Sciencemadness Discussion Board

Preparation of Methylammonium nitrate

AJKOER - 23-9-2012 at 15:59

Here is a list of preparations for Methylammonium nitrate that may be already known to some.

1. This one is based on the known reported reaction in Wikipedia upon treating formaldehyde with ammonium chloride:

NH4Cl + H2CO → [CH2=NH2]Cl + H2O
[CH2=NH2]Cl + H2CO + H2O → [CH3NH3]Cl + HCOOH

The proposed idea is to replace NH4Cl with NH4NO3, then one would expect:

NH4NO3 + 2 H2CO + H2O --> [CH3NH3]NO3 + HCOOH

Some support for this position was recently indirectly implied by AndersHoveland (http://www.sciencemadness.org/talk/viewthread.php?tid=19106 ). To quote: "It is also well known that ammonium nitrate can be made to condense with formaldehyde, and dehydrated to the nitramine, using a strong dehydrating agent such as acetic anhydride." together with the statement "Dimethylnitramine has been prepared in 65% yield by the dehydration of dimethylamine nitrate in acetic anhydride to which 4% mole percentage anhydrous zinc chloride had been added."
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2. Another route is first the preparation of CH3NO3 via the treatment of CH3I with AgNO3 in an alcoholic solution:

CH3I + AgNO3 --> CH3NO3 + AgI (s)

Source: "Chemistry for students" by Alexander William Williamson, page 256, link: http://books.google.com/books?id=aBAFAAAAQAAJ&pg=PA279&a...

Interestingly, Iodomethane, CH3I, (unlike CH3Cl and CH3Br) is a dense, colorless, volatile liquid at room temperature. Also, CHI3 is a stronger alkylating agents than CH3Cl or CH3Br, but is perhaps more dangerous in the lab being highly reactive.

Then, the final step per Franklyn (http://www.sciencemadness.org/talk/viewthread.php?tid=744&am... ): "Heated with alcoholic ammonia [referring to CH3NO3], it yields methylamine nitrate. CH3NH2.HNO3"

So, upon adding ammonia to the alcoholic products of the CH3I and AgNO3 after filtering out the AgI and applying heat, one has [CH3NH3]NO3. Support for this synthesis is also found in a prior thread (http://www.sciencemadness.org/talk/viewthread.php?tid=11319&... ), to quote Klute: "Or react ammonia or (mono-, di-, tri-)methylamines with excess methyl nitrate".
-----------------------------------------

3. Another path is based on the ammonolysis of Chloromethane to first form methylamine, CH3HN2:

CH3Cl + NH3 --> CH3NH2.HCl --> CH3NH2.HCl + NH3 --> CH3NH2 + NH4Cl

Source: See http://www.docstoc.com/docs/68188299/CHAPTER13

Note, Chloromethane can be produced by a photo-chemical induced chain reaction:

CH4 (g) + Cl2 (g) --> HCl (g) + CH3Cl (g)

which is desribed by Wikipedia as a moderate to fast (see: http://en.wikipedia.org/wiki/Free-radical_halogenation ).

The next step is to add HNO3 to create dimethylamine nitrate:

H(+) (aq) + CH3NH2 (aq) --> CH3NH3(+) (aq)

As a source, see top of last page at: http://math-wizard.com/netionic.pdf and also Wikipedia that notes "It [Methylammonium nitrate] is the salt formed by the neutralization of methylamine with nitric acid." Link: http://en.wikipedia.org/wiki/Methylammonium_nitrate
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4. On a prior short answer thread (http://www.sciencemadness.org/talk/viewthread.php?tid=11319&... ), to the question: "Any idea how to synthesize tetramethylammonium nitrate?", an answer by Not_Important: "React tetramethylammonium chloride/bromide/iodide with AgNO3 in solution, filter off the silver halide ppt."

Actually this source (http://guweb2.gonzaga.edu/faculty/cronk/CHEM240pub/L21-index... ) notes the reaction between CH3I and NH3 to form methylammonium iodide in a similar fashion to CH3Cl + NH3 --> CH3NH2.HCl in [3] above. However, unlike Synthesis [3], the suggested nitration occurs via AgNO3 used in Synthesis [2].
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Please comment on any of the above synthesis or supply more methods.

Thanks.
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Background Material (Wiki: http://en.wikipedia.org/wiki/Methylammonium_nitrate )

"Methylammonium nitrate was first used as an explosive ingredient by the Germans during World War II.[1] It was originally called mono-methylamine nitrate, a name that has largely stuck among chemists who formulate energetic materials.
Methylammonium nitrate is somewhat similar in explosive properties to ammonium nitrate (AN) which yields 85% of the power of nitroglycerine when the ammonium nitrate is incorporated into an explosive. The addition of the carbon-containing methyl group in methylammonium nitrate imparts better explosive properties and helps create a more favorable oxygen balance.
Following World War Two, relative to less costly ammonium nitrate, methylammonium nitrate was largely ignored by explosives manufacturers. Ammonium nitrate fuel-oil mixtures (ANFO) were sufficient for most large-diameter explosives uses.
Methylammonium nitrate saw a resurgence when E. I. du Pont de Nemours and Company, seeking to lower the cost of its TNT-based "Tovex" water gels, incorporated a mixture of methylammonium nitrate with ammonium nitrate which served as a basis for DuPont's water gels manufactured under the names "Tovex" "Extra" and "Pourvex" "Extra". Methylammonium nitrate, also known as PR-M (which stands for "Potomac River - Mono-methylamine nitrate") soon was seen as the possible path toward creating a low cost blasting agent (water gel explosives) that might replace the explosives based on nitroglycerin (dynamites).
In late 1973, DuPont started to phase out dynamite and replace it with water gels based on PR-M. However, PR-M proved to have unusual "mass effects". "


[Edited on 24-9-2012 by AJKOER]

Motherload - 26-9-2012 at 21:23

I don't believe reacting AN with CH2O will produce MeAN.
That reaction is used to figure out the purity of AN as it produces HNO3 which is titrated against a base.

AJKOER - 27-9-2012 at 05:03

As to Motherload point, here is a reference referring to the "The Formaldehyde Method for Determining Ammonium Nitrate" at http://pubs.acs.org/doi/abs/10.1021/ie50122a026 . Upon reading the extract, however, I suspect a select base, temperature or other catalyst is, in fact, needed to produce the reaction I noted, as the author states that with an excess of NaOH the formation of Sodium formate as the result of the creation of Formic acid. An important reaction noted (as will be explained below) is the formation of Hexamethylenetetramine (or HMT):

6 CH2O + 4 NH4NO3 + 4 NaOH --> C6H12N4 + 4 NaNO3 + 10 H2O

Another source is more supportive (see http://www2.dupont.com/Methylamines/en_US/uses_apps/explosiv... ) to quote: "Water gel explosives have been used in the mining industry due to their ease and safety in handling. The prime ingredient is monomethylamine nitrate made from MMA [which the author defines as CH3NH2], formaldehyde, and ammonium nitrate." Note, per Wiki (see http://en.wikipedia.org/wiki/CH3NH2 ) "Methylamine is a good nucleophile as it is highly basic and unhindered, although, as an amine it is considered a weak base. Its use in organic chemistry is pervasive" so I am not surprised on its use here.

Now, another more source ("Riegel's Handbook of Industrial Chemistry" by Emil Raymond Riegel, James Albert Kent, pages 1328 and 1329, link: http://books.google.com/books?id=j3AwCqvqIzEC&pg=PA1328&... ) notes, quite interestingly, that both RDX and HMX are cyclic nitramines that can be made by the nitrolysis of HMT. For example per the cited author's Reaction 1 which may actually require a catalyst (like ZnCl2, see AndersHoverland comments in the opening thread):

HMT + 4 HNO3 <--> RDX + NH4NO3 + 3 CH2O

where HMT, per above, is a product of the reaction of AN and CH2O in the presence of a base. Now, NaOH is cited above but using NH3 (speculation) generated from, say, the low temperature (under 200 C) 1st stage thermal decomposition of AN which includes HNO3, may create NH4NO3 in place of NaNO3 and the freed HNO3 could react with HMT per Reaction 1. More likely, adding a strong dehydrating acid (H2SO4 or H3PO4) to the reaction products of CH2O, NH4NO3 and NaOH, may form RDX per the reaction above.

An important pertinent cited Reaction 2 is:

3 CH2O + 3 NH4NO3 + 6 (CH3CO)2O <--> RDX (CH2 N NO2)3 + 12 CH3COOH

noting the direct creation of RDX with CH2O, AN and Acetic anhydride in large excess. Prior thread quote (link: http://www.sciencemadness.org/talk/post.php?action=reply&... ):
Quote: Originally posted by AndersHoveland  
The so called "E" method of nitration, initially developed by Ebele, does not require any nitric acid, but does require a large excess of acetic anhydride. Later, in 1940, independant from the research of the german Ebele, Ross and Schiessler, at McGill University, obtained RDX from formaldehyde, ammonium nitrate and acetic anhydride in the absence of nitric acid.
"Addition of boron fluoride to the mixture promotes the initiation of the reaction and increases its safety"
"The conduct of the reaction in the presence of boron fluoride reduces the number of by-products formed"
[Chemistry and Technology of Explosives Vol. III, T. Urbański, 1967 - Pg.109]


Caution, those attempting any synthesis using commercial grade CH2O should be forewarned on common impurities including metal ions. As these are known to sensitive AN (and possibly derivatives thereof), particular precautions should be exercised.


[Edited on 28-9-2012 by AJKOER]

SM2 - 27-9-2012 at 08:51

keep in mind, methyl ammonium nitrate is probably double fold watched. methylamine, in any of it's salts, and just the formally innocent fertilizer/Bomb. If you were to add methylammoniumnitrate to a solution of lye, you'd get methylamine. And even plain ammonium nitrate now being demonized as the assistant crack whore's favorite way of making meth.

So you see, this simple compound has three things running against it, to consider.

[Edited on 27-9-2012 by Fennel Ass Ih Tone]

AJKOER - 27-9-2012 at 10:28

Fennel Ass lh Tone:

Good point.

This thread has an added advantage in enlightening the casual garage chemist against accidentally making something (and keeping it and/or making a public inquiry) on a substance in quantities that would be hard to explain in closely watched environments.

In addition, large purchases of precursors noted above may also bring about unwanted scrutiny. These would possibly include CH2O, NH4NO3, HNO3, AgNO3, CHI3, CH3Cl, (CH3CO)2O,..


[Edited on 27-9-2012 by AJKOER]

Rosco Bodine - 27-9-2012 at 22:13

Maybe look through some of these search hits
http://www.sciencemadness.org/talk/search.php?token=&src...

The two " formite " ( formaldehyde / AN reaction mixture ) patents that I know about are

EP0037862

GB1548827


Patent related to such mixtures value in cast melts

US1968158

Related reaction under alkaline conditions which
produces hexamine instead

US3660182

Slurry related hexamine containing AN composition

US3496040

also maybe these search hits would be interesting
http://www.sciencemadness.org/talk/search.php?token=&src...



[Edited on 28-9-2012 by Rosco Bodine]

AJKOER - 28-9-2012 at 05:23

In actuality, many of the synthesis outlined in the opening thread are intricate. For example, the following procedure is archived in the "The Hive":

Methylamine Hydrochloride from Ammonium Chloride and Formaldehyde
-----------------------------------------------------------------------------------------------------
In a 5 liter round-bottomed flask, fitted with a stopper holding a condenser set for downward distillation and a thermomether which will extend well into the liquid, are placed 4 kg (3711 ml, 47-53 moles) of technical formaldehyde (35-40 percent; d 1.078 at 20°C) and 2 kg (37 moles) of technical ammonium chloride. The mixture is heated on the steam bath until no more distillate comes over and then over a flame until the temperature of the solution reaches 104°C. The temperature is held at this point until no more distillate comes over (four to six hours). The distillate, which consists of methylal (bp 42-43°C), methylformate and water may be treated with NaOH solution to recover methylal and sodium formate. The contents of the reaction flask are cooled too room temp and the ammonium chloride which separates is filtered off. The mother liquor is concentrated on the steam bath under reduced pressure to 2500 ml, and again cooled to room temp, whereupon a second crop of ammonium chloride separates. The total recovery of ammonium chloride up to this point amounts to 780-815 grams. The mother liquor is again concentrated under reduced pressure until crystals begin to form on the surface of the solution (1400-1500 ml). It is then cooled to room temperature, and a first crop of methylamine hydrochloride, containing some ammonium chloride is obtained by filtering the cold solution. At this point 625-660 grams of crude product is obtained. The mother liquor is now concentrated under reduced pressure to about 1000 ml, and cooled, and a second crop of methylamine hydrochloride (170-190 grams) is then filtered off. This crop of crystals is washed with 250 cc of cold chloroform, and filtered to remove most of the dimethylamine hydrochloride which is present. After the washing, the product weighs 140-150 grams. The original mother liquor is then evaporated under reduced pressure, as far as possible, by heating on a steam bath, and the thick syrupy solution (about 350 ml) which remains is poured into a beaker and allowed to cool, with occasional stirring, in order to prevent the formation of a solid cake, and the crystals obtained are washed with 250 ml of cold chloroform, the solution is filtered yielding 55-65 grams of product. There is no advantage in further concentrating the mother liquor, which contains mostly tetramethylmethylenediamine hydrochloride, but no trimethylamine hydrochloride. The total yield of methylamine hydrochloride is 830-850 grams. The product contains water, ammonium chloride and some dimethylamine hydrochloride. In order to obtain a pure product, the impure methylamine hydrochloride is recrystallized from absolute ethanol (solubility 0.6g/100ml at 15°C), or preferably butyl alcohol (even less soluble). The recovery of ammonium chloride amounts to 100-150 grams, making the total recovery 850-950 grams. The yield of recrystallized methylamine hydrochloride is 600-750 grams (45-51 percent of theory, based on the used up ammonium chloride).
A standard run, from 250 grams ammonium chloride and 500g 37% formaldehyde (containing 15% methanol), gives 100-134 grams methylamine hydrochloride, 27 grams dimethylamine hydrochloride and 81 grams of recovered ammonium chloride. The distillate contains methylal (formaldehyde dimethyl acetal) and methyl formate, which after treatment with NaOH can yield 25g of sodium formate and 30 grams of methylal, as the compound cannot be separated by fractional distillation, neutralization is the way to go. Ammonium chloride is very sparingly soluble in a concentrated solution of methylammonium chloride, making the separation of the compounds pretty sharp.

Similarly, Hexamine and HCl may be used as the reactants instead, illustrating that the order of reaction of CH2O, NH3, and acid does not matter.

AJKOER - 28-9-2012 at 05:51

Thanks Rosco Bodine for the patent references.

In particular Patent EP 0037862 makes an important point on the need for Urea. To quote "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"

Link: http://www.google.com/patents/EP0037862B1?cl=en

AndersHoveland - 28-9-2012 at 05:53

Quote: Originally posted by AJKOER  
NH4NO3 + 2 H2CO + H2O --> [CH3NH3]NO3 + HCOOH

Yes, I had this same idea before. The only reason I can think of that this might not work is the fact that NH4NO3 begins to become a reactive oxidizer at elevated temperatures. The reaction to make methylamine hydrochloride salt tends to become self-sustaining at around 90°C. I am not sure if that is hot enough to create a potential danger with the NH4NO3, but the effects of localised heating at the bottom of the flask should also be considered if the reactants are not dissolved in some solvent.
Quote: Originally posted by AJKOER  
Another route is first the preparation of CH3NO3 via the treatment of CH3I with AgNO3 in an alcoholic solution:
Source: "Chemistry for students" by Alexander William Williamson

I have some doubts about this. Another online educational chemistry site mentions that an alcohol and haloalkane react in the presence of silver nitrate to form an ether, silver halide, and nitric acid.
Nucleophilic Substitution Reactions, by C. Snelling
http://www2.volstate.edu/chem/2010/Labs/Sn1_Sn2.html

Benzene or toluene would be a more guaranteed bet as the solvent for the reaction. Benzene has the unique ability to be able to dissolve several silver salts.

This site may also be informative:
http://www.chemguide.co.uk/organicprops/haloalkanes/agno3.ht...

If I remember correctly, I believe I had also read somewhere that silver nitrate can react with ethanol under certain conditions to form an explosive product (whether it is silver fulminate or ethyl nitrate I am not sure). Just to be completely clear, this reaction could proceed without any initial nitric acid, as obviously we know that silver fulminate is made from a combination of these 3 chemicals.

I am also not entirely sure whether silver nitrate could potentially oxidize ethanol. "Alcoholic silver nitrate" is certainly mentioned in several places in the literature. Tollen's regent does not attack alcohols (but does oxidize aldehydes).

Apparently silver carbonate can oxidize alcohols when refluxed (heated) in benzene.
"Fétizon’s Reagent: Silver Carbonate on Celite", Gabriel Tojo, Marcos Fernández, from "Oxidation of Alcohols to Aldehydes and Ketones", Basic Reactions in Organic Synthesis, 2006

Something else you should realise is that these types of substitution reactions tend to be very slow. This related reaction may be of interest:
Quote:

The product of the reaction between solid silver perchlorate and methyl iodide "explodes violently when struck" [M. F. Radies and T. Iredale, J. Phys. Chem., 48, 224 (1944)]. Handle the silver perchlorate very carefully, since it, too, detonates with disturbing frequency when struck or jarred. The reaction is rather slow. Assuming 0.7 M CH3I and 0.5 M AgClO4 concentrations, at standard temperature, it is calculated that it will take forty-five hours to convert 98% of the silver perchlorate to methyl perchlorate.


[Edited on 28-9-2012 by AndersHoveland]

AJKOER - 31-10-2012 at 21:09

I would like to qualify my prior comment:

"Note, Chloromethane can be produced by a photo-chemical induced chain reaction:

CH4 (g) + Cl2 (g) --> HCl (g) + CH3Cl (g) "

I should have noted that this reaction, which is performed industrially, is carried out in diffused sunlight as direct sunlight is reported to produce a detonation with Chlorine proceeding as follows:

CH4 + 2 Cl2 --> C + 4 HCl
-------------------------------------------------------------

As a side note, apparently CH3NH2 can be readily prepared in a laboratory by the action of Ca(OCl)2 on Acetamide (for clues on CH3CONH2 preparation see http://www.sciencemadness.org/talk/viewthread.php?tid=18777#... ) followed by warming and treatment with NaOH (see as a source http://www.scribd.com/doc/62402536/The-Preparation-of-Methyl... ). I would think one could substitute for Ca(OCl)2 any equivalents including by the action of Cl2 on NaOH, HOCl, Cl2O.. and a strong base. Bromine can also be used and here is a referenced (http://www.pdfdocspace.com/docs/65323/nitrogen-containing-co... ) reaction:

"4. Hofmann bromamide reaction

CH3CONH2 + Br2 + 4KOH = CH3NH2 +2KBr + K2CO3 + 2H2O "

[Edited on 1-11-2012 by AJKOER]

PHILOU Zrealone - 1-11-2012 at 05:25

1°)Trimethylamine chloride is formed aside dimethylamine chloride and methylamine chloride!
So you need to separate CH3-NH3Cl from NH4Cl and the rest

Methylamine chloride synthesis:
http://orgsyn.org/orgsyn/prep.asp?prep=cv1p0347

Trimethylamine chloride synthesis:
http://orgsyn.org/orgsyn/prep.asp?prep=cv1p0531

2°) Trimethylamine forms faster than dimethylamine wich forms faster than methylamine when methyl halide is reacted with ammonia...so one must work with a large excess of ammonia to lower quantity of higher MW amines!

3°)With NH4NO3 and CH2=O under heating is a wish for an incident since CH3-NH3NO3 is more sensitive than NH4NO3 to heat...spontaneous ignition might result during reaction process. Hexamine dinitrate also forms.

4°)Chloration of CH4 into CH3-Cl suffers also from higher reactivity towards Cl2 in the sequence:
CH4 << CH3-Cl << CH2Cl2 << CHCl3
Thus also a big excess of CH4 must be used and fractionnal distillation to isolate each.

[Edited on 1-11-2012 by PHILOU Zrealone]

[Edited on 1-11-2012 by PHILOU Zrealone]

Rosco Bodine - 3-11-2012 at 09:15

Trimethylamine perchlorate is a material of interest because of its sensitivity at a drop test of 25 cm .....twice as sensitive as Guanidine Perchlorate at 50 cm.....compared with picric acid 85 cm. I haven't found any output data regarding TMA perchlorate .....so does anybody have any lead block expansion or velocity data for TMA perchlorate ?? The drop test figure indicates it should be easy to initiate. So the next interest would be what sort of energy it has.

ANFO_ - 3-11-2012 at 09:51

Rosco, on that note, do you have any information on trimethylamine-n-oxide perchlorate's explosive properties?

Rosco Bodine - 3-11-2012 at 11:08

No. I did see it listed while searching for the energy data for TMA perchlorate, but I did not look at the n-oxide variant.

What I was thinking about collaterally as an interest is the possible mixture of nitrocholine perchlorate with TMA perchlorate. The nitrocholine perchlorate is heat sensitive and might form a synergistic blend with TMA perchlorate which might be fuse sensitive to a cookoff and self-accelerating high order detonation. And yet the synergistic system there would contain no primary explosive nor metallic salts whatever. So the technology there could be very interesting. Possibly also such a system could be arranged as a sequential loading with the nitrocholine perchlorate as an initiator for the TMA perchlorate. Going further, with use of triaminoguanidine perchlorate as the initiator, or alternatively DDNP ....a detonator having no metallic salts whatever could be made which could fit the bill as a "green" technology detonator having no metallic residues as byproducts yet still be cheap, relatively low tech in complexity and usable with a blackpowder fuse ignition.

[Edited on 3-11-2012 by Rosco Bodine]

AndersHoveland - 8-11-2012 at 07:45

Quote: Originally posted by Rosco Bodine  
does anybody have any lead block expansion or velocity data for trimethylamine perchlorate ??

Pyridine perchlorate has a lead block rating of 95% TNT, so it should not be too difficult to extrapolate.

Rosco Bodine - 14-11-2012 at 01:04

Quote: Originally posted by ANFO_  
Rosco, on that note, do you have any information on trimethylamine-n-oxide perchlorate's explosive properties?


See attached files.
If I understand correctly the GB1364131 patent Nobel composition is an anhydrous low melting eutectic mixture containing some urea which is a liquid not segregating by crystallization stable down to -20C and provides a Trauzl lead block expansion test for 10g of 525cc Compare to TNT 452cc and PA 470cc would provide a RE 1.16 for the Nobel patent liquid explosive.

Methylamine Perchlorate has an RE of 1.67
Guanidine Perchlorate has an RE of 1.3
ETN has an RE of 1.51
PETN has an RE of 2.0



Attachment: Trimethylamine oxide perchlorate ACS monograph 1960.pdf (66kB)
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Attachment: Trimethylamine - PATR Vol. 9 Q-T-2.pdf (102kB)
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Attachment: TMA - PATR Vol. 9 Q-T.pdf (103kB)
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Attachment: GB1364131 Nobel amine perchlorate explosives.pdf (398kB)
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Attachment: Methylamine perchlorate RE 1.67 PATR - Vol. 2 B-C.pdf (48kB)
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Attachment: guanidine Perchlorate RE 1.3 PATR - Vol. 2 B-C-2.pdf (52kB)
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[Edited on 15-11-2012 by Rosco Bodine]

Ral123 - 17-11-2012 at 03:54

How can PETN be 2.0 and ETN be 1.51? I'm looking for tables with the performances of different explosives with different tests.

Rosco Bodine - 17-11-2012 at 08:43

Quote: Originally posted by Ral123  
How can PETN be 2.0 and ETN be 1.51? I'm looking for tables with the performances of different explosives with different tests.


Guanidine perchlorate also seems low for its reported RE. I have also seen other reported RE values that seem a bit low to me. I did not perform the same tests using a 10 gram sample. PATR Vol. 2 is where a few pages of these values are found. But the PATR data is quoted from an original publication.

Attached is the whole section of related pages from PATR

Attachment: Brisance pages PATR Vol. 2 B-C.pdf (2MB)
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