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Rosco Bodine
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Engager's Tetrazole Paper as pdf
The paper which Engager has shared with us has
been converted to a pdf which is more efficient for reading
and printing. Sorry for my being delayed in getting to this file conversion.
Here is the download link.
http://sciencemadness.org/scipics/tetrazoles(english).pdf
file is 8.89 MB and 31 pages Thanks to Engager for your excellent work
http://www.youtube.com/watch?v=kLuzaKVjVxA&fmt=18 Jade Forest
[Edited on 20-9-2009 by Rosco Bodine]
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Engager
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Synthetic route to tetrazoles from urea and ammonium nitrate: In prepublication
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franklyn
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5 phenyl Tetrazole
The salient problem as I see it with high energy density nitrogen heterocyclic
compounds is the number of steps to synthesis. The following citation outlines
a synthesis of the Tetrazole moiety as depicted in the attachment below.
Apparently DMSO solvent facilitates higher yield.
5 phenyl Tetrazole
www.che.gatech.edu/ssc/images/pdf%20research/synthesis.pdf
Yields often are much higher under solvent free conditions. An advantage of
using no solvent (or less solvent), is that reaction times can also be shorter.
This baits the question whether acetonitrile can be substituted and provide a
facile pathway to the group described in this other paper here.
1 & 2 Methyl-5-Nitrotetrazoles
http://handle.dtic.mil/100.2/ADA099627 , refers to this next url
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA099627&Locati...
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Rosco Bodine
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So....what are the prospects for an attempted synthesis of guanylazide fulminate 
other of the guanylazide salts may be interesting also
guanylazide tetrazylazide would be be another possibility,
and of course guanylazide styphnate
[Edited on 16-10-2009 by Rosco Bodine]
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franklyn
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On it's own the aryl compound is of no interest , unless one were to nitrate it.
I was just noting the potential of procuring tetrazole in good yield as a leaving group.
Of course if you regard this impertinent I'll refrain from doing so again.
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Rosco Bodine
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franklyn, the production issue for the mad science community does not involve the number of steps being so much of an issue, but rather the issue of
more concern is
the facile synthesis routes, which parallels fecal synthesis routes, that is to say being able to most easily make your desired shit from mundane
feedstock materials, even if the production requires that each bite be chewed twenty-three times in advance of the ultimate production of your desired
shit. It really chaps my ass also that nitriles and azides are not abundantly on the shelves at the local grocer, but hey ....you gotta play with the
hand you are dealt. Instead of zinc dust for example, I would wonder how the reduction of nitroguanidine may alternately proceed using amalgamated
sheet zinc, or amalgamated aluminum wire from electrical cable, or the electrolytical reduction possibility using a mundane material for a cathode.
But probably even more pertinent I would wonder about the possibly even more facile route presented by possibly reacting any guanidine salt with
hydrazine sulfate to produce aminoguanidine, or diaminoguanidine, or triaminoguanidine, dependant upon the ratio of hydrazine sulfate utilized for the
reaction.
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franklyn
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I'm all for obtaining novel end products from mundane feedstock.
I'm much less enthusiastic about taking the long way around to
get there. We are not reduced to procuring precursors for CHNO
HEDM by resorting to lumps of coal , water , and air , as often
depicted in the distopian wastland of popular fiction.
I do know that technically it is now feasible to build a machine
perhaps the size of a refrigerator the only input to which would
be air, water condensed from air, and electricity, the continuous
product of which would be a brisant high value explosive. Surely
a novel energy storage scheme for photovoltaics. Doubtlessly
there would be export restrictions on such technology.
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Rosco Bodine
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There's another thread we shall properly call a keeper
I have converted that thread to a pdf for convenience in
saving, portability, and/or printing that file.
Attachment: Tetrazoles via Urea - NH4NO3 - precipitated silica.pdf (1.8MB)
This file has been downloaded 3489 times
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franklyn
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http://www3.interscience.wiley.com/journal/120748224/abstrac...
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franklyn
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Safe and fast tetrazole formation in ionic liquids
B. Schmidt, D. Meid and D. Kieser
Tetrahedron, 63, 2, 492-496(2007).
The [2+3] cycloaddition of nitriles and azides is reliable for intramolecular
reactions, but the hazards with volatile azides in intermolecular reactions are
tremendous. Zinc catalysis in aqueous solution is a magnificent improvement,
but requires the removal of the zinc salts from the acidic product. Herein, we
report safe solvents featuring low vapor pressure and good solubility of NaN3.
Ionic liquids based on alkylated imidazoles combined with microwave heating
turned out to be a solution for the given tasks.
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The_Davster
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About the azidotetrazoles and ethyleneditetrazyl azide mentioned in the early parts of this thread. Looks like the old patent made something else or,
they the patent made an impure oil of a product. The following paper states the ethylene bridged azidotetrazole to be a solid.
http://www3.interscience.wiley.com/journal/122512017/abstrac...
(This is not the first instance of something being discussed on this board being published a few years later...  )
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Taoiseach
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I recently prepared some 5-aminotetrazole (5-ATZ). After leaving the solution for 2 days, no more crystals appeared. I was wondering how much more
5-ATZ was left in the solution, so I filtered it and tried to form different metal salts.
Works nicely 
The most promising salt seems to be cobalt(II)-5-aminotetrazolate (Co-5-ATZ). This was made by adding a warm solution of CoCl2 dropwise to the
solution containing 5-ATZ. A flocculent dark-salmon colored precipate appeared immediately. The chromium(III) salt seems to be the most soluble (no
precipate at all).
Maybe Co-5-ATZ can be used to recover 5-ATZ nearly quantitatively from solutions containing it?
The salt is somewhat difficult to dry and seems to go through several stages of hydration, but once thoroughly dried it makes DDT quite readily. 50mg
wrapped in aluminium foil and heated over a flame are quite impressive, given the fact that its energetic properties are solely due to the high
nitrogen content (there's no oxidizing species whatsoever in this stuff!)
I'm wondering if the guanidinium and hydrazinium salts of 5-ATZ have similar properties.
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franklyn
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Pared down to omit cookie demand.
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Engager
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Quote: Originally posted by Taoiseach  | I recently prepared some 5-aminotetrazole (5-ATZ). After leaving the solution for 2 days, no more crystals appeared. I was wondering how much more
5-ATZ was left in the solution, so I filtered it and tried to form different metal salts.
Works nicely
The most promising salt seems to be cobalt(II)-5-aminotetrazolate (Co-5-ATZ). This was made by adding a warm solution of CoCl2 dropwise to the
solution containing 5-ATZ. A flocculent dark-salmon colored precipate appeared immediately. The chromium(III) salt seems to be the most soluble (no
precipate at all).
Maybe Co-5-ATZ can be used to recover 5-ATZ nearly quantitatively from solutions containing it?
The salt is somewhat difficult to dry and seems to go through several stages of hydration, but once thoroughly dried it makes DDT quite readily. 50mg
wrapped in aluminium foil and heated over a flame are quite impressive, given the fact that its energetic properties are solely due to the high
nitrogen content (there's no oxidizing species whatsoever in this stuff!)
I'm wondering if the guanidinium and hydrazinium salts of 5-ATZ have similar properties. |
Sorry to disappoint you but this salts can be actually salts of byproducts, at least they are surely heavily contaminated. If you remember reaction
mechanism you must realize that solution after filtering off badly soluble ATZ surely contains some azide (product of alkaline decomposition of
guanylazide), unreacted guanylazide, and may be some unreacted aminoguanidine salt. All this byproducts can form insoluble salts or complexes with
Co2+ ions. So precipitated product is surely contaminated with cobalt azide, and by simple or complex salts of cobalt/guanylazide and
cobalt/aminoguanidine. To make pure ATZ salts one must dissolve some solid 5-ATZ in pure water and precipitate it with corresponding salt.
[Edited on 18-2-2010 by Engager]
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Taoiseach
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Yes could be impure. I gotta test this with pure 5-AZT again and see if I get the same result.
But there's certainly no cobalt azide in it, which is readily soluble in water. Cobalt azide also detonates from flame contact (it is one of the most
bristant of all inorganic azides) which the salmon-colored precipate does not.
There's a basic cobalt azide, Co(OH)N3 but it is said to be violet and forms by prolonged heating of a solution of the the normal azide.
N3(-) can also coordinate to Co(2+) and form tetraazidocobaltate, [Co(N3)4](2-). This complex is known to precipate large organic cations.
So maybe there's guanylazidetetraazidocobaltate in it 
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Rosco Bodine
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| Quote: Originally posted by The_Davster | About the azidotetrazoles and ethyleneditetrazyl azide mentioned in the early parts of this thread. Looks like the old patent made something else or,
they the patent made an impure oil of a product. The following paper states the ethylene bridged azidotetrazole to be a solid.
http://www3.interscience.wiley.com/journal/122512017/abstrac...
(This is not the first instance of something being discussed on this board being published a few years later... ) |
If you have the complete article please post it. It could be the temperature is low for which crystal data is referenced, or it could be a different
isomer, or something different entirely from the material referenced in the patent.
Edit: Thanks to solo for the article attached
[Edited on 19-2-2010 by Rosco Bodine]
Attachment: Alkyl-Bridged Bis-5-azidotetrazoles- A Safe Way of Preparation.pdf (249kB)
This file has been downloaded 1243 times
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The_Davster
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What we do not know, if the interaction of sodium azidotetrazole with alkyl halides gives substitution on the same nitrogen of the tetrazole ring as
given in the above paper. Using azidotetrazole as a nucleophile could produce the N-C bond on the 2 nitrogen instead of the 1 nitrogen.
For the ethylene bridged, the melting point is said to be 159C.
[Edited on 19-2-10 by The_Davster]
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Rosco Bodine
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The hydrogen of the NH group of the tetrazole is I believe the usual generalized cation of tetrazole which is an organic amino acid.....and the
hydrogen of the CH behaves more like a ring hydrogen of benzene and behaves as a "substitution hydrogen" if I am seeing this right. Therefore
different isomeric forms are possible, involving the more or less likely schemes for which of the two hydrogens is displaced. As I see it, tetrazole
could even exist as a dimer, where two differing isomers combine with the "loss" of H2, (probably by an indirect reaction route, but likely not a
spontaneous dimerization) and form a ditetrazole or bitetrazole joined at the respective rings CH to HN and leaving C - N bonding the two rings as a
dimer. The classic formula for tetrazole as CH2N4 would probably be better written as HN4CH or HN2CN2H or perhaps better still could be regarded as
methyleneiminoazide (H2CN)N3 .....but all that is just off the top of my head so I won't swear to it
Anyway, it is possible that in the case of the ethylene bridged tetrazoles there are three different resulting compounds
which may be formed ......one each where the pair of tetrazoles are each the same one of the two different possible isomers .....and a third
possibility where the ethylene bridges one of the isomers on one side and the other different isomer opposite. So there does exist three distinct
isomeric forms possible for the ethylene bridged
ditetrazylazide.
Hey Davster .....what you said above about the journals, it is curious how that seems to happen isn't it .....
nothing like peer review to stroke the egos of all us "know nots" Ha! Are you listening out there...all you academics with your noses in the air ???
I'll just bet you this particular "amateur science forum" has quite a few readers who are no amateurs  And we are soooooo flattered ...gee does
this mean we can keep our extra large "chemistry sets" ?
Don't worry sweet Nanny or Ma , if we should discover a way to blow up the world .....we promise you'll be the first to know !
http://www.youtube.com/watch?v=O0-bbSSaNFE&fmt=18 Melanie circa 1970 Look What They've Done
[Edited on 20-2-2010 by Rosco Bodine]
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wolfman
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I did a search for Triaminoguanidine Perchlorate, and this thread was what popped up.
Since I seen the Chlorate mentioned here, I thought I'd share the little info I got on the Perchlorate:
PATR 2700 vol 9 page T28 for reference.
Crystalline explosive prepared by hydrazinolysis of aminogunidine sulfate and treatment of the product with barium perchlorate.
CH9N6ClO4
mw 333.0
N 37.8%
OB to CO2 -60.0%
Forms as needles
melting point 132 degrees
density 1.09-1.62g/cc
vod 7730 at 1.56g/cc and 5970 at 1.09g/cc
Can be detonated with a black powder fuse and is hydroscopic.
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mnick12
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Azotetrazoleate
I recently acquired 250grams of 5-aminotetrazole.
I already synthesized 5-nitrotetrazole following engager's procedure but 1/10th the scale. And I must say that was the scariest thing I have ever
done...
But I have a question, I plan on making some 5,5-azotetrazolate but I do not have any potassium permangenate to preform the oxidation. But I do have
CrO3 and potassium dichromate. So my question is could I use either of those to oxidize aminotetrazole instead of permangenate?
Thanks.
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Engager
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| Quote: Originally posted by mnick12 | I recently acquired 250grams of 5-aminotetrazole.
I already synthesized 5-nitrotetrazole following engager's procedure but 1/10th the scale. And I must say that was the scariest thing I have ever
done...
But I have a question, I plan on making some 5,5-azotetrazolate but I do not have any potassium permangenate to preform the oxidation. But I do have
CrO3 and potassium dichromate. So my question is could I use either of those to oxidize aminotetrazole instead of permangenate?
Thanks. |
Well... I guess you encountered this nasty "microexplosion" fun stuff, how do you feel yourself after that? Now on azotetrazole, i think that other
oxidizers may also be suitable but i advise to proceed with caution, since KMnO4 procedure was taken from literature and is well studied. Steps on
unknown route can produce some unpredicted hazard situations, witch are definitely unwanted then working with sensitive explosive materials.
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mnick12
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Yes I did encounter a few mircro explosions, but perhaps more scary that that was the CuNT. As I continued the synthesis the copper salt began
precipitating, and while I was stirring some got splashed up near the top of the beaker. I did not notice it until later when I was adding more of Sol
B. But by then it had dried creating an ultra-thin sensitive crust which exploded when I started to stir again. It scared me so much I decided to stop
continue the synthesis and let my nerves calm down!
I think I will wait until I can buy some permangenate before I try the azotetrazole, since it is rather cheap.
Thanks.
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Microtek
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When I synthesized NTZ some years ago I used a similar method, but with a small difference that was supposed to eliminate those micro-explosions. It
worked fine, and I didn't get any explosions during the synthesis, but unfortunately I can't recall what the difference was.
All I can remember is that it was a patent and it began some steps before getting to aminoguanidine (I remember because I had aminoguanidine and so
had to adapt the procedure).
Edit: Oh, and I pretty sure it was a US patent.
[Edited on 24-6-2010 by Microtek]
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Taoiseach
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I made a few miligrams of sodium 5,5'-azotetrazolate and was very impressed by its power - a few crystals put over a flame first turned pale yellow
due to dehydration and then exploded with a deafening report.
Does the ammonium salt exist? I figure it could be prepared from barium 5,5'-azotetrazolate and ammonium sulfate. Does it crystallize with water of
hydration?
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Taoiseach
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Preparation of diammonium-5,5´-azotetrazolate:
150 mg barium-5,5´-azotetrazolate was added to a solution of 66 mg (0.50 mmol) ammonium sulfate in 10 mL H2O.
After stirring for 30 minutes the yellow solution was filtrated and evaporated. Yield: 95mg (95 %).
The ammonium salt crystallizes with no water of hydration and thus is quite sensitive to shock and friction. Melting point: 204 °C (decomp.)
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