2,3,5,6-Tetraazidobenzoquinone

I come across this in a review article regarding organic azides and looked like a possible and more readily available alternative to cyanuric triazide, there was only a passing mention of it which said it was investigated for its use as an explosive with reference to Sorm, F.: Chem. Obzor. 14, 37 (1939) or Chem. Abstracts 33, 7286 (1939), another reference on its preparation was given as <a href="http://www.sciencemadness.org/talk/viewthread.php?action=attachment&tid=9319&pid=109472"></a> its mentioned but I couldn't find the prep in that article. 2,3,5,6-tetraazidobenzoquinone is formed by the reaction of sodium azide with 2,3,5,6-tetrachlorobenzoquinone aka chloranil.

I had a look for preparations of chloranil in the literature, and there is a lot, too many in fact so its hard to pin point the one most convenient to the amateur. Urbanski volume 1, in the section on picric acid mentions:

"When reacted with chlorine, aqua regia or potassium chlorate in the presence of hydrochloric acid, picric acid yields chloranil along with chloropicrin."

The picric acid route looks easy enough but simpler precursors may be had, this from MERK:

"Prepd (chloranil) from p- phenylenediamine or phenol by treating with KClO3 and HCl. Because of its great resistance to further oxidation, chloranil is formed as the final product of the chlorate-HCl oxidation of many aromatic compds. For comprehensive list see Hunt ress, Organic Chlorine Compounds (New York, 1948). Laboratory procedure starting with phenol or p- chlorophenol: Fierz-David, Blangey, Grundlegende Operationen der Farbenchemie (Vienna, 5th ed., 1943) p 140."

The two examples are not readily available but what of the "many other aromatic compounds" Aniline likely would as well. Possibly p-dichlorobenzene?, need a use for that crap. If not p-DCB then nitration to activate one of the chlorines then remove with NaOH giving mainly 4-chloro-2,6-dinitrophenol, its known that picric acid and p-chlorophenol can be oxidised/chlorinated to chloranil so that probably has merit if p-DCB itself is unreactive.

I requested another article regarding the oxidation/chlorination of phenol and hydroquinone with HCl-H2O2 to chloranil, retrieved by solo <a href="http://www.sciencemadness.org/talk/viewthread.php?action=attachment&tid=9319&pid=109471">here</a>.

[Edited on 7-11-2007 by Axt]

Wonder if some common materials like aspirin , salicylic acid ,
and methyl salicylate could be on that list .

It might be interesting to substitute sodium tetrazylazide
(sodium 5-azidotetrazole) for the sodium azide

Alkaline hydrolysis of tetracene using NaOH should provide the sodium 5-azidotetrazole , with expulsion of ammonia
as a byproduct . See the first page of the sticky thread on
5-ATZ related materials , about halfway down the first page .

http://www.sciencemadness.org/talk/viewthread.php?tid=8144

That should yield a tetra-tetrazylazide ( C10-N28-O2 )
( bet you can't say its name without stuttering )
I'll leave that tongue twister to somebody else


[Edited on 7-11-2007 by Rosco Bodine]

We need some Belgian input here
Where's Philou Zrealone when you need him ?

Need a nice clean dioxin free chloranil synthesis ,
from OTC materials so how about it ?

Still can't find any reference to my above named
tongue twister . Any predictions on its density
and stability , sassiness ?

On the tongue twister, I can't see it being too high density with all the long tetrazyl azide groups hanging off with all sorts of deviations from planarity. How accurate is chemsketch's density predicter anyway?(this molecule is too big for it).
I cannot see it not being extremely frisky...following the general increase in friskyness from azide to tetrazylazide.
EDIT for clarity: I think it would be more powerfull than the simple azide flavour, but I worry about how stable to minute stimulus it would be.
Now hanging some nitrotetrazoles off there...

[Edited on 10-11-2007 by The_Davster]

The action of aqua regia on paracetamol closely met the description of that of p-aminophenol as posted above. On mixing 15g paracetamol with 100ml 32% HCl, then adding 50ml 70% HNO3 after a short time a rapid reaction commenced with much foaming. After this died down the mixture was heated @ 80°C for 2 hours whereby the evolution of gasses had ceased. A sulphur yellow precipitate remained.

[Edited on 4-12-2007 by Axt]

1.6g of the supposed chloranil obtained from paracetamol was suspended in 28ml of ethanol (as methylated spirits). Into this was added 1.9g of sodium azide and the solution swirled for two hours. The mixture quickly turned orange then reddish brown then finally black. It was left sit overnight (~8hr) then poured into 200ml water, swirled and filtered. Obtained was a bluish-black crystalline substance.

Small quantities amounting to about 1/4 matchhead were scooped onto the back of separate matches for drying, and the remainder on the filter paper was flushed into the lawn with water to dispose of it.

Even when wet, the 1/4 matchhead of tetraazidobenzoqunone would detonate with a sharp ear ringing report when touched with a flame.

Sodium nitranilate synthesis was reported in <a href="http://www.sciencemadness.org/talk/viewthread.php?action=attachment&tid=9319&pid=111612">this translation</a> of ber, 20, 2027 (1887). They added a saturated solution of chloranil in acetone to a concentrated solution of NaNO2 in water. The problem is a saturated solution of chloranil is about 4g in 150ml acetone thus on addition to the smaller volume of NaNO2/water presumably you would get a precipitate of NaCl. I tried to simplify this by just boiling chloranil (which was already a very fine powder) in aqueous NaNO2 until the sodium nitranilate went into solution , then cool to precipitate it. I've previously attached its solubility data for the Na/K salts <a href="http://www.sciencemadness.org/talk/viewthread.php?action=attachment&tid=433&pid=69514">here</a>, which is 0.724g/100ml @ 30°C and 0.567g/100ml @ 30°C respectively.

2g of chloranil was stirred into a solution of 5g of sodium nitrite in 200ml of water. Gradually all the chloranil went into solution giving it a deep orange colour. The solution was left to boil to a volume of 100ml then cooled to 5°C whereby a yellow orange precipitate formed. This was filtered and dried. Yield was ~1g.

0.4g of the presumed sodium nitranilate was dissolved into 100ml of boiling water. Into this was added 0.6g lead acetate in 20ml water. A dark reddish orange precipitate formed which was filtered and dried.

The lead nitranilate took the form of small copper coloured needles which in pinch sized quantities detonated with a loud report when touched by a flame.

The pictures below are sodium nitranilate of filter paper, the precipitate of Pb nitranilate and the lead salt under microscope. The bottom row is the ignition of Pb nitranilate.

Actually over 100 years earlier, the first report of the oxidation/chlorination of salycilic acid to chloranil using KClO3-HCl was in <i>Annalen der Chemie</i>, 78, 4 (1851). Which is well before even aspirin was patented. Though the melting point given for chloranil in FEMEP is 100°C too low!

Also, while ber, 20, 2027 (1887) also mentions ethanol as being a suitable solvent it pours this into an aquous solution of NaNO2. I'm not totally sure of the mechanism of this reaction but the only way I can see the hydroxy groups being added is via the reaction of the chlorine or nitro substitute (ortho to the other nitro groups) with water. With only ethanol I'd expect a phenetol derivative.

With mine, after filtering the tiny copper coloured needles and leaving the yellow solution sit, a further small crop of crystals did form in the solution which met the description in FEMEP, golden plates. Though on filtering and drying these they would only pop and splutter when exposed to flame. There is only a description of the basic lead salt in PATR2700 which is said to be red. Presumably I had the normal salt.

That possibly novel compound I suggested above ,

2,3,5,6-tetra-tetrazolylazidobenzoquinone

represents something of a curious physiological anomaly ,

given that it is both a tongue twister .......
and a fanny puckerer simultaneously

Sorry , I know that's bad .....
but I just couldn't resist

Anybody run a simulation model on that one ,
any predicted density , energy , ect . ??

Oh its not me that insists on 2 OH's! thats simply the known structure of nitranilic acid, and I only (well, nearly) followed the known synthesis for this. If "tetranitrobenzoquinone" were aromatic this would be the expected reaction where nitro groups ortho to each other being unstable, being replaced by hydroxyl group via water. See <a href="http://v3.espacenet.com/origdoc?DB=EPODOC&IDX=DE407416&F=0&QPN=DE407416">DE407416</a>, I dont know if theres anything interesting in there but you can read it and its the only known reference to the lead salt of nitranilic acid.

Also probable are peroxidic explosives derived from chloranil. There is reference to a tricyclic C6O6 (imagine the most obvious product of Na2O2 with chloranil) in the following article. Though I suspect it is just a theroretical study.

Gernot Frenking "The Structure of Cyclic C6S6 and C6O6" <i>Angewandte Chemie International Edition</i>
Volume 29, Issue 12, 1990, Pages: 1410-1412

And

Fariba Nazari "Stable structures of oxocarbons and pseudooxocarbons of group VI" <i>Journal of Molecular Structure: THEOCHEM</i> Volume 760, Issues 1-3, 2006, Pages 29-37

Surprise surprise, your compound is not listed in scifinder Rosco, I'm shocked Actually there was no tetrazole derivatives listed.

Quote:

Originally posted by Axt Surprise surprise, your compound is not listed in scifinder Rosco, I'm shocked Actually there was no tetrazole derivatives listed.

Maybe it's an unlisted experimental roo medicine

Lead adducts of polynitro aromatic acids

I left some of the tetraazide on a slide under the microscope, the decay after 40 days can be seen in the attached picture.

Also KNO3 + HCl can be used just as effectively as HNO3 + HCl for the production of chloranil from paracetamol. The reaction runs much the same though is less vigourous in the initial stages. The crude yield from 12g paracetamol, 65g KNO3 and 150ml 32% HCl was 12.8g on the first try and 13.4g on the second, effectively the same. For simplicity the first try used the whole tablet including gelatine capsule with the presumption that chloranil would be the only product to resist the aqua regia.

paradichlorobenzene is a good cheap OTC source as mentionned hereabove. I have like 10kg or so bought as toilet desodouriser (maybe 5$ the kg).

What is super interesting with chloranil, it the ease with what it is done an the exchange ability of its chlorine atoms.

[Edited on 24-1-2008 by PHILOU Zrealone]

The answer must be yes when you see how easilly it fixes NO2(-) and N3(-).
Although with chemsketch, you get a very bulky starshiplike structure...density is very hard to predict.
Maybe by plotting cyanuric triazide with cyanuric tritetraazolylazide,vs tetraazidoquinone it might give a density hint for tetratetraazolylazidoquinone (TTAAQ).

On another aspect nitranilic acid makes a very beautiful planar molecule with H bondings or with the keto oxygen or with the nitro next to it...making pseudo polycycloaromatics structures...Resonance of the pheno-keto-nitro groups allow transient passage to a triketo and tetraketo ring apparented to the hexacarbonyl ring...the proton or sodium atom then jumping from the phenol group to the vicinal nitro group turned into a nitronic acid...this might explain the sensitivity of nitranilates.

I suspect the tetranitro compound can be formed in anhydrous media...but like it is the case with hexanitrobenzene turning into trinitrophloroglucidol (1.3.5 trihydroxy-2.4.6 trinitrobenzene), you have one of the two vicinal nitro that is subject to nitro-nitrito rearrangement and subsequent fast hydrolysis.This effect is enhanced by the keto group.

Would also be interesting to test for tetracyanocompound by substituing the chloroatoms with NaCN or AgCN...this should be an energetic fuel...most organic cyanides do have a lot of energy to give...see the heat of combustion of cyanogen (C2N2) vs acetylene vs ethylene vs ethane...you can reach >4000°C in the flame.

Actually also sodium nitroformiate, sodium dinitramide, disodium dinitrourea would be woth a try

[Edited on 25-1-2008 by PHILOU Zrealone]

Since the topics turned into any energetic chloranil derivative, heres an idea to produce the hexaoxime which should be an interesting precursor to other energetics. Or used alone as its salts being empirically similar to the fulminates, structurely different but I've previously shown the Pb and ag salts of glyoxime to be quite energetic. Theres also possible furazan and furoxan (eg. BTF) derivatives from NaOH and NO2 respectively.

So its all OTC paracetamol -> chloranil -> tetrahydroxyquinone -> cyclohexanhexone -> cyclohexane hexaoxime.

Putative chloranil has been worked out in this thread.

Tetrahydroxyquinone even though it seems obvious it cannot be produced from NaOH in water, at least not easily. This is from J. Chem. Soc., Abstr. 60, 1027-8 1891.

<i>"Chloranilic acid is obtained when chloranil (10 grams) is moistened with alcohol and added to a solution of sodium hydroxide (9 grams) in water (200-220 c.c.) heated to 80°, or to a solution of potassium hydroxide (12 grams) in water (250 c.c.). After remaining 1-2 hours, common salt (20 grams) is added, and the precipitated sodium derivative is washed with a 10 per cent. solution of common salt until the filtrate is colourless; it is then redissolved in water, and the chloranilic acid precipitated with hydrochloric acid. The yield is 62 per cent. of the weight of the chloranil."</i>

So it will only replace two of the chlorines before the others are deactivated. Though a way around this seems to be found in Zeitschrift fuer Naturforschung, Teil B: Anorganische Chemie, Organische Chemie (1978), 33B(10), 1201-3. This is the abstract, I'll try source the full article.

<i>"A simple synthesis of 1,4-tetrahydroxybenzoquinone.
Tetrahydroxy-p-benzoquinone (I; R = H) was prepd. by methoxylation-hydrolysis of chloranil and converted into various ethers (I; R = C2-C5 alkyl, EtOCH2CH2) by treatment with the alc. in the presence of NaOH."</i>

So it seems the alcohol derivative is first formed and hydrolised to tetrahydroxybenzoquinone. Hopefully its as simple as reacting it with a hydroxide in ethanol. There is another preparation in Organic Syntheses; Vol. V, p. 1011 though its an awful waste on glyoxal.

Cyclohexanhexone is formed as its octahydrate by oxidation of the sodium salt of tetrahydroxybenzoquinone with 25% HNO3, the simple preparation is in J. Org. Chem.; 1986; 51(26); 5241-5243. Its just a mix, let react, cool, filter reaction.

Cyclohexane hexaoxime is an unknown, presumably it will form from Cyclohexanhexone and hydroxylamine though there is no references to it. Even scifinder gives nothing except a few suppliers for it in milligram quantities, so it is at least a known compound.

[Edited on 20-5-2008 by Axt]

Food for thought on precursors

Triquinoyl ( cyclohexanehexone )

There it is

Unfortunately no synthesis is given, only a reference to Berichte der Deutsche Chemische Geselschaft. Most probably they made it from nitralinic acid, not the bisodium salt.

Regarding the chloranile synthesis, is it possible to purify OTC paracetamol by dissolving in EtOH (12g should dissolve in 80ml EtOH) and precipate with water?

[Edited on 9-11-2008 by Taoiseach]

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Quote:

Originally posted by Taoiseach There it is Unfortunately no synthesis is given, only a reference to Berichte der Deutsche Chemische Geselschaft. Most probably they made it from nitralinic acid, not the bisodium salt.

The second article

Wow, thieves.

My preparation posted in 2007:

<i>"2g of chloranil was stirred into a solution of 5g of sodium nitrite in 200ml of water. Gradually all the chloranil went into solution giving it a deep orange colour. The solution was left to boil to a volume of 100ml then cooled to 5°C whereby a yellow orange precipitate formed. This was filtered and dried. Yield was ~1g."</i>

Their preparation published 2008, citing Z. Naturforsch. B: Chem. Sci. 1994, 49, 1021 – 1030.

<i>"Chloranil powder (2 g, 8.1 mmol) was added at room temperature to a solution of sodium nitrite (5 g, 72 mmol) in water (200 mL). The reaction mixture was gradually heated to reflux. After stirring for 2 h at reflux, the clear deep orange reaction mixture was concentrated to 100 mL, and then cooled to 5°C where a yellow-orange crystalline precipitate was formed. It was collected by filtration, washed with cold water (20 mL), dried in vacuum to afford the product (1.2 g, 54%). No further purification was needed."</i>

Also mine:

<i>"I've previously attached its solubility data for the Na/K salts here, which is 0.724g/100ml @ 30°C and 0.567g/100ml @ 30°C respectively."</i>

Theirs:

<i>"The solubilities of potassium and sodium nitranilates at 30°C are only 0.724 and 0.567 g per 100 g H2O, respectively."</i>

All literature preps I'd seen used a non-aqueous solvent for chloranil during the prep so unless theres some freak coincidence that the Z. Naturforsch. B: Chem. Sci. article happened to have what I posted here near word for word .... Oh well, imitation is the sincerest form of flattery

[Edited on 30-12-2008 by Axt]

Indeed, though it irks me a little that they had the hide to cite someone else

TCCA is of course a chloramine this not completely related, though it has been discussed in the past. It's reaction with AgNO2 has been mentioned in the literature however it does not result in the nitramine of the parent compound, which would be very unstable. No mention was given of the product of the reaction only that it didn't work. There was some discussion on chloramines to nitramines in the <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=4282">ethylenedinitramine thread</a>.

Quote:

Originally posted by Axt ... so unless theres some freak coincidence that the Z. Naturforsch. B: Chem. Sci. article happened to have what I posted here near word for word .... Oh well, imitation is the sincerest form of flattery

Quote:

Originally posted by Axt Quote: Originally posted by Axt ... so unless theres some freak coincidence that the Z. Naturforsch. B: Chem. Sci. article happened to have what I posted here near word for word .... Oh well, imitation is the sincerest form of flattery I got hold of that article just to see what was in it. Its on the structure of Na & K nitranilate. As for the preparation they give I cant work it out, being in german. Though it seems to give it in low yield, 17%.

Quote: Originally posted by chemoleo

Regarding the interesting patent that Axt attached above: What is perhaps interesting that these lead salts aren't obvious acid base products, but adducts of some sort, and that they involve the nitrogroups themselves. They are formed by dissolving the polynitroaromatic acid in excess of PbO, or by dissolving the lead salt (as formed by precipitating with PbAc2) in excess PbO. Using *less* than i.e. 4 moles of PbO with lead picrate, however, does not yield the desired (precipitated) product, so it does need this 4x excess. It is however possible to add 1 mol of Pb to each nitro group if a PbO (6 molar excess rather than 4) is stirred into *hot* solution of lead pictrate. The reaction takes some time and its completion is indicated in all cases by precipitation of the adduct. They tested this for (where the starting compound was the ordinary lead salt in all cases) - Lead picrate, forming an adduct containing C12H4O18N6Pb5 (4 mole PbO to 1 Pb picrate) - dark yellow and insoluble - Lead trinitroresorcinate (red powder, deflagration at 255 deg C), containing C6HO11N3Pb4 (3mole PbO to 1 PbTNR) - Lead trinitrobenzoic acid (red powder), C14H4O20N6Pb5 (4 mole PbO to 1 PbTNBA) - Lead nitranilate (red powder) (2 mole PbO to 1 PbNA) C6O10N2Pb3 I wonder what the structures of these things are, for instance the adduct of the PbTNBA... All these adducts are different to the normal lead salts because of - higher insolubility than normal lead salt - higher sensitivity, i.e. the Pb picrate adduct explodes when exposed to flame while normal Pb picrate doesn't.

some followup ideas

Quote: Originally posted by Rosco Bodine

I am wondering if the procedure was modified for the synthesis of sodium nitranilate, so that the chloranil was present in 50% excess of theory for (two) sodium nitranilates, if the two sodium nitranilates would form as an intermediate and then further react with the excess chloranil to form four sodium chlorides and one 2,5 - 3,6 di-nitranilato-benzoquinone This would involve overall three chloranils reacting with four sodium nitrites. Diazoguanidine Nitranilate ( Guanyl Azide Nitranilate ) is another interesting possible compound which may be worth an experiment. [Edited on 17-2-2009 by Rosco Bodine]

On the preceding page is an article cited by Taoiseach and posted by sparkgap, attached again here, for sodium nitranilate and derivative compounds. Compound 6 is
(Di)-aminoguanidinium nitranilate. (Nitranilic acid is a dibasic acid). Aminoguanidinium perchorate and other aminoguanidinium salts can be diazotized to form the corrresponding guanyl azide (also known as diazoguanidine or azidoformamidinium) salts. This should be a significantly more sensitive and more energetic compound than is the (Di)-hydrazine nitranilate salt. It is considered that the (Di)-azidoformamidinium nitranilate may have properties which would qualify it as a primary explosive, similar as is azidoformamidinium perchlorate. There would be predicted a perfect chemical compatibility for such initiators in physical contact with an azidoformamidinium picrate base charge.

Also of possible interest is a hypothetical energetic compound formed by the reaction of chloranil with four molecules of the ammonium or sodium salt of 3,5-dinitro-1,2,4-triazole. The hypothetical energetic compound would be 2,3,5,6-Tetra[3,5-dinitro-1,2,4-triazolium]benzoquinone.


Another possible hypothetical energetic compound may be formed from the reaction of chloranil with two molecules of the disodium salt of Bis[3-(5-nitroimino-1,2,4-triazolate)].
The hypothetical energetic compound would be 2,3-5,6-Di-Bis[3-(5-nitroimino-1,2,4-triazolium)]benzoquinone (nomenclature corr?) Sorry if the names are awkward ...
I tried ...but these names give me a headache

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Attachment: JACS Bis[3-(5-nitroimino-1,2,4-triazolate)]-Based Energetic Salts.pdf (99kB)
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[Edited on 18-6-2011 by Rosco Bodine]