FOX-7 (1,1-diamino-2,2-dinitroethylene), Alternative Synthesis

[Backdraft]

Hi all, i have adapted a alternative route to a FOX-7 synthesis. Some ideas came up following megalomanias files and might that the following procedures are not even costly. The procedure consists two steps and requires 1,1-dichloroethylene.

Redacted until proof provided. NBK


Step 1, Preparation of 1,1-dichloro-2,2-dinitroethylene:
Into a 1000 mL round-bottomed flask prepare a mixture of 50 g of dichchloroethylene and 490 mL of concentrated (96-99%) sulfuric acid. Place the flask to a salt ice bad, dropwise add 85 mL (42,75 ml calculated) of concentrated (99-100%) nitric acid and mantain the temperature of the addition below 20 °C. After the addition is complete, remove the flask from the salt ice bad, stir the mixture for an hour and allow to heat to 30 °C during the period. The mixture is then stirred for additional 30 minutes and the temperature of the reaction is monitored at all times, a external cooling bad may help. After that, slowly stir the mixture into a large flask with 2000 mL of ice water, let stand the flask at 0 °C for an hour, pour the content of the beaker over a filter to collect the crude crystals of 1,1-dichloro-2,2-dinitroethylene. Wash them with with a portion of 10% sodium hydrogen carbonate solution, several small portions of cold water and let them dry on a warm place or under vacuum.

Step 2, Preparation of 1,1-diamino-2,2-dinitroethylene:
Dissolve the obtained 1,1-dichloro-2,2-dinitroethylene (around 96 g) from the previous step in 800 mL of toluene in a large round-bottomed flask. Place the flask to a weighing machine and bubble dry ammonia gas through the solution until the FOX-7 precipitates and no weight is increased. Pour the content of the flask over a filter to collect the crystals, wash them several times with samll portions of water and dry them under vacuum. Yield is 73 g or 97%.


I was also thinking a various variety of nice and friendly nucleophilic substitutions was developed to obtain the material. I`m lucky my first post keep me away from banning.

[nbk2000]

Pictures of apparatus required.

Not random white crystals, but apparatus, as that costs, and bullshitters wouldn't have it.

RTPB: Trust, but verify.

[Chris The Great]

I don't think he's actually DONE the procedure, am I correct? Where did you get the original procedures (or the ones these are based on, if that is the case?)

The reactions seem legit but verification would be nice, it certainly wouldn't be hard to do if the starting material was obtained... where would one get that anyway? Is there an OTC source?

[megalomania]

That’s a very interesting synthesis, but have you actually tried that yourself? You see, you can’t just nitrate an alkene with highly concentrated nitric acid and sulfuric acid and not break the double bond. You will only get trace amounts of nitroalkenes doing it that way. Even if you used a more mild nitration reaction with dilute nitric acid, which is the preferred method of avoiding breaking the double bond, your yields will still be pitiful. What you will end up with is almost exclusively 1,1-dichloro-1,2-dinitroethane.

Your second step is even worse than the first. The primary amine that is your intended product will also be reactive towards ammonia and this will create a competing reaction. Alkyl halides will react by nucleophilic substitution, but so will the formed alkyl amines. You will form dialkyl amines, and even those will react further to form trialkyl amines. You end up with a very pitiful yield of FOX-7 by directly adding ammonia.

Your chemistry works in theory, but it fails in practicality. Congratulations, you just invented a synthesis for FOX-7 that costs $100,000,000 a Kg, call the pentagon as they might be interested.

[deiki]

Since this molecule has similarities with TATB, tweaking its synth should give the obvious route to FOX-7. Unfortunately it doesn't work :p . See the link here ( 2nd page )

'http://www.dsto.defence.gov.au/publications/2412/DSTO-TR-1238.pdf'

It starts from 1,1-diiodoethylene, but unfortunately, it doesn't end with FOX-7 as the amination step doesn't work with ammonia. It is still possible to do it with a primary amine though. You could try aminating it with urea, and hydrolysing the amide bonds to end up with FOX-7, but I still highly doubt it would be successful.

[hereno]

Being one of the very few explosives of industrial/military significance, I would think that all obvious routes to it have been thoroughly studied. The above article gives about $2-300 per 100g from "chemical supply" chemicals.

Anyway, the product of the attempted amination of diiododinitroethylene, as also shown in the above article wasn't the expected FOX-7. The actual product obtained was brought up at sciencemadness, as being dinitrocyanomethane http://www.sciencemadness.org/talk/viewthread.php?tid=6898 . Whatever the case these products are nicely reactive intermediates which would be useful, but no, its not FOX-7.

BTW: Is there a FOX-6, FOX-2 etc. like there is CL-20, CL-16 etc. It would be interesting to have a list of these explosives that were interesting enough to be studied by the various laboratories.

[Hex]

There's FOX-12, which is guanylurea dinitramide.
New routes to FOX-7 are still being investigated; it's still an expensive synthesis and the dinitromethane by-product is a bad waste stream to have industrially.

[Hystrix]

2 Backdraft
It was an attempt of similar synth some years ago (IIRC authors of that article were Baum & Co.). They nitrated 1,1,2,2-tetraiodoethylene to 1,1-diiodo-2,2-dinitroethylene and then treated it with amines. Such route allowed to prepare some alkylated analogs of FOX-7 but using ammonia they obtained ammonium salt of dinitroacetonitrile only. Therefore I doubt your dichloro pathway will be successful. And yet more I doubt that 1,1-dichloroethylene can be nitrated in such manner.