Author Topic: methylamine synthesized ala Bright Star´s:it´s good enough?  (Read 1849 times)

akcom

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #20 on: October 30, 2010, 01:18:42 PM »
Just to be safe you could always put a drying tube over your flask/vessel

coincoin

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #21 on: December 28, 2010, 05:48:44 PM »
what about a simple quick sigh yielding and otc method... like chloromoethane (methanol + nacl  h2so4) bubbled in warm nh3 ?

Sedit

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #22 on: December 29, 2010, 06:39:45 AM »
Whats your definition of high yeilding? Trying to get MeCl from that method is not that simple or high yeilding and to top that off as the ammonia concentration goes down it starts to form Di and Tri methylamines meaning that atlest a 10-20x molar concentration of Amine must be kept at all times to ensure alternative products from your 5-20% yeild of Chloromethane from the first part of the synthesis.

Sorry But I have seen this proposed many times and I doubt it can be pulled off with any usefullness. Im positive there are simpler ways.
There once were some bees and you took all there stuff!
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jon

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #23 on: December 29, 2010, 06:56:25 AM »
i dunno how many times i have to go over this methylamine is about temp being exactly 106C i used saturated salt baths(boil exactly that temp) to make mountains of methylamine and slight vacum i get no ammonium chloride back it's easy for me i don't understand why is this so complicated?
i probably made at least 50 batches wigging my ass off it was so easy.
« Last Edit: December 29, 2010, 06:58:06 AM by jon »

coincoin

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #24 on: January 02, 2011, 01:43:35 PM »
Same thing... I get chloromethane in high yields (MeCl being taken off the solution the equilibrium goes to the right...) and then again high yields of MeNH2. I'd say it contains around 5% DiMeNH2 but can be easily purified with solvent extraction

jon

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #25 on: January 02, 2011, 10:04:23 PM »
you get zero dimethylamine if the temperature is kept exactly at 106 C the sweet spot taking co2 off under a slight (i mean very slight) vacum improves yeilds considerably.
this way i noticed no ammonium chloride precipitated.
saturated solutions of salt water boil exactly at this temp making this a breeze to do.
i used to bung 32 oz beer bottles to aspirators flowing at a trickle in a pot of boiling salt water with the lid on it to keep the temp right and prevent the solution from evapotating.
you gauge your vacum by looking at the co2 evolvolution.
if the vacum is right it will evolve from the top if it is too high it will foam over if it is too low the co2 evolves from the bottom.
this works every time.

Sedit

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #26 on: January 03, 2011, 03:29:18 AM »
Coin care to do a writeup with pictures and a melting point test if you are able. I have seen many others suggest otherwise on MeCl being anything but high yeilding (<30%)and thats even with a catalyst like Zinc Chloride avalible.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

overunity33

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #27 on: January 03, 2011, 01:02:26 PM »
you get zero dimethylamine if the temperature is kept exactly at 106 C the sweet spot taking co2 off under a slight (i mean very slight) vacum improves yeilds considerably.
this way i noticed no ammonium chloride precipitated.
saturated solutions of salt water boil exactly at this temp making this a breeze to do.
i used to bung 32 oz beer bottles to aspirators flowing at a trickle in a pot of boiling salt water with the lid on it to keep the temp right and prevent the solution from evapotating.
you gauge your vacum by looking at the co2 evolvolution.
if the vacum is right it will evolve from the top if it is too high it will foam over if it is too low the co2 evolves from the bottom.
this works every time.



beautiful level of detail, very nice jon.

Balkan Bonehead

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #28 on: January 08, 2011, 06:17:57 AM »
The following is an alteration of Eleusis' variant of the ethanol method. Into a 2:1 molar ratio mixture of formlin:NH4Cl in a suitable open vessel is added ethanol dropwise or in portions under stirring at room temperature or slightly warmed, until the rumlike odor of ethyl formate can no longer be detected. Then, the mixture is heated to drive off water and worked up as per usual.

akcom

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #29 on: January 08, 2011, 07:04:18 AM »
It's important to reflux the mixture for an hour after the ethyl formate is distilled off or else yields will be abysmal.

Balkan Bonehead

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #30 on: January 08, 2011, 08:38:19 AM »
As Eleusis and Android have demonstrated, that isn't necessarily the case. See this writeup:

Quote
Methylamine Hydrochloride from HMTA, Eleusis' version [with comments by Rhodium]{with SWIM's comments in white)

140g of Hexamine is carefully dissolved in 400mL of Muriatic Acid(swimming pool) (31.45% HCl) to which at least 100mL of (preferably) absolute ethanol(SWIM used denatured) has been added. Add the hexamine slowly while stirring vigorously and with good ventilation as some nasty fumes are produced. Allow all to stir at room temperature for at least 8 hours but preferably 16(SWIM would leave it under the overhead stirrer for 16hrs). The solution will become turbid within several hours of the initial mixing. I *believe* this is the formation of a formaldehyde(ammonium chloride) trimer of some sort and I suspect that the original equation for the conversion of hexamine into methylamine fragments is therefore incorrect. [There is no trimer of any sort formed, if enough water and formaldehyde is present. Eleusis uses 4 moles of amine to 6 methylenes, which is enough, but gives less yield.] At any rate, filter off this white precipitate which is obviously not an amine salt due to it being fluffy even in Florida's humidity (almost all simple amine salts are hygroscopic) [With the exception of ammonium chloride, and this is it]. Finally, remove the excess water, hydrochloric acid and freako volatile products by, ideally, heating the liquid at low to medium heat in a porcelain saucepan(Visionware pot). Stove-proof glass would be ideal, but stainless-steel, aluminum and copper are definitely not! [Rather use a RB flask, with a water aspirator attached, smells considerably less]. The concentration can generally be left unattended for a couple of hours, but try to stick around and babysit it at least the first time so you will have a good idea of how long it takes for your particular stove/pots/etc... [Or else it'll BURN!] Also, the methylamine HCl will form a melt if heated too long at which point it will sublimate off. It will then appear as if it's taking forever for the stuff to concentrate when in fact you are merely boiling your product away. After the concentrated slush has become sufficiently "thick", take it off the heat every so often to see if it doesn't soldify, insuring that the water is mostly gone and that not too much sublimation has occured (some is inevitable and even desireable). The yield of Methylamine HCl should be around 200g as white deliquescent crystals(beautiful, closer to 100g after all is said and done). Note, ACS-grade methylamine HCl is colorless. We aren't using ACS-grade production techniques here, so don't expect ACS-grade product. However, the methylamine produced by this method is eminently suitable for the many purposes normally intended and if allowed to sublimate some when heating, no adjustment for "purity" or "water content" need be made in subsequent uses of it. [I can't understand how he can get 200g of product. 140g hexamine gives 80 grams of NH4Cl, and HOPEFULLY more than 100g of methylamine]. If the crystals are opaque white and do not deliquesce quickly in air of average humidity (65% rh), they may be contaminated with some Hexamine or some bizarre polymer. [Or ammonium chloride. Recrystallize from methanol, then wash with CHCl3]. Washing 100g of the crude product with 100mL of Chloroform by stirring in a beaker then filtering, repeated as many times as necessary, will remove Hexamine. Methylamine HCl is insoluble in Chloroform whereas Hexamine is at the rate of 1g to 10mL. As a final note, I have been informed that hexamine is available in some areas in the form of "fuel tablets" for small camping stoves. I have received mixed results from various individuals using this so, as the saying goes, Caveat Emptor.(the fuel tablets are the bomb, if still available, and the faintest smell of ammonium chloride is always present but SWIM never cleaned it with chloroform and product still produced so...)
There's also a good read by Osmium making methylamine this way that is quite helpful. I'll see if I can find it(or it may already be in that write-up..read that..it was written during those times and is much more concise with the play by play tricks and what-nots..

However, this is not an optimal reaction, because AmCl is present in excess and some ethanol evaporates. The version above means to correct this. A dash of HCl might help things along by catalyzing the esterification.

akcom

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #31 on: January 11, 2011, 08:09:53 PM »
Everlasting, if one is using straight hexamine, is it important to stir for 8 hours like Eleusis recommends or can one simply combine hexamine, HCl, ethanol, stir and distill off volatiles then proceed to distill off the water?  How slow should the process be?

salat

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #32 on: April 24, 2011, 08:43:26 PM »
xBee has done a slew of methylamine synth's and I got permission to post his notes.  The best one we've found using hexamine is baalchemist's fav synth.  And the tip of using boiling dry IPA to extract the methylamine works great.

So the following is from an old hive post by baalchemist, with notes and updates by xbee from many trials.

Baalchemist Favorite Methylamine Synth (with Notes by xBee)

Bill of materials
  • HCl (28%), 480ml/mol of HMTA
  • HMTA, 140g/mol
  • Isopropanol, 1180ml/mol HMTA

SPECIFIC BOM EXAMPLE – 4 MOL BATCH
  • HMTA: 560g
  • HCl (28%), 1920ml (make it an even two litres)
  • Isopropanol: 5920ml (call it 6 litres – 1210 followed by 3x770 + 6x400)

Example of procedure
[NOTE: ½ mol batch size]:

A RB flask is charged with 240ml of 28% HCl and a stir bar.  Stirring is begun, 70g hexamine (“Fuel Tablets”) is added to the flask, and the glassware is set up for a vacuum reflux.  Vacuum is applied (c.a. 20-22” Hg) and the flask is heated, but only to a gentle reflux [stirring continues].  The reflux is maintained for about 3 hrs, then the glassware is changed for vacuum distillation and the solution volume gradually reduced over several hours’ time.

Volume reduction continues until only a “mush” [slush] remains in the flask [no fluid sloshing around!].  The “mush” [slush] is made of methylamine HCl, Ammonium chloride, and what’s left of the water.

Working quickly so as not to allow the IPA time to cool, the mush is extracted with 4 110ml portions of DRY IPA.  For each extraction, the IPA is dumped into the mush, the flask is swirled to dissolve as much MeAm as possible before the IPA cools very much [perhaps a short time refluxing would be a better approach – eliminates rushing], then the IPA is decanted from the mush and the next 110ml added.  

The four extractions are pooled and the IPA removed under diminished pressure until, again, only a yellowish mush remains.  This “new” mush is in turn extracted six times with 50ml portions of DRY IPA, working quickly and decanting as one did earlier.  The six extractions are again pooled and, as the IPA cools, crystals will/should spontaneously form.  [NOTE: six extractions are nuts – suggest 100, 100, 50, 50 instead of 6x50ml]  The pooled extracts are placed in a freezer for about an hour to further encourage the MeAm to crash out.

Once crystallization is complete, the cold solution is vacuum filtered to isolate the crystals, which should represent about an 80-95% yield.  The crystals must quickly be stored in an airtight container as MeAm is hygroscopic.

Points to note

  • Ammonium chloride begins crashing out somewhere along the way [depends on vacuum] and it will eventually stall the stirbar.  One can/should remove the NH4Cl when the stirbar stalls; the subsequent extractions are then much easier.
  • A 4 mol batch is the most one can squeeze into a 3 litre flask.
  • Refluxing instead of adding boiling IPA seems to greatly accelerate MeAm extraction.  Consequence is that 3rd and 4th first-level extracts seem to be primarily ammonium chloride (soln is also cloudy as well rather than clear like the first two).  Although it is also possible that the two litres had some water in them even tho they should not have.
  • Three hours reflux is NOT enough – more like 5 to 6 hrs needed.
  • One MUST add the HMTA to the acid, not the other way round.  Especially, don’t dissolve the HMTA first in water – yields REALLY suck.

Salat (and xBee)
« Last Edit: April 24, 2011, 08:49:38 PM by salat »
Salat

xxxxx

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #33 on: April 24, 2011, 09:57:55 PM »
Thanks alot for those notes Salat and xBee! I'll try give this a go over the next week and report back with a few photos of how it goes!

akcom

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #34 on: April 25, 2011, 02:15:51 AM »
This looks a hell of a lot easier although I've yet to put it into practice:
Quote
100g hexamine (pulverized fuel tablets) and 30g nh4cl were added to a 1L rbf, followed by 120g den. etoh, followed by 330g 31.45% hcl.  This mixture was stirred vigorously and heat was evolved.  Gradual heating was applied with an oil bath (took three hours to reach >60c).  Two layers formed and distillate was collected between 34c and 60c with the majority of it around 55c.  Once no more distillate came over in that range, the heat was turned up and the remaining alcohol was distilled out. The flask was then cooled to room temperature and the solids were filtered.  The water in the remaining mixture was then quickly distilled away with an oil bath of ~150c.  The isolated methylamine was recystallized with anhydrous ipa to yield ~120g meam.hcl.

jon

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #35 on: April 25, 2011, 02:34:23 AM »
hexamine works really good.
just do this mix those prortions up in  a 30 oz beer bottle. bung it to a water aspirator and pull the slightest vacum until you see all the co2 bubbling off the top.
dunk it in saturated boiling salt water (hits the exact temp) cover the pot to prevent evapotartion of the water.
and reflux like that for 6 hours until the fish smell appears.
then take it off under a aspirator vacum un til you see crystals set the bottle next to a fan let it aircool then filter out all the ammonium chloride.
then take off more until you see a scum set it by the fan and filter the methylamine always let it cool or you be filtering endlessly.
that's about as easy as you can get.
no need to overcomplicate shit.
in this way you can do large batches and get good conversion rates it gets very pure because the temperature is spot on and the slight vacum gives quatitative yeilds of formalin coversions.
because its pure it isnt hygroscopic as much and easier to purify

beanhead

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #36 on: April 25, 2011, 09:30:42 PM »
Hexamine, hcl and reflux does in fact work fine...

Otherwise caffeine in a concentrated lye solution and distill off methylamine. 100gr caffeine has about ~15g methylamine yield.

If you do the reaction in anhydrous ethylene glycol (antifreeze) you can distil off dry methylamine gas.

akcom

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #37 on: April 25, 2011, 10:29:41 PM »
I guess I just really like to avoid vacuum refluxing if at all possible. Hopefully I'll have some results to share on the above procedure after exams are over

jon

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #38 on: April 25, 2011, 11:01:27 PM »
so why ask for advice?
if you know better no need to ask us.

akcom

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Re: methylamine synthesized ala Bright Star´s:it´s good enough?
« Reply #39 on: April 26, 2011, 12:49:41 AM »
I definitely don't know better, infact it sounds like you've got this thing down to a T. I was just hoping someone would have some personal experience doing these reactions without vacuum reflux.  In fact, I'm wondering now why people don't do it this way?  Anyway, like I said, hopefully I'll have some time to tinker soon.
« Last Edit: April 26, 2011, 12:54:54 AM by akcom »