldehyde separately, rather than trying to do it all in one pot.

[HoneySuckle]

Seems to me the smelliest parts would be the initial vac-reflux and vac-distillations.  Did you (hypothetically ) run a tube from the end of the asperator all the way down the drain? (in hopes the smell goes with the water) If not, would this help to minimize those toxic aromas?

When you say "crude MeAm with some impurities" are those impurities NH2Cl and tablet binder mostly? Also, is it neccessary to crush up the tablets before refluxing? I imagine they'd disolve fine if you just threw in the individual chunks of tablets.

Sorry for all the elementary questions... it does say "newbee" by my name. thanks
-HoneySuckle

[Chromic]

IPA recrystallisations will remove the excess AmCl, DCM washes with remove the excess dimethylamine hydrochloride. A little AmCl in your Al/Hg isn't going to hurt anything, but excess dimethylamine hydrochloride will form inactive N,N-dimethyl-3,4-methylenedioxyamphetamine when you go to reduce.

[Jasium]

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
"fuck the media"

[baalchemist]

The "impurities" Baal mentioned would be AmmChloride specifically,no binders.  Baal ran the vac tubing thru a couple bubblers first and exhaust tubing was ran outside.

800g's of Hexamine could make alot more than 1kg if done under reduced pressure.

"GodisEverywhere">Hahahahahahahahaha, yeah right,I bet Jesus is right next to him, w/the tooth fairy & Santa leading the way.


GODISNOWHERE

[Jasium]

no crap?
swinj tried it with 300g of hex 1nce and only got 200g at reduced pressure at 65c maybe he fucked up, and diden't reduce the pressure enough(20hg here) or should let it reflux longer (8 hours instead of 6) and a lower stable temp of 55-60c would help. he used an aspirator here to get rid of fumes because his big boy vac diden't have an inline valve at the time. best he's seen with 800g hex was 1.1kgs. oh well back to the drawing board, to try her again!thanx
j
"fuck the media"

[Jasium]

oh by the way when you vaccum distilled the distillate came over at around 70-75c right. did you ever notice any higher yields by adding a little more formalin? swinj will try it your way next time and vac reflux for 3 hours before distillation. sumerian did know his meam! guess you do too.
wanting those quantitive yields!
j
"fuck the media"

[brownhornet]

baal tried your reflux method but failed?
vac refluxed 1kg hexamine (white and dry.made via 29% nh3oh and formaldehyde)  with 3300ml 31.45% muratic for 4 hrs and @ 20 mmhg, vac distilled to get a mush that turned out to be mostly ammonium chloride and a little methylamine.
dont like an extra step of ammonium chloride and formaldehyde to get the rest of methylamine.
how can i get close quantity yeilds like you in one step.
running same tonite but reflux longer from 4 to 8hrs at 20 mmhg.
will let you know but help me on this one bro
thnx bh

[terbium]

I favour the classic procedure where no vacuum is used and the temparatue in the pot is held at 104°C for 4-5 hr.

Post 209576 (missing)

(terbium: "Re: Methylamine; So many problems? Is it the Altitude", Newbee Forum)

[Argox]

What terbium said.

Hex plus HCl

works like a charm. 
best method.
Guaranteed.

Argox.
In the port of Amsterdam, there's a sailor who sings
Of the dreams that he brings...

[RoundBottom]

ok, so i decided to post after all, chromic, if only to give you some incentive  

chromic has a method that is simple, fairly high yielding, and uses a simple set of reagents.  it is basically a different and much simpler workup to the standard HCl and Hexamine method.

SWIM has done it, but not used the results, and it's long, but easy.

c'mon chromic, you can do it.
i learned a thing or two from charlie dontcha know.

[Chromic]

I really should run the MeAm synth again to get a better idea of the procedure, and take some pics before publishing it... RB, I blame it all on my laziness...

[brownhornet]

chromic very interested in a simpler workup procedure than than hcl/hexamine vac reflux method.  not working, getting more ammonium chloride than methylamine.
conditions; 20mmhg vac,  80-85c reaction temp, 6-8hrs total. vac distilled to get mush then extract with methanol.
would like your help since baals method has got me stirred. rhodiums site under methylamine synth also mentions "at least 95% yeilds under vac reflux and distillation".
thnx bro

[cheeseboy]

Jasium, so what you're saying is  that adding some formaldehyde to the mix will react with the the ammonium chloride to get even better yields and using the ammonium chloride instead of worrying about filtering it or having it as an impurity. And there is alot of ammonium chloride produced when using HCl to hydrolyse Hexamine. Brilliant jasium... jasium where are you? Oh ya, they took you away, always sorry to hear that.
May De Sorce Bee Wit Chu-Always

[Flinger]

[Chromic]

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...

[Chromic]

I should have mentioned that 3mol of MeAmCl should come from 1mol hexamine because each hexamine molecule becomes 6 formaldehyde and 4 ammonium chloride. 2 formaldehydes are needed for each molecule of methylamine (ie from 1 comes 6 comes 3... make sense?), and so there is excess ammonium chloride.

[Chromic]

Ok, brownhornet. Here's what I've done (short writeup):

70g hexamine, stir bar added to 250ml rb flask. 200ml of cold 31.45% HCl is added. The flask is setup for simple distillation. 100ml is *slowly* distilled off over about 12hrs (the slower the better). The flask is cooled, AmCl filtered off. The AmCl is washed with 50ml MeOH, the MeOH put back into the flask. The flask is then distilled until it starts to smoke (AmCl sublimating). Everything is allowed to cool. 125ml of MeOH is added. Refluxed for 5 min. The heat is turned off and it is cooled slowly and undisturbed to room temp. Then it's moved to the fridge. Then to the freezer. Then it's suction filtered with saran wrap to squeeze out all the liquid possible. Then the crystals are put in 60ml of acetone and filtered again. Then you can throw them into a vacuum dessicator if you've got it, or just spread them out on a surface at 70-90C. Normally yields about 45-50g. The yields aren't stellar but this is by far the easiest MeAm that gets you really good quality MeAmCl with not much work.

If anyone is unhappy about the quality of MeAmCl they are making, I invite you to try this. The purity is really good (esp compared to BS's method!).

[Organikum]

It is possible that ya have thy same problem as I had some time ago.

UNIT CONVERSION

Baal says 22" vacuum, what means 22inch Hg and may be about 540mm Hg (or Torr).
If ya got down to 20mm Hg this seems to be a bit low.....
By my interpretation only a little vacuum was applied to get rid of thy fumes and to lower the boiling temperature just below thy magic 104°C.

Maybee
ORGY
"I hope I'm becoming more eccentric. More room, you know.
 More room in the brain."

[RoundBottom]

chromic, if i could follow your writeup, then i'm sure most bees won't have a problem.  give both your and my writeups to rhodium, that should be enough info for all.
i learned a thing or two from charlie dontcha know.