LaBTop
(Daddy)
06-08-03 03:33
No 438541
      High yield synthesis for Methylamine nitrate
(Rated as: excellent)
 Bookmark   

Polverone gave this link in his hydrazine thread Post 411522 (Polverone: "optimized OTC hydrazine sulfate synth", Chemistry Discourse):
http://www.sciencemadness.org/talk/viewthread.php?tid=470
so I went to this interesting forum website, and found that Mr. Anonymous gave another present in that thread:

""In the previous communication about the usefulness of urea, I failed to mention a patent which shows the usefulness of urea in synthesis of methylamine. EP 0037862 discloses a high yield synthesis for methylamine nitrate. Also see GB1548827 for a closely related synthesis. It is my guess that paraformaldehyde would react with a diluted urea/ammonium nitrate eutectic. There was a mention of the nitrate process at the Hive, but no details or followup information was posted in the methylamine FAQ. Also see GB168333.""

===================================================================


So, EP0037862 discloses a high yield synthesis for methylamine nitrate:

Description of patent:
Blasting explosive compositions, generally in the form of slurry explosive compositions, which contain ammonium nitrate as the sole or principal inorganic oxidising salt and a methylamine nitrate mixture as the sole or principal sensitizer, are prepared by reacting in the liquid phase ammonium nitrate and formaldehyde to form an oxidizer/sensitizer blend which can then be mixed with other appropriate constituents to form the required blasting explosive composition, the reaction of the ammonium nitrate and formaldehyde being carried out in the presence of urea in order to reduce the amount of free formic acid which is unexpectedly produced in the reaction, since the presence of formic acid in the reaction mixture is undesirable in that it affects the production of a stable gel therefrom and if converted into a formate reduces the strength of the explosive composition.

Procedure:
800g of a 37% by weight aqueous formaldehyde solution were mixed with 48 g of urea and to the resulting mixture were added 800 g of solid ammonium nitrate. On warming the so formed mixture to 60C an exothermic reaction set in and the temperature rose to 90-95C. The reaction mixture was maintained at a temperature of 95-100C by applying heat when necessary for a period of 3 to 4 hours. Considerable quantities of CO2 were released and at the end of the reaction period the reaction mixture had the following composition:
Solids     :   67%
Formic Acid:    1%
Water      :   32%

The reaction mixture so formed, containing unreacted ammonium nitrate and a methylamine nitrate mixture, can be evaporated in any suitable evaporation system to a desirable water content. The distillate thus obtained contains only a minor quantity of formic acid, which can easily be neutralised with Ammonia and disposed of without causing environmental problems.
Then you can distill the foregoing reaction mixture in vacuo until 250 ml of water has been collected in the receiver. (we go on until all water is removed)

They proceed to add f,ex. solid sodium perchlorate (NaClO4.H2O) for the next steps of producing in the end an explosive mixture.  We better forget those steps, we are not interested in explosives in this context.

So after total water removal, you have a mixture of :
Ammonium nitrate
monomethylamine nitrate
dimethylamine nitrate
trimethylamine nitrate

They indicate that the amines content of one of their final explosives was:
monomethylamine nitrate :  16.5 %
dimethylamine nitrate   :   4   %
trimethylamine nitrate  :   2   %

This gives a rough indication of the percentual content of the amines you can find if you follow the above procedure, which are around the 40% yield, however they didn't give any content of ammonium nitrate, so you have to find out yourself in practice how much methylamine nitrate can be produced. But mr Anonymous said "a high yield synthesis for methylamine nitrate.""

Then you have to choose a practical manner of separating the amines from the Ammoniumnitrate, and then the separation of solely Methylamine-nitrate from the 2 others, which is much more difficult, better said impossible. But their presence is much lower, so therefor it's more logical to remove in later reduction steps their reaction products in that reduction, which could be possible.

I see no reason why this procedure could not be done with Ammonium chloride instead of Ammonium nitrate, as explained in:
../rhodium/chemistry /methylamine.html
But then instead an extra addition of Urea to suppress the formation of excess Formic acid.


Here are some exerpts from GB1548827 (no Urea, but Sodium formate addition):

(Please read the whole patent, if you are also interested in a good explanation of the reaction mechanisms of Methylamine salt production (MethylAmmoniumChloride, here often also called Methylaminechloride, MeAmCl) from Formaldehyde and Ammonium Chloride).

It has been found that by the addition of 5% Sodium formate to a reaction mixture of 800 parts by weight of Ammonium nitrate and 620 parts by weight of 37% (commercial grade) Formaldehyde it is possible, by controlling the reaction temperature to lie between 95 C and 105 C, that the yield of the mixed alkylammonium nitrates (mono, di and trimethylamine nitrates) increases considerably from 30% (without formate) to above 40% (with formate).
The reaction mixture at the end is practically free from Formic acid and requires very little alkali to neutralise it.

Procedure:
A mixture of 800 parts by weight of Ammonium nitrate, 620 parts by weight of 37% commercial grade Formaldehyde and 50 parts by weight of Sodium formate is heated slowly untill the temperature reaches about 70 to 80 C and as the reaction is exothermic, it can maintain itself between 95 to 100 C.
The reaction is, however, maintained at 100 to 105 C by additional sparse heating for 2 hours.
At the end of this period the water content of the reaction mixture is reduced by vacuum distillation to about 12% by weight to give after neutralisation with Ammonia an oxidiser blend(used as base for explosive mixtures, we ofcourse drive off all the water then).

Patent GB168333:
This Danish patent from 1920 describes the production of high explosive mixtures of perchlorate compounds and methylamines.
However, there is a nice remark :
""Furthermore, this perchlorate explosive can be produced at low costs,
since the Methylamine may be EASILY obtained by hydrogenation of hydrocyanic acid, or by distillation of sugar residues.""

I see that in those times scientists were not very impressed by HCN : very poisonous
see: http://www.nsc.org/library/chemical/hydrocy0.htm ,
so forget that, but that distillation of sugar residues is never mentioned here IMHOP. LT/

WISDOMwillWIN
 
 
 
 
    LaBTop
(Daddy)
06-21-03 23:13
No 441594
      No comments?  Bookmark   

?

WISDOMwillWIN
 
 
 
 
    Rhodium
(Chief Bee)
06-22-03 21:58
No 441743
      Methylamine Nitrate variation  Bookmark   

I think it is a clever thing, and a good complement to the ammonium chloride procedure, but I believe that a lot of our members here will run into more trouble aquiring ammonium nitrate than ammonium chloride, because the former is often watched due to its use as explosive. Or, as it is where I live, in a country where it *is* possible to aquire agricultural ammonium nitrate wiyhout any questions asked, it is always sold as a mixture with 10-15% of calcium and/or magnesium salts (carbonate or sulfate) to desensitize it.

Also, do you really think it is possible to use methylamine nitrate for reductive aminations? I mean, the nitrate is pretty oxidizing, and would very likely act as a reduction inhibitor. This salt would only be useful for the production of freebase methylamine to be bubbled through methanol or other solvent to make a solution before use.
 
 
 
 
    hCiLdOdUeDn
(Hive Addict)
06-23-03 23:10
No 442027
      Ammonium Nitrate  Bookmark   

Ammonium Nitrate is easily found OTC in the US in instant cold packs. There is an average of 150g NH4NO3 in a $1 instant cold pack.

The method looks very good because of its simplicity, yet the seperation of the ammonium nitrate/methylamine nitrate still needs fractional crystallization.

Anyone know the solubility of methylamine nitrate? Ammonium nitrate solubility is 118g per 100mL H2O at 0C. Ammonium nitrate is probably wont crystalize out, so methylamine nitrate should be the first crop to crystalize out.
 
 
 
 
    LaBTop
(Daddy)
06-24-03 12:59
No 442142
      More  Bookmark   

Rhodium: Yes, I had in mind it would be useful for the production of freebase methylamine to be bubbled through methanol or other solvent to make a solution before use.
Because the production of a 10% MeAm gas in Methanol solution seems to be the main culprit for many here.
I see that you added some text to ../rhodium/chemistry /hydrazine.sulfate.html
but my question still stands:

Can anybody try the addition of Urea out on that Ammonium chloride procedure at Rhodium.ws?



hCiLdOdUeDn : Solubility of methylamine nitrate : ?

Notes:

Monomethylamine nitrate, MMAN , it is also called methylamine nitrate, MAN , or  methylammonium nitrate, (CH3NH3+) (NO3).
It is a powerful and stable primary explosive compound. It's quite stable, but when it explodes it will detonate even insensitive explosives. The only problem with it is that it is a hygroscopic compound, so keep it very tightly sealed in storage.

When you evaporate a liquid with methylamine nitrate in it, to precipitate the crystals of MMAN by heating until a slurry is reached, then use vacuum drying to remove the rest of the liquid, f.ex. water. Because the MMAN is hygroscopic, it will be impossible to drive off all the water unless heated under vacuum or placed in a desiccator. Extreme care must be taken when heating an explosive IT CAN EXPLODE. MMAN is safe enough that it only burns when strongly heated. Use either a hotplate, steam bath, or oil bath to heat the explosive. If you have access to vacuum equipment use the vacuum drying method.
Chemical formula = CH3NH3ONO2
Density = 1.2 g/mL
Molecular mass = 94.070 g/mol


METHYLAMINE CH3,H2(N)
is a colorless gas; has a fishy, ammoniacal odor; inflammable; is the most soluble gas known, one volume H2O dissolving 1,154 volumes of Methylamine at 12.5 degree C.
The solution is strongly alkaline and caustic. The aqueous solution possesses the odor of the gas, and is highly caustic and alkaline. It neutralizes the acids with formation of methylammonium salts(e.g.,CH3,H3,N,NO3=methylammonium nitrate),which are for the most part crystallizable and very soluble in H2O. Its chlorate crystallizes in beautiful golden-yellow needles, soluable in water, alcohol, and either. Its chloroplatinate crystallizes in golden-yellow scales, soluble in water, insoluble in alcohol.


DIMETHYLAMINE (C2H5)2HN
is a liquid below 8 degree c.; has an ammoniacal odor, and is quite soluble in H2O. it constitutes about 50 percent of the commercial trimethylamine, which also contains 5 to 10 % of trimethylamine, the remainder being a mixture of monomethylamine, isobutylamine, and propylamine. Its chloroplatinate forms long needles.


TRIMETHYLAMINE (CH3)3N
is formed by the action of methyl iodide upon NH3, and as a product of decomposition of many organic substances, it being one of the products of the action of potash on many vegetable substances, alkaloids, ect... It also occurs naturally in cod liver oil, ergot, chenopodium, yeast, guano, human urine, the blood of the calf, and many flowers. It is an oily liquid, having a disagreeable odor of fish; boils at 9 degree c.; alkaline; soluble in H2O, alcohol, and either; inflammable. It combines with acids to form salts of trimethyl ammonium, which are crystallizable. It has been found to be an important product of the putrefication in fish, starch-paste, brain tissue, muscular tissue, and other albumionoid substances, being accompanied by lesser quantities of monomethylamine, dimethylamine, ethylamine, and diethylamine, as well as by other pecular alkaloidal bodies. It has also been observed accompanying more active alkaloids in blood-serum,ect, which it has served for the culture of various bacilli. Its chloroplatinate crystallizes in octahedra, insoluble in alcohol. The commercial trimethylamine, obtained by the dry distillation of distillery-waste, contains but 6-10 % of the substance whose name it bares. (see dimethylamine above)

WISDOMwillWIN
 
 
 
 
    hCiLdOdUeDn
(Hive Addict)
06-24-03 17:24
No 442191
      removal of di- and tri-methylamine via chloroform  Bookmark   

Dimethylamine and trimethylamine salts are all soluble in chloroform while methylamine salts are not. This may be a great way of purification. Still one has the problem of seperating ammonium nitrate over the methylamine nitrate.....maybe metathesis reaction with NaCl to convert NaCl to NaNO3 and methylamine nitrate to methylamine hydrochloride? This way methylamine can crash out of solution? Im not sure, i guess the best way would be for a bee to experiment.

Would this reaction work without the addition of urea?
 
 
 
 
    LaBTop
(Daddy)
06-25-03 00:02
No 442255
      Yes, it would also work,  Bookmark   

but the presence of urea is to reduce the amount of free formic acid, which is produced in fair amounts (see patent) in the reaction if you don't add the urea.
But for some of you, formic acid would be an added present instead of a nuisance. LT/

WISDOMwillWIN
 
 
 
 
    hCiLdOdUeDn
(Hive Addict)
06-29-03 20:55
No 443333
      ahh i forgot this...  Bookmark   

methylamine nitrate is soluble in boiling ethanol, while ammonium nitrate is not.

Proposed ways of purification from post Formaldehyde/ammonium nitrate rxn.:

1) Wash & SHAKE the post rxn contents with 3x150mL chloroform to remove di- and tri-methylamine salts. Tap off the chloroform and discard or reclaim your chloroform.

2) Distill of the water/formic acid to leave a solid of ammonium nitrate and methylamine nitrate.

3) Add ethanol to the flask and heat until the boiling. The methylamine nitrate will dissolve into the hot ethanol while the ammonium nitrate will not. Filter/decant the hot ethanol from the ammonium nitrateand let it cool to 0C and filter off the precipitate which -should- be relativley pure methylamine nitrate.

This methylamine nitrate may not be pure enough for lab uses so a bee could add a conc. NaOH solution to the solid and form methylamine gas and bubble it through water or ethanol to make a methylamine sol.

The good thing about this method is that in SWIMs area, ammonium nitrate is found cheaply in huge quantities. SWIM hasnt tried this, but is guessing the above method should work.