Sciencemadness Discussion Board

2,3,5,6-Tetraazidobenzoquinone

Axt - 6-11-2007 at 14:54

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]

TABQ.jpg - 7kB

Rosco Bodine - 6-11-2007 at 19:16

Quote:
Originally posted by Axt
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
Huntress, Organic Chlorine Compounds (New York, 1948).


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 :D

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 ) :P
I'll leave that tongue twister to somebody else :D


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

Sickman - 7-11-2007 at 00:17

Here are some US patent numbers that seem among the best for the home production of chloronil:

US5334735

US2872461

US2519319

US2414008

Rosco Bodine - 7-11-2007 at 09:47

It looks to me like the H2O2 + HCl reaction might be applicable to the common and cheap analgesic paracetamol , ( "tylenol" , acetaminophen , p-acetamidophenol ) to produce chloranil .

I haven't yet found a reference directly for this suspected
reaction , but it seems the most likely approach using OTC
precursors .

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

artem - 8-11-2007 at 00:34

The main disadvantage of C6(N3)4O2 is its decay at RT (mass loss 4.9%/10days). Interesting, can it be converted, for example, -> C6(N3)4(=NOH)2 or C6(N3)4(=NNH2)2 in order to increase the stability?

Rosco Bodine - 8-11-2007 at 01:33

I wonder .....does this exist , is it already known ?
It sure seems likely , even straightforward .

2,3,5,6-tetra-tetrazylazidobenzoquinone , or

2,3,5,6-tetra-tetrazolylazidobenzoquinone

Wonder what its properties would be ?

artem - 8-11-2007 at 23:54

Quote:
Originally posted by Rosco Bodine
I wonder .....does this exist , is it already known ?...

If you mean C6(N3)4O2:
Blue non-volatile cryst., 10mg det. at 91C (5K/min), sol.in acetone, spar.sol.EtOH, insol.H2O. High friction sensitivity, impact 0.5kg*0.2m, expl.in flame. 20mg, pressed at 50-100MPa, initiated TNT.

not_important - 9-11-2007 at 05:52

Quote:
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.


Just mono-nitrate it and then reduce to 2,5-dichloro-aniline which should oxidise to the quinone.

It may be possible to combine the HCl-H2O2-MgCl2 reaction with a Fenton-style oxidation of p-DCB by adding a trace of Fe(II) or copper salts. The Fenton puts a HO- onto the aromatic ring, that phenol then gets taken to chloranil. Too much Fenton activity will result in complete oxidation of the aromatic substrate, so it would be a balancing between the two reaction paths.

Rosco Bodine - 9-11-2007 at 07:58

We need some Belgian input here :P
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 ?

The_Davster - 9-11-2007 at 17:34

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...:P

[Edited on 10-11-2007 by The_Davster]

Rosco Bodine - 9-11-2007 at 18:12

Hmmmm ...I was thinking high density octagonal plates
might be possible with adjacent molecules interlocking like pairs of 4 projection castle nuts . And yeah there are other interesting possibilities . I'm not sure about the
nitro variant ...IIRC the nitro group can actually be a diluent in tetrazole energetics , in contrast with its
more usual effect .

I don't follow what you are saying about the power ,
as it would for damn sure be stronger than the azide ,
just going by the nature of the additional nitrogen where tetrazole and azide are combined could give a near hundred percent increase over azide alone . Tetrazylazides are described as "extremely brisant" .

I was thinking this could be a non-metallic primary .
It might also plasticize with ethyleneditetrazylazide .

Axt - 11-11-2007 at 21:24

The tetraazide has an entry in PATR2700 under benzoquinone and derivatives.

The stability info artem provided kinda rules out practical usage, even though its initiating ability is very high. Where did that info come from artem?

The instability isn't mentioned in PATR2700 although it does say that it dissolves with decomposition in organic solvents which would make conversion of the carbonyl oxygens to the hydrazone/oxime difficult. Also the chlorines in 2 and 5 positions are very labile, as is the azido groups, thus reaction with the amines would likely replace those in preference to, or as well as the oxygen.

artem - 13-11-2007 at 01:23

Quote:
Originally posted by Axt
..Where did that info come from artem?..

This is from hand-book (Chmelnitsky); the origin - previously mentioned F.Sorm. Chem Obzor.

Axt - 15-11-2007 at 18:54

Found a second entry in PATR2700 which does mention its instability, pg T71 "decomps in air forming a yel-grn powder which when touched with a flame, ignites but does not deton as does the original compd".

But anyway, heres the french citation that gives the synthesis of mono,di and tetrazidobenzoquinones. Havn't tried to read it but I ocr'ed it for pasting into google translator.

Attachment: azidobenzoquinones - BullFr, 35,1190 (1924).pdf (753kB)
This file has been downloaded 964 times


Axt - 2-12-2007 at 22:07

The attached article mentions the effect of aqua regia on many organic substances with chloropicrin and chloranil being the major products.

Aniline only gives a small yield with much tarry prducts and no other convenient precrsors were described but some were hinted at, namely aspirin and paracetamol which rosco mentioned. The most simular compound to paracetamol, p-aminophenol is mentioned to give a good yield withoud tar. Heres some select extracts;

"It (chloranil) has been obtained by the action of a mixture of hydrochloric acid and potassium chlorate on aniline, phenol, salicylic acid, nitrosalicylic acid and dinitrosalicylic acid."

"By the action of aqua regia, which has a far greater oxidizing and chlorinating action than potassium chlorate and hydrochloric acid, on aromatic compounds, chloranil is very frequently formed ; and as chloranil itself breaks up into chloropicrin by the action of aqua regia, this is also a general product of such reactions."

"In the case of hydroxy and amino substituted products, chloranil is formed, but is accompanied by a large amount of tarry and other secondary products."

"p-Aminophenol- On adding p-aminophenol to a mixture of nitric and hydrochloric acids, at first there is no action, but soon afterwards the action commences with frothing. The mixture is then warmed on the water bath for two hours, and at the end of the operation a sulfur yellow crystalline product is produced. In this case no tarry product is formed. The yellow product obtained is crude chloranil which is purified by sublimation and is found to melt at 289° in a sealed capillary tube."

Chloranil can also be used to prepare nitranilic acid.

Chloranil according to ber, 20, 2027-2031 (1887) when treated with an aqueous solution of NaNO2 gives nitranilic acid, (C(OH)-C(O)-C(NO2)=)2, this is mentioned in PATR2700 D1290 though through a different route. Its lead salt "explodes on impact or frictional influences" referencing to german patent DE407416.

[Edited on 3-12-2007 by Axt]

Attachment: chloropicrin and tetrachlorobenzoquinone from aqua regia- JACS,1916; 38(9); 1813-1821.pdf (625kB)
This file has been downloaded 1178 times


Axt - 3-12-2007 at 23:40

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]

para-chloranil.jpg - 24kB

Axt - 6-12-2007 at 20:43

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.

TABQ.jpg - 23kB

Axt - 7-12-2007 at 11:44

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.

lead-nitranilate-scimad.jpg - 38kB

arkansas - 8-12-2007 at 07:46

On the explosive properties of tetraazido-p-benzoquinones
William H. Gilligan and Mortimer J. Kamlet
Tetrahedron Letters, Volume 19, Issue 19, 1978, Pages 1675-1676
The diazido-dichloro-p-benzoquinone (II), while it does not explode upon heating, does have an impact sensitivity of 14 cm. This indicates that II is a sensitive explosive despite Winkelmann's contention that it has no explosive properties. It should be handled with due caution.

Attachment: tl1978.pdf (102kB)
This file has been downloaded 905 times


franklyn - 8-12-2007 at 19:04

Quote:
Originally posted by Axt
Sodium nitranilate synthesis was reported in 1887


1887 ! Wow
I new I'd seen this before, here's a more recent preparation from
CIA Field Expedient Methods of Explosives Preparation

Chloranil :
A slurry of 5.0 grams of salicylic acid and 100 ml of concentrated hydrochloric acid was
heated to 80ºC and 5.0 grams of potassium chlorate added in portions ( with effervescence ).
An additional 400 ml of concentrated hydrochloric acid and 5.0 grams potassium chlorate was
added and the mixture allowed to heat at 80-90ºC for four hours. After filtering, washing with
water and air drying, the yellow crystals melted at 190-200ºC ( sealed tube ). The yeild was
5.45 grams.

Sodium Nitranilate :
A mixture of 5.0 grams of chloranil and 200 ml of ethyl alchohol were heated to boiling and
treated with a solution of 5.6 grams of sodium nitrite in 100 ml of ethyl alcohol. The mixture
was heated with stirring for one hour and allowed to cool. The orange-gold crystalline product
was collected on a filter, washed with ethyl alchohol and air dried. Yeild was 1.85 grams.

Lead Nitranilate :
A solution of 1.0 gram of sodium nitranilate in 100 ml of boiling water was filtered and the
filtrate treated with 2.9 grams of lead nitrate in 10 ml of water. The mixture was stirred for
one half hour and the gold platelets collected on a filter and washed with water. After drying
at 80ºC for three hours, the product weighed 1.23 grams. The product ignited with a loud
report on flame contact.

__________________________________________________________________________


Yes I know, not the most reliable source but it approximately corresponds to your experience.
Someone went to a lot of trouble working this up and it's not a commonly seen recipe.
The Desert publication is from 1977 and the text dates to well before that.

Back when this was contrived using Salicylate, Acetaminophen was not OTC but by presciption only ,
called Dilone for mitigating menstrual cramps. Interestingly investigation of it also dates to the late
19th century.

Quote:
Originally posted by Rosco Bodine
It looks to me like the H2O2 + HCl reaction might be applicable to the common and cheap analgesic
paracetamol to produce chloranil .

Quote:
Originally posted by Axt
The action of aqua regia on paracetamol closely met the description - as posted above


.

Axt - 9-12-2007 at 08:46

Indeed that method in FEMEP has its basis in journal literature, but I have some issues with it.

Quote:
Back when this was contrived using Salicylate, Acetaminophen was not OTC but by presciption only


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.

nitranilic acid sc.jpg - 7kB

chemoleo - 16-12-2007 at 16:27

Great stuff!

I don't understand why you insist on these OH's being present at two positions, where did you hear of this?
Why would the tetraazido form exist, but not the tetranitro?

Rosco Bodine - 16-12-2007 at 19:13

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 :D ;) :P

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

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

Axt - 16-12-2007 at 20:43

Quote:
Originally posted by chemoleo
I don't understand why you insist on these OH's being present at two positions, where did you hear of this?


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 :P Actually there was no tetrazole derivatives listed.

Rosco Bodine - 16-12-2007 at 21:34

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


Maybe it's an unlisted experimental roo medicine :P

Lead adducts of polynitro aromatic acids

chemoleo - 28-12-2007 at 14:56

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.

Axt - 22-1-2008 at 23:54

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.

tetraazidobenzoquinone-decay.jpg - 18kB

YeOldeImpurities - 23-1-2008 at 12:58

I tried NH4NO3+HCl, also works fine.

PHILOU Zrealone - 24-1-2008 at 06:16

Quote:
Originally posted by Axt
I left some of the tetraazide on a slide under the microscope, the decay after 40 days can be seen in the attached picture.


Axt,
Maybe good to test if it is really a decay or simply sublimation.
By making the test in a tiny hermetically closed vessel.
Overpressure in the vessel will confirm the decay.Large cristal growth on the detriment of tiny ones would mean sublimation. Or maybe both processes are in action.


Quote:
Originally posted by Rosco

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 ?


;) 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]

Rosco Bodine - 24-1-2008 at 09:43

That's great , finally having a way to make use of the
chlorinated variant of moth crystals .

That is something which was being discussed in Axts pentryl thread , but nitration seemed to be undesirable
as way of making the paradichlorobenzene into another
more reactive ring compound . So converting the moth crystals to chloranil would be much easier , and then finding possible usefulness for the chloranil as an intermediate would be more practical .

So .......what do you think about the possible reaction
of chloranil with sodium tetrazolylazide , do you think
the theoretical compound I proposed would result in
2,3,5,6-tetra-tetrazolylazidobenzoquinone ?

PHILOU Zrealone - 25-1-2008 at 04:44

Quote:
Originally posted by Rosco Bodine
So .......what do you think about the possible reaction
of chloranil with sodium tetrazolylazide , do you think
the theoretical compound I proposed would result in
2,3,5,6-tetra-tetrazolylazidobenzoquinone ?


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 :) :cool:

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

Axt - 8-2-2008 at 05:23

Quote:
Originally posted by PHILOU Zrealone
Axt,
Maybe good to test if it is really a decay or simply sublimation.


The decomposition at room temperature is well documented in the literature, I just provided the visual reference to it. The crystals changed colour and jumped around the place like "fleas" to use a recent analogy from another member, for a different compound.

The reaction of chloranil is immediate with bases, both NaOH and Na2CO3 immediately turn the solution dark purple, the product is soluble in water. If done in H2O2 solution the initial dark purple would turn clear if left stand.

I tried to form a peroxidic compound from cloranil by treating a slurry in methanol with NaOH + H2O2 solution. Again it turned dark purple but a tan coloured solid remained, this was filtered. On ignition it smouldered, though every now and then it would POP! So something energetic was in there, somewhere. A pure compund was never expected by this route though it may be possible to increase the "active oxygen" to the point where an explosive is produced.

I did this as a simular method has been used to produce peroxides from cyanuric trichloride.

[Edited on 8-2-2008 by Axt]

Axt - 19-5-2008 at 15:06

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]

cyclohexane hexaoxime.jpg - 12kB

Food for thought on precursors

franklyn - 19-5-2008 at 21:44

* N O T E
It may be necessary to use the following proceedure to extract the files
http://www.sciencemadness.org/talk/viewthread.php?tid=8997&a...

.

[Edited on 20-5-2008 by franklyn]

Attachment: C6O6 derivations.zip (1.3MB)
This file has been downloaded 321 times


Triquinoyl ( cyclohexanehexone )

franklyn - 21-5-2008 at 15:25

References

J. Lerch, Ann. 124, 34 (1862)
R. Nietzki and T. Benckiser, Ber. 18, 499 (1885)
R. Nietzki and T. Benckiser, Ber. 18, 1833 (1885)
R. Nietzki and F. Kehrman, Ber. 20, 322 (1887)
F. Henle, Ann. 350, 330 (1906)
F. Bergel, Ber. 62, 490 (1929)
B. Eistert and G. Bock, Angew. Chem. 70, 595 (1958)
B. Eistert, G. Bock, E. Kosch, and F. Spalink, Chem. Ber. 93, 1451 (1960)


Triquinoyl octahydrate C6O6 8H2O
forms microscopic needles, melting at 95º C, evolving CO2.
Insoluble in cold water, alchohol and ether. Is hydrolysed into
hexahydroxybenzene in acidic solutions with lewis acid catalyst
of SnCl2

.

Axt - 23-5-2008 at 13:01

I couldnt find any reference to the reaction of hydroxylamine with triquinoyl so I looked at hydrazine to see if it at least reacted like a normal ketone thus forming a hydrazone, however it does not. Rather its reduced to hexahydroxybenzene. Well at least I gather thats what the following abstract is saying. I think where they said "cyclohexenone" they meant "cyclohexanehexone", the last entry.


<b>Reaction of organic compounds with hydrazine. XI. Reaction of quinone compounds with hydrazine hydrate.</b> Akita, Tadashi. Univ. Tokushima, Yakugaku Zasshi (1962), 82 91-5. CODEN: YKKZAJ ISSN: 0031-6903. Journal language unavailable. CAN 57:48998 AN 1962:448998 CAPLUS

Abstract
cf. Tokushima Daigaku Yakugaku Kenkyu Nempo 9, 11(1960); CA 55, 19925e. p-Benzoquinone (1.1 g. ) in 20 ml. EtOH and 2.5 g. 80% N2H4.H2O heated 30 min. on a H2O bath, the EtOH removed, the residue acidified with HCl, and the product extd. with Et2O gave 1 g. hydroquinone, m. 172° (EtOH). The same result was obtained by using 20 ml. diethylene glycol as solvent and heating 2 hrs. at 180-200°. Similarly, redns. of the following compds. with N2H4 were carried out (starting material, product, % yield, and m.p. given): o-benzoquinone, pyrocatechol, 81, 105°; 1,2-naphthoquinone, 1,2-(HO)2C10H6, 80, 103-4°; 1,4-naphthoquinone, 1,4-(HO)2C10H6, 79, 190-1°; 1-methylp-benzoquinone, methylhydroquinone, 80, 124-5°; hydroxy-p-benzoquinone, 1,2,4-C6H3(OH)3, 83, 140°; nitrop-benzoquinone, nitrohyaroquinone, 62, 133-4°; bromop-benzoquinone, bromohydroquinone, 66, 113-15°; 2,3-dicyano-p-benzoquinone, 3 ,6 ,1,2-(HO)2C6H2(CN)2 , 75, 230° (decompn.); chloro-p-benzoquinone, chlorohydroquinone, 60, 106°; 2,6-dichloro-p-benzoquinone, 2,6,1,4-Cl2C6H2(OH)2, 77, 157-8°; 2,5-dichloro-p-benzoquinone, 2,5,1,4-Cl2C6H2(OH)2, 77, 172°; 2,3-dichloro-p-benzoquinone, 2,3,1,4-Cl2C6H2(OH)2, 77, 144-5°; chloranil, tetrachlorohydroquinone, 60, 232° 2,5-dihydroxy-3,6-dichloro-pbenzoquinone, 3,6-dichloro-1,2,4,5-benzenetetrol, 66, --; cyclohexenone, benzenehexol, 88, above 300°.

SilencePlease... - 7-11-2008 at 15:41

Sorry to be such a bother, but as I'm devoid of a fume cupboard (chloropicrin) I was pondering over other methods of chloranil, preferably those with decent yields.

As described by the "CIA Field Manule"; ASA + HCl + KClO3.
I was thinking about the use of p-acetylaminophenol + HCl + MnO2/Al
Would NaOCl suffice? I know it chlorinates other ketone, but looking at this mechanism, it seems unlikely.

Am I being over-paranoid? Should I just allow it (NO2Cl method) to take place at the bottom of my garden on a windy day?

Many thanks, SP...

Axt - 7-11-2008 at 18:55

Quote:
Originally posted by SilencePlease...
Am I being over-paranoid? Should I just allow it (NO2Cl method) to take place at the bottom of my garden on a windy day?
...


I couldn't detect any chloropicrin being formed when aqua regia (its NOCl) was acted on paracetamol, in fact I think the smell was quite agreeable. Doing it outside will be fine assuming your not looking to produce Kg's of the stuff.

Taoiseach - 9-11-2008 at 03:55

Ammonium nitranilate. Also sheds some light on the bonding/structure in nitralinic acid:

http://journals.iucr.org/q/issues/1964/03/00/a04104/a04104.p...

Axt - 9-11-2008 at 06:16

That journal requires subscription Taoiseach.

Taoiseach - 9-11-2008 at 08:00

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]

Attachment: a04104.pdf (710kB)
This file has been downloaded 671 times


SilencePlease... - 20-11-2008 at 12:36

In reply to my above paranoia, chloranil via paracetamol and NOCl proceeded well. Regrettably only about half the mass of paracetamol converted to chloranil. The vessel, unlike Axt's became thick with ppt, and had slightly orangey lumps.

I shall try again.

Formatik - 21-11-2008 at 14:23

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.


Ammonium nitranilate is also described in Ann. 215, 140 by Nietzki as pretty barely soluble leaflets. This reference is also mentioned here, where it was obtained by neutralizing the acid with ammonia.

Taoiseach - 27-12-2008 at 05:47

I just made some chloranil from paracetamol+NH4NO3+HCl. It worked niceley, altough the product is contaminated with occasional brown-black lumps. I will try to recrystallize it from acetone.

Here's an interesting paper, unfortunately its in German and I cannot DL it: Nitralinic acid from chloranil.

http://www3.interscience.wiley.com/journal/112372484/abstrac...

Taoiseach - 27-12-2008 at 13:59

Hydrazinium nitranilate & other high-density energetic nitranilates:

http://www3.interscience.wiley.com/journal/121569461/abstrac...

Again I cant DL this shit...

I recrystalized my chloranil from boiling acetone. It gave nice dark-orange crystals which are easier to handle than the yellow powder I originally obtained.

Formatik - 27-12-2008 at 14:43

Quote:
Originally posted by Taoiseach
I just made some chloranil from paracetamol+NH4NO3+HCl. It worked niceley, altough the product is contaminated with occasional brown-black lumps. I will try to recrystallize it from acetone.

Here's an interesting paper, unfortunately its in German and I cannot DL it: Nitralinic acid from chloranil.

http://www3.interscience.wiley.com/journal/112372484/abstrac...


That's from the Ber. 20, 2027-2031. See page 1.

Quote:
Originally posted by Taoiseach
Hydrazinium nitranilate & other high-density energetic nitranilates:

http://www3.interscience.wiley.com/journal/121569461/abstrac...

Again I cant DL this shit...

I recrystalized my chloranil from boiling acetone. It gave nice dark-orange crystals which are easier to handle than the yellow powder I originally obtained.


That's quite interesting; the hydrazine salt with a VOD very close to RDX. PCJ also very close 31.7 GPa (RDX: 33.8 GPa).

I was also reading in Liebig's Annalen (1892), p.15 about a compound, hexachloro-p-diketo-R-hexene made from chloranil, HCl + MnO2, or from p-aminophenol by action of Cl2 (procedures in that ref). If this could have the Cl2 atoms replaced by -N3, then the compound hexaazido-p-diketo-R-hexene would have the same C and O content as the title compound, but two more azido groups making it more energetic.

[Edited on 27-12-2008 by Formatik]

The second article

sparkgap - 27-12-2008 at 18:55

referred to by Taoiseach is attached. Quite the mix of computational and synthetic chemistry, it was.

sparky (~_~)

Attachment: nitranilat.pdf (409kB)
This file has been downloaded 1594 times


Taoiseach - 28-12-2008 at 11:24

The NH4-nitranilate synthesis worked but the yield was pathetic. Orange crystals that turn brown on drying. Deflagrates on ignition.

Anyone tried the silver salt yet?

Axt - 29-12-2008 at 08:32

Quote:
Originally posted by sparkgap
referred to by Taoiseach is attached. Quite the mix of computational and synthetic chemistry, it was.

sparky (~_~)


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 :P

[Edited on 30-12-2008 by Axt]

Plasmapyrobattics - 29-12-2008 at 17:20

Hi Axt

I’ve been here long time only as a reader and I enjoy your posts very much, since they are very professional, stimulating and enjoyable (shared together with a few other great posters / people here). Today I decided to join in.

Indeed I agree here that someone might have been copying your work above as mentioned, but I suppose that happens. I also would feel the same about imitation. Excellent indeed.

I hope not to be somewhat off-topic, but I would like to add / ask something about Trichloroisocyanuric acid (and its salt, Sodium dichloroisocyanurate) – since we are discussing halogenated molecules like Chloranil and the effect of Sodium Nitrite on it (which leads to interesting and practical results indeed).

Question : What is the prospects of adding Sodium Nitrite to an aqueous solution of Sodium dichloroisocyanurate (a relatively available Pool Shock Treating Agent) ? Is there a reasonable chance to obtain Sodium dinitroisocyanurate ?

Or otherwise : Dissolving powdered Trichloroisocyanuric acid [Pool Chlorinating agent / Chlorine Pills] in water (containing HCl), and adding excess Sodium Nitrite – to possibly (maybe) obtain Trinitroisocyanuric acid ? My guess is that both these suggested materials (results) might hydrolyze too easily and thus decompose. Am I wrong ?

What is your views on this ?

Thanks

Plasmapyrobattics

Axt - 29-12-2008 at 17:53

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

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>.

Taoiseach - 30-12-2008 at 04:37

Axt, have you had any success with the tetrahydroxyquinone/ cyclohexanhexone synthesis from chloranil? Since it is so easy to produce from ASA/ paracetamol I would love to know what other interesting compounds can be made from it - not necessarily energetic ones.

Axt - 30-12-2008 at 18:56

No I never tried it nor retrieved that article detailing it. I couldn't find any uses for it though maybe other amine condensation products would be interesting, ones more stable then hydroxylamine/hydrazine products.

[Edited on 31-12-2008 by Axt]

Axt - 11-1-2009 at 00:34

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 :P


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%.

Attachment: Structure of nitranilates - Z. Naturforsch. B Chem. Sci. 1994, 49, 1021 – 1030.pdf (438kB)
This file has been downloaded 2717 times


Formatik - 11-1-2009 at 09:01

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 :P


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%.


I'm assuming you just want to know the short details quantities, and not the whole procedures. They used 3g 1,4-diacetylhydroquinone for the aromatic phenol source. Fuming HNO3 was used for the nitro source. And used 4g KOH to form dipotassium nitranilate. The potassium salt yield was 600 mg (17% theory). For the preparation of the disodium nitranilate-dihydrate, it was "analogous" to the K-salt using NaOH (no amount mentioned), but yield was 960 mg (23% theory) of the sodium salt. I think that tells you what you wanted to know.

benzylchloride1 - 21-1-2009 at 21:46

In an attempt to alter the synthesis of p-chloranil from p-acetamidophenol, I ended up producing p-benzoquinone in a yield of 80%. I was trying to conserve nitric acid and see what effect low reaction temperatures has on this oxidation reaction. I started with p-acetamidophenol recrystallized from tylenol tablets, dissolved 15g of the recrystallized material in 100 mL of concentrated hydrochloric acid and then I added 33 mL of concentrated nitric acid. The foam produced by the reaction filled a 1000 mL beaker. The mixture was stirred with a glass rod and allowed to sit in a snow drift for 3 hours. Yellow crystals of the crude quinone formed. 300 mL of cold water was added with stirring and the mixture was filtered. The filter cake was pressed to remove excess water and the benzoquinone was dissolved in about 200 mL of 91% 2-propanol. The solution was heated to boiling and allowed to cool. Yellow, needle shaped crystals of p-benzoquinone filled the liquid upon cooling. The crystals were filtered off, pressed and allowed to dry for one day. The final percentage yield was 80% of theoretical. The melting point was taken with a Haake-Buchler melting point apparatus, the product melted at 117 celsius one degree above the value in the CRC Handbook of Organic Compound Identification, due to a fairly rapid heating rate. The benzoquinone was instantly decolorized by bisulfite solution, and when added to a solution of hydroquinone, peacock green crystals of quinhydrone formed. I plan on making some chloranil in the near future for dehydrogenation reactions. The oxidation of aromatic compounds with aqua regia could be a very useful method for the synthetic amateur chemist.

[Edited on 21-1-2009 by benzylchloride1]

Rosco Bodine - 22-1-2009 at 03:24

The ammonium nitranilate may form a tetraammine copper complex salt, analogous to for example tetraammine copper perchlorate via a similar method. For example
a warm concentrated solution of copper nitrate is added
to a warm saturated solution of ammonium nitranilate
in NH4OH. During cooling the tetraammine copper nitranilate should, (may) precipitate as crystals. Similar ammine complexes may be possible for nickel, cobalt, zinc, and silver.

A hydrazinium complex with nickel may also be possible
analogously for the hydrazinium nitranilate.

[Edited on 22-1-2009 by Rosco Bodine]

Taoiseach - 23-1-2009 at 04:28

@benzylchloride1

This is most interesting. Can you give a formula for the reaction? I dont understand why you got p-benzoquinone and not chloranil. Is it due to the low temperature or dissolving in isopropyl alcohol? Sorry if that question is dumb, I'm not an organic chemistry expert at all.

benzylchloride1 - 29-1-2009 at 22:20

The reaction was conducted at a very low temperature, the chlorination requires the large excess of nitric acid and prolonged heating the mixture at 80 celsius. The reaction procedes through p-benzoquinone as an intermediate that is chlorinated when the mixture is heated. The yield from this procedure is better then most of the procedures for producing this compound that can be found in sources such as Vogels text book. p-aminophenol is very easily oxidized; and probably would be destroyed by direct oxidation. The p-acetamidophenol is first dissolved in HCl, which hydrolyzes the amide group and protonates the now free amino group. The protonated amine reacts slower with the oxidizing agent, aqua regia, producing a fairly high purity p-benzoquinone. The isopropyl alcohol is just used to recrystallize the p-benzoquinone.

[Edited on 29-1-2009 by benzylchloride1]

Taoiseach - 29-1-2009 at 23:11

Thx for clarifying that.
p-acetamidophenol is just paracetamol right?

Rosco Bodine - 17-2-2009 at 15:42

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]

Rosco Bodine - 5-4-2009 at 05:47

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.


Such compounds are called clathrates or inclusion compounds. My own theory concerning the mechanism of formation is there is a hydrated basic hydroxide, superhydrated expanded gel intermediate which in part reacts with the nitrophenol, and then the hydrogel destabilizes, losing water it collapses, and like flocculating agent it can trap molecules of specific size and character
within the crystallizing gel.

Taoiseach - 6-4-2009 at 21:14

What exactly is "trinitrobenzoic acid" and how can it be made?

not_important - 6-4-2009 at 22:54

1) did you even attempt a search? 1st Google hit is "Production of 2,4,6-Trinitrobenzoic Acid", Org. Synth.; Coll. Vol. 1 also has it.

2) which trinitrobenzoic acid are you asking about, there are 5 isomers.

3) why did you post in this thread?

Taoiseach - 7-4-2009 at 05:10

1) Yes I searched. Can you plz post a link? I do NOT get this as first google hit, infact I dont get ANY synthesis/preparation when I google

2) I dont know which one

3) "Lead trinitrobenzoic acid " was mentioned in this thread as a adduct of a nitroaromatic acid

not_important - 7-4-2009 at 06:26

Off the 1st Google page

http://www.osti.gov/bridge/purl.cover.jsp?purl=/769293-j2T6r...

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv1...


12332123 - 24-2-2010 at 15:48

I know this thread has been dormant for a while, but I was wondering if you could react two moles of dinitrourea salt with one of chloranil, such that each dinitrourea would replace two chlorines one one side forming a tricyclic compound. This would undoubtedly be nicely dense and powerful, though possible quite susceptible to hydrolysis.

some followup ideas

Rosco Bodine - 16-6-2011 at 20:25

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 :D

Attachment: nitranilat.pdf (409kB)
This file has been downloaded 399 times

Attachment: JACS Bis[3-(5-nitroimino-1,2,4-triazolate)]-Based Energetic Salts.pdf (99kB)
This file has been downloaded 537 times

[Edited on 18-6-2011 by Rosco Bodine]