Sciencemadness Discussion Board

Good way to Methylamine HCl?

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Foss_Jeane - 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.

crazyboy - 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.


UnintentionalChaos - 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]

crazyboy - 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?

UnintentionalChaos - 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]

Sedit - 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.

UnintentionalChaos - 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.

Sedit - 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.


Hydrogen cyanide hydrogenation

Helgoland - 31-12-2009 at 17:40

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]

Vogelzang - 1-1-2010 at 05:47

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

[Edited on 1-1-2010 by Vogelzang]

Organic Synthesis Vol 1(1943) PDF

Vanilla47 - 24-9-2010 at 17:54

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

[Edited on 9-3-2011 by madscientist]

bbartlog - 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'.

Melgar - 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.

Waffles SS - 20-7-2011 at 05:59

anyone tried Paraformaldehyde + ammonium chloride method?

jon - 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.

ivory - 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]

jon - 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]


mr.crow - 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

jon - 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.

Melgar - 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.

cal - 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.

thanos thanatos - 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.

cal - 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.

cucei - 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

manimal - 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?

S.C. Wack - 26-10-2013 at 20:13

Quote: Originally posted by manimal  
Does anyone have an idea what the mechanism for this supposed reaction is?


Probably a simpler one than all that.

II. — Action des acides sur l'hexaméthylèneamine et ses composés.

Tous les dérivés de l'hexaméthylèneamine sont décomposés à froid par les acides, l'hexaméthylèneamine elle-même, assez stable à l'état libre, ainsi que nous l'avons vu précédemment, se décompose très facilement, non seulement en présence d'un excès d'acide, mais également lorsque l'acide est insuffisant pour former le sel neutre. Suivant la quantité et la concentration de l'acide, il se forme soit de l'ammoniaque soit une série de bases; nous étudierons d'ailleurs dans un chapitre suivant cette question.

Si l'on chauffe, on obtient de la monométhylamine. Cette réaction a d'ailleurs été signalée, mais au lieu d'être une simple réaction secondaire sans importance, c'est au contraire une réaction capitale, puisque la transformation est quantitative d'après l'équation:

C6H12N4 + 4HCl + 4H2O = 4(CH3NH2.HCl) + 2 CO2.

Si l'on fait l'opération en tube scellé, à 100-120° pour aller plus rapidement, on constate dans les tubes une forte pression, le gaz qui se dégage est de l'acide carbonique absolument pur. Il reste dans la solution un peu de chlorhydrate d'ammoniaque, cela tient à ce qu'une portion très légère de l'aldéhyde formique s'est combinée avec le chlorhydrate de monométhylamine. Cette action se produit avec tous les acides à la température de l'ébullition. Tous les sels d'hexaméthylèneamine traités de la même façon se comportent naturellement de même.

http://books.google.com/books?id=qqIfAAAAIAAJ&pg=PA394

Whether or not ammonium chloride and formaldehyde is intermediate is not the point, I'm just saying this extra stuff like alcohol or zinc may not exactly be necessary, even if patents such as DE73812 suggest otherwise.

[Edited on 27-10-2013 by S.C. Wack]

manimal - 28-10-2013 at 00:43

Yes, but the book says that the reaction takes place on heating to 100-120C, which is basically the classical reaction between formalin and ammonium chloride, which hexamine degrades to in hydrochloric acid.

testimento - 28-10-2013 at 06:46

Hexamine is reacted with hydrochloric acid. The reaction is quite simple: one just dumps the hexamine tablets into HCl, lets them sit for few days, and then refluxes the mixture for 2-3 hours, and after that the water is distilled off, until a mushy white coagulant is acquired. This is mixed with boiling ethanol, cooled down to room temp, filtered, and mixed with new batch of ethanol and repeated until the ethanol is clear. The ethanols are mixed and distilled off to leave white mushy residue, which is flushed with chloroform and dried.

Another variation is to use ammonium chloride and formaldehyde, which kicks in when heated up, and then it'll be controlled for a while, and afterwards water is boiled off.

Aqueous methylamine can be made by mixing the salt with hydroxide and water and brought to boil, and gases lead through cold trap into water, in which up to 40% solution can be made. The meth boils at -7C, so one can condense it using calcium chlorinated water which freezes at -51C.

S.C. Wack - 28-10-2013 at 15:19

Quote: Originally posted by manimal  
Yes, but the book says that the reaction takes place on heating to 100-120C, which is basically the classical reaction between formalin and ammonium chloride, which hexamine degrades to in hydrochloric acid.


What happens in between would be an unimportant detail if their equation would give the maximum yield of methylamine. If there is experimenting to be done, what they are saying in that article should be where to start. I'm not convinced you simply figure amounts needed to get it to the OS procedure and that's best.

S.C. Wack - 15-1-2015 at 19:06

Some somewhat relevant original literature.

Werner said near the beginning of his isomerization article, "This interesting reaction, which does not appear to have been hitherto recorded"...

...was already recorded by 1880.
https://books.google.com/books?id=BdcsAAAAYAAJ&pg=PA275
There is a big difference here from Werner's 15 minutes @ 275C vs. 2 hrs in a bomb at 300C.

..."Methyl sulphate of ammonium is an unstable salt, decomposable by a moderate amount of heat, while acid sulphate of methylamine is a much more stable body, hence it becomes probable that if the unstable substance be heated the atoms in the molecules of which it is composed will tend to arrange themselves in that order which is most stable at the temperature to which they are subjected, and therefore that in this case acid sulphate of methylamine will be produced. Such, in fact, is the case. A portion of dry methyl sulphate of ammonium was heated by itself in a sealed tube to about 300° C. for about two hours, nearly the whole of the salt being converted into acid sulphate of methylamine.

When the tube, after cooling, was examined, it was found that a very small portion of the salt had undergone a complete decomposition, some carbon being set free. On opening the tube a small quantity of gas was given off, which was inflammable, and smelt somewhat etherial, with a trace of sulphurous acid. The salt had been fused, and had solidified to a crystalline mass, and now possessed a strongly acid reaction.

This salt, distilled with caustic potash, and the evolved gas collected in hydrochloric acid, the solution, evaporated to dryness on the waterbath, gave a hydrochlorate which, on heating with lime, gave off an inflammable gas in abundance, was deliquescent, soluble in alcohol, and when warm possessed the smell of methylamine hydrochlorate.

Several portions of methyl sulphate of ammonium were heated to different temperatures and for different lengths of time, in order to find out the most advantageous method of preparing the substance"...

The reaction of sulfamic acid with lower alcohols is naturally quite early and in German.
https://books.google.com/books?id=s-81AQAAMAAJ&pg=PA700

..."Ammonium ethyl sulphate is obtained when finely-powdered amidosulphonic acid is dissolved in absolute alcohol by gently boiling the mixture for three or four hours. It forms colourless, transparent crystals, is very hygroscopic, dissolves easily in Water, more sparingly in absolute alcohol, is insoluble in dry ether, and absorbs water from wet ether to form oily drops. It gives up its water over sulphuric acid, and when dry melts at 99°. The dry salt decomposes above its melting point into acid ammonium sulphate and ethylene, and at 210——220° the latter is evolved in a regular stream.

Ammonium methyl sulphate, obtained in a similar way, forms hygroscopic leaflets, melts at 135°, and is precipitated from its solution in methyl alcohol by ether"...

[Edited on 16-1-2015 by S.C. Wack]

S.C. Wack - 21-1-2015 at 20:54

Others have also been more careful and less optimistic than Werner. These authors were also unaware of the earliest work; but optimized similarly.

The Preparation of Methylamirie from Ammonium Methyl Sulphate.
By WILLIAM SMITH DENHAM and LIONEL FREDERICK KNAPP
JCS 117, 236 (1920)

Attachment: CT9201700236.pdf (217kB)
This file has been downloaded 1026 times


Bright Spark - 3-3-2015 at 08:20

Ok Guys, I am new here, I am trying to get my head around whats legal and whats not

Then I find this thread, doen't this thread break any rules?

Confused

Bert - 3-3-2015 at 08:46

Here's the FAQ on board topics:

http://www.sciencemadness.org/madscifaq.html#2.1_Board_topic...


Quote:

Do not request spoonfeeding of information for clandestine drug manufacture. However, every sort of chemistry is a permissible topic of discussion if you discuss it like a scientist. If someone is asking about obtaining chemicals used in drug manufacture and using the vocabulary of a SWIM—"someone who isn't me"—-mer more than a chemist, report it and the thread will be dealt with after a moderator has confirmed your findings. Similarly, if someone is asking for help with a synthetic "recipe" for a known street drug, report that too. Don't bother to berate the cooks in the thread itself instead; that doesn't bring the mods any faster. In truth the mods and most members dislike any thread where someone is seeking or using a "recipe" and doesn't show any deeper interest in chemistry, but this has been mostly a problem with drug synthesis because of the many people who want to quickly get rich or high.

Certain topics are unwelcome no matter what section they are posted in. The discussion of criminal enterprises or weapons production is inappropriate.


If we could not discuss any chemistry or chemical POSSIBLY related to drug production, there might not be too much organic chemistry left to discuss.

On the other hand, starting a thread with "Yo, SWIM givin da big shout out ta Walter White, wutz yer fave shake-n-bake rezipee, dogs?! will not stay on the organic chemistry forum long.

Mush - 10-6-2017 at 13:40

Quote: Originally posted by kmno4  
I have just evaporated CH3NH3Cl solution [ prepared from absorbing CH3NH2 gas in HClaq; gaseous methylamine was released (by adding NaOH) from brown, impure product of reduction of CH3NO2 with Fe/HClaq ).
Quickly, cheaply and easily :P
On the picture : about 0,6 mole of hydrochloride

[Edited on 26-6-2009 by kmno4]


Could you share the reaction conditions for us , please?

Melgar - 13-6-2017 at 12:49

Quote: Originally posted by Mush  
Could you share the reaction conditions for us , please?

I've done it too, it's easy. I actually use it to test the reducing power of various aluminum alloys I'm researching. Make eutectic gallium/indium alloy by combining them in a 3:1 mass ratio. Then add 10% of the total mass of that, in tin. (Most lead-free solders are mostly tin, and work well for this.) Then melt 10x your combined mass of metal, in 1034 or purer aluminum alloy, and mix everything together very well. Allow it to cool slowly, preferably in a flattened shape. When it gets cool enough to handle, break it up into chunks. These chunks can be dropped into mixtures of nitromethane containing a protic solvent (lower alcohols, typically), and if your goal is collecting methylamine gas, 30% nitro glow fuel can usually be used directly. Be aware that suckback WILL happen at some point, and you'll need to condense the methanol and water vapors somehow, or they'll carry over.

kmno4 - 17-6-2017 at 14:33

Quote: Originally posted by Mush  
Quote: Originally posted by kmno4  
I have just evaporated CH3NH3Cl solution [ prepared from absorbing CH3NH2 gas in HClaq; gaseous methylamine was released (by adding NaOH) from brown, impure product of reduction of CH3NO2 with Fe/HClaq ).
Quickly, cheaply and easily :P
On the picture : about 0,6 mole of hydrochloride

[Edited on 26-6-2009 by kmno4]


Could you share the reaction conditions for us , please?

Nothing interesting to share, just standard reduction of nitrocompounds with Fe. In this case, because MeNO2 is rather soluble in water, no co-solvent is needed. Just ~10% HCl + Fe + MeNO2 in some bottle, shaken from time to time until the odour of MeNO2 dissapears (several hours at room temp. but it strongly depends on frequency and time of shaking). Do not use Fe powder, because it quickly turns to hard mass of Fe/Fe2O3.
Practically, all Fe in converted to Fe2O3 (not chlorides), almost no H2 is evolved, so the bottle can be stoppered and pressure released from time to time. Impure amine hydrochloride is obtained by evaporation of filtered solution.

Mush - 24-6-2017 at 12:53

Quote:

Nothing interesting to share, just standard reduction of nitrocompounds with Fe. In this case, because MeNO2 is rather soluble in water, no co-solvent is needed. Just ~10% HCl + Fe + MeNO2 in some bottle, shaken from time to time until the odour of MeNO2 dissapears (several hours at room temp. but it strongly depends on frequency and time of shaking). Do not use Fe powder, because it quickly turns to hard mass of Fe/Fe2O3.Practically, all Fe in converted to Fe2O3 (not chlorides), almost no H2 is evolved, so the bottle can be stoppered and pressure released from time to time. Impure amine hydrochloride is obtained by evaporation of filtered solution.


This is great, thanx!
Did you use iron sponge (steel wool)?



[Edited on 24-6-2017 by Mush]

kmno4 - 25-6-2017 at 13:34

No, I used iron scraps of all possible kind: corroded and not corroded nails (1-5 cm long), wire (about 1 mm diameter, just was at hand), fragmenst of cores of old transformers (EI shape), snippets of zinc-coated iron plate.... simply whatever.
I used at least 2-3 molar excess of these scraps, also remember that in first few experiments I used long glass rod to crush this iron mass (from time to time), but later I used strong shaking only, without of changes in time of reaction.
When the bottle (1 liter volume) is shaking for some longer time (minutes), it becomes warm (~30 C): just reduction accelerates.
Practically, the cost of reductor is negligible.

gatosgr - 3-2-2018 at 15:08

Can't you just react methanol with ammonia to make methylamine?
A possible route but not convenient would be from glycine or trimethylglycine if you decompose them via heat you will get mixtures of tri, di or mono methylamines then you react with a ruthenium catalyst in the presence of ammonia to make methylamine.

edit: https://www.jstage.jst.go.jp/article/kakoronbunshu/28/1/28_1...

[Edited on 3-2-2018 by gatosgr]

S.C. Wack - 3-2-2018 at 19:40

Quote: Originally posted by gatosgr  
Can't you just react methanol with ammonia to make methylamine?


When not making P2P, Walter White could have used his thoria tube furnace to make his main object of desire methylamine; things would have gone a lot better and less dramatically for him if he had.

gatosgr - 4-2-2018 at 03:53

Quote: Originally posted by S.C. Wack  
Quote: Originally posted by gatosgr  
Can't you just react methanol with ammonia to make methylamine?


When not making P2P, Walter White could have used his thoria tube furnace to make his main object of desire methylamine; things would have gone a lot better and less dramatically for him if he had.


If he was really hardcore he would use this.

methsy.png - 15kB

[Edited on 4-2-2018 by gatosgr]

gatosgr - 6-2-2018 at 02:29

I should have added heat to the first reaction.

ketosis - 2-9-2021 at 09:33

Hi, this may LOOK like my first post. Next topic:
I found a substantial improvement to the sulfamic acid route. This improvement would also be applicable to any route that does not automatically yield the hydrochloride salt(such as formaldahyde + methanol).

A quick way to explain it:
there's is never any need to gas methylamine into any liquid. ever.

-some claim to be wizards at it, but most seem to agree that it's very very difficult.
I have grown 2 moles of huge ammonium methyl sulfate crystals before. My final MeAm.Cl yield would be like 4 grams. Even with stirring, with a diffuser. Chilled receiving liquid. etc.

So:
sulfamic acid boils with methanol, after a long reflux, the ester ammonium methyl sulfate is formed.
we know that heating this in a closed container briefly to the upper 200C range will thermally rearrange the contents to a mixture of inorganic Ammonium.H.SO4 and organic Methylamine.H.SO4, also known as bisulfate.

Turns out that the bisulfate salts, as well as the neutral sulfate salts have the same solubiliy profile as the chloride salts.

Even if it's a black goo.

In fact, not just isopropanol or ethanol, even methanol will hardly dissolve any inorganic ammonium salts, ever. ANd will dissolve organic alkyl.amine salts easily.

Also chloroform can be ommitted if one has some half-decent crystallization skills, single-solvent, from isopropanol.

I believe this can be applied to the nitomethane route, as well as others.

draculic acid69 - 10-9-2021 at 06:37

Quote: Originally posted by madcease  
What is the best way to go about storing and transfering MeAm HCL from its salt form into a gas canister for storage and 99% anhydrous usage. Ive read that 50% of base makes the gas but how does one go about filling canister or tank for use later on?



https://m.youtube.com/watch?v=I_DD2_7QkRk

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