What is FOX-7?

[megalomania]

I have recently heard about a new kid on the block called FOX-7, that’s milspeak for 1,1-diamino-2,2-dinitroethylene. I believe it may have been first synthesized in 1998, although I am very likely wrong on this. The handful of references I have seen thus far never mention it by name before then. It is a surprisingly simple looking molecule, rather reminiscent of dinitroethane, but it is being lumped in with the high-energy high-density (HEDM) group of explosives. It is reported as being more resistant to impact and friction as HMX or RDX, which is purported to be because of pi resonance of the ethylene portion. The explosive performance (read into that what you may) is only rated at 85-90% of HMX.

For more of those details people who are not me enjoy, check out <a href="http://www.sainc.com/onr/detsymp/PaperSubmit/FinalManuscript/pdf/Karlsson-165.pdf" target="_blank">http://www.sainc.com/onr/detsymp/PaperSubmit/FinalManuscript/pdf/Karlsson-165.pdf</a>
Alas I have no synthesis information other than an outline. It seems rather simple to make IF the necessary precursor can be obtained. We begin with some 2-methylimidazole and nitrate it, it becomes something quite complex, and then we add some aqueous ammonia and poof it snaps off the complex stuff leaving the simple FOX-7 molecule. Now if I only had some 2-methylimidazole… Not many of these new explosives (or should I say none) go from a complex molecule, to a more complex molecule, to a simple molecule that looks like it should have been made 150 years ago.
See <a href="http://www.sainc.com/onr/detsymp/FinalPapers/DE197.pdf" target="_blank">http://www.sainc.com/onr/detsymp/FinalPapers/DE197.pdf</a> for yet more.

[Mr Cool]

Hmmm... but how to get to 2-methylimidazole..?
Condensation of ethanoic acid with 1,2-diaminoethene maybe (in a similar sort of way to making triazolone), but how would we get the latter compound? Perhaps we could halogenate ethyne to get 1,2-dihaloethene and react that with ammonia.

Unless we can find an OTC product that can easily be converted to 2-methylimidazole, and that can be bought in bulk, then I don't think it'd be a practical HE for us, although it'd be interesting to make.

[Mr Cool]

From "New Explosives" pdf:

"A synthesis more amenable to scale-up involves the condensation of acetamidine hydrochloride and diethyl oxalate in MeOH to yield a mixture of 2-methylene-4,5-imidazolidinedione and 2-methoxy-2-methyl-4,5-imidazolidinedione (23). Recrystalisation of the mixture from MeOH yields 23 which was nitrated and treated with ammonium hydroxide [at pH 8-9] to yield FOX-7 in 50% overall yield."

pH 8-9 is also used in the step with ammonium hydroxide in the process that Mega outlined.

It's also called DADNE, which might help when searching for info.

VoD is 8870 m/s, PoD is 34.0 GPa.

<small>[ December 26, 2002, 06:21 PM: Message edited by: nbk2000 ]</small>

[kingspaz]

i'm probably spouting crap here but can't ethene be made from dehydrating ethanol in 98% H2SO4? so maybe that could be another route to it. not the ethene, but if you made a saturated version with an H and OH on it (in place of the double bond) then treatment with H2SO4 would yield the FOX-7.

[ALENGOSVIG1]

Ether is produced by reacting sulphuric acid and ethanol. But if the reaction runs too hot ethane is made.

[DeusExMachina]

<a href="http://www.verkstaderna.se/mtt/pdf/200102/energetic%20materials.pdf" target="_blank">http://www.verkstaderna.se/mtt/pdf/200102/energetic%20materials.pdf</a>

this PDF page taks about Fox-7 but I think it is mainly focused on ADN, an underwater explosive. It says that Fox-7 is a little less powerful than RDX.

[megalomania]

There is a thread of hope in obtaining the necessary precursors, if all the chemistry works out. There is a close relative to methylimidazole, namely imidazole itself. This stuff has been known for quite some time, it is made by reacting glyoxal, aka ethanedial, with some ammonia and formaldehyde. Presumably the ammonia goes after the carbonyl carbons of the glyoxal and then both the nitrogens go after the carbonyl of the formaldehyde and everything forms a ring, at least that’s what I guess would happen. Glyoxal can itself be made by reacting acetaldehyde with nitric acid, and those two should not be that hard to obtain.

The question then is how to get that methyl group on there. If the formation of imidazole happens the way I think it does, then the presence of an extra methyl on formaldehyde, which would be acetaldehyde, should give us the final product. That means this explosive can be made from little more than acetaldehyde, formaldehyde, ammonia, and nitric acid.

I can see where the interest the military has comes in. If those are the starting ingredients, this stuff should be quite cheap to churn out. Looking in the Aldrich catalog for 2-methylimidazole, they have 500 g for $40.80, which is cheap for Aldrich prices and implies it should be cheap to make.

I have made a graphic to help illustrate the proposed formation of the essential precursor 2-methylimidazole. Theoretically one should be able to vary the choice of aldehyde that reacts with the imine, in this case we use acetaldehyde instead of formaldehyde and viola.
<img src="http://www.roguesci.org/images/imidazole_synth.gif" alt=" - " />

[nbk2000]

It may be that the methyl version is the most desirable militarily, but not the only version that explodes. If you used formaldehyde instead of acetaldehyde, would it not still form the "wobbly H" molecule?

And, if I'm not mistaken, imidazole compounds are used in drugs. Perhaps The Hive might have some info on their synthesis?

[megalomania]

No it would not work if formaldehyde was used and just imidazole was obtained. The ethene portion of FOX-7 plays a very important role in this explosive, and that only comes from 2-methylimidazole. When 2-methylimidazole is nitrated it happens thusly:
<img src="http://www.roguesci.org/images/FOX-7.gif" alt=" - " />

Unless you mean form the imine itself from formaldehyde, in which case all you would get is H₂C=NH. I think the whole reason the ring is so important is that it acts as a protecting group for either the amine portions or the double bond during the nitration. Otherwise it would be very difficult to get an ethene from 1,1-diamino-2,2-dinitroethane and double bonds tend to be too reactive which would make an amination or nitration too difficult. Again this is likely why FOX-7 has only recently become a hot commidity even though the chemical players and reactions have been known for 150 years, nobody bothered to play with such a big molecule like this :) Why imagine if they had this stuff in WWI or WWII, they knew about Imidazole since the late 1850's (obtained from coal or oil) and figured out how to make it in the early 1900's. There is probably some info at the MOA website as a matter of fact. It is quite possible that such a compound may have stretched the organic fuel stock of one side or the other. The Japs were always running out of petrochemicals, namely aromatics. If acetaldehyde became a major feedstock it could have extended the munitions of the Axis powers. Maybe just enough... Just my 2 cents.

[nbk2000]

A quick check at the USPTO site for 2-methylimidazole came up with more than 6,000 hits. When I threw in "preparation", "production", or "purification" as second terms, it still came up with more than a thousand. :(

Is there a more generic term for it? Like how methyl chloride would be called an alkyl halide? Usually, with patents, the more generic the term, the better the results because the inventors try to cover as broad a class of chemicals as possible.

A search using "imidazolidinedione AND production" came up with only 160 results, but I'm not familiar enough with complex chemistry to recognize which processes are usable for production of 2-methoxy-2-methyl-4,5-imidazolidinedione.

I did find that acetamidine is used in quite a number of patents for hair relaxing cremes. Guanidine carbonate also. It's used in the liquid activator of the two part systems. Seems niggers are good for something after all. :p Might want to go to the local ghetto beauty supply store and start reading labels...if the korean doesn't chase you out for not buying anything! :D

For a lab production see <a href="http://www.orgsyn.org/orgsyn/orgsyn/prepcontent.asp?print=1&showprint=1&prep=cv1p0005" target="_blank">Organic Synthesis, CV 1, pg. 5</a>

Prep of Methyl Oxalate (Dimethyl ester of Oxalic acid) is <a href="http://www.orgsyn.org/orgsyn/orgsyn/prepcontent.asp?print=1&showprint=1&prep=cv2p0414" target="_blank">found here</a>.

Don't know if this is the same as Dimethyl Oxalate, but it might be. In which case, simply substitute ethyl for methyl and you have the needed precursors for makng FOX-7. :D

The prep for <a href="http://www.orgsyn.org/orgsyn/orgsyn/prepcontent.asp?print=1&showprint=1&prep=cv3p0471" target="_blank">Imidazole</a> gives you an idea of the complexity of making the molecule.

<a href="http://www.orgsyn.org/orgsyn/orgsyn/prepcontent.asp?print=1&showprint=1&prep=cv3p0438" target="_blank">Glyoxal</a> has been made back in the 1800's by the hydrolysis of the product resulting from the action of fuming sulfuric acid upon tetrahaloethanes. Canned air for dusting electronics is tetrafluoroethane. <img border="0" title="" alt="[Wink]" src="wink.gif" />

<small>[ December 27, 2002, 04:30 PM: Message edited by: nbk2000 ]</small>

[megalomania]

I checked the MOA website today for stuff on glyoxal and glyoxaline (imidazole) and I did find some things. I also checked Organic Synthesis earlier. Glyoxal can be made by adding nitric acid to ethyl alcohol and letting it sit for a few days, that sounds simple enough. There were three references to methods of synthesis for glyoxal at Org Syn in Chemische Berichte and Liebig's Annalen der Chemie which I will try to get. There is also a reference for 2-methylimidazole in Beilstein volume 23 page 65. My library has an incomplete collection of Beilstein’s, so if anybody has ready access to that and would like to check please do. At the very least Beilstein should have references to published methods of synthesis.

Apparently the formation of imidazole can happen without formaldehyde, which means a different mechanism may be at work than I envisioned. Two equivalents of glyoxal can form the ring and formic acid splits off. This is what all references at the MOA website had to say. There is of course some later work that does use formaldehyde, another old reference in Chemische Berichte. There may be hope yet.

I actually have the procedure to make acetaldehyde on my website, so there is one less hurdle. It might be easier than getting tetrahaloethanes… I haven’t had the occasion to look through the patent literature yet. 2-methylimidazole could be under some variant of “glyoxaline.” Ah ha, I did find this little gem, US patent 4,209,631 which is all about nitrating 2-methylimidazole, and that’s one step in the process for making FOX-7. My my, it took somebody 18 years to add ammonia to that stuff?

Doesn’t this exemplify the plight of the improvisational chemist? Here we have one chemical on the cutting edge, ripped from the headlines so to speak, and here we have to scramble around finding hundred year old literature to be able to get the necessary chemicals. Ahh but it is good fun :)

20 minutes later…
After looking at the patent database I got too much for 2-methylimidazole… nothing for just abstracts… too much for alkyl imidazoles… AH HA! By searching for individual compounds that I want to react, namely glyoxal, ammonia, and acetaldehyde I found this from US patent 6,177,575 from way back in 2001:

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> EXAMPLE 11

To a 200 ml RB flask was added 16.45 g (208.1 mmol) of ammonium bicarbonate, 10 g of water, 4.58 g (104.0 mmol) of acetaldehyde, and 15.09 g (104.1 mmol) of aqueous glyoxal. After stirring at RT for 2 h, volatiles were removed on a rotary evaporator and NMR spectra obtained on the resulting yellowish brown solid. .sup.1 H NMR (DMSO-d.sub.6, ppm): 2.253 (s, 3H, Me), 6.848 [s, 2H, CH(4,5)], 8.20-8.40 (very broad, 1H, may be NH). .sup.13 C NMR (DMSO-d.sub.6, ppm): 13.69 (Me), 121.19 [CH (4,5)], 143.53 (C2). Minute impurity resonances were observed at 121.5, 135.2 and 165.3. The product was a light yellowish brow solid. Yield 95%. The product was crystallized from tetrahydrofuran/hexane as colorless crystals, mp 140-141.degree. C. .sup.1 H NMR (DMSO-d.sub.6, ppm): 2.235 (3H, Me), 6.817 [2H, CH (4,5)]. 13C NMR (DMSO-d.sub.6, ppm): 13.78 (Me), 121.22 [CH (4,5)], 143.395 (C2).

When a similar reaction was performed with ammonium carbonate, and the order of addition was ammonium carbonate, then glyoxal, then acetaldehyde, 2-methylimidazole was obtained. However it was a dark colored liquid and not as pure as obtained above.</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">To translate that means we prepare a solution of 16.45 g of ammonium bicarbonate in 10 mL of water in a 200-mL round-bottom flask. Add 15.09 g of aqueous glyoxal to the solution (I would presume that some time is allowed to elapse so a reaction may occur), and then add 4.58 g of acetaldehyde. Stir this solution for 2 hours at room temperature. Here is the kicker, we can boil everything away because 2-methylimidazole melts at 142 degrees, spare bicarb might not go anywhere, acetaldehyde boils away at 21 degrees, but glyoxal will EXPLODE when mixed with air. This is likely why they use a rotovap to do the dirty work (they use vacuum). Not even I have one of those. I am not confident that my ghetto method of using propane as an “inert” gas is such a good idea to begin with, let alone having something that is explosive.
In lieu of real inert gasses like nitrogen, the best thing a ghetto chemist has available is propane. A distillation in a propane flushed atmosphere excludes air. But I get ahead of myself… First of all, I am thinking with my standards of “all inclusion” which limits chemical procedures to the lowest common availability of equipment, which is not the case here as I can get nitrogen. Second of all, I should state that my intent is to perform a distillation to remove the excess reactants, and then add the remaining 2-methylimidazole to a solvent where presumably ammonium bicarbonate does not dissolve. If 2-methylimidazole is soluble in the same stuff as imidazole, then it can dissolve in alcohol; ammonium bicarbonate cannot.
Third of all I said that is a ghetto procedure where life is cheap and accidents always happen, using propane as an inert gas is a last resort for war torn fugitives in despotic countries, or the future tyrannical rule of the NWO.
Fourth, its quite late, way past my bedtime, and I am not sure I am making much sense. I am also writing this post over a period of several hours and putting it together in random ways that may not fit.

Now then, I rewrote the procedure because the patent implies that the acetaldehyde before glyoxal method is somehow something other than 2-methylimidazole although on further reflection it may be 2-methylimidazole. It is somewhat ambiguous in that respect. If both make 2-methylimidazole then what I wrote is less desirable, just swap aldehydes and do like the patent suggests. What do you guys think thing the patent means?

EDIT: Duh, all I have to do is translate that C13 spectral data they provided and see if it matches 2-methylimidazole (but not tonight). The melting point is also very close to the published (Aldrich) melt point for 2-methylimidazole.

<small>[ December 28, 2002, 03:51 AM: Message edited by: megalomania ]</small>

[cutefix]

Mr Cool was right and the method using the 2-methylimidazole was never recpmmeded by the Swedisn as it sometimes produce unstable intermediate that lowers the yield of the product.

There is an alternative method developed by the Swedish Defense Research Agency that uses diethyl oxalate and acetamidine HCl as the beginning materials.However this method uses voluminous quantities of methanol.
They are the one who developed this energetic material and have done extensive studies about the best way of making it.This following procedure was even borrowed by other western countries who want to test more this FOX-7.

It was three step process that start with the preparation of the precursors and intermediate before the final material is obtained.

) 2-Methoxy-2-methyl -4,5 imidazolidinedione.
A 2 liter round bottom flask equipped with magnetic stirrer bar, dropping funnel .
The flask was charged with methanol 860ml and sodium methoxide 30% in 232 ml CH3OH).
Acetamidine hydrochloride 36.48 gram was added to the stirred solution at room temperature. to form a suspension.
Diethyl oxalate 55.88 g in methanol 400ml was added to the mixture over a period of 3 hours.The pH of the reaction was adjusted to 9 by the addition of conc.HCl at &lt; 30degC.The insoluble salt were rempved bu filtration through a filter aid APS 1739 and the filtrate was evaporated to dryness at lesser or about 30 deg C to dryness to form a white solid.The solid was added to 320 ml of boiling CH3OH and a HOT filtration was performed to remove insoluble salts.The total volume of the filtrate was then reduced to 320 ml.After cooling in the refrigerator overnight the resultant white crystalline product 35.54 g .64% yield was collected and filtered and dried.

2) 2,2-Dinitromethylene-4,5-imidazolidinedione.
A 500 ml round bottom flask with magnetic stirrer,thermometer,dropping funnel and drying tube was charged with conc,H2SO4, 198 ml in an ice bath.
2-Methoxy- 2-methyl-4,5 methylenedione,35.4 g was added slowly into the cooled acid solution dissolving to form a clear yellow solution .Nitric acid,70%/43ml was added dropwise over a 60 minutes at less than 30 deg C.The mixture changing from yellow to deep red and eventually a pale orange suspension.The suspension was stirred at ambient temperature for 30 minutes.The crude product was collected by filtration and air dried before being used in the next step.

3) 1,1- Diamino-2,2 -dinitroethene
The crude2,2 dinitromethylene4,5-imidazolidinedione was added to water 120 ml in a 500 ml conical flask with stirring. The suspension was cooled to less than 30 deg C.
Aqueous ammonia ,30% was added at a rate such that the temperature was maintained between 20-30 deg C until the pH 9 was reached.The resultant suspension was stirred at ambient temperature for 2hours before the solid product was collected by filtration and washed with water four times.After air and vacuum drying,60 deg C /7mmHg the bright yellow crystalline solid of 1,1-diamino-2,2-dinitroethene, DADNE or FOX-7, 19.66 g/54% yield was obtained.
The calculated cost for a laboratory scale synthesis using reagent grade ingredients;is about 150 US dollars per 300 gram of the pure FOX-7; much cheaper than producing TNAZ :p

<small>[ December 28, 2002, 06:49 AM: Message edited by: cutefix ]</small>

[nbk2000]

Ah, sodium methoxide is something that's made in situ with metallic sodium reacted with methanol. That's a rather hard chemical to get because of its drug manufacturing use.

[kingspaz]

i thought it could also be made by boiling anhydrous methanol with NaOH. don't they use this in biodiesel manufacture?

edit: got a link...

<a href="http://journeytoforever.org/biodiesel_aleksnew.html#easymeth" target="_blank">http://journeytoforever.org/biodiesel_aleksnew.html#easymeth</a>

<small>[ December 28, 2002, 12:16 PM: Message edited by: kingspaz ]</small>

[nbk2000]

From Organic Synthesis:

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> A solution of sodium methoxide, previously prepared (Note 3) from 23 g. (1 atom) of sodium and 230 cc. of absolute methyl alcohol... </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Now, it may be possible that it's also formed by reaction with NaOH, but I've never seen that mentioned in chemical literature. It's likely just an error on the part of the bio-diesel folks to be calling it that.

[Mr Cool]

No, it is true. Something must be added to remove the water.

[ALENGOSVIG1]

US patent 4,267,396 discusses making sodium methoxide with NaOH, MeOh and CaO.

And sodium isnt too hard to get. Just too valuble to be making sodium methoxide with IMO.

<small>[ December 28, 2002, 02:49 PM: Message edited by: ALENGOSVIG1 ]</small>

[megalomania]

You can use strong bases in reaction with alcohols to produce metal alkoxides quite easily, I have done it myself. Things like sodium or potassium methoxide and ethoxide are quite useful for a varity of chemical applications, that's probably why they are also forbidden for drug manufacture. The good stuff always is. I had to make some sodium ethoxide in a chemistry class once for use in a reaction from sodium hydroxide and ethanol. The procedure with sodium is no longer recommended because of the hazards of sodium metal, and apparently it dosn't store well sometimes (plus it's way more expensive to purchase) so sometimes you have to make it. The biodesal people have a good procedure.

EDIT: The scheme that cutefix outlined does seem much more efficient than using 2-methylimidazole. The reaction is actually quite the same, using very similar chemicals as the graphic below will show. The only big difference is the lack of dinitro groups on the 4 or 5 carbon which now both have oxygen on them.
<img src="http://www.roguesci.org/images/FOX-7_b.gif" alt=" - " />

I do believe that both diethyl oxalate and acetamidine hydrochloride have their preparations detailed in Organic Synthesis. The one for acetamidine is there, but in the Merck Index it says diethyl oxalate is in Collective Volume 1 page 256. At the website that page is ethylene cyanohydrin, and nowhere on it that I can see does diethyl oxalate exist. Either Merck is wrong, the website is wrong, and I missed something.

<small>[ December 29, 2002, 01:00 AM: Message edited by: megalomania ]</small>

[cutefix]

That was a nice schematics Mega .Similar to the original defense literature.
Indeed these method which was developed jointly by the AB Bofors and Swedish defense agency was succesfully scaled up to pilot scale and they were able to produce already in hundred kilos of it.The previous method of using 2-methyl imidazole produce an intermediate which was also an energetic material itself and prone to decompose sometimes violently,which makes it unsafe.

BTW, is difficult to find a detailed synthesis of diethyl oxalate in the net although its synthesis looks simple.
There is one explained by chinese authors:
<a href="http://www.bjb.dicp.ac.cn/jngc/2002/20020302.pdf" target="_blank">http://www.bjb.dicp.ac.cn/jngc/2002/20020302.pdf</a>
However they did not explain or show the experimental details but just an overview of the actual synthesis.
It uses carbon monoxide and ethyl nitrite as reactant.
I think its better of buy the reagent as it is widely available;but there is one hitch this material was used in the production of phenobarbital.
<a href="http://www.reillyind.com/our_products/diethyl_oxalate.html" target="_blank">http://www.reillyind.com/our_products/diethyl_oxalate.html</a>
So I presume it is in the chemicals watch lists for drug manufacture.

<small>[ December 29, 2002, 03:41 AM: Message edited by: cutefix ]</small>

[Hystrix]

Here is the simplest way to 2-methylimidazole:
Ethylenediamine with CH3COOH gives bis-acetamido-ethane.
Bis-acetamido-ethane treated with CaO gives 2-methylimidazoline. Heating of this stuff with Raney nickel gives hydrogen and 2-methylimidazole. Sorry but I don't remember details of process 'cause I'm not at home now (but if anybody is interested I'll search the detailed description).

[nbk2000]

Well here's the synth for <a href="http://www.orgsyn.org/orgsyn/orgsyn/prepcontent.asp?print=1&showprint=1&prep=cv1p0261" target="_blank">Ethyl Oxalate</a>.

Doesn't the structure of Ethyl Oxalate look mightily familiar? <img border="0" title="" alt="[Wink]" src="wink.gif" />

<img src="http://server3001.freeyellow.com/nbk2000/EtOxalate.gif" alt=" - " />

Mega, how would you go about tacking on an extra methyl group onto this?

I thought I had seen a synth for this chemical in one of the drug books from the FTP because of it's use in making barbituates. I checked "Psychedelic Chemistry", Fester, and "Recreational Drugs. Nothing. <img border="0" title="" alt="[Frown]" src="frown.gif" />

<small>[ December 29, 2002, 01:27 PM: Message edited by: nbk2000 ]</small>

[megalomania]

You could run the same reaction for ethyl oxalate, but with n-propyl alcohol instead to get dipropyl oxalate. Unless you wanted the methyl somewhere else, or only on one side? I assume you have some type of "candy" in mind?

Eh, stupid synonyms, I never searched for anything other than diethyl oxalate. I assumed because they had that chemical listed with no synonyms and used that name in other procedures, that was it. They should really cross reference that procedure like they do for others. That’s what I get for assuming.

I noticed the procedure to make ethyl oxalate in Organic Synthesis may seem a bit complex with all the difficult glass works, but one could substitute that with a homemade assembly of PVC pipe glued together and rubber hoses. I would take a 3 inch length of 1-inch diameter pipe, drill a hole on one side about 0.5 inches from the top and another hole on the other side 1 inch down. On the bottom you can affix a pipe cap with a hole drilled in the center. Take a plastic T tube, one of the barbed kind available at the hardware store, and cut it into 3 straight pieces. These pieces go into the holes of the pipe. Connect the bottom barb to the topmost one with tubing, having a T tube connect them in the middle. The left tube just needs a piece of tubing attached to it. This setup will closely resemble the picture given in the procedure nbk linked to. This setup is necessary to drain off the lighter water portion and to send the carbon tetrachloride portion back into the reaction flask. One could do this manually by distilling the mix into a cylinder and dumping the bottom layer into the flask from time to time, but this would be very boring and require quite a few hours of constant attention.

Now the question is where to get all the oxalic acid? I checked Rhodium’s site because I remembered seeing some info there, but it was not exactly useful. According to my Great Chemical Survey, Zud cleaner was $2.99 for 453 g (1 lb). I don’t know how much can be extracted from the cleaner via the ghetto procedure on Rhodium’s site, but there must be a better way to make the stuff <a href="http://www.geocities.com/Baja/Canyon/2609/cleaners.html" target="_blank">(it is here)</a>. I have this feeling I have seen pure oxalic acid at a hardware store for cheap not too long ago… I also found that I finally have a procedure I wrote on Rhodium’s site, I’m so happy :D

[Mr Cool]

Nitric acid will oxidise sucrose to give you oxalic acid, but nitric is very precious to many people.
You can indeed buy it pure, look for wood bleaches...

[Zach]

Nitric or oxalic acid in wood bleaches?

[megalomania]

It is oxalic acid in the wood bleach, I just finished reviewing the Hive posts today. In this context I now remember where I say the oxalic acid at the hardware store. It was a small plastic tub about 12 oz maybe, I forget the price. I also saw mention on the Hive about the nitric acid/sugar route. I wonder if there is any possibility of nitrate recovery after such a reaction?

EDIT: There is an even older process, the first industrial method of producing oxalic that the ancients used. They reacted sawdust with sodium hydroxide by roasting them, presumably by boiling a conc. solution of lye and sawdust, which makes sodium oxalate. The sodium oxalate is reacted with lime to form calcium oxalate, which is then digested with sulfuric acid making oxalic acid and precipitating calcium supfate. This process may be a bit more economical if nitric acid is too precious to use.

<small>[ December 30, 2002, 05:58 PM: Message edited by: megalomania ]</small>

[nbk2000]

So I can assume that the ethyl oxalate syth I found at the OrgSyn site was the one needed for diethyl oxalate?

No "candy" involved. I actually misphrased my statement. By "tack on a methyl" I meant "substitute methyl for ethyl" to make dimethyl oxalate.

In Dicks, it refers to making oxalic acid by roasting sawdust and lye on an iron plate over a fire till it's almost (but not quite) carbonized. From there much workup ensues.

Couldn't you add a soluble calcium salt to the oxalic acid cleaners to form an insoluble oxalte salt, then filter it out and decompose it back to free oxalic with sulphuric?

I've bought pounds of oxalic acid at the hardware store before from a giant bag of it, right next to the bluestone while buying the Solid-Ox pellets. :D

But this was 15 years ago at a ma and pa store. I've never found it at the Big Box Stores like Homebase/Home Depot. <img border="0" title="" alt="[Frown]" src="frown.gif" />

[ALENGOSVIG1]

Nitric acid is way too valuble to make oxalic acid with IMO. On rhodiums site they recorded getting a yeild of 10-11g of oxalic acid per 150 ml of nitric. I've done the synth self and i didnt even get that much. Although it is fun reaction to watch. Theres plumes of nitrous fumes constantly pouring outa the beaker. :)

The sawdust idea sounds interesting though. Still i think the best thing to do is buy it from chem supplier.

<small>[ December 30, 2002, 11:51 PM: Message edited by: ALENGOSVIG1 ]</small>

[cutefix]

Yeah it is a waste of nitric acid and that method was pioneered by Scheele centuries ago and nitric acid was still not discovered as useful for the preparation of energetic substances.
As this item is not on the watch list then it will be easy to procure it .
besides oxalic acid is plentiful in nature .Rhubarb contains moderate amount of oxalic acid.Many sour fruits contain varying traces of it. :)

[kingspaz]

you can buy oxalic acid in homebrew shops.

[megalomania]

I actually have a quite detailed procedure for the production of oxalic from sawdust, as well as one from sugar and nitric acid. The sugar-nitric route is said to be quite inefficient, another reason not to waste your nitric.

This then is the detailed method the old timers used to use to produce oxalic acid. This method was replaced by better means of producing carbon monoxide and bubbling it into sodium hydroxide, the current method: Prepare a concentrated solution by mixing 2 parts of sodium hydroxide and 1 part of potassium hydroxide in a minimum amount of water. A density of 1.35 is the optimum goal here. Add this solution to enough sawdust as to make a thick paste. Spread this paste in a thin layer on an iron plate and gradually heat with constant stirring.
If I may interject, I don’t think the use of iron plates is all that necessary, I am sure they had a reason back then, but I’ll be damned if I know what it is. I doubt it has some catalytic effect, maybe it was just more convenient for an industrial process. On the lab scale a shallow glass bowl, or even a frying pan, should do the trick. I also find it rather hard to imaging myself trying to stir this crap on an iron plate without it going all over the place.
At this point the mixture expels much hydrogen and carbon monoxide gas, along with water vapor. A note of caution, these are flammable gasses, and of course carbon monoxide is toxic. After this initial heating the temperature is maintained at 204 degrees C (400 degrees F) for several hours. For this I would recommend an oven. Care should be taken to not heat this too high or the oxalic acid will decompose. What remains after heating is a gray powder. This powder is treated with 15.5 degree C water that will leave the oxalic acid undissolved. This liquid can be used again as it contains much alkali, it should be boiled down to get the crystals.
After removing the water what remains is sodium oxalate. This should be washed with water several times to remove any impurities, and finally boiled with a solution of lime and water. This boiling treatment converts the sodium oxalate into calcium oxalate. The calcium oxalate is added to some sulfuric acid, which forms oxalic acid and precipitates unsoluable calcium sulfate. The liquid is decanted from the calcium sulfate (which can be disposed of) and is boiled down to get crystals of oxalic acid. The oxalic acid can be purified by recrystallizing from water.
The hydrated form of oxalic acid, which is what this procedure makes or that which is bought OTC, can be dried by gently heating. There is a more detailed procedure at the Organic Synthesis website.

Oxalic acid by nitric acid and sugar: One part of sugar is gently heated in a retort with 5 parts of nitric acid (d 1.42, ~70%) diluted with twice its weight of water. Copious red fumes will then be disengaged, and the oxidation of the sugar proceeds with violence and rapidity. When the action slackens, heat may be again applied to the vessel, and the liquid concentrated by distilling off the superfluous nitric acid until it deposits crystals on cooling. These are drained, redissolved in a small quantity of hot water, and the solution is set aside to cool.

That’s about it, unless one wishes to go the current industrial route. I have seen a few other notes on the sawdust method which indicate using potassium hydroxide isn’t necessarily important. Using the nitric method, one could possibly recycle those nitrogen dioxide fumes back into nitric acid. Theoretically, you could get it all back.

[nbk2000]

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">...used to use to produce oxalic acid. This method was replaced by better means of producing carbon monoxide and bubbling it into sodium hydroxide, the current method...</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Does this mean that oxalic acid is currently produced by bubbling CO through NaOH? :confused:

If so, then simply hooking up a hose to a cars exhaust (prior to the cat.) and bubbling the exhaust through the lye solution would be the easiest way.

I think the reason they used THICK iron plates was to provide an even surface for heating since this was very likely done over an open fire which could cause hot spots that'd cause unwanted charring of the mix.

I wouldn't try this in glass because of the high heat required would make the lye extremely corrosive to the glass.

[Mr Cool]

Car exhaust fumes might be a bit dirty I think, and there would be a lot of CO2 which'll just make carbonate. It's simple to make CO though, using a copper pipe full of charcoal, ignite it at one end, blow air through, and CO comes out the other end.

[nbk2000]

Actually, you have to use CO₂, instead of straight air.

O₂ + C = CO₂

CO₂ + C = 2CO

The reaction of CO₂ with carbon is highly endothermic, so you have to supply exterior heat to maintain it at red heat.

If the ratio of CO to CO₂ gas that was coming from the car exhaust was proper, then any formed carbonate would react with the oxalic acid to form sodium oxalate. This would then be processed with sulfuric to form pure oxalic. At least that's what I think.

[Kalium]

A lot of warrant officers of our army likes to say: "If you haven't problems yet, you should make it to solve then".
May be homemade oxalic acid is a top of pyrotechnics skill, but I think that would be better just to buy it. Try to search it in a simple shops - it shouldn't cost so much!
I think I would try to make DADNE in a nearest future and than write the results...

[megalomania]

I too have longed to flex my creative improvisational muscles by synthesizing this intriguing compound. I am actually more interested in making ethyl oxalate by the procedure described in Organic Synthesis. This procedure is so complex it is practically begging to be improvised and simplified. I would also like to use the opportunity to take some pictures of the modified non-glassware setup I theorized would be sufficient.

Cutefix, do you happen to have a link to the procedure you outlined, or the title of the article and journal it was derived from? The procedure is adequate as written, but I like to keep original published references for my personal curiosity. I also wonder what other pearls of knowledge the Swedish Defense Research Agency has hidden away.

I will begin cobbling the information presented in this post on to my website on the morrow. Hopefully I can write everything such that it is easier to follow and concise. Look for it Thursday at the latest.

In other news, I have recently seen a brief snippet about an azide version of FOX-7 although I have no idea, now, where it was I saw it. A web search turned up nothing. I was wither reading an explosives journal or searching through the abstracts of the Beilstein Index when I saw it. I think this version replaced one of the amines with the azide. If anybody has anything on this please let me know.

[Hex]

Might have been the hydrazo substituted one you were thinking of, with one -NH2 replaced by -NHNH2. Both Fox-7 -NH2's can be replaced using ethylene diamine to give a cyclic product too.

Can't find an electronic version of this anywhere, but somebody might be able to dig it up.

Bellamy, Anthony J.; Latypov, Nikolaj V.; Goede, Patrick. Transamination reactions of 1,1-diamino-2,2-dinitroethene (FOX-7). Journal of Chemical Research, Synopses (2002), (6), 257, 641-661

[cutefix]

Mega, the source of the FOX-7 synthesis was culled from notes derived from classified document shared to my by a friend.I have not seen the title exact title of the document but it had some origin in the defense agency.
Meanwhile I found a new information about FOX-7.See it this will further be of use to you.
<a href="http://www.sainc.com/onr/detsymp/PaperSubmit/FinalManuscript/pdf/Karlsson-165.pdf" target="_blank">http://www.sainc.com/onr/detsymp/PaperSubmit/FinalManuscript/pdf/Karlsson-165.pdf</a>

[megalomania]

I think it may have been this article:
2,2-dinitro-ethene-1,1-diamine (FOX-7) - properties, analysis and scale-up. Ostmark, Henric; Bergman, Helena; Bemm, Ulf; Goede, Patrick; Holmgren, Erik; Johansson, Martin; Langlet, Abraham; Latypov, Nikolaj V.; Pettersson, Anna; Pettersson, Marja-Liisa; Wingborg, Niklas; Vorde, Carin; Stenmark, Helen; Karlsson, Lars; Hihkio, Maija. Department of Energetic Materials, Swedish Defence Research Agency, FOI, Tumba, Swed. International Annual Conference of ICT (2001), 32nd(Energetic Materials), 26/1-26/21. CODEN: IACIEQ ISSN: 0722-4087. Journal written in English. CAN 135:332996 AN 2001:605052

Or at least they used some of your document in this conference. Classified literature suits me just fine though :) This rather reminds me of another explosive synth I have been trying to track down, LLM-105. The synthesis is detailed in an article submitted to Propellants, Explosives, Pyrotechnics back in 1998, but every reference to it says the same “yet to be published.” Ug, when will they publish the damn thing?

I thank you for that link cutefix, but check my first post in this thread.

I have assembled a list of every reference currently available pertaining to FOX-7:
Bibliographic Information

Structural studies and EOS of diaminodinitroethylene (DADNE, Fox-7) under static compression. Peiris, S. M.; Pangilinan, G. I.; Zerilli, F. J.; Russell, T. P. Energetic Materials Research and Technology Department, Naval Surface Warfare Center, Indian Head, MD, USA. AIP Conference Proceedings (2002), 620(Shock Compression of Condensed Matter, Pt. 1), 181-184. CODEN: APCPCS ISSN: 0094-243X. Journal written in English. AN 2002:631395 CAPLUS (Copyright 2003 ACS)

Abstract

Structural and mol. changes in diaminodinitroethylene compressed to static pressures up to 4.2 GPa were investigated. Angle-dispersive x-ray diffraction expts. were performed with synchrotron radiation to monitor the compression and any phase changes. The results indicated higher compression along the b-axis than along the a- or c- axis. In addn., the ambient temp. isothermal equation of state of FOX-7 was generated from this data. Raman spectroscopy covering a 300 to 3400 cm-1 range showed expected hardening of most vibrational modes. However, two modes in the energy regions corresponding to N-O stretching and H wagging, softened with pressure. This indicates the possible increase of intermol. H bonding within the zigzagging planes of FOX-7 at increased pressures.

Bibliographic Information

Transamination reactions of 1,1-diamino-2,2-dinitroethene (FOX-7). Bellamy, Anthony J.; Latypov, Nikolaj V.; Goede, Patrick. Royal Military College of Science, Cranfield University, Shrivenham, Swindon, UK. Journal of Chemical Research, Synopses (2002), (6), 257, 641-661. CODEN: JRPSDC ISSN: 0308-2342. Journal written in English. AN 2002:610708 CAPLUS (Copyright 2003 ACS)

Abstract

Treatment of 1,1-diamino-2,2-dinitroethene (FOX-7) with a variety of amines and hydrazine, results in at least one, and in some cases both, of the amino groups being replaced to give N-substituted and N,N'-disubstituted 1,1-diamino-2,2-dinitroethenes.

Bibliographic Information

A simple method for predicting the metal acceleration ability of high explosives. Makhov, Michael N. N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia. International Annual Conference of ICT (2002), 33rd(Energetic Materials), 74/1-74/12. CODEN: IACIEQ ISSN: 0722-4087. Journal written in English. AN 2002:605601 CAPLUS (Copyright 2003 ACS)

Abstract

The dependence of metal acceleration ability on the energy content of high explosives is discussed. A simple method for predicting explosive performance in cylinder test is suggested. This method is based on the assumption that the coeff. of conversion of the chem. energy to the kinetic energy depends on the volumetric mole no. of gaseous products. The amt. of gases has been shown to affect not only the position of the isentrope of products in InP-InV plane but the slope of the isentrope as well. Semi-empirical relations were developed using the Gurney model. The results of cylinder wall velocity calcns., performed for some well-known and new explosives, are presented.

Bibliographic Information

Formulation of PBX's based on 1,1-diamino-2,2-dinitroethylene (FOX-7). Eldsaeter, C.; Edvinsson, H.; Johansson, M.; Pettersson, A.; Sandberg, C. Grindsjoen Research Centre, Swedish Defence Research Agency, FOI, Tumba, Swed. International Annual Conference of ICT (2002), 33rd(Energetic Materials), 63/1-63/14. CODEN: IACIEQ ISSN: 0722-4087. Journal written in English. AN 2002:605584 CAPLUS (Copyright 2003 ACS)

Abstract

1,1-Diamino-2,2-dinitroethylene (FOX-7) is a new energetic material with promising properties as a insensitive munitions (IM) explosive. Thermochem. calcns. show that PBX's based on FOX-7 and energetic binders could serve as a replacement of Compn B even at rather low solid loadings. A castable compn. of FOX-7 and polyGlyN was prepd. Small-scale safety tests show that the compns. were not sensitive to friction and the thermal stability at 65° was excellent. Larger-scale detonation tests and small-scale slow cook-off tests show that the FOX-7 based PBX did not detonate at a diam. of 25 mm and upon slow heating (3.3°/h) it ignites at 150° and burns without damage to the container or the surroundings.

Bibliographic Information

Substitution reactions of 1,1-diamino-2,2-dinitroethene (FOX-7). Bellamy, Anthony J.; Goede, Patrick; Sandberg, Camilla; Latypov, Nikolaj V. Royal Military College of Science, Cranfield University, Shrivenham, Swindon, UK. International Annual Conference of ICT (2002), 33rd(Energetic Materials), 3/1-3/9. CODEN: IACIEQ ISSN: 0722-4087. Journal written in English. CAN 138:26487 AN 2002:605479 CAPLUS (Copyright 2003 ACS)

Abstract

1,1-Diamino-2,2-dinitroethene (FOX-7) is thermally stable, impact insensitive explosive with a calcd. performance close to that of RDX. In order to explore the chem. stability of 1,1-diamino-2,2-dinitroethene, its reactivity towards nucleophilic species such as amines (predominantly primary amines), hydrazine and guanidine is studied. At least one, and in some cases both, of the amino groups can be replaced by transamination, to give N-substituted and N,N'-disubstituted 1,1-diamino-2,2-dinitroethenes by reaction with amines, and 1-amino-1-hydrazino-2,2-dinitroethene by reaction with hydrazine. The latter forms a hydrazinium salt with excess hydrazine. With guanidine, deprotonation to form the guanidinium salt of the conjugate base of 1,1-diamino-2,2-dinitroethene occurs in preference to transamination. This work has generated several new energetic compds. and has given a better understanding of the chem. stability of 1,1-diamino-2,2-dinitroethene.

Bibliographic Information

Effect of intermolecular forces on some properties of explosives. Vavra, Pavel; Pospisil, Miroslav; Repakova, Jarmila. Department of Theory and Technology of Explosives Faculty of Chemical Technology, University of Pardubice, Pardubice, Czech Rep. Editor(s): Vagenknecht, Jiri. New Trends in Research of Energetic Materials, Proceedings of the Seminar, 5th, Pardubice, Czech Republic, Apr. 24-25, 2002 (2002), 357-368. Publisher: University of Pardubice, Pardubice, Czech Rep CODEN: 69CSE3 Conference written in English. CAN 137:249858 AN 2002:437901 CAPLUS (Copyright 2003 ACS)

Abstract

Values of total sublimation energy and its van der Waals, Coulomb, and hydrogen-bond energy contributions were calcd. for a selected set of explosives on the basis of their structural data, and their non-negligible effect on sensitivity parameters, densities and melting temps. were established. These parameters are significantly affected by hydrogen bonds and total magnitude of intermol. forces. Also other factors affecting these parameters are discussed.

Bibliographic Information

Acid-base characteristics of FOX-7 and its monohydrazo analogue. Sandberg, Camilla; Latypov, Nikolaj; Goede, Patrick; Tryman, Rolf; Bellamy, Anthony J. Swedish Defence Research Agency, Department of Energetic Materials, FOI, Tumba, Swed. Editor(s): Vagenknecht, Jiri. New Trends in Research of Energetic Materials, Proceedings of the Seminar, 5th, Pardubice, Czech Republic, Apr. 24-25, 2002 (2002), 292-299. Publisher: University of Pardubice, Pardubice, Czech Rep CODEN: 69CSE3 Conference written in English. CAN 137:265184 AN 2002:437896 CAPLUS (Copyright 2003 ACS)

Abstract

1,1-Diamino-2,2-dinitroethylene, FOX-7 is a novel explosive with high performance and low sensitivity. In addn. 1-amino-1-hydrazino-2,2-dinitroethene (Hydrazo FOX-7, HDF) has recently been prepd. by reaction of FOX-7 with hydrazine. Several studies of FOX-7 were performed and complementary studies with acid-base characterization of both FOX-7 and HDF are presented in this paper. The effect of varying pH on both FOX-7 and HDF and the formation of their resp. salts are discussed along with the basic hydrolysis of FOX-7 to dinitromethane.

Bibliographic Information

Characterisation of explosive materials using molecular dynamics simulations. Pospisil, Miroslav; Capkova, Pavla; Vavra, Pavel; Zeman, Svatopluk. Department of Chemical Physics and Optics, Faculty of Mathematics and Physics, Charles University Prague, Prague, Czech Rep. Editor(s): Vagenknecht, Jiri. New Trends in Research of Energetic Materials, Proceedings of the Seminar, 5th, Pardubice, Czech Republic, Apr. 24-25, 2002 (2002), 262-270. Publisher: University of Pardubice, Pardubice, Czech Rep CODEN: 69CSE3 Conference written in English. CAN 137:249855 AN 2002:437893 CAPLUS (Copyright 2003 ACS)

Abstract

Classical mol. dynamics simulations of the unimol. decompn. were performed for selected mols. exhibiting different impact sensitivity and different detonation energy: (1) (CH2NNO2)3, more commonly known as RDX, (2) (CH2NNO2)4, known as HMX, (3) (NH2)2CC(NO2)2, known as DADNE, and (4) (NH2)2CNNO2, known as NQ. A potential energy was described by using empirical force field (consistent force field 950). Mol. dynamics simulations were carried out in Cerius of Y. Kohno et al.(1996) modeling environment. The anal. of dynamic trajectories enabled to reveal step by step the mechanism of decompn. and to characterize the impact sensitivity and explosives performance (detonation energy) of these energetic materials. The characteristic parameters detd. from the dynamics trajectory simulations are in agreement with the exptl. measured sensitivity and detonation energy.

Bibliographic Information

Energetic deterrent coatings for gun propellant grains for improved combustion rate. Cramer, Randall J.; Peters, Susan; Simmons, Ronald; Mitchell, Steve. (United States Dept. of the Navy, USA). U.S. (2002), 4 pp. CODEN: USXXAM US 6345577 B1 20020212 Patent written in English. Application: US 2000-670338 20000927. CAN 136:169941 AN 2002:113989 CAPLUS (Copyright 2003 ACS)

Patent Family Information

Patent No. Kind Date Application No. Date
US 6345577 B1 20020212 US 2000-670338 20000927

Priority Application Information
US 2000-670338 20000927

Abstract

Gun propellant compns. are coated with an energetic deterrent coating that reduces the combustion rate at the surface of the propellant grain and causes the propellant to burn more evenly and progressively. Such use of energetic materials that are slightly sol. in the coating solvent improve the combustion properties of the propellant without decreasing the chem. energy. Suitable solvents include water, alc., di-Et ether, Et acetate, and acetone. Suitable energetic compds. as deterrents include TATB, HZTZ (dihydrazinotetrazene), PITNE [1,3,5-tris(2-nitroxyethylamino)-2,4,6-trinitrobenzene], PINANE [1-(2-nitroxyethylamino)-3-(2-nitroxyethylnitramino)-2,4,6-trinitrobenzene], LLM-105 (diaminodinitropyrazine-1-oxide), and FOX-7 (diaminodinitroethylene).

Bibliographic Information

A Quantum Mechanical Investigation of the Relation between Impact Sensitivity and the Charge Distribution in Energetic Molecules. Rice, Betsy M.; Hare, Jennifer J. U.S. Army Research Laboratory, Aberdeen Proving Ground, MD, USA. Journal of Physical Chemistry A (2002), 106(9), 1770-1783. CODEN: JPCAFH ISSN: 1089-5639. Journal written in English. CAN 136:281590 AN 2002:90769 CAPLUS (Copyright 2003 ACS)

Abstract

Quantum mech. detd. electrostatic potentials for isosurfaces of electron d. of a variety of CHNO explosive mols. are analyzed to identify features that are indicative of sensitivity to impact. Models were developed for prediction of impact sensitivity of CHNO explosives using approxns. to the electrostatic potentials at bond midpoints, statistical parameters of these surface potentials, and the generalized interaction properties function [J. S. Murray, et al., J. Mol. Struct (THEOCHEM) 1994, 307, 55] or calcd. heats of detonation. These models are parametrized using a set of 34 polynitroarom. and benzofuroxan explosives for which impact sensitivity measurements exist. The models were then applied to a test set of 15 CHNO explosives from a variety of chem. families in order to assess the predictive capability of the models. Patterns of the surface potentials of these mols. suggested that the level of sensitivity to impact is related to the degree of pos. charge buildup over covalent bonds within the inner framework of these explosives. The highly sensitive explosives showed large pos. charge buildup localized over covalent bonding regions of the mol. structures, whereas the insensitive explosives do not exhibit this feature. For the nitroarom. and benzofuroxan compds., sensitivity appears to be related to the degree and distribution of pos. charge build-up localized over the arom. ring or over the C-NO2 bonds.

Bibliographic Information

Some specific features of acid nitration of 2-substituted 4,6-dihydroxypyrimidines. Nucleophilic cleavage of the nitration products. Astrat'ev, A. A.; Dashko, D. V.; Mershin, A. Yu.; Stepanov, A. I.; Urazgil'deev, N. A. Tekhnolog Special Construction Technology Bureau, St. Petersburg State Institute of Technology, St. Petersburg, Russia. Russian Journal of Organic Chemistry (Translation of Zhurnal Organicheskoi Khimii) (2001), 37(5), 729-733. CODEN: RJOCEQ ISSN: 1070-4280. Journal written in English. CAN 135:371705 AN 2001:634605 CAPLUS (Copyright 2003 ACS)

Abstract

The nitration of 2-substituted 4,6-dihydroxypyrimidines in concd. sulfuric acid yields the corresponding 5,5-dinitro derivs. When the substituent in position 2 is an alkyl group, the nitration occurs both at position 5 and at the a-carbon atom of the side chain. Hydrolysis of 2-substituted 4,6-dihydroxy-5,5-dinitropyrimidines leads to formation of 1,1-diamino-2-R-2-nitroethylene derivs. 1,1-Diamino-2,2-dinitroethylene was obtained by nitration of 4,6-dihydroxy-2-methylpyrimidine and subsequent hydrolysis of 4,6-dihydroxy-5,5-dinitro-2-(dinitromethylene)-2,5-dihydropyrimidine.

Bibliographic Information

Porous graphitic carbon (PGC) - a convenient column packing material for the HPLC analysis of FOX-7. Holmgren, Erik; Goede, Patrick; Latypov, Nikolaj; Crescenzi, Carlo; Carlsson, Hakan. Department of Energetic Materials, FOI, Swedish Defence Research Agency, Tumba, Swed. International Annual Conference of ICT (2001), 32nd(Energetic Materials), 119/1-119/8. CODEN: IACIEQ ISSN: 0722-4087. Journal written in English. CAN 135:333018 AN 2001:605131 CAPLUS (Copyright 2003 ACS)

Abstract

An HPLC method for the anal. of FOX-7 is developed. Several different column packing materials were evaluated. FOX-7 has shown relevant affinity only for the graphitized carbon surface of the Hypercarb column. With this column, and with a suitable eluent phase, bulk FOX-7 and some possible byproducts were sepd. and analyzed by PDA-UV.

Bibliographic Information

Explosion heat and metal acceleration ability of high explosives. Makhov, M. N. N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia. International Annual Conference of ICT (2001), 32nd(Energetic Materials), 97/1-97/11. CODEN: IACIEQ ISSN: 0722-4087. Journal written in English. CAN 135:333036 AN 2001:605113 CAPLUS (Copyright 2003 ACS)

Abstract

The dependence of metal acceleration ability on the energy content of high explosives is considered in the paper. A semi-empirical method for evaluating explosive performance in metal acceleration applications is suggested. This method has been developed on the basis of the assumption that the amt. of explosive energy, transferred to the driven metal, depends on the volumetric no. of moles of gaseous products. The results of calcns., performed for some well-known and new explosives, are presented in the paper.

Bibliographic Information

2,2-dinitro-ethene-1,1-diamine (FOX-7) - properties, analysis and scale-up. Ostmark, Henric; Bergman, Helena; Bemm, Ulf; Goede, Patrick; Holmgren, Erik; Johansson, Martin; Langlet, Abraham; Latypov, Nikolaj V.; Pettersson, Anna; Pettersson, Marja-Liisa; Wingborg, Niklas; Vorde, Carin; Stenmark, Helen; Karlsson, Lars; Hihkio, Maija. Department of Energetic Materials, Swedish Defence Research Agency, FOI, Tumba, Swed. International Annual Conference of ICT (2001), 32nd(Energetic Materials), 26/1-26/21. CODEN: IACIEQ ISSN: 0722-4087. Journal written in English. CAN 135:332996 AN 2001:605052 CAPLUS (Copyright 2003 ACS)

Abstract

The properties and possible prodn. scale-up of 2,2-dinitro-ethene-1,1-diamine (FOX-7) have been studied. The Koenen test gave a type "F" reaction at 6 mm nozzle diam. The activation energy (Ea = 56 kcal/mol) was measured by differential scanning calorimetry (DSC). The ignition temp. was detd. by Wood's metal bath at 215°. Accelerated rate calorimetry (ARC) showed that FOX-7 has a runaway reaction around 230°. A relation between the particle size of FOX-7 and the decompn. temp. in DSC has been found. Four phases of FOX-7 (FOX-7(a), FOX-7(b), FOX-7(g) and FOX-7(d)) are established. Time to ignition measurements with a CO2-laser showed that FOX-7 is more difficult to ignite than RDX. Mass spectroscopic studies showed that FOX-7 is a very stable mol. compared to RDX and HMX. An HPLC method based on the porous graphite carbon (PGC) column packing material has been developed for the anal. of FOX-7. FOX-7 is compatible with a variety of materials that might be used in propellants or explosives. The synthesis of 2,2-dinitro-ethene-1,1-diamine (FOX-7) has been studied and the process has been scaled up to 7 kg batches. Calcns. based on reaction calorimeter show the flow of energy in the process and this study has contributed to a safe and convenient pilot scale process.

Bibliographic Information

Electronic density of molecule and some properties of high explosives. Vavra, Pavel. Department of Theory and Technology of Explosives, University of Pardubice, Pardubice, Czech Rep. Editor(s): Zeman, Svatopluk. New Trends in Research of Energetic Materials, Proceedings of the Seminar, 4th, Pardubice, Czech Republic, Apr. 11-12, 2001 (2001), 345-351. Publisher: University of Pardubice, Pardubice, Czech Rep CODEN: 69BKIC Conference written in English. CAN 135:228906 AN 2001:476863 CAPLUS (Copyright 2003 ACS)

Abstract

Based on calcd. electron densities in mols. of 20 high explosives it was possible to est. partial charges at the bonds in C-NO2, N-NO2, and O-NO2 groupings. The comparison of sum of abs. magnitudes of the charges with the exptl. measured X-NO2 bond lengths proved that an increase in polarity causes a shortening of the bond. A possibility of prediction of structures of insensitive high explosives on the basis of electron d. distribution, non-covalent interactions of the mols., and detonation energy were discussed.

Bibliographic Information

Synthesis and properties of 1,1-diamino-2,2-dinitroethylene. Jalovy, Zdenek; Marecek, Pavel; Dudek, Kamil; Weidlich, Tomas. Department of Theory and Technology of Explosives, University of Pardubice, Pardubice, Czech Rep. Editor(s): Zeman, Svatopluk. New Trends in Research of Energetic Materials, Proceedings of the Seminar, 4th, Pardubice, Czech Republic, Apr. 11-12, 2001 (2001), 151-161. Publisher: University of Pardubice, Pardubice, Czech Rep CODEN: 69BKIC Conference written in English. CAN 135:213009 AN 2001:476844 CAPLUS (Copyright 2003 ACS)

Abstract

The title compd., a novel energetic material proposed for application as IHE (Insensitive High Explosive), was synthesized by hydrolysis of 2-(dinitromethylene)-4,5-imidazolidinedione, which was prepd. by two independent ways. The product was identified by 1H-, 13C- and 15N-NMR spectra and elemental anal. The purity of the sample was checked by HPLC. DSC and DTA measurements were provided in order to compare the thermal stability of the compound with other explosives.

Bibliographic Information

Study of the energy of explosives. Vavra, Pavel. Katedra Teorie a Technol. Vybusin, Univ. Pardubice, Pardubice, Czech Rep. New Trends in Research of Energetic Materials, Proceedings of the Seminar, 3rd, Pardubice, Czech Republic, Apr. 12-13, 2000 (2000), 223-232. Publisher: University of Pardubice, Pardubice, Czech Rep CODEN: 69BKLF Conference written in Czech. CAN 135:213017 AN 2001:464571 CAPLUS (Copyright 2003 ACS)

Abstract

Explosives internal, detonation, and compression energies E, ED and EC were calcd. in virtue of the detonation velocity and pressure knowledge. The relation of energies to explosives sensitivity is detd. Effect of hydrogen bridges on sensitivity and the other properties of high explosives is discussed.

Bibliographic Information

Classical and Quantum-Mechanical Studies of Crystalline FOX-7 (1,1-Diamino-2,2-dinitroethylene). Sorescu, Dan C.; Boatz, Jerry A.; Thompson, Donald L. Department of Chemistry, Oklahoma State University, Stillwater, OK, USA. Journal of Physical Chemistry A (2001), 105(20), 5010-5021. CODEN: JPCAFH ISSN: 1089-5639. Journal written in English. CAN 135:60939 AN 2001:288207 CAPLUS (Copyright 2003 ACS)

Abstract

First principles MO and plane-wave ab initio calcns. have been used to investigate the structural and vibrational properties of the highly efficient low sensitive explosive 1,1-diamino-2,2-dinitroethylene (FOX-7) in both the gas and solid phases. The ab initio MO calcns. performed at second-order (MP2) and fourth-order (MP4) M.ovrddot.oller-Plesset levels and using d.-functional theory (DFT) methods with B3LYP functional indicate that in the gas phase FOX-7 is the most stable isomer relative to its cis-1,2 and trans-1,2 isomers. The calcd. MP2 and DFT structures for the FOX-7 mol. agree well with the exptl. X-ray configuration but with twists of the nitro and amino groups much larger than in the solid phase. The calcd. fundamental vibrational frequencies at the DFT level generally compare well with the MP2 results. The IR spectra were computed for the three isomers. The structural properties of the FOX-7 crystal have been studied by a plane-wave DFT method. These calcns. were done with periodic boundary conditions in all three directions. The optimization of the crystal structure has been done with full relaxation of the at. positions and of the lattice parameters under P21/n symmetry. The predicted crystal structure is in good agreement with X-ray data. We have developed an intermol. potential to describe the structure of the FOX-7 crystal in the approxn. of rigid mols. This potential is composed of pairwise exp-6 Buckingham terms and Coulombic interactions. Crystal-packing calcns. without symmetry constraints performed with the proposed potential accurately reproduce the main crystallog. features and yield very good agreement with the estd. lattice energy. This intermol. potential was further tested in isothermal-isobaric mol. dynamics simulations at atm. pressure and in the temp. range of 4.2-450 K. It is found that the increase of temp. does not significantly change the orientations of the mols. inside the unit cell. The thermal expansion coeffs. calcd. for the model indicate anisotropic behavior with the largest expansion along the b crystallog. direction.

Bibliographic Information

Theoretical study on structure and property of diamino-dinitroethylene. Ji, Guang-Fu; Xiao, He-Ming; Dong, Hai-Shan; Gong, Xue-Dong; Li, Jin-Shan; Wang, Zun-Yao. Dep. Chem., Nanjing Univ. Sci. Technol., Nanjing, Peop. Rep. China. Huaxue Xuebao (2001), 59(1), 39-47. CODEN: HHHPA4 ISSN: 0567-7351. Journal written in Chinese. CAN 134:102904 AN 2001:67097 CAPLUS (Copyright 2003 ACS)

Abstract

1,1-Diamino-2,2-dinitroethylene recently synthesized is a new energetic compd., which may be insensitive high explosive (IHE). In this paper, the fully optimized mol. geometries and the total energies of diamino-dinitroethylene compds., 1,1-diamino-2,2-dinitroethylene (I), cis (II) and trans (III) 1,2-diamino-1,2-dinitroethylene, have been calcd. using ab initio method at the HF/6-31G**, MP2/6-31G**//HF/6-31G** level and DFT method at B3LYP/6-31G** level, resp. The result shows that the order of stability of the title compds. is I &gt; II &gt; III. Based on the anal. of mol. geometry and frontier orbital component, it is found that the p-electron conjunction and delocalization of the title compds. are I » III &gt; II. The computed vibrational frequencies of 1,1-diamino-2,2-dinitroethylene is in good agreement with the corresponding expt. results. The thermodn. properties of DADNE were also calcd. and discussed. These data are helpful to the mol. design of new IHE.

Bibliographic Information

Reduced-smoke gas generating compositions with improved mechanical stability for inflation of vehicle airbags. Blomquist, Harold R. (TRW Inc., USA). U.S. (2000), 6 pp. CODEN: USXXAM US 6113713 A 20000905 Patent written in English. Application: US 99-359005 19990722. CAN 133:195582 AN 2000:623657 CAPLUS (Copyright 2003 ACS)

Patent Family Information

Patent No. Kind Date Application No. Date
US 6113713 A 20000905 US 1999-359005 19990722
DE 10035376 A1 20010222 DE 2000-10035376 20000720

Priority Application Information
US 1999-359005 19990722

Abstract

Reduced-smoke solid gas-generating compns., esp. for inflation of vehicle airbags, consist of 20-70 wt.% of an inorg. salt oxidizer and 30-80 wt.% of 1,1-diamino-2,2-dinitroethylene as the fuel component. The oxidizer is selected from ammonium nitrate, phase-stabilized ammonium nitrate, potassium nitrate, potassium perchlorate, and ammonium perchlorate. An addnl. component can be a binder, selected from cellulose-based binders, polycarbonates, polyurethanes, polyesters, polyethers, polysuccinates, thermoplastic elastomers, polybutadiene, and polystyrene.

Bibliographic Information

Multistep synthesis of dinitromethane salts from 1,3-diazines, 1,2-diazoles, and 1,2,4-triazoles. Latypov, Nikolai; Wellmar, Ulf; Langlet, Abraham. (Forsvarets Forskningsanstalt, Swed.). PCT Int. Appl. (2000), 14 pp. CODEN: PIXXD2 WO 0034223 A1 20000615 Designated States W: AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ, TM. Designated States RW: AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, BF, BJ, CF, CG, CI, CM, GA, ML, MR, NE, SN, TD, TG. Patent written in English. Application: WO 99-SE2301 19991208. Priority: SE 98-4252. CAN 133:32444 AN 2000:401775 CAPLUS (Copyright 2003 ACS)

Patent Family Information

Patent No. Kind Date Application No. Date
WO 2000034223 A1 20000615 WO 1999-SE2301 19991208
W: AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ, TM
RW: GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW, AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG
SE 9804252 A 20000609 SE 1998-4252 19981208
SE 513222 C2 20000807
EP 1137622 A1 20011004 EP 1999-964846 19991208
R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE, SI, LT, LV, FI, RO
US 6340780 B1 20020122 US 2001-856465 20010607

Priority Application Information
SE 1998-4252 19981208
WO 1999-SE2301 19991208

Abstract

Dinitromethane salts, suitable as intermediates and starting materials for prodn. of explosives and propellants, are prepd. in three steps from 1,3-diazines (I), 1,2-diazoles (II), and 1,2,4-triazoles (III), or their tautomers, by: (1) nitration to form a gem-dinitro group on a carbon atom in a corresponding heterocyclic ring, (2) aq. hydrolysis of the gem-dinitro intermediate to form dinitromethane, and (3) neutralization of the intermediate dinitromethane to form the corresponding salt. The starting materials have the above general formulas, in which X1 and X2 are ( :o ), (:S), OH, SH, halogen, NH2, NHR (R = alkyl); X3 = H, alkyl, NO2, ( :o ), (:S), OH, SH, N3, CN, CNO, NCO, CHO, CO2H, CO2R1,C( :o )SR1, C(:S)SR1, C( :o )NR1R2 (R1 and R2 = alkyl or aryl). Nitration is typically carried out at from -20° to 50° in the presence of HNO3 or common HNO3-based mixed acids. Neutralization is advantageously carried out in aq. soln., with sepn. of the dinitromethane salt by adsorption on an adsorbent (e.g., activated carbon, silica gel, or zeolites).


Bibliographic Information

Proposed Mechanism of 1,1-Diaminodinitroethylene Decomposition: A Density Functional Theory Study. Gindulyte, Asta; Massa, Lou; Huang, Lulu; Karle, Jerome. Department of Chemistry, Hunter College, New York, NY, USA. Journal of Physical Chemistry A (1999), 103(50), 11045-11051. CODEN: JPCAFH ISSN: 1089-5639. Journal written in English. CAN 132:63815 AN 1999:720619 CAPLUS (Copyright 2003 ACS)

Abstract

We have investigated the heretofore unknown unimol. decompn. pathway of the explosive mol. diaminodinitroethylene (DADNE). With the use of DFT methods, whose accuracy has been calibrated by means of ab initio calcns. (MP2, MP4, G2) on a simpler but related mol., nitroethylene, we have been able to characterize the entire decompn. reaction pathway. Importantly, we find that the reaction is initiated by a nitro-to-nitrite rearrangement with a calcd. energy barrier of magnitude 59.1 kcal/mol obtained by use of B3LYP (59.7 kcal/mol B3P86) which is very close to the exptl. activation energy of 58 kcal/mol. We have been able to characterize every step in the decompn. reaction path leading to fragments NO, HONO, CO, NH2, and HNC. These may interact to yield final stable products, CO, N2, H2O with an energy release that on av. is adequate to initiate two addnl. DADNE mol. decompns., and thus, sustain a chain reaction. The structural parameters we have calcd. for DADNE are consistent with the known exptl. crystallog. structure, and also with previous theor. calcns. Addnl., we have obtained the structural parameters of the initial transition state, as well as each subsequent step along the decompn. pathway. Thus we consider the unimol. decompn. of DADNE to be well characterized.

Bibliographic Information

1,1-Diamino-2,2-dinitroethylene: a novel energetic material with infinite layers in two dimensions. Bemm, Ulf; Ostmark, Henric. Weapons and Protection Division, Defence Research Establishment (FOA), Tumba, Swed. Acta Crystallographica, Section C: Crystal Structure Communications (1998), C54(12), 1997-1999. CODEN: ACSCEE ISSN: 0108-2701. Journal written in English. CAN 130:117661 AN 1999:82557 CAPLUS (Copyright 2003 ACS)

Abstract

(C2H4N4O4) is a novel and interesting high explosive with high performance and low sensitivity. Crystallog. data and at. coordinates are given. Single-crystal x-ray diffraction studies of the compd. show that the mols. in the crystal structure have bond lengths and bond angles as expected for this type of push-pull ethylene. There are two intramol. H bonds present between the nitro-O atoms and the amino-H atoms. The geometry of the mol. indicates that there is extensive rr conjugation present. The mol. packing is built up by infinite two-dimensional wave-shaped layers, with extensive intermol. H bonding within the layers and ordinary van der Waals interactions between the layers. The crystal packing explains some of the physicochem. properties of the compd., such as the absence of a m.p., its low soly., and its low sensitivity to friction and impact compared with the common high explosive RDX (1,3,5-triaza-1,3,5-trinitrocyclohexane).

Bibliographic Information

Synthesis of diaminodinitroethylene explosive by nitration and hydrolysis of intermediates. Latypov, Nikolai; Langlet, Abraham; Wellmar, Ulf. (Forsvarets Forskningsanstalt, Swed.). PCT Int. Appl. (1999), 23 pp. CODEN: PIXXD2 WO 9903818 A1 19990128 Designated States W: AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, GW, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ, TM. Designated States RW: AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, BF, BJ, CF, CG, CI, CM, GA, ML, MR, NE, SN, TD, TG. Patent written in English. Application: WO 98-SE1304 19980702. Priority: SE 97-2735; SE 98-900. CAN 130:127117 AN 1999:77530 CAPLUS (Copyright 2003 ACS)

Patent Family Information

Patent No. Kind Date Application No. Date
WO 9903818 A1 19990128 WO 1998-SE1304 19980702
W: AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, GW, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ, TM
RW: GH, GM, KE, LS, MW, SD, SZ, UG, ZW, AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG
SE 9800900 A 19990117 SE 1998-900 19980318
SE 511791 C2 19991129
AU 9883636 A1 19990210 AU 1998-83636 19980702
EP 1007503 A1 20000614 EP 1998-934028 19980702
R: AT, BE, DE, DK, FR, GB, IT, NL, FI
NO 2000000205 A 20000315 NO 2000-205 20000114
US 6312538 B1 20011106 US 2000-462479 20000118

Priority Application Information
SE 1997-2735 19970716
SE 1998-900 19980318
WO 1998-SE1304 19980702

Abstract

1,1-Diamino-2,2-dinitroethylene (I), suitable for use as an explosive, is prepd. in a multistep synthesis by: (1) nitrating a heterocyclic 5- or 6-membered ring contg. structural elements II and III (Y = alkoxy), to yield 5- and intermediates of 5- and 6-membered heterocyclic rings contg. structural elements IV and V (n ³1), followed by (2) neutralization to pH 8-9 (esp. with NH3) and aq. hydrolysis, in which I separates out as a ppt. The precursors are nitrated at low temp. (preferably 0-30°), in which the acidity of the nitrating acids is selected such that intermediates IV and V are produced in high yield. Suitable starting materials include 2-methyl-4,6-pyrimidinedione, 2-methylimidazole, 2-methyl-4(3H)-imidazolone, 2-methyl-4,5-imidazoledione, 2-methoxy-2-methyl-4,5-imidazolidinedione, substituted 2-methyl-1,3,4-triazoles, 2-methyl-1,3-diazines, and 2-methyl-1,3-diazoles. The starting materials are nitrated in the presence of HNO3 and a second acid, typically chosen from H2SO4, HClO4, H3PO4, P2O5, AcOH, Ac2O, CF3CO2H, and (CF3CO2)2O.


Bibliographic Information

Synthesis and reactions of 1,1-diamino-2,2-dinitroethylene. Latypov, Nikolai V.; Bergman, Jan; Langlet, Abraham; Wellmar, Ulf; Bemm, Ulf. Natl. Defence Res. Establishment, Tumba, Swed. Tetrahedron (1998), 54(38), 11525-11536. CODEN: TETRAB ISSN: 0040-4020. Journal written in English. CAN 129:290091 AN 1998:595327 CAPLUS (Copyright 2003 ACS)

Abstract

Low temp. nitration of 2-methylimidazole gave, in addn. to the known 2-methyl-5(4)-nitroimidazole, 2-(dinitromethylene)-5,5-dinitro-4-imidazolidinone (3) and parabanic acid. The tetranitro compd. (3) was also obtained by nitration of 2-methyl-4,5-dihydro-(1H)-5-imidazolone. Thermal decompn. of 3 gave 2-(dinitromethylene)-4,5-imidazolidinedione (4), which also was the product from nitration of the new compd. 2-methoxy-2-methyl-4,5-imidazolidinedione. Treatment of 4 with aq. ammonia gave the previously unknown 1,1-diamino-2,2-dinitroethylene (5). The phys. properties and chem. behavior of (5) are described.

Bibliographic Information

Computational investigation of the structures and relative stabilities of amino/nitro derivatives of ethylene. Politzer, Peter; Concha, Monica C.; Grice, M. Edward; Murray, Jane S.; Lane, Pat. Dep. Chem., Univ. New Orleans, New Orleans, LA, USA. THEOCHEM (1998), 452(1-3), 75-83. CODEN: THEODJ ISSN: 0166-1280. Journal written in English. CAN 130:3571 AN 1998:504543 CAPLUS (Copyright 2003 ACS)

Abstract

Eight amino and/or nitro derivs. of ethylene were studied computationally at the d. functional B3P86/6-31+G** level. The mol. geometries and relative stabilities reflect the varying roles of push-pull+- electronic delocalization and intramol. H bonding. The same 2 factors affect, to varying extents, the computed C-NO2 and C-NH2 bond dissocn. energies, which are also presented, as are the heats of formation, vaporization and sublimation of the 3 diaminodinitroethylenes. The potential of the latter as energetic compds. is briefly discussed.

Bibliographic Information

Chemistry of polynitroethane derivatives. Baum, K. Fluorochem Inc., Azusa, CA, USA. Avail. NTIS. Report (1992), (ARO-25761.5-CH-S; Order No. AD-A249264), 9 pp. From: Gov. Rep. Announce. Index (U. S.) 1992, 92(16), Abstr. No. 243,310. Report written in English. CAN 119:159639 AN 1993:559639 CAPLUS (Copyright 2003 ACS)

Abstract

1,2-Difluorodinitroethylene was prepd. by pyrolysis of 1,2-difluorotetranitroethane. Reactions of 1,1-diiododinitroethylene with nucleophiles were studied. Nitrations of 1,1-diamino-2,2-dinitroethylenes gave trinitromethyl derivs. Fluoride ion reacted with 1,1-diiododinitroethylene to give trifluorodinitroethane salts, used to prep. 3,3,3-trifluoro-2,2-dinitropropyl compds. Thermolysis of 1,1,2-tribomotrinitroethane gave 1,2- and 1,1-dibromodinitroethylene.

Bibliographic Information

Quantum chemical study on the effect of the substituent and the conjugated length in substituted polyenes on second order nonlinear-optical coefficients. Cao, Yang; Qiu, Guofang; Wang, Youliang. Dep. Chem., Suzhou Univ., Suzhou, Peop. Rep. China. Huaxue Xuebao (1992), 50(8), 783-7. CODEN: HHHPA4 ISSN: 0567-7351. Journal written in Chinese. CAN 118:38202 AN 1993:38202 CAPLUS (Copyright 2003 ACS)

Abstract

The second order nonlinear-optical coeffs. of a series of substituted polyenes have been calcd. by the semi-empirical CNDO/S-CI method. The results show that the introduction of the electronic donor or acceptor and the increase in the distance between the substituents and the length of the conjugated chain may enhance nonlinear optical response. It is also shown that the calcd. In bvec is linear with the no. of double bonds in planar and linear trans-polyenes. A satn. effect in substitution is discovered. The theor. explanations are presented for these results. Based on the above discussion one can get the guidelines for synthesis of mols. with larger SHG (second harmonic generation) coeffs.

[Hex]

LLM-105 synth

Bibliographic Information

Aminonitropyridines and their N-oxides. Hollins, Richard A.; Merwin, Lawrence H.; Nissan, Robin A.; Wilson, William S.; Gilardi, Richard. Res. Technol. Div., Naval Air Warfare Cent. Weapons Div., China Lake, CA, USA. Journal of Heterocyclic Chemistry (1996), 33(3), 895-904. CODEN: JHTCAD ISSN: 0022-152X. Journal written in English. CAN 125:247556 AN 1996:499186 CAPLUS

Abstract

2,6-Diamino-3,5-dinitropyridine 1-oxide has been prepd. by mixed acid nitration of 2,6-diaminopyridine, followed by oxidn. using hydrogen peroxide in acetic acid. 3,5-Dinitro-2,4,6-triaminopyridine has been prepd. by oxidative amination of 2-chloro-3,5-dinitropyridine or 2,6-diamino-3,5-dinitropyridine using potassium permanganate in liq. ammonia, or by "vicarious nucleophilic amination" of 2,6-diamino-3,5-dinitropyridine using hydroxylamine in aq. potassium hydroxide. 3,5-Dinitro-2,4,6-triaminopyridine 1-oxide has been prepd. by oxidn. of 3,5-dinitro-2,4,6-triaminopyridine using hydrogen peroxide in acetic acid, and by "vicarious nucleophilic amination" of 2,6-diamino-3,5-dinitropyridine 1-oxide. NMR spectroscopy and single crystal X-ray diffraction studies have shown that these compds. have the planar structures and intra- and inter-mol. hydrogen bonding necessary to confer on the materials the high d., the thermal and chem. stability, and the explosive insensitivity required for new insensitive energetic materials.

APNZ precursor: USP 3,808,209, SU 1,703,645 A1

APNZ can be oxidised to LLM-105 using 30%H2O2 in trifluoroacetic acid at room temp.

<small>[ February 18, 2003, 06:30 AM: Message edited by: Hex ]</small>

[cutefix]

This LLM –105 is interesting being one of those lesser known heterocyclic explosives that come to be developed and applied to PBX and IHE application.
I have got some brief information from this:
<a href="http://www.sainc.com/onr/detsymp/PaperSubmit/FinalManuscript/pdf/Tran-238.pdf" target="_blank">http://www.sainc.com/onr/detsymp/PaperSubmit/FinalManuscript/pdf/Tran-238.pdf</a>
and this
<a href="http://www.sainc.com/onr/detsymp/FinalPapers/DE200.pdf" target="_blank">http://www.sainc.com/onr/detsymp/FinalPapers/DE200.pdf</a>

[megalomania]

I have finished the addition of FOX-7 to my website finally. There you will find a synthesis for it and the main precursor. I still need to add the stuff for the other precursors to make that precursor though. It was about time I updated my site. I have not updated it for months despite numerous changes.

[THe_rEaL_dEaL]

What happened to the NAOH + ethanol reaction for sodium methoxide?
It sounds so straight forward.


If not does anyone know of a tried and tested diethyl oxalate synth link?

[Dave Angel]

I've been looking into the synthesis of acetamidine hydrochloride and came across a route at Organic Syntheses: http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV1P0005

It requires acetonitrile which I have no experience with (I'm expecting high toxicity), but it seems to be affordable and available from chemical suppliers if you have one that will sell to you.

Also required are dry ammonia and HCl gasses which can't be that hard to produce with the relevant solution, a heat source and a suitable drying agent. The EtOH should be no problem.

I can't see us making FOX-7 from OTC chems unless we go through the unstable 2-methylimidazole route, but I would like to synthesise FOX-7 just to have done it. If I need OTC I'd go for something simpler like RDX for example.

[Edit] On reading through the entire thread again I see mega already pointed out the acetamidine hydrochloride synthesis in Org Synth. Well it was 5am when I wrote it!

And naturally after saying EtOH should be no problem, I've just seen the prices for absolute alcohol... Does anyone know if anhydrous industrial methylated spirits could be used in it's place? I believe the 5% MeOH will mean impurities (a little dimethyl oxylate for example), but I should still think that the majority of the product will be derived from the EtOH. Does anyone know any better?

[Piglet]

Sodium methoxide: It's a cute material and there is a newer synth. Methanol & sodium hydroxide in a 2-phase reaction with toluene. I will get the details when I find them, but you can see the logic. The methoxide WILL mix with toluene and the other compounds will not. I know people who use this method to convert hydroquinone to 1,4 dimethoxy benzene. It's a useful route to 2,5 dimethoxy benzaldehyde... A drug precursor.

[Lavoisier]

What happened to the NAOH + ethanol reaction for sodium methoxide?

A mixture of NaOH and ethanol at equilibrium actually yields only scarce amounts of sodium ethoxide (not methoxide, which would require methanol). To estimate how much is present at equilibrium, you need the pKA of the acids involed. In this case, these are ethanol (16.0) and water (15.7). The equation describing the equilibrium is :

Keq. = 10-[pKA(acid consumed)-pKA(acid produced)]

so we write :

Keq. = 10-[(16.0)-(15.7)] = 0.50

Which is quite small. Now, you still have to extract this ethoxide salt from the mixture, and I wonder how one could do that...

Methanol & sodium hydroxide in a 2-phase reaction with toluene. I will get the details when I find them, but you can see the logic. The methoxide WILL mix with toluene and the other compounds will not.

No, I can't see the logic there. Methanol is miscible with toluene but methoxide isn't much. Where are the two phases coming from?

I know people who use this method to convert hydroquinone to 1,4 dimethoxy benzene.

I would like to know how they do that, because such a mixture would rather generate the disodium salt of hydroquinone than 1,4-dimethoxy benzene. The latter usually asking for dimethyl sulfate or methyl iodide.