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Author: Subject: Good way to Methylamine HCl?
PHILOU Zrealone
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[*] posted on 31-3-2009 at 03:59


Quote: Originally posted by madcease  
Just as i thought. If a solution of Hexamine, HCL, H20 has been added together. One would have thought the Ammonia Chloride would crash out immediately and then reacts.
Have seen a reaction done where no Ammonia has precipitated even after 8 hours which makes me believe maybe the solution of HCL was too concentrated?

Is the HCL acid touchy in regards to this process as ive seen most of them in the past precipitate with AmChloride.


Hexamine hydrochloride doesn't hydrolyse very fast; it is also quite soluble in water just as NH4Cl is...

[Edited on 31-3-2009 by PHILOU Zrealone]




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[*] posted on 31-3-2009 at 04:06


Will the reaction still work if there is no Solids of NH4Cl floating around whilst refluxing.
Reason asked is NH4Cl is very soluble in water and have seen other reactions where it is seperated from the water.

Maybe that is because there is so much water in the mix.
I think by adding some alcohol helps with this reaction not to get over temps as such
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Formula409
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[*] posted on 25-6-2009 at 20:47


I have a question. In Eleusis's prep with Methylamine HCl via metal/HCl reduction, he says:
Quote:

*CAUTION*
The lower nitroalkanes form shock and/or temperature sensitive EXPLOSIVE compounds with amines and hydroxides. BE CAREFUL, DAMNIT! You have been warned.

What are these compounds? Should I be worried when basifying and distilling my reaction mix? I'm more than ready to give a Zn/HCl reduction a go but naturally I don't want to get exploded lol.

Formula409.
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[*] posted on 25-6-2009 at 21:06


Nitronate salts. If I remember correctly they are harmless in solution and are only an issue once dry.



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[*] posted on 26-6-2009 at 05:36


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]

DSCN0049.JPG - 412kB
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ItalianXKem
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[*] posted on 26-6-2009 at 14:26


but CH3NH2 + HCl = CH3NH3(+)Cl(-) ?
however
can you make :
a luminol synthesis step use Na2S2O4 to reduce NO2- to NH2-
you can find nitromethane (typical is used for propellant in rocket model)
and N2S2O4 , react
after you have MethylAmine CH3-NH2
pay attention , methamine is stinky and toxic , high
also maybe how the monomethylhydrazine & co
is carcinogenic , teratogenic or sim bad failures in body
after make a salt with hydrochloric acid HCl
bye , night




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Vogelzang
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[*] posted on 28-6-2009 at 04:37


Alcoholysis of sulfamic acid produces ammonium akyl sulfates. On page 629 of the attached article it discusses an example where methanol refluxed with sulfamic acid for several hours yields ammonium methyl sulfate. Ammonium methyl sulfate rearranges at high temperature to methylamine sulfate.

See ammonium.methyl.sulfate.pdf here
http://psychedelichosting.info/Ionium/Rhodium/pdf
or http://80.244.243.200/archive/rhodium/pdf/index.html



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jon
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[*] posted on 7-7-2009 at 17:53


call me oldschool what's wrong with the traditional way of making methylamines????
if it works why reinvent the wheel?
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[*] posted on 7-7-2009 at 18:49


Because if we stoped at the wheel people would not be flying around in airplanes right now. Its all about progress.




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[*] posted on 9-7-2009 at 14:48


I'd like to contribute an improvement to Organikum's ethanol procedure. The reactants are combined in the ratios set forth, but instead of refluxing them, they are confined under pressure in a hot water bath. Thus may or may not be an improvement, but I view it as such because it requires little or no attention when running.

A brandy bottle with a screw-on cap was employed, and the mixture was held in the water bath at 85-90C overnight (approx. 14 hrs). Then it was opened and the liquids boiled off and worked up as per usual. Methylamine was obtained in an as yet unmeasured quantity, but no formaldehyde odor was detected when boiling off the solvents. When working up the traditional method, it had sent me retreating with eyes watering severely.

Ethyl formate smells of rum according to the literature. I guess it could smell like rum; it's been a very long time since I smelled rum. To me, it smells exactly like ether-based starting fluid.
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[*] posted on 10-7-2009 at 04:21


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?




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[*] posted on 10-7-2009 at 08:42


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.




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Sedit
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[*] posted on 10-7-2009 at 18:17


Vogelzang do you have references that show more indepth the process because I have attempted a .5 Sulfamic to 1 MeOH molar ratio and there appears to be no reaction after two hours of reflux as the Sulfamic does not dissolve.

I have since added equal volume of H2O in hopes that it will push any reaction along so we will see but none of the papers provided appear to exemplify how the reaction is carryed out in any detail.






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[*] posted on 11-7-2009 at 04:03


Yesterday i have tested this method in attempt to produce ethylamine hydrosulfate. 300 ml 97% ethanol was refluxed with 100g of sulfamic acid, solid quickly dissolved and reflux was continued for 2 more hours (3 hours total). Solution is then allowed to cool and small ammount of lustrous solid precipitated, witch gave white precipitate with SrCl2 solution - that was NH4HSO4 produced by water hydrolisys (C2H5OH + NH2SO3H => C2H5OSO3NH4 ; C2H5OSO3NH4 + H2O => NH4HSO4 + C2H5OH). Solution was filtered and distilled to remove solvent. About 250 ml of C2H5OH was collected by destilation on water bath, witch was then removed and evaporation was continued on open flame to force complete removal. 50 more ml of liquid was collected. Temperature was raised to about 150-190C and mixture in reaction flask started to foam, foaming slowly subsided while temperature of reaction mixture reached ~290C. Mixture maintained at this temperature for 15 minutes and allowed to cool to crystallize the melt. Product is crystalline solid almost insoluble in alcohol and forming white precipitate with SrCl2 solution (sulphate presence). Wonder what this product is, so i want to use melting point to identify it, but can't find ethylamine hydrosulphate in avialable literature. Somebody knows melting point of ethylamine hydrosulphate?



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[*] posted on 11-7-2009 at 07:09


Quote: Originally posted by Engager  
Yesterday i have tested this method in attempt to produce ethylamine hydrosulfate.

Supposedly, that reaction produces ammonium hydrosulphate and ethene, so bear that in mind when identifying your product. It's quite unfortunate that ethylamine and higher amines cannot be produced using this method - maybe you'll prove us wrong :)

Formula409.
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[*] posted on 11-7-2009 at 09:43


I think the MeOH has to be anhydrous, Sedit.
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[*] posted on 11-7-2009 at 10:03


Nothing appeared to happen at all other then the MeOH taking on a slightly yellow tinge when it was anhydrous yet I added a bit of H2O and some oil appeared after a few minutes on the surface of the mixture. After cooling large crystals(.25-.5 inches) the shape of benzene appeared and settled on the bottom. They are very thin plates and fragile looking.

I am assuming for the time being that the thin(1mm or so) top oil layer is the product and the crystals are sulfamic acid precipitate but I haven't much time to look into it just yet.






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[*] posted on 11-7-2009 at 14:46


According to the Merck Index, sulfamic acid is sparingly soluble in alcohol and methanol (alcohol probably refers to ethanol). The ie50342a005-sulfamates.pdf reference says sulfamic acid is slightly soluble in methanol. Maybe you have to reflux it longer and use stirring. Maybe the product, ammonium methyl sulfate, is also slightly soluble or insoluble in methanol. Water hydrolyzes both sulfamic acid and the product.
See US patent 1931962, German patent DE558296

The ammonium.methyl.sulfate.pdf article here http://tinyurl.com/lp8dkq is the same as the one here: http://www.rsc.org/ejarchive/CT/1896/CT9140502762.pdf

See also http://en.wikipedia.org/wiki/Sulfamic_acid

[Edited on 11-7-2009 by Vogelzang]
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[*] posted on 11-7-2009 at 15:05


Maybe the following method may be useful for people who have easy acces to phthalic anhydride.

http://en.wikipedia.org/wiki/Gabriel_synthesis
http://www.organic-chemistry.org/namedreactions/gabriel-synt...

Phthalimide is VERY easily produced, simply by heating phthalic anhydride with urea. You will get a melt wich will suddenly froth up, indicating the end of the reaction. I have done this and it is easier than making aspirin. However, phthalimide sublimes easily and you get a lot of phthalimide smoke , wich is teratogenic AFAIK, so outside is adviced

I'm not sure how the next step should be done (what solvent?), but I guess just adding the phtalimide to aq. KOH and bubbling in MeBr would be sufficient. MeBr is very easiliy prepared, unlike MeI or MeCl, simply by adding a MeOH/H2SO4 by dropping funnel to a boiling alkali-bromide solution, then condensing H2O/MeOH/azeotropic HBr, and leading the MeBr gas straight into the potassium phtalimide solution.
Then you would need to hydrolyse. According to a source (can't find it at the moment, to lazy to search, somwhere in google.books), base is suficient.
Then extract the amine (ether?), and lead HCl (H2SO4+NaCl) in the solvent to precitipate the pure HCl salt of the amine.
Phthalic acid can be recovered by adding HCl to the remaining aqeous soilution, precitpating phthalic acid. I think this is easily converted to phthalic anhydride by heating.

Just and idea, I'm probably not going to try this as I don't have any use for these amines.

[Edited on 11-7-2009 by Jor]
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[*] posted on 12-7-2009 at 08:50


I would like to announce success in producing the ammonium methyl sulfate. I will conduct the thermal rearrangement soon and report on yields.

A 250mL RB flask was charged with 22.28g of sulfamic acid, finely powdered in a mortar and pestle and 100mL of anhydrous methanol. A stirbar was added and the flask was set up for reflux with a calcium chloride drying tube. The mixture was brought to a heavy reflux under stirring and maintained that way for an hour and a half at which point the sulfamic acid had completely dissolved. Reflux was maintained for an additional 45 minutes and then the solution was allowed to cool to room temperature. No crystals formed, so the solution was transferred to a 400mL beaker and boiled down to 40% of it's original volume. At this time, a drop of solution was mixed with a drop of concentrated strontium chloride solution. No precipitate formed, indicating the reaction mixture was effectively free from sulfate ion contamination. On slow cooling, elongated, translucent white plates seperated from solution. These were broken up with a stirring rod, and vacuum filtered through a medium porosity fritted glass buchner funnel. They were washed with 25mL of ice cold methanol, transferred to an evaporating dish, and placed in a dessicator over concentrated sulfuric acid. The dried crystals weighed 13.79g (46.5% of theoretical) and are extremely soluble in water, deliquescent in humid air, but reasonably stable in dry air.

The filtrate was boiled down to 15mL in hopes of getting a second crop of good crystals, but when cooled, tons of tiny acicular crystals formed which solidified the mixture. A small piece of the damp crystals were dissolved in two drops of water and tested with strontium chloride again. Only after a few minutes did the faintest cloudiness appear, which may have been due to hydrolysis of the methylsulfate anion in that period. Since there was no appreciable sulfate contamination, the crystal slush was placed in the dessicator to dry for later thermal rearrangement experiments.

Does anyone know of any insoluble methylsulfate salts at all? Information seems to be spotty and from what I can tell it solvates just about everything.

[Edited on 7-12-09 by UnintentionalChaos]




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[*] posted on 12-7-2009 at 09:49


Congratulation.
Now I have to figure out whats going wrong over in my neck of the woods.

The only thing I could possibly think is that my Sulfamic is not Sulfamic acid. I have used it many times for septic systems as im a plumber by trade and this has been sitting on my shelf for sometime. The label has since worn away but it appears to be the same stuff I have seen many times. Since Sulfamic acid hydrolyses in H2O perhaps the fact that it has been sitting around for years has ruined it.

Im going to get some brand new Sulfamic and attempt this again to see what I can find out.





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[*] posted on 12-7-2009 at 10:09


Quote: Originally posted by Formula409  
Quote: Originally posted by Engager  
Yesterday i have tested this method in attempt to produce ethylamine hydrosulfate.

Supposedly, that reaction produces ammonium hydrosulphate and ethene, so bear that in mind when identifying your product. It's quite unfortunate that ethylamine and higher amines cannot be produced using this method - maybe you'll prove us wrong :)

Formula409.


Just a thought here, but can an inert solvent be used to generate the ammonium alkylsulfates of long-chain alcohols, then these destructively distilled to yield the terminal alkene?

Perhaps the esterification need not even be carried out. I know sulfamic decomposes when molten, but perhaps it'll still work as a molten fusion.

[Edited on 7-12-09 by UnintentionalChaos]




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[*] posted on 12-7-2009 at 11:22


I wonder how ammonium methyl sulfate would work for making phenolic ethers. See

US patent 2490842 Anisole manufacture
Column 2 lines 6+
The methyl sulfate may also contain a metal substituent on the sulfate radical, as in the case of sodium methyl sulfate or potassium methyl sulfate, it may contain an ammonium substituent as in the case of ammonium methyl sulfate, or it may contain a hydrogen substituent as in the case of methyl acid sulfate.

US patent 2529887 Process for the preparation of anisole
Column 5 lines 30+
Suitable methylating agents for phenol include, for example, a methyl sulfate having the methyl group directly attached to the sulfate radical such as dimethyl sulfate, sodium methyl sulfate, potassium methyl sulfate, ammonium methyl sulfate, or methyl acid sulfate; also methyl halides such as methyl chloride, methyl iodide, and methyl bromide; and organic methyl esters such as methyl acetate.
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[*] posted on 12-7-2009 at 17:27


I repeated the above procedure tonight, using 50.05g of sulfamic acid and 100ml of anhydrous methanol. I do not have yield numbers yet, but will add them to this post when I do. It took 3 hours and 45 minutes of reflux with stirring for complete dissolution/reaction of the sulfamic acid. I continued reflux for another 45 minutes to ensure the reaction was complete.

So, this begs the question, which do you value more, your solvent or your time?

Update: Simple slow cooling of this reaction mix down to ice-bath temperatures followed by vacuum filtration (I omitted the methanol wash this time) gave 39.44g of glittering white crystals (59.2% of theoretical). The secondary crops are still drying.

Here's a little teaser: the first crop of ammonium methylsulfate crystallizing out upon cooling. The picture of the dried crystals was significantly more boring.



[Edited on 7-13-09 by UnintentionalChaos]




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[*] posted on 12-7-2009 at 17:40


I value my solvents more. The time spent is something I enjoy but shelling out money for more solvent is not :D.


Just as a side note to everyone ignore my previous post because after running some test it has become obvious that my Sulfamic acid is not that. This is a good thing as sulfamic is cheep I can attempt another run with better materials now and hopefully arrive at what I want this time.





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