Author Topic: Methylamine  (Read 1509 times)

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zed

  • Guest
Methylamine
« on: April 13, 2002, 03:34:00 PM »
Methylamine, are you sure you need it? The reaction of glycine with a p2p produces a glycine-imine. This Amino-Acid
imine, can then be thermally (or otherwise) decarboxylated, to produce a p2p-methylimine. Which, of course, can be reduced to the p2p-methylamine. Since the progression of the
reaction would be condensation with H2O removal, followed by higher temp. to de-carboxylate, followed by hydrogenation. This might be done easily. I don't suggest you use this for anything illegal. It is just a interesting idea. Keep in mind, the terrible jail sentence that Eluisis received was based largely on the Hexamine/Methylamine found in his possession. The decarboxylation of aminoacids/
iminoacids to produce amines is now well documented. This
sequence merely isolates and reduces the intermediate imine
rather hydrolysing it to produce ketone + amine.

Rhodium

  • Guest
Refs
« Reply #1 on: April 13, 2002, 04:42:00 PM »
Do you have any references to back that up?

zed

  • Guest
refs
« Reply #2 on: April 13, 2002, 07:02:00 PM »
Somewhere in my vast slovenly abode, I have a reference. Digging it out won't be easy, but I'll try. The paper, as
I recall, simply describes reacting ketones with aminoacids,
with removal of the resulting water to form iminoacids.
Heat is then applied to achieve decarboxylation. This produces the imine, which after hydrolysis
yielded the starting ketone plus the amine derived from the amino acid. The idea of hydrogenating or otherwise reducing
the intermediate imine seems reasonable, but I don't have a reference on that one. And, I do not know the stability of
p2p.methylimine ;if stable all is well.....if not....poly-meric crap might result. I think it is worth exploring. In
general, this is the same reaction that is used to decarboxylate tryptophane to produce tryptamine, or phenylalanine to produce phenethylamine. The approach I'm
postulating simply reduces the imine intermediate. Do any
of you bee's out there have insight or additional references? Please post! I'm long retired and you guys have
a lot more paper than I do.

Sunlight

  • Guest
MDP2P and glycine
« Reply #3 on: April 14, 2002, 04:30:00 PM »
I had the same idea after foxy2 posted in the tryptamines forum references of decarboxylation of aminoacids (tryptophan) using hydroxy propiophenones.
I tried it. 2.5 gr of glycine and 2 gr of MDP2P were heated in an oil bath, at 170-190 C started effervescence and methylamine release. Like when you heat glycine with soda lime at 230 C, other brownish organics where formed that condensed in the wall of the flask. After 1 hour or a bit more, the rxn was done and there was in the flask a brownish lquid, I was very excited thinking it worked. On cooling it solidified. I added methanol and refluxed it with stirring, and let cool again, there was only a bit of undissolved tar. The decanted liquid was treated with NaBH4 and workup as usual gave nothing. I think that nothing means just it doesn't work, if it worked and I failed in something, I would get a bit of product. It was very dissapointing.
It could a good way to get methylamine, but not with MDP2P. Perhaps it works with P2P, who knows...

zed

  • Guest
Thank you
« Reply #4 on: April 14, 2002, 07:24:00 PM »
Working in the distant past, I too found that Glycine seems
to generate methylamine upon heating. Since Glycine is pretty cheap for an aminoacid, and it is probably still easy to procure, this would seem to be a useable method to
produce methylamine. Now, as for my still unfound reference,
as I recall it; all the water formed by the condensation of
amino acid and ketone, was removed by azeotropic distillation,(dry isopropyl alcohol might work) followed by addition of a higher boiling solvent(to promote decarboxlation), followed by reflux.
If indeed, the imino acid was formed, then decarboxylated,
the anhydrous conditions present, prevent it from becoming
P2P + methylamine. The reaction mixture doesn't have the required water for hydrolysis. So, distilling off the high boiling solvent, and hydrogenating the product in anhydrous
methanol should produce the N-methyl-phenylisopropylamine.
Since there is no water present in the reaction mixture,
and none is formed during the reaction. And because no ketones are present to attack the product, No excess of amine is required to drive the reaction. What you see, is what you get. Now, I wouldn't suggest actually trying this
on a P2P, unless you have a permit, or you are a student doing an approved research project at a university.
That could cause problems. But, it is an interesting idea,
and it might be tried with some less expensive, non-restricted ketone. If you are successful, and the technique
really hasn't been done before. It could produce a good paper for publication, or even a patent. Thank you for your
interest.....Zed


Sunlight

  • Guest
Imine and water
« Reply #5 on: April 15, 2002, 08:52:00 AM »
Water was quickly evaporated in a flask inmersed in oil at 170-190. Glycine was solid and insoluble in the ketone, but as it formed the imine, water evaporated with effervescence due CO2 and methylamine release. I think the imine is not stable, if it was, methylamine would not be released, it would stand in the the imine. NaBH4 rdxn, wich ususally gives 85 + % yield gave nothing...
I don't discard repeat the experience with other solvents/conditions, but that first approach was dissapointing.
In the tryptamine forum is the reference that uses hydroxy propiophenones, it gave me the idea.

zed

  • Guest
Rubies vs.Emeralds
« Reply #6 on: April 15, 2002, 09:45:00 PM »
This thought experiment is going very well! We were looking for an imine to amine reduction, and all we succeeded in doing, is generating Methylamine gas.

So, all we have to do now, is get rid of that nasty co2, and
we are left with pure, sweet methylamine gas! Can any of you bees out there think of a use for methylamine gas?

We have discovered that heating OTC glycine in the presence
of a ketone, generates Methylamine gas.

We went looking for Rubies, and we found Emeralds. We still
don't know if the Rubies are there. But, I suggest the Emeralds we found, may be treasure enough.

Do any of you bees out there, have further insight?

Sunlight

  • Guest
Not new
« Reply #7 on: April 16, 2002, 12:16:00 PM »
No Zed, Ive discovered nothing, there's post in the Hive I have not found now in wich is said that heating glycine and alanine with certain ketones methylamine and ethylamine are produced. It's one of the things I would like to investigate, but I'm making probably too many things at once. Furthermore I posted my attempt a weeks ago. I don't understand why most people don't try to research any of the multiple promising procedures are posted in the forum.

Aurelius

  • Guest
Ethyl amine
« Reply #8 on: April 16, 2002, 03:54:00 PM »
Hey Sunlight, alanine with which ketone for ethylamine?  and is water a good enough solvent for ethylamine to pick it up as it's formed?

Sunlight

  • Guest
Ketones
« Reply #9 on: April 16, 2002, 06:03:00 PM »
Patent GB 1008594, posted by Foxy2 in the tryptamine forum.
Ketones are acetophenones and benzophenones. So I thought it could work with benzyl methyl ketones and if the imine was stable go straight to reduction, but it didn't work as I made, what does not mean ther's no a way in wich it could work.
I would swear that in this or other similar post was said that glycine and and alanine gave methylamine and ethylamine, but I don't find it now, may be it has been edited or I had a funny illusion.

zed

  • Guest
Numbers
« Reply #10 on: April 16, 2002, 06:19:00 PM »
Sunlight, there are about 3000 topics just in the Chemistry
forum. The posts on those topics total a far greater
number. There are a lot of forums. The Fuckin Search Engine,
is called that for a reason; It can't find anything!
In fact, you can't find said reference yourself, and you have seen it.  Generating Methylamine from Glycine isn't
little...It's BIG! Thousands of Bees would be interested in
knowing a good proceedure. Rhodium's site doesn't mention this route. Most proceedures for making methylamine are in-
credibly lame, and you can't buy it.  Glycine is OTC, un-restricted, and unwatched. In bulk, it probably costs a couple of dollars a pound. Columbus didn't really discover
America. In fact, he was looking for something else. America got in his way. Is America less valuable because it
isn't India? Methylamine from Glycine is good. It
isn't what you were trying to do, but it is still good.

lugh

  • Guest
Illusions
« Reply #11 on: April 16, 2002, 06:26:00 PM »
The search engine is easy to use if one simply truncates the terms to eliminate the inevitable typos  :)  See the threads starting with

Post 26411

(user1634: "glycine -> MeAm", Chemistry Discourse)
,

Post 190214 (missing)

(obituary: "methylamine", Chemistry Discourse)
,

Post 189968

(element109: "Decarboxylation (sigh..)", Tryptamine Chemistry)
,

Post 180820 (missing)

(goiterjoe: "synthesis of ethylamine/isopropylamine", Stimulants)
(

Post 181049 (missing)

(PolytheneSam: "Re: synthesis of ethylamine/isopropylamine", Stimulants)
),

Post 108611 (missing)

(dormouse: "methylamine via glycine(Amino acid) (Page 1) -hellman", Novel Discourse)
,

Post 98260 (missing)

(hellman: "success with glycine--methylamine", Chemistry Discourse)
, Sunlight, your memory is fine  :)



zed

  • Guest
Ethylamine
« Reply #12 on: April 16, 2002, 06:53:00 PM »
Aurelius, I saw your post. I would suggest Alanine. I would
also suggest that passing the reaction gases over NaOH pellets will scour out water and CO2. Otherwise, you might
end up with some Amine Carbonate(AKA smelling salts)in your
product. As for a solvent to trap the ethylamine in, methanol would be nice. But, whatever solvent you need it
to be in for your reaction would be best. As for reaction
solvent, and catalyst. Student has a very interesting Tryptophane decarboxylation in the Tryptamine Forum. He uses
Turpentine as the solvent, and Spearmint Oil as catalyst.
I don't know if it is applicable, but it is worth a look.



Aurelius

  • Guest
Nitroethane
« Reply #13 on: April 16, 2002, 10:37:00 PM »
Just looking for a quick-easy-dirty way to make ethylamine for oxidation into nitroethane.   aurelius was thinking that if Glycine + various bases or ketones + heat--> methylamine, then ethylamine can be had similarly from alanine.  Ethylamine bubbled into water.  then add dichromate. or perhaps bubbled into a heated, acidic solution of dichromate in a continuous train of vessels to steam distill out the final product of nitroethane.  Perhaps?
suggestions?
Comments?
Lugh?- how ya' been?

zed

  • Guest
Sand as Solvent
« Reply #14 on: April 17, 2002, 01:00:00 AM »
Amino acids like to polymerize into horrible brown junk when heated. If finely ground glycine is mixed with lots of Clean, dry, fine sand. The sand seems to interfere somewhat with the polymerization process. The premise being that the
glycine molecules get less opportunity to come in physical
contact with other glycine molecules. This favors the decarboxylation reaction vs. polymerization. So that, if you
bake this mixture, a fair amount of methylamine seems to be
generated. A useful procedure might be to take an old electric stove, bore a hole in the side of it, to allow an
exit tube for the generated gasses. Place a reaction vessel
with a large diameter vent tube afixed to it, in the oven,
with the tube passing out through the hole in the side of the oven. Then bake it, and trap the gases in liquid. Much of the product in my experiments seemed to be methylamine carbonate, a Chunky, slurry, of white Crystaline material,
with a "Snap your Head Back" odor. I never worked up the product, or made tests on it to confirm it's identity. As, I
retired from Bee..Dom about that time, I left it in other
hands. I make no warrantee, but it might be worth trying.
It isn't very elegant, and it is uncatalysed so it requires a lot more heat than other decarboxylation reactions might.
That is the story of sand as a solvent.  
Thank you for your patient attention,   Zed

Regarding nitroethane, I believe there are some pretty good
proceedures to make it by simpler means. It might even be possible to buy it. In Zed's day, legitimate Chem. companies
might respond to a purchase request, by saying,"We can give
you a great price....if you buy a 50 gallon drum".

As always, I assume that your experiments are legal in the
country where you reside.

Sunlight

  • Guest
More
« Reply #15 on: April 17, 2002, 05:01:00 AM »
I've seen two ways for decarboxylation of glycine, and both them works but gave byproducts (brown polymers). Heat glycine with soda lime, at 220-230 or so starts the evolution of gasses, wich include organics, you could add a refluxer to get them in initial flask and recover the methylamine in a HCl solution. It could contain NH3 as well, but smell seemed nethylamine...
The other one is heating with the ketone, and we could consider other ketones diluted in solvents, such as acetone in tetralin etc...

zed

  • Guest
Thank you.
« Reply #16 on: April 18, 2002, 02:35:00 AM »
Sunlight, thank you for all the great references, I will study them carefully. To this point, I haven't found a reference, to anyone doing what both of us considered to
be possible....decarboxylating to the methylimine, followed by reduction to amine. Quite correctly, you stated that most
experiments produce nothing. I spent years conducting experiments that usually ended that way; In O Chem. experimental results trump theory most of the time. To my
great pleasure, occasionally I have dreamt a reaction sequence that worked really well! I will puzzle over this problem and contact you if a light clicks on. In the meanwhile, I will continue to be of the opinion that, for the present, in-situ reduction of nitromethane to
methylamine by disolving metal reduction, or hydrogenation..
may be the most effective way to aminate Phenylisopropanones.

Nitromethane is easily acquired, but not good to have around
the lab, as it seems to create suspicion with law enforcement agents: A problem many of the Bees are concerned with. A wise solution to this problem, is to store
such reagents underground, in a remote location. Ammo boxes
work very well for such storage. They are hermetically sealed, and if well wrapped in plastic, and buried, they
provide safe dry storage for many years. Large diameter ABS tubing (Soil or Drain pipe)also provides excellent storage.
A foot long section, with screw caps glued on it's ends, makes a very strong, waterproof, storage container. A post hole digger can quickly make a hole two feet deep. Just slip the cylinder in, and bury it. Thereafter, sleep soundly at night. This is not to suggest doing anything illegal. It is simply that a person of refinement, should at all times, avoid the appearance of impropriety.
Being a bee is something, most people rapidly grow out of.
It is best that they grow out of it naturally. Not, because
some terrible legal misunderstanding, leads to incarceration.

 Oh, we didn't discuss the possibilty of reducing the amino-
acid imine, before decarboxylation. Then heating the product
to decarboxylate. I don't know if an N-Substituted aminoacid
can be decarboxylated. Do you? Oh, I know microbes can do it, but they can do anything. Every living cell on earth has 2.5 Billion years of O-Chem backround.

Decarboxylation after reduction seems less elegant, than the
initial approach. But, what the heck, it could be O.K......
If my glassware wasn't in another time zone, I would try it
right now.

Thanks again for your input...........Zed

Sunlight

  • Guest
tests and fiascos
« Reply #17 on: April 18, 2002, 05:07:00 AM »
It's the same for me, lots of "nothing", but when you find something, wow, it's really good.
I've had only one experience, so it can't be concluding, may be if the imine is formed in a solvent it will be more stable. Probably th probem is that glycine decarbosylates but also decomposes in other things, that can react with the imine. I've thought also about reducing the imine before decarboxylation, but I guess it won't work satisfactorily due that that aminoacid will be difficult to isolate from glycine.
Having that NaBH4 procedure produces excellent yields, I think that the best reasearch will be oriented to the decarboxylation of imine and production of methylamine form it, as you say nitromethane is not so common and safe like glycine, and in other hand I doubt that the direct reduction/decarboxylation in any order can  give 85 % yield of the amine.