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Author: Subject: Good way to Methylamine HCl?
Foss_Jeane
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[*] posted on 12-7-2009 at 23:04


Why not use the Hoffman Rearrangement to make the methylamine? It's easy, doesn't require anything exotic, and produces a clean product.

Acetamide should be easy to get, and certainly is easy to make via the ammoniolysis of either methyl or ethyl acetate. And these esters could be easily made via the Fisher esterification reaction.

You can use either NaOCl (best prepared fresh as opposed to using something like Chlorox) or Ca(OCl)2.

That would be my choice.
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[*] posted on 12-7-2009 at 23:59


Nice looking crystals Chaos, but that doesn't address the claim in the article posted by Polverone that ammonium methyl sulfate doesn't decompose to methylamine sulfate but rather to dimethylammoniuin hydrogen sulphate.

Personally I tried a hexamine/HCl route but only got ~5g of product :( and I'm out of hexamine, so I need to get some more... The reaction yielded a considerable amount of ammonium chloride but I don't have any formaldahyde or paraformaldahyde.

If Chaos proves methylamine can be made from ammonium methyl sulfate I will take that route, if not I may try Hofmann rearrangement as well as attempting to repeat my failed hexamine route with significantly lower temps.





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UnintentionalChaos
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[*] posted on 13-7-2009 at 00:16


Quote: Originally posted by Polverone  
Quote: Originally posted by Engager  
Quote: Originally posted by Vogelzang  
Ammonium methyl sulfate rearranges at high temperature to methylamine sulfate.


Is it possible to produce monoethylamine salt by means of rearrangement of ammonium ethyl sulfate? If so, what is temperature required for isomerization?


Unfortunately it is not possible according to this article.


Read it again. :P

ETHYLsulfate does not generate ethylammonium bisulfate upon heating. Instead, it pries an alpha hydrogen off the ethyl group and generates ethene. I suggested this as a possible clean way to make terminal alkenes earlier on. The typical route to sulfate half-esters is via chlorosulfuric acid, which is horrible, horrible unpleasant stuff and uses oleum in the synthesis. I will look more into this later.

[Edited on 7-13-09 by UnintentionalChaos]




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crazyboy
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[*] posted on 13-7-2009 at 00:29


Quote: Originally posted by UnintentionalChaos  

Read it again. :P
[Edited on 7-13-09 by UnintentionalChaos]


Oops ok then just one question the paper says "when ammonium methyl sulphate is heated it will dissociate with the production of methylamine and sulphuric acid"

Do you think you will be able to heat the ammonium methyl sulfate and bubble the resulting gas through HCl or will the methylamine gas instantly combine with the sulfuric acid leaving methlyamine sulfate which will need to be reacted with NaOH and then bubble through HCl to leave the hydrochloride salt?




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UnintentionalChaos
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[*] posted on 13-7-2009 at 00:48


No gas leaves the mixture except for a small amount of sideproduct ethene (yes, with methylsulfate) The mixture after cooling (mostly methylammonium bisulfate) should probably be dissolved in conc. aqueous NaOH, heated, and the gas bubbled into HCl. I haven't gotten that far yet.

I did test a small sample of the salt. I didn't bother to properly decompose it, but I melted it and held it that way for 12ish minutes. On cooling and addition of NaOH solution, I could smell the methylamine over the regular ammonia.

[Edited on 7-14-09 by UnintentionalChaos]




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[*] posted on 16-7-2009 at 19:11


Today I attempted to repeat the Ammonium methyl sulfate experiment using 100ml MeOH and 50.1 grams of Sulfamic acid.

The solvolysis reaction was pretty uneventful but it took quite a while without stirring leading to a medium reflux for 6 hours or so before all the sulfamic acid was consumed.

After it completed I decided to distill the remaining MeOH out which I did recovering 50ml of Methyl alcohol before very little would come over but no doubt trace amounts where left in the post reaction mixture. The distillation of the MeOH was a bit unusual as not once did the contents ever boil. Not even a bubble just a slow steady drip of MeOH out of the condenser.

After slow cooling I expected to see the pearlescent crystals that I seen before but instead the mixture stayed a liquid even 2 hours after turning the heat off. I decided to pick the flask up to see if any crystal formation has occured and instantly the whole of the liquid solidified into long pearly crystal mass that looked just like Sodium acetate "hot ice" experiments.

Now its just a matter of placing the flask on a hot plate and slowly raise the temperature to 220-230C for a little while until the isomerization is complete. The text stated that above 240C the production of ethylene became more appearent and that they only did 15 minute rearrangment test inorder to prove that heat played more of a factor then time in the isomerization so I want to heat it at a slightly lower temperature for a slightly longer period of time and see how that yeilds.





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UnintentionalChaos
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[*] posted on 16-7-2009 at 19:31


I ran one small sample at the full 275C for 15 minutes just to check. I had about 55% decomposition to ethylene based on weight loss during that time. It was still bubbling after that time, so it can't even be assumed that the other 45% isomerized. The decomposition is by no means trivial.

I'm getting a nice set of small flasks soon that'll let me collect lots of useful data on decomposition/isomerization via weight loss and titration and I plan to run a number of tests to establish ideal time/temp.




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[*] posted on 16-7-2009 at 20:05


" The decomposition is by no means trivial."

Thats what im thinking.

After small sample test with the last batch I noticed a quick slight heating to the point where the bubbles just started to form produced a strong smell of MeNH2 yet heating longer diminished the smell of MeNH2. Reading the papers over and over just made me see its more complicated then it first seems largely inpart of secondary reactions forming Ethylene. If you notice Ethylene formation its wasting product.

Ill see what I can do to help to determine the ideal times and temperatures but my analytical equipment leaves alot to be desired. I did however notice something from the paper that was of interest stating the AMS in solution should have near neutral PH yet they where able to determined the amount of conversion thru monitoring PH change over various temperatures at a fixed time of 15 minutes.






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[*] posted on 31-12-2009 at 17:40
Hydrogen cyanide hydrogenation


I found lots of info about nitrile hydrogenation on the net, but none of them dealing with hydrogen cyanide. I don't have any personal experience with this; it being a gas might be a problem. Otherwise it's pretty much nitrile + hydrogen+ catalyst; it won't get any more straightforward than this, I think. What do you think?

[Edited on 1-1-2010 by Helgoland]
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[*] posted on 1-1-2010 at 05:47


How about hydrogenation of acetonitrile? That would give you ethylamine.

[Edited on 1-1-2010 by Vogelzang]
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cool.gif posted on 24-9-2010 at 17:54
Organic Synthesis Vol 1(1943) PDF


Organic Synthesis Vol 1(1943)
Methaminehydrochloride Recipe
as Downloadable Free PDF
[link removed]

[Edited on 9-3-2011 by madscientist]




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[*] posted on 24-9-2010 at 19:06


Hey Vanilla...
- all of the Organic Syntheses material is available online (orgsyn.org). Not much point hosting it yourself.
- the correct reference appears to be Organic Syntheses, Vol. 3, p. 67 (1923); Coll. Vol. 1, p.347 (1941).
- it's 'methylamine', not 'methamine'.
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Melgar
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[*] posted on 25-9-2010 at 07:00


Not sure if this has been discussed already, but if anyone has access to a machine shop where they make plastic prototypes, pieces of white Delrin plastic can be boiled in a mixture of muriatic acid and ammonium chloride. It'll hydrolyze into formaldehyde and combine with the ammonium to form the imine. Then more formaldehyde will reduce it to methylamine, being itself oxidized to formic acid and then CO2. In lieu of ammonium chloride, muriatic acid can just be mixed with a strong ammonia solution such that it's still very acidic. Once crystals start to precipitate, they'd be filtered off with a Buchner funnel and then washed with methanol. The methanol can be evaporated off to give crude methylamine HCl. That's the best way to separate ammonium and methylamine salts that I know of; methylamine HCl is really soluble in methanol whereas ammonium chloride is not. Anyway, the NH4Cl can then be thrown back in the reaction vessel to react with more formaldehyde.

Another way involves getting a jug of glow fuel that has nitromethane in it. Get one of those galinstan thermometers at walmart for like $5, and break it open and mix the galinstan thoroughly with decently pure molten aluminum. Drop your aluminum alloy nugget into the glow fuel and send the vapors through some suck-back-prevention device (otherwise this WILL suck back) into a flask of muriatic acid. This will give a purer product, but you'll need a torch and more glassware.
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[*] posted on 20-7-2011 at 05:59


anyone tried Paraformaldehyde + ammonium chloride method?
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[*] posted on 20-7-2011 at 20:08


that's the only method i ever used.
the campa chem stuff has surfacants and dyes nevermind the dyes the surfacants have to be removed by washing with water.
this is important they foam up when your cooking methylamine.
the best way is to boil it in a bath of saturated salt water (as much salt as the water will carry)
the reason is simple temperature control it boils exactly at 106C and temperature control is essential for this method to work.
a slight vacum (judge it by the evolution of co2 you should see co2 evolving vigorously from the top not the bottom)
the vacum really improved yeilds to the point where there was no need to separate ammonium chloride because it had reacted completely.
when you do this exactly right the methylamine crops out very pure and is easier to handle because it is'nt so hygroscopic.
ammonium sulfate also worked.
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[*] posted on 2-8-2011 at 18:59


Crack open an airbag and remove the sodium azide. Then:
NaN3 + CH3Br----------> CH3N3(methyl azide) +2[H] (lithium alluminium hydride)---------> methylamine
I'm really interested in whether or not one could reduce hydrogen cyanide to methylamine as well, maybe with some sort of bubbler? I smell almonds :(

[Edited on 3-8-2011 by ivory]
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jon
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[*] posted on 2-8-2011 at 20:13


wow! so that means you are genetically capable of detecting cyanide.
sodium azide is'nt much safer either.
if this is your last post we know what happened to you.

Sodium azide is acutely toxic. Symptoms are often compared with those of cyanide. Ingestion of dust or solutions can induce the following symptoms within minutes: rapid breathing, restlessness, dizziness, weakness, headache, nausea and vomiting, rapid heart rate, red eyes (gas or dust exposure), clear drainage from the nose (gas or dust exposure), cough (gas or dust exposure), skin burns and blisters (explosion or direct skin contact). Exposure to a large amount of sodium azide may cause these other health effects as well: convulsions, low blood pressure, low heart rate, loss of consciousness, and lung injury, respiratory failure leading to death.[8]





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[*] posted on 3-8-2011 at 15:00


Quote: Originally posted by ivory  
Crack open an airbag and remove the sodium azide. Then:
NaN3 + CH3Br----------> CH3N3(methyl azide) +2[H] (lithium alluminium hydride)---------> methylamine
I'm really interested in whether or not one could reduce hydrogen cyanide to methylamine as well, maybe with some sort of bubbler? I smell almonds :(

[Edited on 3-8-2011 by ivory]


Methyl bromide isn't dangerous enough. Better use methyl fluorosulfonate instead




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jon
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[*] posted on 3-8-2011 at 19:38


hey now that sounds like a great idea, perfect leaving group, looks great on the drawing board.
in the flask with deadly fumes in your environs well hell, that's a different ballgame altogether.
paraformaldehyde ammonium chloride even sulfates i used diffferent salts always get the same result.
the key is spot on temperature control 106 C being optimal and a slight vacumn and i mean slight.
too much and you boil all your formalin off (same thing happens when it gets too hot) before it can react.
just enough vacumn so you can visually spot the co2 effervescing from the top and not from the bottom.
this is pusing the equilibrium to the right moving co2 out of the way so more formic acid can reduce the formaldimine.
the result is quantitative recovery of methylamine and no unconverted ammonium salts to deal with this makes workup a breeze.
also the methylamine is pure white so it is easier to handle it is'nt as hygroscopic.
don't ask me how i know this but if you do things right the first time it saves a lot of work later.




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Melgar
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[*] posted on 4-8-2011 at 22:33


Also, if you're sorting through plastic scraps for paraformaldehyde (Delrin), the best way to tell it apart (that I've found, anyway) is to hold a lighter to it and smell it. If it smells like formaldehyde, you have a winner. Of course, that's a last test, since you don't want to be inhaling the vapors from something like PVC. PVC is typically either rubbery or stiff and opaque. Delrin is kind of translucent. Actually, you should be able to tell all plastics from Delrin just by looking at them and feeling them, except nylon, which i reserve the flame test for.
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[*] posted on 3-3-2012 at 12:45


Quote: Originally posted by Mumbles  
Perhaps give this a try? http://www.orgsyn.org/orgsyn/default.asp?formgroup=base_form...

I can just get those chemicals much easier than Hexamine.


Hexamine is sold as solid camping fuel squares otc.
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[*] posted on 4-3-2012 at 11:43


Quote: Originally posted by Melgar  
Also, if you're sorting through plastic scraps for paraformaldehyde (Delrin), the best way to tell it apart (that I've found, anyway) is to hold a lighter to it and smell it. If it smells like formaldehyde, you have a winner. Of course, that's a last test, since you don't want to be inhaling the vapors from something like PVC. PVC is typically either rubbery or stiff and opaque. Delrin is kind of translucent. Actually, you should be able to tell all plastics from Delrin just by looking at them and feeling them, except nylon, which i reserve the flame test for.


Generally speaking, using the old vapor smell test to distinguish between two carcinogenic chemicals (formaldehyde and the dioxins from burning PVC) is a bad idea.
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[*] posted on 4-3-2012 at 19:12


Quote: Originally posted by cal  
Quote: Originally posted by Mumbles  
Perhaps give this a try? http://www.orgsyn.org/orgsyn/default.asp?formgroup=base_form...

I can just get those chemicals much easier than Hexamine.


Hexamine is sold as solid camping fuel squares otc.

That link just goes to Chemdraw so it is useless to those of us who have the software.
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[*] posted on 26-4-2012 at 12:45


I've been searching for the solubility of methylamine hydrochloride in isopropanol but i cant find it , if someone could please help me i would appreciate . Thanks in advance for your assistance
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[*] posted on 26-10-2013 at 18:01


The following is an excerpt from Rhodium's 'Methylamine Synthesis FAQ' (paragraphs added by me): http://www.erowid.org/archive/rhodium/chemistry/methylamine....

Quote:

Methylamine Hydrochloride from HMTA, Eleusis' version [with comments by Rhodium]

140g of Hexamine is carefully dissolved in 400mL of Muriatic Acid (31.45% HCl) to which at least 100mL of (preferably) absolute ethanol 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.

The solution will become turbid within several hours of the initial mixing. I *believe* this is the formation of a formaldehyde 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. 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. 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.


Apparently, this is a modification of the procedure posted by Organikum earlier in the thread, involving refluxing ethanol and removing ethyl formate. The one I just posted appears to run in the cold, with no reflux.

Does anyone have an idea what the mechanism for this supposed reaction is? Also, I notice that the amount of ethanol given is less than the molar amount required to bind all of the formic acid. Furthermore, what is to stop wastage of ethanol and formaldehyde by reaction to form ethylal?
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