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Author: Subject: Catching FOX no. 7 (with pics)
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cool.gif posted on 6-7-2018 at 05:14
Catching FOX no. 7 (with pics)


1,1-Diamino-2,2-dinitroethene or FOX-7 is an explosive developed in the late 1990's by the Swedish Defence Research Agency. FOX-7 shows significant improvements in sensitivity compared to RDX, particularly in response to friction and shock.

Molecular formula: C2H4N404
VOD : 8870m/s
Density : 1.88g/cm3
O2 balance : -21.6%
Molar mass : 148.08

I will be using FOI method 2 taken from the pdf file "FOX-7 a new insensitive explosive" by DSTO group.
All reagents were purchased or synthesized to as high standard as possible.
The synthesis is split up into three steps, the following is the first step performed in a half size batch.


REAGENTS

* 430ml methanol (dried with MgSO4 and freshly distilled)
* 116ml 30% Sodium methoxide solution (made with Na metal)
* 18.24g Acetamidine hydrochloride (lab grade)
* 27.92g Diethyl oxalate (collected at still head temp 170-185)
* 200ml dry methanol to dissolve Diethyl oxalate in

2-METHOXY-2-METHYL-4,5-IMIDAZOLIDINEDIONE

A 1 litre three neck flask was charged with 430ml methanol, and 116 ml 30%wt sodium methoxide solution.
18.24g Acetamidine hydrochloride was added and the solution stirred. The flask was fitted with a dropping funnel, drying tube and the final neck was just stoppered. Solution is milky white.

The diethyl oxalate in methanol was added at a slow drip rate over a period of 1.5-1.7 hours and then the reaction mixture was stirred for an additional hour. Solution has changed to light yellow after addition.

The whole reaction mix was dumped into a 2 litre beaker and acidified to ph 4 by the addition of 35% concentrated hydrochloric acid and ph test strips. Temperature did not rise much at all during this step.

The solution was double filtered with a vacuum pump and buchner and the solution (now clear) placed in a pyrex oven dish to evaporate. The paper says the temperature of evaporation must not be above 30C which means nearly 750ml of methanol plus a small amount of water must be evaporated at room temperature :o.
Will update upon recovery of the solid product.





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[Edited on 6-7-2018 by greenlight]

[Edited on 6-7-2018 by greenlight]

[Edited on 7-7-2018 by greenlight]




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[*] posted on 6-7-2018 at 05:24


Following this closely, as FOX-7 is something i've always been interested in.

Just one thing, i'm not sure what the actual reaction you are doing here, why are you making the imidazolidinedione? Is it a precursor to 2-methylimidazole? Just confused why that is starting point in the reaction diagram but not mentioned. I am slow though so sorry if its obvious
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[*] posted on 6-7-2018 at 05:32


I accidentally uploaded the wrong diagram haha.
The 2-Methoxy-2-methylimidazoledinedione is the heterocyclic intermediate product. Nitration of this intermediate and then hydrolysation with ammonia produces the final FOX-7.

[Edited on 6-7-2018 by greenlight]




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[*] posted on 6-7-2018 at 12:42


The need for FOX-7 in cast-cured formulation has been eliminated by various reduced sesitivity RDX formulation.
FOX-7 is still going to beat RDX in pressed formulations, though. Seeing a pressed formulation: 50 % FOX-7, 10 % AP, 10 % polymer and 30 % Al would be nice.
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[*] posted on 6-7-2018 at 19:37


Sounds fun, if I could find a route to the reagents I would love to try it.
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[*] posted on 8-7-2018 at 11:04


Quote: Originally posted by Hunterman2244  
Sounds fun, if I could find a route to the reagents I would love to try it.

2-METHOXY-2-METHYL-4,5-IMIDAZOLIDINEDIONE is one of them.




Oh, hello! :)

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[*] posted on 8-7-2018 at 12:03


Quote: Originally posted by joseph6355  
Quote: Originally posted by Hunterman2244  
Sounds fun, if I could find a route to the reagents I would love to try it.

2-METHOXY-2-METHYL-4,5-IMIDAZOLIDINEDIONE is one of them.

Yeah, I know. I would need to find routes to work towards the starting materials.
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[*] posted on 9-7-2018 at 02:53


The biggest problem with this method both on an amateur scale and a commercial level is the first 2-methoxy-2-methyl-4,5-imidazolidinedione step.

The reagents are hard for an amateur to find but the rest of the synthesis just requires easy to get acids and ammonia solution.
The other problem is the amount of solvent used. In the paper, the author uses over 1.5 litres of methanol to yield just under 20 grams of FOX-7. Using less solvent significantly lowers yields so on an industrial scale the reactors would have to be huge and not to mention the quantities of dry methanol needed.

On a brighter note all 750ml of methanol has nearly evaporated and the solid has crystallized out on top of the small amount of water remaining from the HCl addition. Soon I can recrystallize to get rid of the sodium chloride impurities before nitration.

[Edited on 9-7-2018 by greenlight]

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[Edited on 9-7-2018 by greenlight]




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[*] posted on 9-7-2018 at 03:35


why not bubble dry hcl gas in vigorously stirred mixture? then no added water!
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[*] posted on 9-7-2018 at 05:31


Yes, that is actually one of the alternative ways outlined in the paper. I just did it with the aqueous solution because I was pressed for time.



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[*] posted on 9-7-2018 at 07:32



Acetamidine HCl
http://www.orgsyn.org/demo.aspx?prep=CV1P0005




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[*] posted on 11-7-2018 at 12:36


I would think that with aspirator vacuum and a nice tight setup, it would be possible to distil the methanol below 30 C. Then you could recycle the solvent.
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[*] posted on 11-7-2018 at 20:57


This is good suggestion and if I repeat the synthesis, I will try it.
It seems methanol boils at 26.94'C at 140 mm/Hg from a quick Google search.




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[*] posted on 11-7-2018 at 21:09


Seems like a good application of a short path condenser too. Mild vacuum would help, but keep pumping freezing water though the condenser and you'd be able to recover a lot of the methanol.
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[*] posted on 11-7-2018 at 21:51


Ooh I don't have a short path condenser yet, must put it on the list.

I just finished drying the recrystallized product. There is an unusual error in the paper where it says the solid was dissolved in 320ml methanol, insoluble salts removed, and then the volume was reduced to 320ml?!?! before placing in a refrigerator.

Well I dissolved my 28g of solid in 160ml of boiling methanol because it's a half size batch and stirred for a few minutes, hot filtered, and the reduced it to about 1/3 of the initial volume. Then I placed it in a freezer overnight and filtered the next day.
I have 9-10g of insoluble crap and 14g of the intermediate product. This corresponds to only a 53% yield compared to the papers 64%:(
I have lost about 4 or 5 grams, but nevertheless, I will perform the nitration and alter the acid amounts accordingly to the loss of product.




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[*] posted on 11-7-2018 at 22:20


53% on the first run compared to the paper's 64% is mighty fine work and nothing to be sad about I think, great work so far
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[*] posted on 12-7-2018 at 07:17


Thanks Tdep:)

Looking over the next step it involves filtering a concentrated mixture of acids at the end with no water dilution like most He's. That shit eats straight through my filter papers,I just did a test with mixed acids.

I am going to have to order a better filtering funnel, maybe fritted glass for the next step before I proceed.






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[*] posted on 12-7-2018 at 17:15


Trick is get some fiber glass insulation wash thoroughly then blend it a few times fast, then as a wet slurry deposit it on your filter paper a few times to build up thickness,, then let dry, care fully separate it when damp then allow to dry fully.

It is good for one shot, I use this method to filter concentrated sulfuric acid in a large funnel.
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[*] posted on 12-7-2018 at 17:20


I assume that's only good if you're interested in keeping the filtrate. I'm not up with the FOX-7 procedure but I suppose you want to collect the precipitate and remove it from the mixed acids, in which case a glass frit is good. I have used one many times and I stand by them. Just maybe don't pull those fumes into a pump you like.... pulling them into a pump you hate is fine though
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[*] posted on 12-7-2018 at 21:26


Yes, I need to separate and keep the precipitate which is highly acidic and is one of the worst things to filter. I will put a glass fritted funnel on order.




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