5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends

I do not know how much you have looked at the synthesis of furazans(https://sciencemadness.org/talk/viewthread.php?tid=5813), but the intermediate for the synthesis of diaminofurazan is diaminoglyoxime. Diaminoglyoxime is synthesized from glyoxime and hydroxylamine HCl. I believe the OH of hydroxylamine is necessary in the mechanism of hydroxylamine reacting with glyoxime. Without it there is no group to leave, and the mechanism will not work. if a HON3 compound existed, it would be a good one to try in this reaction.
If I am wrong here, and the azide did add somehow to the glyoxime, I cannot see it easily cyclizing, unlike the reaction of a nitrile with an azide, the tetrazole ring is not formed immediatly, a nonaromatic system is formed, and an OH is left on the nitrogen, and there are no simple methods for elimination forming the ring. See the attachment for what I mean.
However if R1 on the azide is a hydrogen or just a negative charge, this could be used to make the tetrazole ring, but only if dichloroglyoxime was used instead of glyoxime, as it would provide a nice leaving group for elimination making the tetrazole ring. But the OH group may be left intact....

In the most recent scheme you posted, I think it could work, or at least I could draw a mechanism by which it could easily work in the presence of a strong base.

[Edited on 28-3-2008 by The_Davster]

I like!
I wonder if 5-ATZ would react with dichloro glyoxime, which could then be formed into a tetrazole substituted furazan?
I think the tetrazole ring would be stable under the ring closing conditions required for making a furazan.

Finaly i got all chemicals i need for synth of DAT (1,5-diaminotetrazole), i found reference on path from thiosemicarbazide via desulfurization and reaction of intermediate with ammonium azide in dimethylformamide solution:



Synth from reference, attached to this message (translated from russian): 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.

However, side reaction of HN3 and PbO surely exists and some lead azide will also form.

Question is how safe is to boil this miture on water bath? Do anyone have references on energetic materials whitch can be made from DAT? (I heard that some complexes such as with Fe(ClO4)2 are proposed as lead azide replacement primaries). Any known properties of DAT salts with strong acids?

[Edited on 12-6-2008 by Engager]

Attachment: diaminotetrazole.djvu (61kB)
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Nitrosation of diaminotetrazole. There was only five (prepared and isolated) structures in the scifinder database that had a string of 7 nitrogens, at least that I could see. Of which only two looked notably energetic, this being one and <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=10555">this</a> the other.

Personally I wouldn't have a problem heating a small amout of Pb azide dispersed in a solvent to 100°C, unless it wanted to bump and splutter but that shouldn't be a problem with DMF. Patent SE154979 precipitates Pb(N3)2 from Pb(NO3)2 + NaN3 at 90°C, a more extreme example is US3345130 which precipitates it from molten KNO3/NaNO3 at 225°C!! (Pb(N3)2's decomposition temp is >300°C).

[Edited on 13-6-2008 by Axt]

Reciently i made some biguanide sulphate, and got an interesting idea, about how another interesting tetrazole can be made. How does it look? Someone have synth procedure for biguanidine or it's salts (first made by Thiele in last century)?

I can find no problems with the synth, and I REALLY like the idea.
The molecule has to be some sort of a record...8 nitrogens connected in a row. I think the diamino version may be explosive by itself, let along the dinitro one

Perhaps dinitrobiguanidine can be made by reaction of fuming nitric acid (or mixed acids) with biguanidine sulphate, just like nitroguanidine can be made from guanidine sulphate + HNO₃. This would shorten the synthesis somewhat .

Even looking at it scares me a little bit, but yeah, I like it .
The only potential problem that I can see could be acid hydrolysis of some of the intermediates, eg dinitrobiguanidine into N-amino-N'-nitroguanidine and nitrourea.
It's definitely worth trying though!

A couple of thoughts on first look...
will have to dig through some references later....

There may be a possible shortcut from the biguanidine
sulfate to the diaminobiguanidine via reaction with hydrazine, ammonia being byproduct.

Possibly a variation on the reaction for producing guanidine salts via calcium cyanamide and ammonium nitrate might preferentially produce the biguanidine salt.

Polymerization to undesired materials could be a real complication, too. Beware the red goo

[Edited on 16-7-2008 by Rosco Bodine]

guanyl azide (diazoguanidine) revisited

In the second article above is mentioned again a material of interest, diazoguanidine, as the nitrate m.p. 129C which was also identified near the end of page 2 as the picrate in the early part of this thread. A parallel British patent GB470418 by the same inventor gives a little more detail about the preparation of the picrate. Analogously, by using half the molar proportion of magnesium styphnate, a guanylazide styphnate would be expected. And likewise using the sodium or ammonium salt of some of the acidic tetrazoles, the guanyl azide salt of those would be expected. Some of these may form mixed metal salts of possible interest also.

And there may be a shortcut to the aminoguanidine precursor from reaction of the ordinary guanidine nitrate salt with hydrazine. And likewise the di and triaminoguanidine bases via this and other routes should be kept in mind as possibly useful in forming salts with the acidic tetrazoles.

Anyway, aside from the new compounds proposed by Engager, there is a reminder there in the readings which
also points back to the beginning of the thread and these
other possibilities. It seems like deja vu all over again

@Engager , in that next to the last reaction above, instead of
Na2CO3 for the base, you should use NH4OH. Right?

[Edited on 17-7-2008 by Rosco Bodine]

Attachment: GB470418 Guanyl Azide Picrate base charge.pdf (265kB)
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Yesterday i decided to try another alternative route to bis-tetrazole. It is well known that it simply forms on action of nitrous acid on oxalic bis amidrazone (see attached patent for example). Main problem with less complicated synths is that they require to work with highly toxic dangerous gas cyanogen. As i wrote in posts before, attempts to react glyoxime with hydrogen azide, and additon of HNO2 to mix of glyoxime and hydrazine vere unsuccessful, however i decided to try another route:



First i made ammonium oxalate from ammonia and oxalic acid:

39g of oxalic acid dihydrate was dissolved in 60 ml of water at 60C, solution is quickly filtered to the flask containing 54 ml of 25% ammonia solution. White precipitate forms imidately, solution is cooled to 25C to further reduce product solubility, and then filtered. Resulting white glistering crystalls of pure ammonium oxalate monohydrate were filtered and air dried. Yield is 34.1g (77.5%).

Ammonium oxalate was converted to oxamide by following method:

28.4g of ammonium oxalate monohydrate is ground to fine state and mixed with 0.66 of P2O5 (catalyst) and wetted with 20 ml water. Mixture is placed to round bottom flask with attached air condenser, joined with distillate flask (to keep condensed water escaping from reaction mixture) and gas outlet (to vent toxic side products such as CO or (CN)2 outside of building). All connections must be tight to ensure no toxic reaction gasses can enter room atmoshpere. Flask with reaction mixture is heated on wax bath to 200C for 2 hours. Solid residue was washed with 2 portions 250 ml of hot water to remove soluble impurities and then filtered to obtain insoluble product - oxamide with 63% yield.

Next i tried to condense resulted oxaimide with hydrazine salts in water and alcohol. Because oxalic bis amidrazone is unstable at temps more then 50C heating can not be applied to help this reaction attempts. Hydrazine salt was used because according to information from the books amidrazones are stable in oxidic conditions and unstable in alkaline, however no reaction accured at all - oxamide does not dissolve. Then other metod is tried, some N2H5Cl is dissolved in ethanol and freebased by sodium hydroxide. Oxamide was fast dissolved and solution was filled with white flakes of product, whitch is insoluble in alcohol, probably oxalic bis amidrazone =)

[Edited on 18-7-2008 by Engager]

Attachment: EP1136476B1.pdf (207kB)
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You might try Copper Acetate in mild acetic acid at pH 4 and add Sodium Nitrite for the diazotization of the oxalic bis-amidrazone (oxamide dihydrazone) and simultaneous conversion to the energetic copper salt of the BHT as the end product precipitate.

Also the use of Copper Nitrate in dilute HNO3 with NaNO2
would probably work parallel to the prior art example 1,
analogous to the silver salt. Other metal salts should form similarly, shortening the synthesis if the metal salt is what is wished to be the end product.

You might want to have a robot do the work while
you remain safely behind a barricade

Attached is the US7122676 filing for the same patent which is easier to navigate.

[Edited on 19-7-2008 by Rosco Bodine]

Attachment: US7122676 preparation of 5,5′-bi-1H-tetrazole.pdf (115kB)
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5-Aminotetrazole on eBay: item 300165803620. $70.50 for 500 gm of 97.0% min. material.

Ref US 5451682 http://tinyurl.com/6hoacl & ChemDraw abstract of 2 azide routes to 5-AT from either cyanamid or dicyandiamide.

[Edited on 30-7-2008 by Ritter]

Quote:

Originally posted by Engager Reciently i made some biguanide sulphate, and got an interesting idea, about how another interesting tetrazole can be made. How does it look?

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.

The synthesis of 1,1'-dinitro-3,3'-azo-1,2,4-triazole uses alkaline permanganate to oxidize the amino function to the azo group.

It would be poly(5,5'-azo-1,1'-bitetrazole) or thereabouts. Are high nitrogen polymers of this type known or even possible?





[Edited on 30-7-2008 by Ritter]

Strange effects observed during attemp to saparate DAT from reaction mixture. First of all i tried to precipitate DAT with tetrahydrofuran (dat is insoluble or weakly soluble in it), this resulted in no precipitate; same thing happens then ethylacetate is added.

Next thing that was tried is benzene, if it is added in large excess to DMF in reaction mixture (3-4 times vol) mixture orange color deminishes and some creme colored product is precipitated, it is glueish like and can not float free in solution. This product is isolated with filtration (product №1), when filtrate is allowed to stand for some time formation of strange brown oily layer is observed, most of liquid is decanted and oily layer is collected by means of separating funnel (product №2). Then brown oil with strange angry smell is dilluted with water (1:1 vol) large quantity of white product is separated momentaly and color discharges to very slightly yellowish transparent, product is separated by filtering (product №3).

Some observations on products: product №1 is good soluble in hot water, however small quantity of insoluble materal remained. Then a drop of this solution is added to drop of CuSO4 solution, this results in imidate formation of brown precipitate. It is most likely that №1 product is traces of unreacted material - inorganic salts, whitch are weakly soluble in benzene, may be containing some azide. Product №2 is very strange, benzene and DMF are miscible with each other in all possible volume rates, so formation of this layer remains mysterious. This brown oil is heavier then mixture of benzene with DMF so it flows on the bottom.

My first idea about that layer was that it is layer with tetrazylazide whitch can form as byproduct in synth of DAT as mentioned in (5-Azido-1H-tetrazole - Improved Synthesis, Crystal Structure and Sensitivity Data article)

http://www.sciencemadness.org/talk/viewthread.php?action=att...

Synthesis of tetrazylazide mentiones about it's extraction from some brown oily layer, as described in this reference:

http://www.sciencemadness.org/talk/viewthread.php?action=att...

But i have to revise it because 5-azidotetrazole and it's alkali metall salts are perfectly soluble in water, so this product is likely to be DAT because it is weakly soluble in cold water. However i'm not completely sure in it.

Any ideas what all this products could be? How to explain this observations? May be someone know qualitive tests for DAT?

I've attched some pictures of this mysterious brown oil, and precipitate it forms on dilution by water:



[Edited on 31-7-2008 by Engager]

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]

@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 perhaps,
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.

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

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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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]

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?

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]

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]

Attachment: DNOAN.pdf (12kB)
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[Edited on 7-4-2009 by PHILOU Zrealone]

Engager's Tetrazole Paper as pdf

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...

.

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]

Quote: Originally posted by Engager

Synthetic route to tetrazoles from urea and ammonium nitrate: In prepublication

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)
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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... )

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.

Quote: Originally posted by The_Davster

The following paper states the ethylene bridged azidotetrazole to be a solid. http://www3.interscience.wiley.com/journal/122512017/abstrac...

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.

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

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... )

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]

Azotetrazoleate

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.

I've tried the synthesis of sodium bis-5,5'-diazoamintotetrazolate for the second time now and each time I failed

First time I tried according to Engager's procedure in his excellent EDOT.pdf, second time I tried according to US pat. 3,064,827 "manufacture of salts of diazotized tetrazole derivatives". The procedures are not much different except that the patent suggests a slightly lower temperature (15°C). Aminoguanidine nitrate, acetic acid and sodium acetate was dissolved in water and NaNO2 added dropwise with cooling. The second time I managed to keep the temperature perfectly within 14-16°C. Mixture turned yellow and produced much foaming upon warming to RT (lots of N2 I guess). Yet even after standing for 1 week no crystals have deposited

Any suggestions/ideas?

Can you give a source where is described synthesis of biguanidine sulphate ?

I have been performed searching in SciFinder and I don't find any informations about biguanidine sulphate.



Name biguanidine = 1,2-Hydrazinedicarboximidamide CAS 6882-47-9

Quote: Originally posted by Engager

Reciently i made some biguanide sulphate, and got an interesting idea, about how another interesting tetrazole can be made. How does it look? Someone have synth procedure for biguanidine or it's salts (first made by Thiele in last century)?

Unfortunately this reaction path is likely to be failure since heating urea with hydrazine produces semicarbazide by replacement of NH2 group with hydrazine group (with evolution of NH3). It seems that such substitution in compounds of urea group is very common, and that hydrazine is unable to condense on urea carbonyl oxygen, like it does in some other cases for example with acetone:

(CH3)2C=O + NH2-NH2 => (CH3)2C=N-NH2 + H2O

In fact if urea can be reacted in such manner it would lead to formation of aminoguanidine:

(NH2)C=O + N2H4 => (NH2)2C=N-NH2 + H2O <=> NH2-C(=NH)-NH-NH2

However it is imposible for hydrazine to act like that on urea oxygen so this scheme is a failure in first step.

And by the way, substance you asked for exists i'm not sure how to name it properly but it can be obtained by reduction of azodicarbomidine - product produced by oxidation of aminoguanidine with KMnO4 (Ref: Chem.Rev. "Chemistry of aminoguanidine and related substances" page 230).

[Edited on 31-8-2010 by Engager]

Quote: Originally posted by Engager

Unfortunately this reaction path is likely to be failure since heating urea with hydrazine produces semicarbazide by replacement of NH2 group with hydrazine group (with evolution of NH3). It seems that such substitution in compounds of urea group is very common, and that hydrazine is unable to condense on urea carbonyl oxygen, like it does in some other cases for example with acetone: (CH3)2C=O + NH2-NH2 => (CH3)2C=N-NH2 + H2O In fact if urea can be reacted in such manner it would lead to formation of aminoguanidine: (NH2)C=O + N2H4 => (NH2)2C=N-NH2 + H2O <=> NH2-C(=NH)-NH-NH2 However it is imposible for hydrazine to act like that on urea oxygen so this scheme is a failure in first step.

Triaminoguanidine nitrate synthesis kinetics

Suprise suprise, the DATZ did crystallize after 1 month Sometimes patience pays off.

Here's a picture of small samples (few miligrams) of several azotetrazolate salts.
From lef to right: disodium-5,5-azotetrazolate, diammonium-5,5-azotetrazolate, dihydrazinium-5,5-azotetrazolate-pentahydrate,
diguanidinium-5,5-azotetrazolate-dihydrate, basic lead 5,5-azotetrazolate; the rightmost picture shows tetrazolylguanyltetracene-hydrate.

The ammonium and hydrazinium salts were made by metathesis reaction of barium azotetrazolate with the corresponding sulphates. The guanidinium salt was made by neutralizing guanidinium carbonate with dilute HCl and adding sodium azotetrazolate to the boiling solution. The solution was then filtered and rapidly cooled in an ice bath. After 30 minutes the salt was precipated as fur-like needle shaped crystals. Yield seems to be excellent due to low solubility in ice cold water (remaining solution was almost colorless).

The basic lead salt was prepared according to GB pat. 986631.

Explosive properties: I only tested heat sensitivity. The guanidinium and hydrazinium salts deflagrate mildly upon flame contact. The carefully dried ammonium and sodium salt react more violently but only a few crystals will explode, spilling the remaining crystals across the table. The sodium salt when heated over the flame first turns pale yellow and then explodes incompletely. The ammonium salt crystallizes without water and thus explodes more readily (without the dehydration stage) when ignited but the explosion is incomplete as well.

The basic lead salt reacts very mildly to flame contact, comparable to lead picrate. A tidbit of confinement will make it DDT tough. 50mg wrapped tightly into 2 layers of aluminium foil caused a sharp report.

Anyways this is far from what I had expected from compounds with such incredibly high nitrogen content. They look good on the paper but propagation is poor (maybe due to low density). Its useless stuff IMHO except maybe for special purpose like smokeless rocket fuel. Maybe ammonium/hydrazinium 5,5-diazoaminotetrazolate has better properties.

Someone gotta find a good route to triaminoguanidine perchlorate, that stuff sounds interesting.



[Edited on 2-9-2010 by Taoiseach]

Here's an interesting paper

Synthesis and Characterization of the Energetic
Compounds Aminoguanidinium-, Triaminoguanidinium and
Azidoformamidinium Perchlorate

Central European Journal of Energetic Materials, 2008, 5(1), 13-30

Note:
Azidoformamidinium Perchlorate = Guanyl Azide Perchlorate

Alternate routes would seem possible. For example it may be possible to react Hydrazine Sulfate with Barium Perchlorate or Calcium Perchlorate and filter out the relatively insoluble sulfate to leave a solution of Hydrazine Perchlorate. The hydrazinolysis of Calcium Cyanamide or Cyanamide or perhaps Sodium Cyanamide, perhaps in the presence of ammonium perchlorate, could then lead to the monoaminoguanidine perchlorate, or diaminoguanidine perchlorate, or triaminoguanidine perchlorate. Likewise hydrazinolysis of a guanidine salt may work as well. Possibly a nitrosation of the monoaminoguanidine intermediate would produce Guanyl Azide Perchlorate. The possible reactions are certainly interesting This should help explain my interest expressed early in this thread about the potential usefulness of polyaminoguanidines and guanyl azide. These are something like an unexplored "branch" of potentially useful energetic compounds which reside on the "reaction tree" associated with tetrazoles.

Attachment: Aminoguanidine Perchlorate, Triaminoguanidine Perchlorate, Guanyl Azide Perchlorate.pdf (316kB)
This file has been downloaded 1661 times


[Edited on 3-9-2010 by Rosco Bodine]

Quote: Originally posted by Taoiseach

Anyways this is far from what I had expected from compounds with such incredibly high nitrogen content. They look good on the paper but propagation is poor (maybe due to low density). Its useless stuff IMHO except maybe for special purpose like smokeless rocket fuel. Maybe ammonium/hydrazinium 5,5-diazoaminotetrazolate has better properties. Someone gotta find a good route to triaminoguanidine perchlorate, that stuff sounds interesting. [Edited on 2-9-2010 by Taoiseach]

Well today I thought I would test some 5-atz.

I mixed a small amount of 5-atz with enough ethyleneglycol dinitrate to make it clump together. 350mg of this mix was packed into and empty .22 shell that still had the priming in it. The shell was placed on concrete then half a gram of Zn/S mix was placed around the base of the .22 (to ignite the primer). Then a tomato sauce can was placed ontop of the the shell. The thing was ignited using a piece of visco. It gave a very loud crack and sent the can flying. Here is a pick of the damage.



keep in mind that is only 350mg.

Quote: Originally posted by Rosco Bodine

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

Quote: Originally posted by AH-Poster

There is also 1,5-Diamino Tetrazole. https://sites.google.com/site/energeticchemical/diamino-tetr... [Edited on 17-10-2010 by AH-Poster]

Quote: Originally posted by Engager

Finaly i got all chemicals i need for synth of DAT (1,5-diaminotetrazole), i found reference on path from thiosemicarbazide via desulfurization and reaction of intermediate with ammonium azide in dimethylformamide solution: Synth from reference, attached to this message (translated from russian): 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. However, side reaction of HN3 and PbO surely exists and some lead azide will also form. Question is how safe is to boil this miture on water bath? Do anyone have references on energetic materials whitch can be made from DAT? (I heard that some complexes such as with Fe(ClO4)2 are proposed as lead azide replacement primaries). Any known properties of DAT salts with strong acids? [Edited on 12-6-2008 by Engager]

擦的 果然是疯狂的东西 5AT硝酸盐不可小视……

Quote: Originally posted by Hydrazinium

<b> The Usage of 5-ATZ as a nucleophile </b> Having kept an eye on the topic concerning 5-ATZ, I have been wondering, has anyone tested the strength of 5-ATZ as a nucleophile? For example, I have been looking at the possibility of using it in a nucleophilic substitution with chloromethane. Has anyone attempted any similar procedures?

Quote: Originally posted by almaz

Obviously what as a result of reaction cyanamide and hydrazine -reaction product aminoguanidine. But i have in its dictation dicyandiamide and hydrazine sulphate. How, in what way you out of dicyandiamide and hydrazine sulphate prepare aminoguanidine bicarbonate? publish the reference.

There is no specific reference to this reaction which I know.

What I understand you are asking about is the possible
depolymerization of dicyandiamide under basic conditions
to then react with hydrazine hydrate and a hydrazine salt in solution. It may be possible to limit this known reaction progress to the monoaminoguanidine stage, by limiting the amount of hydrazine available for reaction to one third the proportion as would lead to the triaminoguanidine derivative, however this is unconfirmed. The reactions of interest are on page 2 of this thread where the desired product is a triaminoguanidine derivative, described in US3285958. Also of interest is US5041661. As a starting point for an experiment it would seem likely the lower reaction temperature and 1/3 the molar amounts of hydrazine values used in Example 2 (table 1 experiment 10)
of US3285958 would be reasonable, with attempted precipitation of the end product using sodium bicarbonate.
It would seem possible that the the required mixture of hydrazine hydrate and hydrazine sulfate in solution needed for the initial reaction for depolymerization of the dicyandiamide could be gotten by partial freebasing of
hydrazine sulfate using NaOH. Poor solubility of hydrazine sulfate would make it a poor choice for this experiment and
it would seem better to use hydrazine nitrate gotten by
reaction of calcium nitrate with the hydrazine sulfate and
filtering out calcium sulfate, followed by partial freebasing
of the hydrazine using NaOH. If the reaction proceeds as hoped, the dicyandiamide will depolymerize and react with the hydrazine nitrate and hydrazine hydrate with evolution of ammonia, to form monoaminoguanidine nitrate. The
soluble aminoguanidine nitrate, if it has formed, should precipitate as aminoguanidine bicarbonate when sodium bicarbonate is used to basify the reaction mixture. Note:
The basic reaction mixture containing unreacted hydrazine hydrate should probably be first neutralized with HCl before being made basic with sodium bicarbonate, for precipitation
of the desired aminoguanidine bicarbonate.

Pure hypothesis is what you are asking about .....
so this is the only reference I can publish

This may work fine, or it may not work at all ....I do not know.

[Edited on 24-5-2011 by Rosco Bodine]

The process is not really thought out completely so it may be workable or not, but a half neutralization of the hydrazine sulfate would result in the highly soluble
dihydrazine sulfate which could then further be reacted with the calcium nitrate.
I haven't drawn this out on paper to try to analyze it or what complications may be encountered. Sodium hydroxide or ammonium hydroxide or sodium hydroxide or sodium carbonate plus ammonium nitrate may be useful followed by the calcium nitrate ...I'll think about these contemplated scenarios further.

A "kitchen" nothing is what should be used there I would think for what is not
really a kitchen process. I use a four inch flexible duct like is used for a clothes dryer mounted in a ring on a ringstand which has its open end positioned a couple of inches away from the opening of a reaction vessel, and pulls a local draft
into that 4 inch intake duct. That duct is twenty feet long and attached to a flange on the intake of a speed controlled centrifugal blower the outlet of which
goes to another thirty feet of 4 inch duct for remote discharge. Additionally is a
shop fan which pulls a lateral draft diagonally across the entire area. I use
lighted sticks of incense as visual smoke streamers to show the draft same
as is done in a wind tunnel. If the draft is effective there is no smelling of the
incense only a visual indicator that ventilation is effective. If incense can be smelled at any time, then there is a problem of turbulent air mixing and the work area is compromised.

With toxic fumes don't play, then you can live another day .....
It is much less challenging to analyze your last experiment,
while you still have a pulse and respiration

That is the method I use for safety when dealing with fumes that are real nasties .....but it isn't IMO the case for low aqueous concentrations of hydrazine. Really the greater concern there is air ingress into the reaction, moreso than
concern over hydrazine fume egress countercurrent to the
usual flow. Hydrazine is a getter for atmospheric oxygen
so keeping air out of your hydrazine is more likely to be the problem than keeping hydrazine out of your air. Truthfully,
the synthesis is in my opinion relatively low risk with ordinary caution and no extraordinary measures are required beyond
ordinary manipulation and common sense. Some people
seem to think chemistry is "cooking" where they should
deliberately smell the "stew" to see if it needs something....
go figure.....and that is Darwin award behavior in progress, but people will do it. Just use common sense and you will be okay, and don't use common sense with chemistry and you are guaranteed to get hurt acting recklessly, sooner or later, and probably not too much later.

[Edited on 29-5-2011 by Rosco Bodine]

Thanks for the fast reply.I also suspected that the low concentrations of hydrazine in the solution and his boiling point will make the process safe enough to be performed in the “kitchen”. Don’t get me wrong. I’m not stupid or ignorant and take my hobby very seriously. The aspirator question was bring to the table just because I move to new place, where every foaming flask on my porch will immidietly catch the attention of mine sweet, brainwashed neighbours.

P.S.

Funny thing is that I’m indeed a chef. Cheers.