Sciencemadness Discussion Board

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

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The_Davster - 28-3-2008 at 19:09

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]

tetrazole mechanisms.JPG - 26kB

Axt - 23-5-2008 at 16:16

Quote:
Originally posted by The_Davster
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....


Arr confirmed, I posted it in the "Glyoxime, Diaminofurazan and Some Energetic Derivatives" before realising the discussion here. http://www.sciencemadness.org/talk/viewthread.php?tid=5813

I'll attach a previous article regarding the diazidoglyoxime intermediate here, although these authors failed to cyclise the azide to tetrazole. See the link above for the cyclisation via HCl in ether.

[Edited on 24-5-2008 by Axt]

Attachment: Evidence on the Existance of Azidoximes - Journal of Organic Chemistry (1961), 26 952-4.pdf (348kB)
This file has been downloaded 1511 times


The_Davster - 23-5-2008 at 17:02

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.

Engager - 12-6-2008 at 09:22

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)
This file has been downloaded 1338 times


Axt - 12-6-2008 at 12:29

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]

nitrosation of diaminotetrazole.jpg - 13kB

Axt - 12-6-2008 at 12:42

And an article on diaminotetrazole perchlorate.

Attachment: Experimental and Theoretical Study of 1.5-Diamino-4-H-Tetrazolium Perchlorate.pdf (1.2MB)
This file has been downloaded 1391 times


The_Davster - 12-6-2008 at 18:57

I imagine it would have a plethora of interesting condensation products with formaldehyde or glyoxal. Unfortunatly I do not know what work has been done on this, I will research it at work.

As for the lead azide, I have heard (High Energy Density Materials, Klapoetke) that this synthesis will produce "large ammounts" of lead azide, and that is why the method from diaminoguanidine is prefered. But this may only be important on industrial scale.
DMF boils at a higher temperature than a boiling water bath, and should be safe from thermal issues. I would advise swirling to mix the reaction as opposed to magnetic or hand stirring to keep friction to a minimum.

Also, the Indian paper Axt posted...an isomer of azidotetrazole/tetrazyl azide! I could have sworn I have seen a paper on interconverting the two, or was it a theoretical discussion paper?

Anyway, in terms of derivitaves, the nitrate and perchlorate are in the attached paper, as are the methylation products with azide, nitrate, and dinitramide counterions

Attachment: DAT derivs.pdf (493kB)
This file has been downloaded 2309 times


The_Davster - 21-6-2008 at 11:14

A paper on DAT condensation with glyoxal... reactions with formaldehyde appear nonexistent.

Attachment: DAT condensations.pdf (572kB)
This file has been downloaded 1587 times


Engager - 14-7-2008 at 18:06

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)?



The_Davster - 15-7-2008 at 08:34

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:D. I think the diamino version may be explosive by itself, let along the dinitro one:P:o

Sobrero - 16-7-2008 at 00:58

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 + HNO<sub>3</sub>. This would shorten the synthesis somewhat :).

497 - 16-7-2008 at 01:22

God that is a lot of nitrogens. I like it. Any practical information on the synth or explosive properties?

Nick F - 16-7-2008 at 05:08

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!

Rosco Bodine - 16-7-2008 at 10:15

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:P

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

Engager - 17-7-2008 at 02:34

Some references on biguanidine:

1. Justus Liebig's Annalen der Chemie, Volume 273, Issue 2-3 (p 133-144). J.Thiele "Uber Nitrosoguanidin" ; http://www.sciencemadness.org/talk/viewthread.php?action=att...

2. Justus Liebig's Annalen der Chemie, Volume 270, Issue 1-2 (p 1-63) J.Thiele "Uber Nitro And Amidoguanidine" ; http://www.sciencemadness.org/talk/viewthread.php?action=att...

Corresponding English translations:

3. http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleFo...
page 389 J. Thiele Nitrosoguanidine

4. http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleFo...
page 1295 J.Thiele Nitro and Amidiguanidin

guanyl azide (diazoguanidine) revisited

Rosco Bodine - 17-7-2008 at 10:13

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:D

@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)
This file has been downloaded 1578 times


Engager - 18-7-2008 at 03:15

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)
This file has been downloaded 1229 times


Rosco Bodine - 18-7-2008 at 20:09

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:D

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)
This file has been downloaded 1469 times


Axt - 20-7-2008 at 23:31

"1 H-Tetrazolo[1,5-d]tetrazole: A solution of sodium nitrite (0.01 mol) in water (5 ml) was added dropwise to a stirred solution of compound diaminotetrazole (0.01 mol) in conc. HCl (5 ml). The reaction mixture was kept at 0°C for 30 min and the precipitated solid was filtered, washed with water, dried and crystallized from ethanol. Yield 0.6 g (55%), m.p. 210°C." J. Ind. Chem. Soc. 82, 172-174, (2005) [attached].

Attachment: Use of 1,5-diaminotetrazole in the synthesis of some fused heterocyclic compounds.pdf (263kB)
This file has been downloaded 1660 times


Ritter - 30-7-2008 at 08:22

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]

5-Aminotetrazole.gif - 17kB

Engager - 30-7-2008 at 08:55

Synth of DAT has been attempted using procedure i've mentioned somethere above, however some serious difficulties has been encountered. Insoluble product after boiling tends to be rock hard, and if it contains significant ammount of lead azide this could result in hazard situation then attempted to separate this black sludge from glass vessel. Liquid was decanted and insoluble black residue on walls of flask was successfully destroyed without problems by long standing with weak nitric acid. Particles of PbS are very small and it is very hard to filter them completely, to get transparet solution whitch has dark orange color.

Another more serious problem has arisen on evaporation of DMF. At boiling water bath in vacuum made by water-stream vacuum pump, DMF is not destilled with any visible speed. Removal of DMF at ordinary pressure is imposible in this case because DMF boiling point is to close to DAT decomposition temperature. It is quite interesting to know that is b.p of DMF in vacuum about ~50 mm. Hg. How to solve solvent removal problem?

Ritter - 30-7-2008 at 12:19

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]

B.gif - 20kB

Engager - 30-7-2008 at 15:06

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]

Rosco Bodine - 30-7-2008 at 17:30

Maybe filter and dry the precipitate gotten from dilution with water.
Redissolve in alcohol and precipitate with methylene chloride to see if crystallization occurs.

I think you probably have DAT there as the white
precipitate from dilution with water, pure enough for use
as is, for further reactions like nitrosation as Axt described, or for permanganate oxidation
and possible polymer formation as Ritter speculated above.

@Ritter
Please edit your attached images width to ~600 pixels so the images don't foul up the text formatting
on the page. The width will be the first pixel dimension stated in the image properties, to resolve
any confusion about which number there specifies the width.

[Edited on 30-7-2008 by Rosco Bodine]

Ritter - 30-7-2008 at 17:46

Quote:
Originally posted by Rosco Bodine
@Please edit your attached images width to ~600 pixels so
the images don't foul up the text formatting on the page.

[Edited on 30-7-2008 by Rosco Bodine]


??? 810x685 pixels for that image. Looks fine to me. Do you prefer 600x600 or ?x??

The_Davster - 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.

Engager - 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]

The_Davster - 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)
This file has been downloaded 2124 times


Swany - 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]

The_Davster - 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]

Swany - 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]

Swany - 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.

Engager - 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.

Rosco Bodine - 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.

Swany - 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.

User - 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

Engager - 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]

Rosco Bodine - 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.

PHILOU Zrealone - 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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hokk - 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.

Engager - 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]

Engager - 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?

PHILOU Zrealone - 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]

Engager - 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]

Microtek - 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.....

User - 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?




Engager - 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.

PHILOU Zrealone - 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]

Attachment: DNOAN.pdf (12kB)
This file has been downloaded 968 times

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

User - 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.

Engager - 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.

Engager's Tetrazole Paper as pdf

Rosco Bodine - 20-9-2009 at 05:17

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]

Engager - 14-10-2009 at 08:00

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

5 phenyl Tetrazole

franklyn - 15-10-2009 at 00:17

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...

.

5 phenyl Tetrazole.GIF - 8kB

Rosco Bodine - 15-10-2009 at 06:51

So....what are the prospects for an attempted synthesis of guanylazide fulminate :D

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]

franklyn - 16-10-2009 at 09:02

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.

.

Rosco Bodine - 16-10-2009 at 13:49

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.

franklyn - 16-10-2009 at 20:00

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.

.

Rosco Bodine - 8-11-2009 at 19:11

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 :D
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 3339 times


franklyn - 7-12-2009 at 10:38

http://www3.interscience.wiley.com/journal/120748224/abstrac...

.

franklyn - 9-2-2010 at 23:44

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.

.

The_Davster - 15-2-2010 at 12:25

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...:P :o )

Taoiseach - 17-2-2010 at 01:19

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.

franklyn - 17-2-2010 at 17:13

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...


Pared down to omit cookie demand.

.

Engager - 18-2-2010 at 04:39

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]

Taoiseach - 18-2-2010 at 06:27

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 ;)

Rosco Bodine - 18-2-2010 at 16:20

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...:P :o )


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 1102 times


The_Davster - 18-2-2010 at 22:16

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]

Rosco Bodine - 19-2-2010 at 06:03

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 :P

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:D :cool: And we are soooooo flattered ...gee does this mean we can keep our extra large "chemistry sets" ? :D

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]

wolfman - 18-3-2010 at 23:17

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.




Azotetrazoleate

mnick12 - 18-6-2010 at 19:26

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.

Engager - 23-6-2010 at 04:03

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.

mnick12 - 23-6-2010 at 12:13

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.

Microtek - 24-6-2010 at 04:28

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]

Taoiseach - 4-7-2010 at 08:27

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?

Taoiseach - 9-7-2010 at 04:09

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.)

Taoiseach - 25-7-2010 at 04:52

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?

Engager - 25-7-2010 at 15:11

I have no idea what can go wrong, but i know that products of this reaction are very dependent on pH of reaction mixture and temperature. Mechanism of this reaction, and photos from my experiment can be found earlier in this thread: http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a.... However, your may examine references by yourself, to get more understanding about process chemistry and attempt to locate your problem point. Excellent review of aminoguanidine chemistry by Lieber & Smith is attached to this message (topic you may be interested at is in pages 232-243). Also i want to remember you that some substances have difficulties in crystallization, as you can see on the photos i've provided from my experiment in pdf and earlier in this thread salt formed is in form of agglomerates witch are microcrystaline or even amorphous, so tendency to difficult crystallization is evident. I remember some long time ago i tried to make some 5-ATZ by Schtolle's method (from dicyandiamide and hydrogen azide) and was very disappointed then after week of standing no product crystallized and i thought that experiment was a failure, but then i accidentally applied glass/glass friction in this solution i was very surprized, because product suddenly crystallized in excelent yield. Solution was greatly supersaturated because of low solubility of 5-ATZ in water, but it not crystallized spontaneously for a week! Pure chemicals, absence of dust, absence of uneven regions in reaction flask are aiding supersaturation greatly. So try to force crystallization by friction of glass rod on the side of reaction flask (below liquid of course) and wait for some more time to make sure you got nothing precipitated. Can you post photo of reaction mixture after standing so i can watch for difference with solution i got from my experiment?

Attachment: Chemistry_of_Aminoguanidine_And_Related_Substances.pdf (975kB)
This file has been downloaded 1054 times



[Edited on 25-7-2010 by Engager]

Taoiseach - 25-7-2010 at 23:33

Rubbing with a glass rod to force crystallization has been tried but to no effect. Comparing your pictures with the solution I obtained it is obvious that it is a much paler yellow. The first time I tried it according to your instructions, there were very very few crystals on the bottom which closely resembled the coarse agglomerates in your picture. So some DATZ must have formed. Also the solution was a much darker yellow, just like in your picture. This time the solution ist much lighter in color, which might be to the lower temperature. I kept the temperature 14-16°C and after the reaction was over, the solution stayed at 15°C for 30 minutes. No N2 or heating was observed. I then started to swirl the flask and it immediatly started foaming and a lot of gass was produced. It also heated up several degrees. This only happened when the flask was swirled; no reaction seemd to take place when it stands still.

The aminoguanidine carbonate is p.a. material from a chemical supplier. Only the acetic acid and sodium acetate are technical grade. The instructions never say wether the anhydrous or trihydrate salt is required, so yes the pH could be wrong.

Do you know the "ideal" pH for this reaction? I might try neutralizing some of the acetic acid with sodium bicarbonate.

Also I wonder if the diazoaminotetrazolic acid is stable under prolonged boiling.



[Edited on 26-7-2010 by Taoiseach]

Inorganic - 31-8-2010 at 09:12

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)?



Engager - 31-8-2010 at 12:28

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]

Rosco Bodine - 31-8-2010 at 23:05

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.


However, it may be possible that hydrazine will react with guanidine splitting off ammonia to give aminoguanidine.
The same mechanism is used in reaction of hydrazine with nitroguanidine to produce nitroaminoguanidine.

If twice the amount of hydrazine is present the product is the diamino derivative, and three hydrazines will yield the triamino derivative.

http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

This reaction may provide a "shortcut" to aminoguanidine via possible reaction of hydrazine directly with guanidine.

One of the polyaminoguanidine salts of particular interest is triaminoguanidine perchlorate which is a fuse sensitive primary and initiating explosive reportedly having high brisance. See attached patent US2929699 Also attached is the similar patent US2929698 regarding the diaminoguanidine compounds which are also energetic.

These compounds are not tetrazoles but reside in a nearby branch of related compounds by virtue of the guanidine and hydrazine reactions.

Also of possible interest is US3293853 which shows a method of obtaining triaminoguandine perchlorate from guanidine perchlorate and hydrazine in isopropanol. The reaction scheme may be adaptable to use of other guanidine salts and other alcohols as well as adaptable to formation of the mono-aminoguanidine and di-aminoguanidine derivatives simply by varying the amount of hydrazine available for the reaction.

Also of possible interest is US3813439 which shows reaction of Calcium Cyanamide in aqueous solution with Hydrazine Nitrate, subsequently converting and precipitating and filtering the Calcium as Carbonate. This process is used for producing Triaminoguanidine Nitrate. However, it is likewise probably adaptable as an alternative method for mono-aminoguanidine or di-aminoguanidine derivatives, by varying the available hydrazine. The value here is for a greater versatility in the use of Calcium Cyanamide. It is very easy to react Hydrazine Sulfate with Calcium Nitrate and filter to obtain a Hydrazine Nitrate solution. Such a process variation may also be helpful for avoidance of the "sludge" and filtration issues which can arise with Calcium Sulfate in other
parts of the reaction, if Hydrazine Sulfate is used differently.
The usual sludge does not seem to form but rather a granular precipitate from the reaction of Hydrazine Sulfate and Calcium Nitrate. So here is a possible alternative manipulation of conditions which may be useful.

Additionally, a patent has recently issued related to some of the previously described "Green Primaries" which were being discussed early in this thread. See US7741353 attached.

Attachment: US2929699 Triaminoguandine Perchlorate Initiating Explosive.pdf (143kB)
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Attachment: US2929698 diaminoguanidine salts.pdf (107kB)
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Attachment: US3293853_EUTECTICS_OF_TRIAMINOGUANIDINE_P.pdf (262kB)
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Attachment: US3813439_TRIAMINOGUANIDINE_SALTS.pdf (154kB)
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Attachment: US7741353_Lead_free_primary_explosives.pdf (67kB)
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Triaminoguandine Perchlorate is something which caught my notice a few years ago. Check the date on the last post on the following page.
http://ysatel.net/ftp/roguesci/www.roguesci.org/theforum/arc...

[Edited on 2-9-2010 by Rosco Bodine]

Triaminoguanidine nitrate synthesis kinetics

Rosco Bodine - 2-9-2010 at 10:00

Attached is a journal article which studies some of the reaction kinetics that are applicable in one reaction scheme for synthesis of triaminoguanidine nitrate. The study is limited to one reaction system, and provides some insight into the reaction, but is not very helpful in shedding light on the intermediate reactions for the mono-aminoguanidine and the di-aminoguanidine, nor does it explore alternative methods.

There is some parallel I would think for observations made with respect to the hydazinolysis of nitroguanidine to form nitroaminoguanidine, and the general reactions involving hydrazinolysis of guanidine, and vice versa.

Kinetics of triaminoguanidine nitrate synthesis

Chan Yuan Ho, Tai Kang Liu, Wen Hai Wu
Ind. Eng. Chem. Res., 1989, 28 (4), pp 431–437
DOI: 10.1021/ie00088a010
Publication Date: April 1989

Attachment: Kinetics of triaminoguanidine nitrate synthesis.pdf (770kB)
This file has been downloaded 1441 times


Taoiseach - 2-9-2010 at 13:32

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.

mgdatz.jpg - 10kB

[Edited on 2-9-2010 by Taoiseach]

Here's an interesting paper

Rosco Bodine - 2-9-2010 at 18:16

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 :D 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 1410 times


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

Engager - 3-9-2010 at 01:27

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]


Diazoaminotetrazolates and azotetrazolates are significantly less powerful explosives then for example 5-nitro and 5-azidotetrazolates, however they also form nasty explosive salts with heavy metals - for example try silver azotetrazolate. Anyways azotetrazole is not much of interest by itself - it is useful as intermediate product for some other good derivatives such as 5-azidotetrazole or isocyanogen tetraazide compounds, some 5-hydrazotetrazole complex derivatives are also of interest since they poses high sensitivity vs laser. As it comes to 5-nitrotetrazolates they have behaviour somethat similar to heavy metal azides, they explode very violently. Remember that explosive properties of tetrazoles are very dependant on nature of group attached to carbon atom at 5 position and from cations in the salts. Some Na,K hydrated salts may behave as you described, then some heavy metal salts (Hg, Cu, Ag) can explode underwater and some even spontaneously.

[Edited on 3-9-2010 by Engager]

mnick12 - 19-9-2010 at 17:59

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.


5-atz.bmp - 697kB
keep in mind that is only 350mg.

Rosco Bodine - 29-9-2010 at 05:07

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...:P :o )


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


@The Davster

With regards to what we were discussing a few months ago, it would seem possible that more specifically what we are talking in circles around but not quite explicitly stating, is that there is probable optical activity which may be found as a dextro or a levo or a dextro-levo (dl-racemic) isomeric forms for certain of these tetrazoles.

Mention of biguanide recently has interest parallel with guanyl azide, triaminoguanidine and guanidine with regards to the perchlorates and here is the link to the biguanide thread
http://www.sciencemadness.org/talk/viewthread.php?tid=10829#...
Possibly also of interest is an expedient method for sodium perchlorate which could be useful for double decomposition or other reactions in pursuit of perchlorate derivatives. I found a patent procedure describing thermal decomposition of sodium chlorate to sodium perchlorate followed by extraction of the sodium perchlorate by acetone. The sodium chlorate precursor is relatively easily gotten by thermal disproportionation of ordinary bleach or electrolysis of sodium chloride using graphite or mmo anodes. So here attached is a thermal decomposition method for obtaining modest quantities of perchlorate, US3151935 Thermal Conversion of Sodium Chlorate to Perchlorate.

An easier and less extreme conditions method for conversion of chlorate to perchlorate in about 30% yield via heating with ordinary concentration HNO3 is described in the following thread http://www.sciencemadness.org/talk/viewthread.php?tid=11849&...

Attachment: US3151935 Thermal Conversion of Sodium Chlorate to Perchlorate.pdf (243kB)
This file has been downloaded 1313 times

[Edited on 29-9-2010 by Rosco Bodine]

Rosco Bodine - 7-10-2010 at 13:32

2,4-dinitrobenzenediazonium perchlorate would likely be compatible in mixture with triaminoguanidine perchlorate or guanyl azide perchlorate and perhaps may even form double or multiple salts of interest as energetic materials. In parallel with the possibility of compatible mixtures or adduct or double / multiple salts with the guanidine / "tetrazole vicinity" related perchlorate compounds, it is also possible that similar compatibility may exist towards other organic perchlorates including Guanidine Perchlorate, Biguanide Diperchlorate, as well as many other perchlorates of a non-guanidine relation, such as Methylamine Perchlorate, Betaine Perchlorate, Nitrocholine Perchlorate, and possibly others. By virtue of the common perchlorate component, there should be good chemical compatibility, with no attendant problems of organic perchlorate / organic nitrate "transesterfication" or double decomposition as could occur involving mixtures of perchlorate and nitrate or nitroester compounds. A parallel compatabilty may also exist for (mono) 3-nitrobezenediazonium perchlorate as I am hypothesizing for the 2,4-dinitrobenzenediazonium perchlorate.

There is a thread regarding the 2,4-dinitrobenzene diazonium perchlorate and 3-nitrobenzenediazonium perchlorate including synthesis of the nitroaniline and dinitroaniline precursors
http://www.sciencemadness.org/talk/viewthread.php?tid=3681&a...

It would seem likely that there are possible combinations among these energetic perchlorates which would be useful as detonators, having desirable properties in regards to storage stability, performance, and reasonable economy.

[Edited on 8-10-2010 by Rosco Bodine]

AH-Poster - 17-10-2010 at 12:43

There is also 1,5-Diamino Tetrazole.
https://sites.google.com/site/energeticchemical/diamino-tetr...

5-DinitroMethylTetrazole also exists. It can actually be made using DADNE is a precursor, although better routes exist.
https://sites.google.com/site/energeticchemical/5-dinitromet...

These two compounds together would form an interesting adduct/ salt, since the first acts like a base and the second as an acid.

[Edited on 17-10-2010 by AH-Poster]

Rosco Bodine - 21-10-2010 at 09:04

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]


I am curious about the original article regarding the second synthesis described on the page linked above. Could you please identify the reference.

Edit: never mind, I found it. You simply copy and pasted the synthesis for thiosemicarbazide from this forum
http://www.sciencemadness.org/talk/viewthread.php?tid=12995



[Edited on 21-10-2010 by Rosco Bodine]

Rosco Bodine - 21-10-2010 at 13:01

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]


In earlier discussion about the possible synthesis routes for aminoguanidine, desulfurization of thiourea was mentioned, and a suggestion was made by me that sodium zincate could possibly be useful. I will need to look at those reactions and structures again, but it would appear there may be worth considering other parallels of reactivity for cyanamide and aminocyanamide to see if there are any interesting analogues. Reportedly the diazotization schemes for aminocyanamide are dangerously pH sensitive (and probably concentration and temperature sensitive) as eight laboratory explosions were reported while trying to identify the proper reaction conditions. It may be an idea worth experimentation to determine if a simultaneous desulfurization and diazotization is possible via reaction with strontium nitrite. Desulfurization alone might be possible by reaction with strontium nitrate. These are purely ideas and no experiments or references have been seen by me concerning these possible uses of strontium compounds.

Interesting file for test data from the following link

http://www.serdp.org/content/download/6513/86128/file/PP-136...

See US7592462 attached

See Hirlinger research paper attached

See essay explosives attached

Diaminotetrazole Chloride article attached

Attachment: essay explosives.pdf (1.2MB)
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Attachment: US7592462_Explosive_complexes.pdf (142kB)
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Attachment: Hirlinger research paper.pdf (789kB)
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Attachment: Diaminotetrazole Chloride.pdf (283kB)
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[Edited on 22-10-2010 by Rosco Bodine]

almaz - 21-12-2010 at 08:30

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.

Hydrazinium - 6-1-2011 at 13:47

<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?

zhanghaodong - 23-2-2011 at 02:24

:mad: 擦的 果然是疯狂的东西 5AT硝酸盐不可小视……

quicksilver - 23-2-2011 at 11:29



"英文水平太低 有中国的疯子们么?"


保留尝试! 某人将回答。我们有中国成员。

The_Davster - 23-2-2011 at 23:47

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?


Not sure about chloromethane, but MeI or Me2SO4 methylates to a mix of 1 and 2 methyl aminotetrazoles.

Ethyl bromide does similar.

Rosco Bodine - 24-5-2011 at 01:23

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 :D

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

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

Jimbo Jones - 29-5-2011 at 01:46

Direct hydrazine sulfate & calcium nitrate reaction will need too much water. Is there any way to convert the sulfate to more soluble salt?

P.S.

By the way Rosco, is it safe to perform your hydrazine sulfate synthesis under ordinary kitchen aspirator?

Rosco Bodine - 29-5-2011 at 11:26

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 :D

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]

Jimbo Jones - 30-5-2011 at 00:21

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.

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