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Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
The_Davster
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[*] posted on 30-7-2008 at 20:40


I have never seen white DAT, only a light brown powder. I think removal of residual lead sulfide particles must be very difficult.



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[*] posted on 2-8-2008 at 15:42


Finialy i got my hands on this crazy molecule from 2 nitrotetrazoles. Molecular structure was computed with 6-31G** DFT B3LYP functional, mesh in the plot is crystalline cell 0.001 e/bohr^3 electron density isosurface. After heat of formation, heat of explosion and density vere computed from quantum chemistry, velocity of detonation was calculated in usual manner by emperical equations. Correction coefficent was obtained by division of 5-NTZ measured/calculated VOD's. Calculated values listed below.



Molecular Mass: 228.0866 g/mol
Heat of formation: +219.90203 kcal/mol
Calculated Crystal Density: 1.996817 g/cm3
VOD: 9916 m/sec (1.99) calculated and justified by divergence coeficent from 5NTZ REAL/CALC.
Explosion gas volume: 687,45818 l/kg
Heat of explosion: 5,5461 Megajoules/kg

For comparsion corresponding 5-NTZ properties are listed below:



Molecular Mass: 115,05124 g/mol
Heat of formation: + 83,59606 kcal/mol
Calculated Crystal Density: 1.771954 g/cm3
VOD: 8900 m/sec (1.73)(experimental) ; 9059 m/sec (1.77)
Explosion gas volume: 778.8 l/kg
Heat of explosion: 4,3227 Megajoules/kg

General note to all people who think that positive heat of formation is wrong - no, you are! This compounds are endotermic as are HN3, azotetrazole, diaminotetrazine and other high nitrogen explosives! The positive heats of formation are exactly the reason of high energy in this exposive compounds. So all this positive heats of formation are correct - learn basic thermochemistry!

[Edited on 3-8-2008 by Engager]




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The_Davster
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[*] posted on 6-8-2008 at 07:56


Attached is a simple synthesis of Nitraminotetrazole in a one step reaction from aminotetrazole.

100% nitric acid is used, but it is one step from 5-ATZ which IMO is an improvement over
a) synthesis of nitraminoguanidine then diazotization
b) preparation of ATZ-nitrate, then dehydration.

Attachment: natz1.pdf (650kB)
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[*] posted on 16-9-2008 at 18:27


So, is there a quintessential tetrazole-based complex that puts all other primaries (or tetrazoles) to shame? Personal favorites? I have some aminotetrazole, sodium azide, sodium nitrite and a urge to explore. Any requests or ideas on where to start?

[Edited on 16-9-2008 by Swany]
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[*] posted on 16-9-2008 at 19:19


Silver nitrotetrazole

The nitrotetrazolato-ferrate complexes are cool as well, but no experience to date with them.

[Edited on 16-9-08 by The_Davster]




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[*] posted on 17-9-2008 at 16:54


I think I will prepare some CuNT and maybe some tetrazole azides, perhaps even a crack at some energetic bidentate ligands. The sodium iron salts look interesting and no one has had luck yet.

EDIT: Bidentate energetic ligands look interesting as well for that matter, though I am not sure if I will get to any of them.

[Edited on 17-9-2008 by Swany]
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[*] posted on 18-9-2008 at 20:44


Preparation of CuNT:

20.8g NaNO2 and 11.0g CuSO4.5H2O were dissolved in 75mL dist. H2O and placed in a large beaker upon a cold water bath with magnetic stirring and a slow stream of air above the solution. A solution of 10.8g 5-ATZ in 180mL H2O with 12.8ml 70% HNO3 and 0.4g CuSO4 was added dropwise over the course of 3 hours. Gas was evolved and the very dark green solution slowly turned light green with a similarily colored precipitate over the course of the addtion. It was then stirred for 30 more minutes and 20mL of 50% HNO3 was added dropwise, and stirring was continued for 30 more minutes. The product was collected on a buchner funnel and washed with dilute HNO3, then with portions of water.

This is how far I am-- and I seriously doubt I will dry large portions of the product. Most will probably be converted into the sodium salt then other anionic complexes.
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[*] posted on 19-9-2008 at 14:30


Acid copper salt is not so sensitive to fear it so much, i used large quantities of dry products up to 20g without any hazard situations. As for aims of synth AgNT is definitely worth trying, but is quite sensitive and extremely powerfull primary explosive. Some complexes have good initiating power as well and far less sensitive, but are bit harder to produce. In my oppinion best aim is BNCP, powerful modernistic primary explosive, i tried this complex and it was very good in many ways.



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[*] posted on 19-9-2008 at 23:05


@Swany
You asked for ideas, so I'm offering one for consideration. Back on page 2 of this thread, fifth post down from the top, was posted a bit of information regarding Azotetrazole , 5,5'Azotetrazole, and a related patent US5877300 containing a synthesis which Engager
confirmed and described on page 3 of the thread.

Engager made a (di)hydrazine derivative salt of
5,5'Azotetrazole.

The patent described a (di)guanidine salt , and it seemed
that as a natural followup, the next interest would be the possibility of a (di)guanylazide salt of 5,5'Azotetrazole.

This perhaps would be covering new ground. It has
continued to intrigue me what might be the energetic
properties of the guanyl azide salts which may form with the acid tetrazoles, which themselves can be formed as the later derivatives of the same guanyl azide which is their precursor. It is something of an incestuous marriage
of the parent and daughter compounds which could result
in interesting energetic offspring, or morons:P perhaps:D,
but it would seem to be a logical experiment to find
exactly what does result from that deliberate "inbreeding"
marriage of energetic structures. There are other possible
guanyl azide salt combinations where a different acid tetrazole could substitute for the 5,5'Azotetrazole.
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[*] posted on 21-9-2008 at 21:12


Thats an intriguing idea Rosco. I might look into that this next weekend.

In other news, I tried to make some Sodium ferro-nitrotetrazolates by dissolving some CuNT in NaOH soln, filtering the precipitated CuOH, adjusting the solution to acidic with HCl, estimating an amount of FeCl2.6H2O to add, doing so, boiling off a large amount of liquid, and throwing it in the freezer, vacuum filtering and washing with cold water. I recieved a crop of pale orange stuff, not unlike what the CuNT I made looked like. It is powderable, not unlike an amorphous nitric acid ester, like a fresh ppt. of MHN or ETN dried. On contact with flame it burns very rapidly, and heating it will result in DDT, as will heating it and then initiating with flame contact. The CuNT I had was still more likely to DDT, but my ratios in preparing the iron salt were determined in a most qualitative manner. I will weigh some out and try it next time.
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[*] posted on 24-1-2009 at 04:22


Ive been reading about tetrazoles alot.
Now I am wondering what is found the be the substance with the highest primairy potential?
Now and then i can't see the trees through the forest :P
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[*] posted on 22-2-2009 at 18:09


I'm finaly completed a big compilation work on derivatives of tetrazole. Everyone who is interested in this topic is welcome to review it Here.

[Edited on 23-2-2009 by Engager]




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[*] posted on 22-2-2009 at 19:41


Here's the link for the locally stored file

http://sciencemadness.org/scipics/Energetic_Derivatives_Of_T...

The file size appears to exceed the limit allowed for attachments so you won't see the download count,
but you should still be able to get the file by the link.
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[*] posted on 24-2-2009 at 03:57


Quote:
Originally posted by Ritter
I'm curious to find out if this diamine can be oxidized to create multiple intermolecular azo linkages, basically polymerizing it into a polymer that would be anout 86% nitrogen.
It would be poly(5,5'-azo-1,1'-bitetrazole) or thereabouts. Are high nitrogen polymers of this type known or even possible?

A tricyclic molecule might also be formed if the two amino groups being on the same side... when bridging
You then get a symetric molecule based on cyclohexaring -C(N-N)2C- core with two cyclopentaring ears then looking a bit like Mickey Mouse :)

[Edited on 25-2-2009 by PHILOU Zrealone]

Attachment: noname01.pdf (11kB)
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[*] posted on 9-3-2009 at 08:53


Quote:
Originally posted by Engager
I'm finaly completed a big compilation work on derivatives of tetrazole. Everyone who is interested in this topic is welcome to review it Here.

[Edited on 23-2-2009 by Engager]
Great work! Interesting reading indeed.

A thougt: Since you have so much experience with the tetrazole derivates, a chapter with your own opinions where you compare the different tetrazoles regarding different factors (ease of synthesis, cost, dangers, performance, sability etc.) would be very valuable.
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[*] posted on 13-3-2009 at 03:17


Quote:
Originally posted by Engager


Synth from reference: 18g (0.2 mol) thiosemicarbazide, 16.3g (0.25 mol) sodium azide, 13.4g (0.25 mol) NH4Cl and 89.2g (0.4) PbO are mixed in 350 ml of dimethylformamide on boiling water bath for 6 hours. Mixture is filtered hot, and filtrate is evaporated to dryness in vacuum. Residue is dissolved in 50 ml of hot water, filtered hot and slowly cooled. Precipitate is filtered, washed with cold water and dried. Yield is 11.8g (59%), white crystals, melting point 186-187C with decomposition (from water). Good soluble in hot water, and water-ethanol mixtures, acids, dimethylformamide, moderately soluble in cold water, ethanol, insoluble in tetrahydrofuran, ethylacetate, methylene chloride, either.

Yesterday i've finaly made successful 1,5-diaminotetrazole synthesis, using one step method from thiosemicarbazide. Thiosemicarbazide & sodium azide & ammonium chloride & lead (II) oxide are refluxed in excess of dimethylformamide. Regretably synth is a real hell, due to many practicial difficulties. First of all desulfurization of thiosemicarbazide by lead oxide leads to formation of lead sulphide, witch solidifies to hard solid layer on bottom of reaction vesel, this leads to difficulty with stirring, forcing you to spend a lot of time to crush this layer at any stirring step. Layer is quite dense and hard, so caution is needed to avoid breaking a glass of reaction vesel. Filtration of risidual lead sulphide particles also makes trouble - this stuff passes through filtering paper! Second big difficulty is vacuum removal of dimethylformamide (it can't be distilled without decomposition at atmospheric pressure). DMF is readily destilled by heating filtered reaction mixture on water bath at 5-10 kPa. Pressure must be controled to not exceed this boundaries, if pressure is too high DMF will not destill while heated on water bath, but if pressure is too low, mixture will boil up imidately, with such intensity, that foaming liquid throws over to condenser. Low pressure also greatly lowers boiling point, so fumes became difficult to condense and can pass through to the oil in vacuum pump, penetrating long condenser without visible difficulty. Vacuum caused dissolved gasses to leave a boiling liquid and it imidately comes to overheated state, so boiling capilary is absolutely essential (it is also used to control pressure in reaction vesel). To make matters worse, residual lead sulphide particles block boiling capilary, forcing you to stop distilation, repressurize vessel and clean up capilary. Anyway vacuum evaporation to dryness and recrystallization from water gave wanted 1,5-diaminotetrazole crystalls with 55% yield, crystalls are probably contaminated by lead sulphide and have light brown coloration mentioned by Davster.



[Edited on 13-3-2009 by Engager]




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[*] posted on 20-3-2009 at 06:11


Reciently i got an idea how bis-tetrazole can be made from oxalic acid, hydrazine hydrate and sodium nitrite. All this chemicals are readily accessibe everywhere so this can be usefull. All reactions give almost quantative yield, however they involve some nasty toxic products and must be carried out on open air with gas mask or under efficent hood. This way of synthesis is patented both in US and in EU (patents EU1136476B1 and US7122676).

Oxalic acid is reacted with ammonia to give ammonium oxalate, witch is subsequently dehydrated on heating in glycerine first to oxamide intermediate with evolution of 2 molecules of water, and finaly to cyanogen with evolution of 2 more molecules of water. Evolved cyanogen is reacted with hydrazine hydrate at temperature slightly lower then room temperature, to form oxalic bis-amidrazone (oxalic acid dihydrazide). Oxalic bis-amidrazone is isolated by filtering and is reacted with nitrous acid to form bis-guanylazide intermediate witch is isomerized to form 5,5'-bis-1H-tetrazole nucleus. Resulted solution can be treated to precipitate some insoluble bis-tetrazole salt (such as Mn), and precipitate can be boiled with NaOH to get pure sodium bis-tetrazolate solution. Reaction scheme is shown below:



All chemicalls here are readily accessible, may be some one will give it a try?




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[*] posted on 31-3-2009 at 04:45


Engager,
Could it be possible that the cyclisation happens on the =NH hold on the other C than the one holding the N3 making thus a bicyclic compound with two hexarings based on a naphtalene skeleton (1.2.3.4.5.6.7.8-octaazanaphtalene).

It could be denser than the bis tetrazole.


Attachment: 1.2.3.4.5.6.7.8-octaazanaphtalene.pdf (11kB)
This file has been downloaded 945 times

[Edited on 31-3-2009 by PHILOU Zrealone]




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[*] posted on 31-3-2009 at 07:26


Quote: Originally posted by PHILOU Zrealone  
Engager,
Could it be possible that the cyclisation happens on the =NH hold on the other C than the one holding the N3 making thus a bicyclic compound with two hexarings based on a naphtalene skeleton (1.2.3.4.5.6.7.8-octaazanaphtalene).
It could be denser than the bis tetrazole.
[Edited on 31-3-2009 by PHILOU Zrealone]


Yes it is probably little denser, comparsion of computed properties shown on picture below:



Mechanism of cyclization shows that cyclization to 1.2.3.4.5.6.7.8-octaazanaphtalene in presence of base may also be possible.



However 1.2.3.4.5.6.7.8-octaazanaphtalene has higher energy and heat of formation (higer thermodinamic instability), so cyclization to bis-tetrazole must be favoured. I'm not sure molecule your propose exists, but if so it must exist as small impurity in bis-tetrazole, made by cyclization of amidrazone.

[Edited on 31-3-2009 by Engager]




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[*] posted on 2-4-2009 at 13:31


That octaazanaphthalene looks quite a lot like a reduced form of DTTO. If it happened to be even a minor product of this reaction, I think a study into possible oxidative procedures might be justified.....
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[*] posted on 6-4-2009 at 10:16


Well it could just be that I missed this, anyways.
Is there a significant difference in yield between using the original thiele's method, or the alternate with HCl when forming 5-atz from AGBC.
Is there anyone who can support this with data or experimental results?







What a fine day for chemistry this is.
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[*] posted on 7-4-2009 at 02:20


As far as i know there are two methods leading to 5-ATZ, both described with yields in "explosive derivatives of tetrazole" article.

1. Thiele method uses aminoguanidine bicarbonate + sodium nitrite, yelds are good - about 65-70%. It doesn't matter witch acid you use, just need to know that corresponding salt of aminoguanidine will be in solution.

2. Schtolle method uses dicyandiamide + hydrogen azide, this method can give up to ~99% yield, but reqires a lot of time, and forces to work with solution of highly toxic and volatile hydrogen azide. HN3 was generated from NaN3 + HCl, however other acid can also be used.




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[*] posted on 7-4-2009 at 06:18


:)
Based on the calculation of Engager:
5-NTZ: (5-nitrotetrazole)
Hf°= 83.6 kcal/mol
Density = 1.77 g/ccm
VOD max = 9059 m/s

bis-5,5'-NTZ (bis-5,5'-nitrotetrazole):
Hf°= 219 kcal/mol
Density = 1.99 g/ccm
VOD max = 9916 m/s

bis 5,5' HTZ (bis-5,5'-H-tetrazole):
Hf°= 171 kcal/mol
Density = 1.66 g/ccm
VOD max = 7836 m/s

OAN (1.2.3.4.5.6.7.8-octaazanaphtalene):
Hf°= 194 kcal/mol
Density = 1.68 g/ccm
VOD max = 8221 m/s

One can estimate the properties of dinitrooctaazanaphtalene :)
DNOAN (dinitrooctaazanaphtalene):
Hf°= +/- 240 kcal/mol
Density = +/- 2.01 g/ccm
VOD max = +/- 10300 m/s

I'm happy to see the calculation of Engager goes in the same way as my theory of the power, density, VOD sequence ...
that follows the rule polymer > tetramers > trimers > dimers > monomer.
The sensitivity should follow the rule polymer >or= tetramers >or= trimers >or= dimers >or= monomer.

In this case the "bis-" molecules are kind of dimers of monomers :)




[Edited on 7-4-2009 by PHILOU Zrealone]

[Edited on 7-4-2009 by PHILOU Zrealone]

[Edited on 7-4-2009 by PHILOU Zrealone]

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[Edited on 7-4-2009 by PHILOU Zrealone]




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[*] posted on 7-4-2009 at 11:55


Thanx engager, that's what i meant.
I was just wondering if the type of acid used would make difference in yield.
It is well known that nitric is much more expensive and only if it would result it higher yields it could be worth the extra money. ]
Thou considering what you said, that it wont make a difference using HCl would be the most logical option (also because its more widely available).

Btw, would addition of "too much" carbonate be of any influence.
Might sound like a stupid question, I ask this because the acid i used is rather old and the concentration might no longer be accurate.
Is it wise to add just a little extra carbonate or leave it acidic and stick to original amounts.




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[*] posted on 7-4-2009 at 18:53


You better to determine exact concentration of your acid and recalculate requested volume, because change in ammount of acid will distract whole following synth procedure. You can determine concentration of your acid by weighting empty measuring cylinder, then filling it with exactly 100 ml of acid and weighting cylinder again. This will give you a density value calculated as (M(with 100ml) - M(empty))/100, after determination of acid density you can use concentration/density table data to determine concentration. Then concentration of your acid is known, just recalculculate volume of your acid required to get same number of moles as moles of nitric acid in original procedure.



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