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Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
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[*] posted on 1-8-2011 at 12:18


Rosco: http://onlinelibrary.wiley.com/doi/10.1002/anie.201100300/ab...



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[*] posted on 1-8-2011 at 12:24


Ha ! :D It's cutting edge current technology stuff we are working on and contemplating ......
soooo...great minds think alike .....what else can be said.

You got that article on you? (sharing is caring)

I just put a request in references and will attach that article here when I get it.

Thanks for that citation

[Edited on 1-8-2011 by Rosco Bodine]
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[*] posted on 1-8-2011 at 15:36


Since we already know the result of diazotization of diaminoguanidine, perhaps we should look into what happens when hydrazones are diazotized.

Hydrazone is R2C=NNH2

https://kb.osu.edu/dspace/bitstream/handle/1811/5721/V72N05_...

The diazotization of triaminoguanidine might result in:
(N3)2C=N-NH-N=C(N3)2


"Diazotization and subsequent dimerization of the triaminoguanidinium cation yielded 1-diazidocarbamoyl-5-azido​tetrazole" the picture shows
(N3)2C=N-N=(N4C)N3
there must be a hydrogen atom on this molecule, but the picture does not show where it is.

tag2.GIF - 17kB

[Edited on 2-8-2011 by AndersHoveland]




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[*] posted on 1-8-2011 at 18:12


Here attached is the article for the nitrosation product of triaminoguanidine. Additionally are a couple of other articles of related interest concerning Dinitromethyltetrazole and an article describing a nitroguanidine guanidine nitrate double salt. Thanks to solo.

At first glance it would seem that the most interesting possibilities operative for the C2N14 are related to the predimerization intermediate which would be interesting to see how it may react with cyanoguanidine particularly, or
some other materials. The C2N14 is itself too sensitive to be
of any practical use, so I would think its predimerization intermediate or C2N14 itself as a higher intermediate would still be interesting.

The C2N14 is isomeric with isocyanogen tetraazide described by US2990412 attached. The stability of the isocyanogen tetraazide is much better than the C2N14 gotten from nitrosation of triaminoguanidine.

Dinitromethyltetrazole is described also in US3173921 attached.

Attachment: C2N14 An Energetic and Highly Sensitive Binary Azidotetrazole.pdf (403kB)
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Attachment: Dinitromethyltetrazole and its Salts A Comprehensive Study.pdf (744kB)
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Attachment: dinitromethyltetrazole.pdf (136kB)
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Attachment: The energetic double salt nitroguanidinium nitrate guanidinium nitrate.pdf (976kB)
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Attachment: US2990412 Isocyanogen TetraAzide.pdf (60kB)
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Attachment: US3173921_DINITROMETHYLTETRAZOLE_AND_SALTS.pdf (140kB)
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Attachment: C2N14_supporting_information.pdf (994kB)
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[Edited on 2-8-2011 by Rosco Bodine]
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[*] posted on 4-8-2011 at 09:56
1,5-Diamino-1H-tetrazole from diaminoguanidine via Nitrite and HCl


@Engager With regards to your work with DAT which has discussion beginning on page 5 of this thread, later on page 8 was posted a link by AH-Poster to a page which contained a synthesis which was a "copy and paste" edit and summary having no attribution as to source. Attached is the source reference which would correspond with that linked page of "excerpted" information which provided no references.

Plainly the reaction of nitrous acid with diaminoguanidine can either lead to DAT as the product in 58% yield by a 1:1 molar ratio in a mineral acid (HCl) as reported by the attached article.

Alternately when the reaction uses a molar ratio of 2:1 and a buffered pH as described in the Lieber and Levering article attached previously, a 77% yield of Tetrazolyl Azide is reported.

Attachment: Diaminotetrazole from Nitrosation of Diaminoguanidine in HCl.pdf (492kB)
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In spite of the observation by Klapotke about various reaction conditions only producing differing yields of one product from the reaction of nitrous acid and triaminoguanidine, the different products gotten by different conditions for the mono and diaminoguanidines, and similar precursors strongly suggests that varied conditions of pH and molar ratios would be expected to produce different products from triaminoguanidine as is the pattern for similar reactions. It causes me to wonder if Klapotke is correct or incorrect, and if Klapotke is correct, then why is triaminoguanidine the exception to the usual pattern?

[Edited on 4-8-2011 by Rosco Bodine]
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[*] posted on 7-8-2011 at 10:47
possible alternate route to guanyl azide or analogue


There seems to be a possible nexus which I have recognized about the reaction conditions involving the reaction of guanidine with nitrous acid to form cyanamide or its dimer,
and the parallel reaction where nitrous acid is reacted with semicarbazide to produce carbamoyl azide (also called carbamyl azide or possibly? carbamazide) See the thread on Azides for additional references.
http://www.sciencemadness.org/talk/viewthread.php?tid=1987&a...



http://www.chembase.com/cbid_458420.htm

http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=4584...

It would seem possible that the carbamyl azide itself or its ammonium azide or sodium azide hydrolysis product would
react with the cyanamide or its dimer gotten from nitrous acid and guandine, eventually leading to 5-aminotetrazole.

The dynamics of the reaction are unknown but the necessary elements are there for a possible one pot reaction for example of semicarbazide salt, guanidine salt, and a nitrite salt to react and produce 5-aminotetrazole or a derivative
or analogue.

Hydrazine sulfate might react similarly as semicarbazide in such a scheme, although less likely since reportedly an elevated temperature was reportedly required for the oxidation of hydrazine to hydrazoic acid by nitrous acid, subject to losses for the elevated temperature and
the limitation of the theoretical 50% yield for a reaction which converts only half the hydrazine, the other half being byproduct ammonia.

Anyway the parallel and similar reactions point to an alternate possible route to 5-aminotetrazole or derivative or analogue.

There is some basis in the literature to support my identification of this nexus involving nitrosation of semicarbazide to carabamyl azide and nitrosation of guanidine to cyanamide in particular, or its dimer, as being a potential alternate reaction scheme for producing 5-aminotetrazole, even though it may require sequencing
or may not go well as a one pot method. See attached article page 2 second paragraph regarding hydrolysis of
dicyandiazide which results in a similar reaction system
where cyanamide and hydrazoic acid then further react to form the 5-aminotetrazole.

CARBONIC ACID AZIDES
Charles Vinton Hart
J. Am. Chem. Soc.
1928, 50 (7), pp 1922–1930
DOI: 10.1021/ja01394a017

Also attached is another article more of interest with regards to the general topic of tetrazoles.

Cyanoguanyl Azide Chemistry
William P. Norris, Ronald A. Henry
J. Org. Chem.
1964, 29 (3), pp 650–660
DOI: 10.1021/jo01026a032

Attachment: CARBONIC ACID AZIDES.pdf (600kB)
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Attachment: Cyanoguanyl Azide Chemistry.pdf (1.5MB)
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@Boffis & @Engager It appears that even if the Williams reported route to aminotetrazole turns out to be a typographical error not caught in editing, or an incorrect oversimplification, Williams still has pointed us to some interesting alternative reactions which should be able to work using hydrazine or a hydrazine derivative. This agrees with the more conventional known reaction schemes, which require use of hydrazine or a hydrazine derivative. So in summary, if the "magic" reaction of Williams doesn't work, a variation using hydrazine or a derivative of hydrazine may prove almost as convenient and more workable.

[Edited on 8-8-2011 by Rosco Bodine]
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[*] posted on 10-8-2011 at 17:39


Quote: Originally posted by Boffis  
Hi Guys,

I have already considered these reactions and there are numerous possibilities. I have already considered the nitrosoguanidine reaction (see the attached pdf of my "thinking document") and I believe the trace contaminant of yellow material in the first crop of crystals to be nitrosoguanidine. I also discuss the possible nitroso compound + amine compound = azo compound. This could lead to a triazene that may de-arrange to aminotetrazole; several such de-arrangements have already been published and I have quoted examples.

Take a look at the attached document and have a go at some of the reactions. And please, I found the claim in Williams book difficult to believe too at first, but as I investigate these reactions it is becoming clear that the chemsitry of urea and guanidines is very complex and very sensitive to conditions. So simply quoting an equation is meaningless without giving the conditions. I am very aware that I have not proved the identity of the product of my reactions but equally I can assure you that cyanamide and urea are not important componenets of the first crop of crystals, cyanamide is too soluble and urea too sensitive to nitrite. After boil down, the second crop of crystals could contain almost anything; cyanoguanidine, melamine etc but a yellow contaminant is still present.

When I am home next I will try preparing nitrosoguanidine by both routes and then try reacting it with guanidine to see if I can isolate the triazene and then make it de-arrange to aminotetrazole. As a say in my document I don't see these reactions as a route to cyanamide particularly but almost any N-N bearing product would be a potential precursor to the tetrazole.

Attached article link from preceding page
http://www.sciencemadness.org/talk/files.php?pid=216853&...



You know I have been looking at your document :D
Okay I'll go out on a limb here with some speculation
which may be right or wrong. There is another possibility here regarding your "hydroxyazoguanidine" ....that it may be unstable.... and lose water to form an azide, and that azide reacts with cyanamide or cyanoguanidine being produced as a parallel reaction product, leading to 5-aminotetrazole. It seems possible in such case that Williams could be in part correct by identifying an end product that does occur, but is incorrect about the reaction mechanism leading to that product. This possibility would allow for the study at Cornell
by Bancroft and Belden to also be correct, since cyanamide or cyanoguanidine would be required for reaction with the azide I speculate may form as a decomposition product of your "hydroxyazoguanidine".

There is identified in the literature a similar reaction involving the nitrosation of semicarbazide, see near the bottom of page 14 of the attached document, where the first product
for the reaction of semicarbazide with nitrous acid then loses water and decomposes to carbamoyl azide. I am speculating that an analogous reaction may occur with
your "hydroxyazoguanidine", which decomposes to NH2CN3 "deoxycarbamoyl azide" (exist?)...(possible?) and further reacts with cyanamide or cyanoguanidine ...(possible?) to form the 5-aminotetrazole

Nicodem should love this :D Alright call in the big guns

Attachment: Ueber Semicarbazid.pdf (1.6MB)
This file has been downloaded 896 times

Attached are solubilities for 5-aminotetrazole monohydrate
low solubility of 1.38% @ 20C
and worth noting the much higher solubility for the guanidinium salt of 5-aminotetrazole which is 75%

Another low solubility product which might possibly appear is cyanuric acid, from trimerization of cyanic acid

Attachment: atz.pdf (87kB)
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Attachment: ga.pdf (87kB)
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[Edited on 11-8-2011 by Rosco Bodine]
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[*] posted on 11-8-2011 at 22:08


There's certainly some interesting chemistry here again and it's going to take a little time to digest it.

However, one thing strikes me about your proposed mechanism is the rearranement of my hypothetical "hydroxy azoguanidine" to an azide. The problem I see is that this requires the migration of a nitrogen moiety from the central carbon atom to a nitrogen and to displace a hydrogen from the imide or amide group. I have been unable to find another such reaction and it sound rather thermodynamically unlikely. The only way I can see to do this is via a bi-molecular condensation and then de-arrangement to give an azide or hydrazoic acid, much along the lines of what I discussed before. Also I think if "deoxycarbamyl azide" (azocarbimine?) were produced it would rearranged to unsubstituted tetrazole directly.

I agree about the cyanuric acid being a possibility and I will test this when I get home.
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[*] posted on 11-8-2011 at 23:09


I agree such a reaction is unlikely. I was thinking cyanamide is probably formed, so it follows that a likely parallel reactant would be an azide leading to hydrazoic acid which could react with the cyanamide. The only similar reaction I could find was the carbamoyl azide formation, which reportedly does hydrolyze further to HN3 and cyanic acid, the cyanic acid then decomposing to NH3 and CO2 by further hydrolysis. The pathways these reactions may follow is uncertain and this has become a guessing game where only experiments and qualitative analysis of the products gotten from various reaction conditions will provide better understanding of the mechanisms.

I still do think using hydrazine sulfate to react with cyanamide from a first nitrosation of guanidine to form aminoguanidine and then a subsequent nitrosation to guanyl azide is probably the easiest way of salvaging the process if it turns out that the product Williams described is incorrect. However, if Williams got it right, then I think the most likely scheme is shown by your reactions #3 and #4 .

I was looking at the carbamoyl azide primarily in connection with the parallel topic thread on azides, since it suggests a possible simplified route to synthesis of azides via nitrosation of semicarbazide, hopefully leaving a solution of ammonium azide as the end product.

The reactions are very similar for carbamoyl azide and guanyl azide ....except that carabamoyl azide does not cyclize directly to a ring compound. I think carbamoyl azide probably would react with cyanamide and lead to aminotetrazole via the hydrazoic acid intermediate from hydrolysis which would add to cyanamide directly.

It is something I have been trying to find whether or not carbamoyl azide forms salts such as a nitrate, picrate, styphnate, or a perchlorate, similarly as does guanyl azide. Those contemplated salts of carbamoyl azide could have useful properties as energetic materials. I can find nothing about such seemingly possible compounds.

[Edited on 12-8-2011 by Rosco Bodine]
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[*] posted on 1-9-2011 at 03:56
NH4FeNT


Does somebody here have some experience with some experience with the ammonium-iron NT complex?
Yes, I read trough Engagers great posts.

In the Green Primaries PDF the mention iron(II)chloride hexahydrate.
To my knowledge, this compound only forms a tetrahydrate...

Or do the mean iron(III)chloride?
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[*] posted on 5-9-2011 at 23:08


Some while back, I nitrated 5-ATZ monohydrate using excess fuming red acid (84 to 90.1%) similar as the method indicated on page six of this thread, but scaled it down by a factor of about four. However, the acid should at best colorless, red fuming acid might be dangerous!!! After the process, the obtained white powder was let dry under the sun. The liquid liquor of this containing some of the powder, nitric acid, and water was saved. The powder should be 5-nitrimino-1H-tetrazole (5-NAMTZ), or its hydrate. With the powder, I couldn't get a reaction using hammer blows it being flat between Al-foil on an iron plate. Reaction to flame: after it melted (maybe the H2O also to come off) it burned off vigorously with a sizzling hiss and an orange-yellow flame.

When the acidic liquor was added to Aq. AgNO3, it gave an immediate precipitate which may have looked white at first but turned light yellow, though it is not very light sensitive. Aq. Pb(NO3)2, Cu(NO3)2 made no precipitates, also not on standing. Aq. Hg(NO3)2 gave a white precipitate, which when dry decomposed and deflagrated only mildly from a flame, even when confined in Al foil. Combining the acidic liquor with vigorous reacting acidic Cu(NO3)2 and N2H5OH, caused this reaction to calm down and left a brown precipitate which after filtering later turned olive-green on drying; a few crystals held in a flame, would dance around burning with a green flame popping weakly, burning incompletley only. A small amount only popped mildly (like silver methylacetylide, but without the soot) when confined in Al foil and heated over a flame.

The silver salt should be silver nitriminotetrazolate: when dry, a big crystal of it snapped weakly from an open flame and left residue and a part of the crystal may have launched off. But when wrapped in Al-foil, a very small mg amount heated over a flame gave a strong detonation with a loud report. Actually, even unconfined heating from underneath on the foil in the open with a flame caused detonation. It has a high "temperature of explosion" because it could be heated over the flame a good few seconds before it responded. A face shield was needed to protect the face from shrapnel. A crystal put into Al-foil flattened normally and then hit with a mild hammer (0.5kg) blow did nothing, strong blows also nothing. It's not very sensitive to shock. An amount around 0.005g of the silver salt can be seen below, next to a pencil for scale and when it was confined in foil and heated, it detonated sounding like a gunshot (amounts near 2 to 5mg yield detonations that sound like gunshots).

The same acidic liquor in aq. solution when combined with N2H5OH ought to give a mixture of hydrazine nitriminotetrazole + hydrazinium nitrate. Combining the liquor and N2H5OH, then evaporating this under the sun for several hours in a dish, gave a thick syrup of faint beige yellow color, and faint hydrazine smell. This didn't react to open flame, but when heated on foil, it boiled off the water and then 'thumped out' violently burning off with a yellow-orange flame.

Hydrazinium aminotetrazolate has a very high detonation rate, even exceeding HMX. But it is very insensitive to initiation and Klapoetke could not initiate it using PETN booster. He speculates wether an RDX booster could work (link here). Perhaps one might be also able sensitize it and improve its energy content, heighten density, by combination with tetranitromethane, hydrazinium nitrate, etc.

I've evaporated a small amount of aq. N2H5OH in excess, which was mixed with 5-ATZ and after a few days left a colorless syrup, which only very slowly crystallized on its own. A drop of this heated over a flame on Al foil caused the H2O to evaporate, then after melting sometime it flashed out vigorously burning off quickly with a noisy orange-yellow flame.

AgNAMTZ.png - 301kB

[Edited on 6-9-2011 by Formatik]
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[*] posted on 6-9-2011 at 09:54


Quote: Originally posted by Formatik  
An amount around 0.005g of the silver salt can be seen below, next to a pencil for scale and when it was confined in foil and heated, it detonated sounding like a gunshot (amounts near 2 to 5mg yield detonations that sound like gunshots).


2-5mg sounds like a gunshot huh.......
that's a lot of sass from such a tiny mass :D

Maybe about 50mg made into a paste with dextrin and dried into a pellet around a bridgewire in a squib cavity could be good for something or another. Pushed firmly against a column of compressed PETN the two could probably really communicate.
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[*] posted on 6-9-2011 at 12:34


Yes, it gave me quite an unexpected shock because of its flimsy reaction to open flame. It could make for a great party gag.

Silver nitriminotetrazolate and disilver(aminotetrazol) perchlorate have been said to be the two most promising compounds for replacing the most useful initiator for insensitive HNS, which is currently Cd(N3)2.

I've thought about another oxidant that will work for forming azotetrazolates: calcium hypochlorite.

Comprehensive Heterocyclic Chemistry by Katritzky (below) states Ca(OCl)2 can be used also, referencing the 8th volume of F.R. Benson's Heterocyclic Compounds. There was also another azotetrazole compound formed using Ca(OCl)2 I was reading about in Beilstein somewhere, but I can't find the details right now.

azotetrazolateoxidant.png - 195kB

Edit: found it. The compound being oxidatively dimerized was 2-phenyl-5-aminotetrazole.


azotetrazoleoxidation2.png - 232kB

[Edited on 7-9-2011 by Formatik]
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[*] posted on 13-10-2011 at 12:19


I've attempted to use aq. NaClO and conc. H2O2, instead of KMnO4 to oxidize the sodium aminotetrazolate. H2O2 did not work. NaClO seemed to work, giving deep-yellow solutions. But the apparent azotetrazolate could not be obtained because it is in a mixture with other sodium salts, likely NaCl, NaClO3 and NaOH, the latter which increases its solubility also. Crystallization gave this contaminated solid mixture. Acidification with an acid that doesn't react with the azotetrazole (hydrochloric and sulfuric acid are reported to give hydrazinotetrazole and nitric acid azidotetrazole), namely acetic acid didn't seem to give a satisfactory result either.

Thiele's method worked great, even when microscaled. The foaming from KMnO4 additions can get out of hand very fast and needs to be well controlled. The preparation of sodium azotetrazolate is very dangerous if the container being heated breaks (this nearly happened to me during heating, it cracked!), the entire contents will spill out and can explode. For preparatory purposes best would be to use a big round bottom flask and heating mantle. The flask would reduce likely hood of spilling, but foaming would need extra care because it would be able to funnel out easily. It looks like Engager used a RB flask in his preparation.
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[*] posted on 16-10-2011 at 12:04


Quote: Originally posted by Engager  
Stickers on boxes may not be correct subtance with sticker Cu(DATZ)2 on box is copper diazoaminotetrazole, that's why i listed correct names above picture. Actualy Cu diazoaminotetrazole is amorphous, but when it dried it stucked to paper in some kind of lumps, in wet state it's olive green, but dry it is almost black. It's quite sensitive to friction, it exploded then i tried to grind it in mortar. Explosion was quite loud, but i don't find any usefull applications for it in literature, only mentions about it's existance. Surely it is highly sensitive and powerfull explosive, but i'm not sure about it's initiative power. I have not tried ammonium complex, because i think it's too sensitive.


I'm certain copper diazoaminotetrazole has detonator properties. It undergoes DDT readily from thermal shock of e.g. burning powders, under light confinement. Copper nitrotetrazole also will DDT in the same instance, but is of course the stronger detonator. There are now copper salt detonators. That field used to belong to Pb, Ag, and Hg salts, but no longer. Another compound, cuprous nitrotetrazole, is touted already as a replacement for lead azide.
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[*] posted on 21-10-2011 at 11:24


Quote: Originally posted by Formatik  
After the process, the obtained white powder was let dry under the sun. The liquid liquor of this containing some of the powder, nitric acid, and water was saved. The powder should be 5-nitrimino-1H-tetrazole (5-NAMTZ), or its hydrate.


I've attempted to characterize this white powder, but I now think that it is in fact aminotetrazole nitrate. Using non-anhydrous ATZ and nitric acid, likely caused only a partial nitration and so then nitriminotetrazole likely passed into the liquor solution. Forming the pale-yellow silver salt could also be done this way (it's best not scaled up because of diazotetrazole risk): a few mg ATZ.H2O added to several drops red fuming nitric acid, this then mixed and let stand a few moments and then taking only the liquid portion of this and adding it to aq. AgNO3 under mixing, then filtering and washing.

The pale-yellow salt's reaction to open flame sounds very similar to Axt's description of the salt he made from the acid. I've attempted Ag determination but much of the fine Ag2O precipitate passed right through the filter paper, and so its silver content could not be determined. It's much less flame and impact sensitive than silver nitrotetrazolate (AgNTZ). It gave no reaction to various hammer blows directly on an iron plate (meaning it's not entierly insensitive, but its sensitivity is low). It is a highly powerful material and so should not be underestimated. It doesn't have texture issues like silver or especially copper nitrotetrazolate, it flows very good. It does not darken on standing like AgNTZ does. The high amount of thermal energy needed to explode it, is indeed in the same area as silver azide.

Concerning impact sensitivity, the sensitivity between aluminium foil does not work well even as a crude impact test. The thought was it would help powder keep from spreading during impact. But hitting several crystals of copper nitrotetrazolate in between the foil on an iron plate even with the hardest hammer blows gave no reaction, though the crystals were crushed. The aluminium foil caused forces to dissipate. A symmetrical pestle mass falling only a few centimeters directly onto the crystal detonated the copper salt (other primaries like silver acetylide complex do this also). Also mechanically speaking, indirect forces are safest there.
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[*] posted on 21-10-2011 at 20:07


Here is my characterization of some tetrazole compounds, of which I think complements some information in this thread. Diazoaminotetrazolates and nitrotetrazolates in particular. I've included a few references, but all of the color descriptions and other reactions were tests I've conducted. Mercury diazoaminotetrazole could be greater than or equal to in strength to other heavy metal diazoaminotetrazolates.

EDIT: Removed possibly inaccurate test information at Formatik's request.

Attachment: characterizations.pdf (63kB)
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[Edited on 10-30-2011 by Polverone]
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[*] posted on 25-10-2011 at 08:57
Guanidine-nitrous acid reaction; further experiments


Returning to the subject of my earlier posts namely the reaction between guanidine hydrochloride and nitrous acid, I have now conducted some further experiments to investigate the effects of using different ratios of reactant and different levels of acidity on the outcome of this reaction.

5 experiments were conducted much as before but instead of using a 1:2 ratio of guanidine hydrochloride to sodium nitrite the new experiments used a ratio of 1:1 or 2:1 since I felt that the original experiments utilized a considerable excess of sodium nitrite.

Experiments 1, 2 and 5 used a 1:1 ratio of guanidine hydrochloride to sodium nitrite while 3 and 4 used an initial ration of 2:1. However, after a couple of days it became apparent that there was much unreacted guanidine present in the reaction solution so further sodium nitrite was added and more product recovered. In all cases less hydrochloric acid was added than initial intended because it was found that even in the cold the acid cause rapid loss of brown nitrogen oxide. In experiments 1 and 3 only a third and half of the theoretical amount on acid required to liberate all of the nitrous acid could be added even at <5°C before excessive brown fumes appeared.

No acid was added to experiment 2 initially to investigate the reaction in neutral conditions when no reaction occur after nearly a week acetic acid was used to acidify the mixture. For those interested in the details of both the reaction and the testing of the resulting product I have attached a detailed account at the end.

The conclusions are as follow:
1- Guanidine hydrochloride and sodium nitrite do not react under neutral or alkaline conditions.

2- Under weakly to moderately acid condition they react in an equimolecular ratio, the outcome of the reaction being dependant on acidity and temperature;
Under weakly acid condition such as in the presence of acetic acid nitrosoguanidine is an important or main product but the yield is less than 15% and contaminated with the white product.
Under more acid condition in the presence of hydrochloric acid and at low temperature <5°C the white crystalline substance is the major product.

3- Under highly acid condition and at room temperature there is a copious evolution of nitrogen with the production of cyanamide or urea (Bancroft and Beldon).

4- The creamy white material remains unidentified but it is not explosive nor does it deflagrate but when heated it decomposes and leaves only a trace of white residue. It is, however, not aminotetrazole.

Work will continue into identifying the white product.

I tried to insert some photos but an error message appears saying that they are too large even though they are clearly not at 500h x 900w pixels. Does anyone know what the problem is?

Attachment: Further Experiments on guanidine-nitrous reaction.pdf (507kB)
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quicksilver
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[*] posted on 25-10-2011 at 09:11


Interesting experiment and nicely documented.

In your notation (2) what was the weight of product yield? If unknown do you have an estimate?

As white material is isolated (4) what tests will you preform on the "white creamy" yield? as you have already tested heat exposure, have you tested impact?

__________
Problems inserting photos:
Photos and all insertions are limited to 2Mb - is it over that limit?



EDIT: digital pH meter is useful tool to find at what point you get your reaction (not expensive either).



[Edited on 25-10-2011 by quicksilver]




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Rosco Bodine
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[*] posted on 25-10-2011 at 10:28


That file attachment is password protected and won't open.

Try a 600 pixel width on the photos
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[*] posted on 25-10-2011 at 11:32


@Rosco, sorry about that try this version.

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[*] posted on 25-10-2011 at 14:48


@Quicksilver When I get time I intend to do a mp determination on the recrystallised creamy white material. I dont have an accurate thermometer at present that operates at over 110 C which is why I haven't do mp before. I also need to find a better solvent because the yellow material is a persistent contaminant when recrystallized from water. I an almost keen to determine if the compound contain a C-N-N-C linkage or even C-N=N-N-C. or whether is is only a C1 compound but I am not sure about how to do this other than a molecular weight determination (which I am currently reading up on)

I am also looking into other tests, I may have sourced some Xanthohydrol and I haven't tried the ammonical silver nitrate test on this product yet.

I put all of the important picture in the attached pdf.
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Rosco Bodine
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[*] posted on 27-10-2011 at 09:31


@Boffis Your experimental results are conflicting with and possibly debunking the published literature or what would be expected and predicted from a reading of the published literature. Were you able to determine if cyanuric acid is present in the product? I am still thinking that some sequencing of reactions but involving hydrazine as an additional reactant may be required. From the time I first was looking at these reactions it seemed to make more sense to me having hydrazine as a component in the reaction sequence. I haven't gotten back into trying to visualize the reactions again for being otherwise occupied.
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[*] posted on 27-10-2011 at 10:58


My results certainly conflict with the claim of Williams but not necessarily with those of Beldon et al since they used more acid conditions. There is still a fair bit of work to do to identify the creamy white material. First I need to find a solvent to remove the the nitrosoguanidine and then determine the melting point.
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[*] posted on 27-10-2011 at 14:16


On the point of cyanuric acid; no but I can't think of a method of testing for it apart, perhaps, from its ability to form insoluble salts with Ag or Pb but in the presence of so much chloride from the initial reactant Pb could not be used and cyanamide reacts with ammonical Ag nitrate so a ppt would probably be inconclusive.

Does anybody know of a test for cyanuric acid? There is a book dating from about 1930 by a German chemist called either Feigl or Angers that is full of useful spot test for organic chemicals if anyone has a copy or know the title. These two chemist later collaberated on a classic text book on inorganic spot test a little later.
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