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Author: Subject: 2,3,5,6-Tetraazidobenzoquinone
Axt
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[*] posted on 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>.
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[*] posted on 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.
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Axt
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[*] posted on 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]
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Axt
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[*] posted on 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)
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Formatik
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[*] posted on 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.
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[*] posted on 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]
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Rosco Bodine
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[*] posted on 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]
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[*] posted on 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.
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[*] posted on 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]
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[*] posted on 29-1-2009 at 23:11


Thx for clarifying that.
p-acetamidophenol is just paracetamol right?
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[*] posted on 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]
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[*] posted on 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.
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[*] posted on 6-4-2009 at 21:14


What exactly is "trinitrobenzoic acid" and how can it be made?
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[*] posted on 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?
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[*] posted on 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
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[*] posted on 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...

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[*] posted on 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.
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[*] posted on 16-6-2011 at 20:25
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 :D

Attachment: nitranilat.pdf (409kB)
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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]
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