Sciencemadness Discussion Board

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

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Formatik - 6-7-2012 at 15:00

Quote: Originally posted by fenolazul  
... I wish all the information possible about acid copper 5-Nitrotetrazolate , please.


Engager was quite modest initially when talking about its sensitivity, but he's an expert who knows how to handle it. Also Engager's great work, Energetic derivatives of tetrazole, in the prepublication section describes the compound a bit more. Some answers to your questions can also be found in my previously mentioned commentary:

Characterization of some tetrazole compounds:
http://www.sciencemadness.org/talk/files.php?pid=225372&...
(again, ignore comments on mercury diazoaminotetrazolate's power)

CuNT is as indicated very impact and friction sensitive. In fact, Klapoetke has said it appears to be more impact sensitive than lead azide. I agree. Hammer blows aren't needed. A pestle weighing a few grams falling from a few centimeters on some crystals can detonate it.

I don't know about dead pressing, and I'm not sure on long term storage. I wouldn't chance it. What if a large crystal forms?

I think you've made too much of a compound you know very little about, especially a primary. I would recommend to dispose of it. Nitrotetrazoles are primaries on steroids. Milligrams can blow off fingers, the amount you made can blow up rooms.

[Edited on 6-7-2012 by Formatik]

fenolazul - 7-7-2012 at 11:30

Quote: Originally posted by Formatik  
Quote: Originally posted by fenolazul  
... I wish all the information possible about acid copper 5-Nitrotetrazolate , please.








By its nature acidic (Ph about 2), once synthesized Copper (II) nitrotetrazolate (CuC3HN15O6.(H2O)n, CuNTZ), storing wet and in permanent contact with distilled water, this primary explosive it is stable for long periods of time, even years?


...or for long periods in closed containers and always wet can be decomposed by itself and cause an accidental detonation? :o

What if WET forms a crystal or large particles? can break safely?

Someone else can make your experience? Perhaps (as noted Formatik) I have synthesized in house too much product and now I'm nervous and restless.



[Edited on 7-7-2012 by fenolazul]

Formatik - 7-7-2012 at 18:32

The compound should make you nervous. If it doesn't you are doing something wrong.

I would think it is stable longterm. Again, I don't know for sure. But that's not really my big concern with storage. Lead azide, if it forms large crystals these could detonate. Considering the material is more sensitive than lead azide, if this were to form a large crystal on storage it could be worse. This can manifest a spontaneous detonation through internal crystalline stress or by mechanical breaking. But, I don't know enough about this material to tell you whether it does this or not.

Cupric nitrotetrazolate is not really a type of material that is stored from what I gather, it is used as an intermediate for other energetics (especially initiators which are less sensitive and better). In that process it is kept wet to reduce sensitivity. It is typically converted to sodium nitrotetrazolate which is also insensitive to hammer blows as a regular hydrate (might still have some static hazard).

fenolazul - 8-7-2012 at 08:50

Quote: Originally posted by Formatik  
I would think it is stable longterm. Again, I don't know for sure. Cupric nitrotetrazolate is not really a type of material that is stored from what I gather, it is used as an intermediate for other energetics (especially initiators which are less sensitive and better).


@Formatik:

here more pictures of acid salt CuNTZ primary explosive and precursor. With the sincere hope that those experts who have made ​​this thread (Engager, Rosco Bodine, The Davster, PHILOU Zrealone, Hokk, Sobrero, Microteck, Chemoleo, User, Franklyn, Swany, JohnWW, Nick F, oket, hokk, quick silver, 497, Pdb, Ritter, Axt, and long etc...) as soon as possible they clarify our doubts concerning to properties, storage, safety and handling of this potent compound, in dry and wet form.

I hope, Formatik... :o

NOTE: Ph around 3 Ok?

IMG417.jpg - 154kB IMG418.jpg - 144kB IMG419.jpg - 182kB IMG424.jpg - 162kB IMG425.jpg - 165kB

[Edited on 8-7-2012 by fenolazul]

IMG423.jpg - 91kB

[Edited on 8-7-2012 by fenolazul]

pdb - 10-7-2012 at 06:59

As a basic rule, you should never concentrate more than 1 gr or less of any primary in the same place, and avoid keeping it for years. Your 73 gr storage, whether dry or moist, is insane.

As CuNT is not widely used, do not expect to find as much information in literature as with century(ies)-known compounds like MF and LA. However, if you die from your 73 gr, it will be a valuable piece of information (in fact a confirmation of the rule) for the community...

Nick F - 18-7-2012 at 08:38

I think if I were you I would add it slowly to a dilute sodium hydroxide solution. This would form a dilute sodium nitrotetrazole solution, which should be fine in storage, and copper oxide which can be filtered off. And then use your sodium nitrotetrazole solution to ppte silver nitrotetrazole or whatever in small quantities as you need it.

The_Davster - 19-7-2012 at 04:50

Just remember, it is far less painful for everyone involved to handle wet CuNT instead of dry.

:o;)

liquidlightning - 25-7-2012 at 17:31

Har har, I see what you did there. And fenolazul, be very careful. Scares me just thinking of storing that much prim explosive.

More investigation into guanidine-nitrous acid

Boffis - 3-10-2012 at 17:59

In a series of earlier posts to this thread (October 2011 or there abouts) I investigated a published claim that guanidine reacts with nitrous acid to give 5-aminotetrazole. A series of experiments however, demonstrated fairly conclusively that this was not the case though unidentified white or creamy yellow products did resulted. At the time these products were fully investigated though there was some evidence that nitrosoguanidine was present in the products.

Since then I have been able to investigate the product further and following careful recrystallization I have managed to isolate three identifiable substances and investigate them. It has not been possible to measure the amount of each compound produced in each experiment because of the amount “lost” to the mother liquor during crystallization. However, it is now clear that in a weakly acid solution acidified with acetic acid that the main products are nitrosoguanidine and surprisingly nitroguanidine. The presence of the former has been reported before from a similar reaction in dilute sulphuric acid but the presence of the later was not expected. It is worth noting that this compound was most abundant in solution that had stood for 4 or 5 days suggesting that it forms slowly probably by oxidation of the nitrosoguanidine by excess nitrous acid/nitrogen oxides.

In the more acid solutions containing free hydrochloric acid the main product appears to be urea in spite of earlier tests such as hydrolysis to ammonia indicating that it was absent. A little nitrosoguanidine was present causing the yellowish tint to the product and a possibly a trace of nitroguanidine.

An ammoniacal solution of nickel acetate gave a red precipitate with the nitrosoguanidine but the reaction products from some experiments, though yellow, only gave a brown precipitate. The amount of brown precipitate was too small to separate from the filter paper and investigate so it is not clear whether this is due to the presence of yet another product or simply nickel III oxide hydrate. No cyanamide or is dimer dicyandiamide could be detected in any of the solid products.

The nitroguanidine and nitrosoguanidine were compared to samples of these products prepared from guanidine nitrate via sulphuric acid dehydration and reduction of part of the resulting nitroguanidine to the nitroso compound with zinc dust and ammonium chloride, both syntheses are described elsewhere in this and related threads.

During the coarse of this work I attempted the synthesis of 5 aminotetrazole by my preferred route from cyanoguanidine and Na azide but decided to try a modification whereby the solid azide was not isolated but generated as an aqueous solution and used direct. The reaction failed but it did generate an interesting orange red product. I report back on this one with some photographs shortly.

Not 5-aminotetrazole either

Boffis - 6-10-2012 at 17:20

I have used the method of producing 5-aminotetrazole outlined in US patent 5451682 on several occasions with complete success. This preparation involves the reaction of sodium azide with dicyandiamide in the presence of boric acid. While dicyandiamide is not easily obtained it can be purchased of the internet freely and cheaply. The same is not true of sodium azide which is hard to obtain and expensive and for most amateurs must be synthesized. There are several methods of preparing alkali azide but the most widely used synthesis is to react hydrazine with an alkyl nitrite in the presence of sodium hydroxide. There are several variations on the basic synthesis but obtaining solid sodium or potassium azide is always tedious and it would be helpful if the isolation of the solid could be avoided, in part because the reaction could then be carried out in and aqueous medium instead of an alcoholic one.

It is reported in an English patent that if a lead salt is added to a mixture of hydrazine nitrate and sodium nitrite lead azide is precipitated. Since no lead is to be introduced into the preparation of aminotetrazole the more readily available hydrazine sulphate was used in this experiment. The product in this case should be hydrazoic acid and sodium hydrogen sulphate:

N2H4.H2SO4 + NaNO2 = HN3 + NaHSO4 + 2H2O

Since hydrazoic acid is not a strong acid the presence of a large amount of bisulphate salt may cause loss of highly poisonous hydrogen azide gas from the solution during manipulation so that after mixing the reaction mixture is neutralised with two molar equivalents of sodium hydroxide. It was decided to add half the sodium hydroxide at the beginning to liberate free hydrazine.

The ultimate goal is to use the resulting solution directly in the preparation of 5-aminotetrazole.

Experimental
Stir 26.01g of hydrazine sulphate into 175ml of water and add 20ml of 10M sodium hydroxide solution and slowly add to the clear solution 13.80g of sodium nitrite in 20ml of water. The remaining half of the sodium hydroxide was not added as the solution did not appear particularly acid.

The solution produce above was placed in a 500ml round bottom flask along with 33.4g of dicyandiamide (cyanoguanidine) and 18.56g of boric acid. The mixture was warmed and swirled around until most of the dicyandiamide had dissolved, a piece of broken porcelain added and the flask then placed in a heating mantle with a reflux condenser attached. The mixture was heating until boiling and then refluxed gently for 23 hours, yielding a pale yellow liquid.

After refluxing the solution was poured into a 1 L beaker and acidified with 60ml of 28-30% hydrochloric acid, the red orange precipitate that formed was filtered at the pump. The precipitate is fine, filtered slowly and difficult to wash and dried after only limited washing. The dried material was re-dispersed into water filtered heated to 70°C, cooled to room temperature, filtered and dried. The yield of a bright orange red amorphous powder was 8.57g. It is clearly not 5-aminotetrazole. The compound is insoluble in cold water, alcohol, isopropanol, toluene and dichloromethane, it is very slightly soluble in boil water and separates out on cooling as a fine red powder. It is soluble in sodium hydroxide forming a dark brown solution that precipitates a brown amorphous product when acidified. It is weakly energetic when heated above its melting point.

The product has not yet been investigated but its weakly energetic nature and its deep orange red colour suggest an azo compound of the nature of azo-bis-formamide H2N.C=O.N=N.C=O.NH2.

The cause of the unexpected reaction product may be the failure to completely neutralise the original azide solution which meant in effect the solution was boiled far too long and any tetrazole derivative that might have formed was decomposed or it may have been due to the presence of unreacted hydrazine and nitrite in the starting mixture. Further experiments will be conducted when time permits using the following modification:



  1. After mixing the hydrazine salt and sodium nitrite raise the temperature to a gentle reflux very briefly and cool.
  2. Completely neutralise the solution completely as was originally intended before adding the cyanoguanidine and boric acid. Alternatively the boric acid can be omitted and the reaction mixture refluxed for a short period of time.


I have just purchased some melting point apparatus off ebay so when I get it working I'll investigate the m.p.'s of this and the products described in the previous post.


5 after acidifing.jpg - 29kB Precipitate on acidifying with HCl



6 final product after 2nd filtration.jpg - 22kB Final product still moist after 2nd filtration

[Edited on 7-10-2012 by Boffis]

[Edited on 7-10-2012 by Boffis]

PHILOU Zrealone - 22-10-2012 at 08:45

Quote: Originally posted by Nick F  
I think if I were you I would add it slowly to a dilute sodium hydroxide solution. This would form a dilute sodium nitrotetrazole solution, which should be fine in storage, and copper oxide which can be filtered off. And then use your sodium nitrotetrazole solution to ppte silver nitrotetrazole or whatever in small quantities as you need it.


Nice idea.
Although if you put Na hydroxyde in the mix, the hydroxyde will not turn into oxyde. You will get turquoise blue Cu (II) hydroxyde precipitate and not the black Cu (II) oxyde.
Cu(NTZ)2 (s) + 2NaOH --> Cu(OH)2 (s) + 2 NaNTZ
Sole problem, both the precipitates Cu(NTZ)2 and Cu(OH)2 will almost look the same color...

[Edited on 22-10-2012 by PHILOU Zrealone]

The_Davster - 22-10-2012 at 22:51

Quote: Originally posted by PHILOU Zrealone  
Quote: Originally posted by Nick F  
I think if I were you I would add it slowly to a dilute sodium hydroxide solution. This would form a dilute sodium nitrotetrazole solution, which should be fine in storage, and copper oxide which can be filtered off. And then use your sodium nitrotetrazole solution to ppte silver nitrotetrazole or whatever in small quantities as you need it.


Nice idea.
Although if you put Na hydroxyde in the mix, the hydroxyde will not turn into oxyde. You will get turquoise blue Cu (II) hydroxyde precipitate and not the black Cu (II) oxyde.
Cu(NTZ)2 (s) + 2NaOH --> Cu(OH)2 (s) + 2 NaNTZ
Sole problem, both the precipitates Cu(NTZ)2 and Cu(OH)2 will almost look the same color...

[Edited on 22-10-2012 by PHILOU Zrealone]


This is the literature procedure. Cu(OH)2 is deep blue whereas CuNT is blue green, the color change on adding NaOH is easily seen. By keeping the solution at around 70C for an hour the hydroxide turns into the oxide which can be filtered leaving a pure solution of NaNT

PHILOU Zrealone - 23-10-2012 at 03:13

Quote: Originally posted by The_Davster  

This is the literature procedure. Cu(OH)2 is deep blue whereas CuNT is blue green, the color change on adding NaOH is easily seen. By keeping the solution at around 70C for an hour the hydroxide turns into the oxide which can be filtered leaving a pure solution of NaNT


OK I stand corrected, thanks for that... :)
I did'nt knew Cu(OH)2 could turn while moist into CuO at such a low temperature. Apparently Cu(OH)4(2-) formed by exces NaOH plays a catalytic role to get this at such a low temp as 70°C. :o

4-amino-3-(5-tetrazolyl)-furazan and tetrazole-5-carboxylic acid

Boffis - 24-10-2012 at 18:30

I was reading a recent article about azole based energetic salts in Chemical Reveiws (Azole Based Energetic Salts, Haixiang Gao and Jean'ne M Shreeve, Chen Rev., 2011 p7377 (ACS Publications)) and came across some tetrazole derivatives that I had not come across before; 4-amino-3-(5-tetrazolyl)-furazan and tetrazole-5-carboxylic acid.

The synthesis of the former is complex but "do-able", the main problem is once again the availability of sodium azide though I have recently seen this on ebay! It is prepared from malononitrile through the reaction first with sodium nitrite and HCl and then hydroxylammonium chloride and NaOH to give 4-amino-5-formamidoximyl-furazan. This compound on oxidation with lead dioxide in glac. acetic acid gives 4-amino-5-cyanofurazan which is then reacted with Na azide in DMF to give the required product. I'll track down the original reference and report further.

4-amino-3-(5-tetrazolyl)-furazan is a fairly strong dibasic acid and forms energetic salts with both metallic cations and organic bases, these are discussed at length in the article cited above. Since this compound has a free amino group I can't help wondering if you could oxidise it with say K permanganate to the bis azo compound as with other aminofurazans.

The tetrazole-5-carboxylic acid is simpler but requires both Na azide and a rather obscure alkyl cyanoformates. However, there may be a simpler though perhaps less efficient method by reacting Na azide with acetonitrile to produce 5-methyltetrazole and then oxidizing the methyl derivative with K permanganate to the corrresponding acid. This compound also functions as a dibasic acid and it's metallic salts were discuss as colourant for pyrotechnics, particularly the Sr, Li and Cu salts too.

The above reference also contains a good deal of quantitative data about 5-nitrotetrazolate salts and 5-nitriiminotetrazolate salts discuss in this thread above.

Microtek - 26-10-2012 at 11:18

I have also used that process (CuNTz*HNT2 + NaOH -> CuO + NaNTz) and found it very satisfactory. However, in connection with experiments with some of the green primaries, I have experimented with a slightly different method:

The CuNTz*HNT2 is first dissolved in water at ca. 90 C with stirring. Then, with continued stirring, aqueous ammonia is added. This precipitates Cu(OH)2 which is instantaneously decomposed leaving free-flowing CuO as the sole precipitate. The decomposition of copper hydroxide under these conditions is fast enough that it happens between drops of ammonia water, ensuring that the mix is never gelled by Cu(OH)2.
In addition, an excess of ammonia is no problem since it can be removed by evaporating the water after filtering off the CuO.
The ammonium nitrotetrazolate produced by this method is more versatile IMO than NaNTz as it can be used for some things that NaNTz can not, and can be easily converted to the sodium analog, should the need arise.

Note however, that I don't have any sensitivity data on NH4NTz; I know that NaNTz detonates with great violence when heated over a flame (which NaN3 does not as far as I'm aware).

The_Davster - 26-10-2012 at 12:17

Quote: Originally posted by Microtek  

Note however, that I don't have any sensitivity data on NH4NTz; I know that NaNTz detonates with great violence when heated over a flame (which NaN3 does not as far as I'm aware).



NH4NT hemihydrate is 4 J for impact sensy., so kinda like PETN. NaNT2H2O is 20 J IIRC
from here: http://pubs.acs.org/doi/pdf/10.1021/ic800353y

I must say, I enjoy both profusely. :) :P ;)



I like your route better for making NH4NT, less Ph control needed than for the sodium salt, and the lit method is gassing an EtOAc soln. of HNT with ammonia. works great, but this is simpler.

Have you made DBX1 yet microtek? it is great stuff!

[Edited on 26-10-12 by The_Davster]

almaz - 27-10-2012 at 09:01

Hi all! the preparation of 5-ATZ of dicyandiamide solution slightly changes color (orange) when pouring HCL. Is this normal?

[Edited on 27-10-2012 by almaz]

Boffis - 27-10-2012 at 09:20

Hi almaz

If you are using pure sodium azide and white laboratory grade dicyandiamide at the end of reflux a slight orange colour is sometime observed but this this disappears when the mixture is acidified. If you are using homemade azide or the dicyandiamide for plastic and resin manufacture (pale brownish bread-crumb like material) then a distinct yellow colour which turns orange when acidified occurs and the crystals are creamy coloured. This can be alleviated by recrystallising the dicyandiamide from water with decolourizing carbon added. What I discribed above was unusually dark coloured and the orange product appears to be the main product. I this this was due to the presence of much unreacted hydrazine and nitrite ions.

The last time I did the dicyandiamide-sodium azide-boric acid reaction I used high quality dicyandiamide and boric acid and recrystallized sodium azide and got 97% yield of a very high quality pure white product.

almaz - 27-10-2012 at 10:14

I use pure dicyandiamide and unknown quality azide. By the way when I did the first time - leave the mixture on for a very long time (about a month) and still not made ​​a big exit. Why?
and what other nitrogenous compounds can be made from dicyandiamide? And then just as for the 5-ATZ I have no idea where to use it ...

[Edited on 27-10-2012 by almaz]

Boffis - 27-10-2012 at 10:52

If the azide is white and is free from alkali metal nitrites and alkyl nitrites you should be OK. Salt and sodium sulphate don't interfer with the reaction but the reaction requires the presence of an acid such as boric acid or ammonium chloride. It also requires 24 hour refluxing! When the reaction is over and acidified it tends to supersaturate rather than crystallize, if no crystals appear after 24 hours stir vigorously with a glass or metal rod making sure you strike the vessel occasionally. This usually triggers crystallization but it can still take another 24 hour or more for full crystallization. Once you have had one lot crystallize you never have the same problem again, the equipment appears to be "innoculated".

This has been discussed extensively before on this thread and I recommend you have a look at the attached patent, this is the source of the method I use most frequently.

There are lots of reactions with dicyandiamide;
With nitriles it gives substituted 1,3,5 triazines
With ammonium nitrate it gives guanidine nitrate
With sulphuric acid biguanide and ammeline

Try the search engine for more

Attachment: 5 aminotetrazole from dicyandiamide 5451682.pdf (146kB)
This file has been downloaded 1302 times

Notes on my attempts based on the this patent

Attachment: 5-aminotetrazole from dicyandiamide.docx (15kB)
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It was an attempt to by-pass the tendious sodium azide preparation that lead to the "orange disaster" described above. I still haven't identified the product.

Rosco Bodine - 2-5-2013 at 04:14

Quote: Originally posted by Boffis  
The product has not yet been investigated but its weakly energetic nature and its deep orange red colour suggest an azo compound of the nature of azo-bis-formamide H2N.C=O.N=N.C=O.NH2.



Excerpt paraphrased from J. THIELE (Annalen, 270, 1-63)
Quote:
Azodicarbonamide, NH2-CO-N=N-CO-NH2 is an orange-red, crystalline powder, very sparingly soluble in hot water, and insoluble in alcohol and cold water. When heated at 180-200", it turns white, with evolution of ammonia, and the residue consists principally of cyanuric acid ; when treated with phenol and concentrated sulphuric acid successively, there is produced a dark-green coloration which becomes yellow on diluting, and green again on adding alkali.


What I have been thinking is there is probably feasible a nitrosation of guanidine to cyanamide possible as reported by Belden occurs in 80% yield, using a scheme that is analogous to the production of R-salt or DNPT via nitrosation of hexamine. When an optimum reaction scheme is found then I believe it is possible to quench the reaction mixture using sodium hydroxide to stabilize the cyanamide in solution as its sodium salt. Possible addition of urea or an ammonium salt would decompose unreacted nitrous acid, leaving a stable solution of sodium cyanamide for use in further synthesis.

To a solution of hydrazine salt or (possibly) in the alternative could be used a hydrazine contributor such as acetone azine (dimethylketazine), to which could then be added the solution of sodium cyanamide which should result in a solution of aminoguanidine. Now a second nitrosation is performed which should convert the aminoguandine to guanyl azide, and this is cyclized by refluxing at appropriate pH to 5-aminotetrazole. I would have to check the references again because I have forgotten the conditions most favorable, but it seemed it was done using ammonia or ammonium acetate or sodium acetate to cyclize the guanyl azide occurring as its nitrate. I think this could all be done as a one pot reaction, but the steps would have to be sequenced and I think the order of addition may be important too, WRT adding the sodium cyanamide to the hydrazine so that it is appearing in excess to the incoming cyanamide and not the reverse scenario. However, a one pot strategy may not work, so in that event a process refinement may be necessary to precipitate the aminoguanidine as its bicarbonate, and then proceed in the known manner from aminoguanidine bicarbonate. pH and order of addition can affect what happens here if I understand this correctly, there is definitely some "algebra" in effect for these type reactions.

It seems probable that a variation on the reaction described in the patent US5451682 could be done using carbamoyl azide instead of sodium azide. In one vessel could be made the cyanamide by nitrosation of guanidine. In a second vessel could be made the carbamoyl azide by nitrosation of semicarbazide or by nitrosation of hydrazodicarbonamide (biurea). The two solutions would then be mixed and the end resulting product should be 5-aminotetrazole.

[Edited on 3-5-2013 by Rosco Bodine]

snooby - 24-5-2013 at 12:29

Hello I am new here and I have a question about obtaining from a solution of Sodium 5-nitrotetrazole. I have prepared a yellow NaNTZ solution, which is 100% the right stuff, because I prepared AgNTZ succesfully with it. But I want to get the pure Crystals. Zo I evaporated the solution on a waterbath until I had wet NaNTZ Crystals. Here starts the problem. If I want to recrystalize it from aceton the Crystals won't disolve.

I think the stuff decompose very quick with high temperatures! So next time I wont gonna recrystalize it bacause of the riskk that the stuff again become useless.

I earlier (the first time I made it) just boiled the solution untill free NaNTZ Crystals apeared, but when the Crystals became visable the problemes started. Does anyone have a good advise about getting the pure Crystals out of the solution?

ps, excuse my frenche, I know there are many errors in my post! Sorry for that.

copper compounds of interest, review and added references

Rosco Bodine - 1-10-2013 at 07:26

Thanks to Dany for the following article attached

Preparation and Explosive Properties of Tetraamminebis(3,5-Dinitro-1,2,4-Triazolato-N^1) Copper(II)

Huynh, M. H. V. & Hiskey, M. A. (2005) Journal of Energetic Materials 23, 27–32

Abstract: The synthesis of tetraamminebis(3,5-dinitro-1,2,4-triazolato-N1)copper(II) is reported along with its physical and sensitivity properties as well as crystal structure. In addition, the detonation velocity and CJ pressure have been determined at 0.5 inch diameter. Los Alamos, NM, USA

Also attached is a related article briefly describing some other metal salts of dinitrotriazole

Earlier discussion in this thread regarding the dinitrotriazole which is obtained from a reportedly high yield reaction between hydrazine dhydrochloride and cyanoguanidine to produce guanazole aka diaminotriazole or DAT which upon reaction with nitrous acid yields the dinitrotriazole.

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

Attached also is US3054800 which describes a 50-50 mixed product of dinitrotriazole and 5-nitrotetrazole from guanazole via Sandmeyer.

Guanazole or diaminotriazole DAT is produced by reaction of hydrazine dihydrochloride with cyanoguanidine.

Such an alternative condition for nitrosation of the guanazole may prove useful as a means of provding a solution possibly useful without separation of the 50-50 mixed product to be used for possible precipitation of a mixed salt, potentially a mixed silver salt or a mixed copper salt, possibly complexed by ammonia, or possibly for obtaining a double salt of different metal salt combinations. It would seem likely that the nitrotetrazole portion of the salt or mixture would tend to make such a double salt or mixture more sensitive and powerful as compared with a salt of the dinitrotriazole alone.

With regards to the mixed tetrammine (or other ammine number of ammonias of complexation) copper salts, the nitrotetrazolate was reported earlier in the thread by Engager
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

The patent referenced by Engager regarding the ammonia complex copper salt shows the compound #4 in Figure 1 and Table 1 and Example 4 of the patent pending attached to the linked post.
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...
Evidently there are stepped levels of specific complexation number of ammonias possible, which results in the hierarchy term used to describe such complexes which are variation ratios forming definite compounds from the same precursors. Also some may be hydrated and others may be anhydrous. It is reasonable to believe possible that the ammonias may number 2, 3, or 4, as stable compounds or as an unstable and volatile transient 6.

A similar complex is identified as being a triamino complex by Klapotke in the article attached as compound #5. However it would be my expectation that this compound would be a tetraammine bis salt structurally analogous to the tetraammine complex of copper with dinitrotriazole. Copper can actually complex with 6 ammonias as a supersaturation, but the hexammine complex is unstable and will lose 2 ammonias being volatile on standing exposed to the air for awhile, and this can be observed for the tetraammine copper perchlorate salt. 4 ammonias tends to commonly be the stable complexation level for copper as 2 seems to be applicable for silver. The color deepens into a dark blue purple for the ammonia complexed copper at the higher 6 level and lightens to a still deep but brilliant blue sapphire color for the tetrammine complex, much like the color of glass that is cobalt blue.

And the tetrammine complex of the dinitrotriazole is reported in the article attached. Both complexes of copper forming under similar reaction conditions from the respective dinitrotriazole and nitrotetrazole make it very likely that the mixed salts or a double salt can be formed directly from the 50-50 mixture product of dinitrotriazole and nitrotetrazole.

Another ammonia complexed copper salt forms from diazoaminotetrazole, which could be a separately added material to possibly form a tertiary composition.
See US2004719 attached. This copper complex salt of diazoamintetrazole was also mentioned earlier in the thread.
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

Attachment: Preparation and Explosive Properties of Tetraamminebis(3,5-Dinitro-1,2,4-Triazolato-N^1) Copper(II).pdf (128kB)
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Attachment: metal salts of dinitrotriazole.pdf (793kB)
This file has been downloaded 1191 times

Attachment: US3054800 50-50 mixed product of dinitrotriazole and 5-nitrotetrazole from guanazole via Sandmeyer.pdf (218kB)
This file has been downloaded 832 times

Also here is a link for an interesting thesis which contains many interesting articles. The file is about 13.9 MB so here is the download link.

http://edoc.ub.uni-muenchen.de/15389/1/Piercey_Davin.pdf

Attachment: US2004719 Copper Ammonium Salt of Diazoaminotetrazole.pdf (190kB)
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Attachment: Less Sensitive Transition Metal Salts of the 5-Nitrotetrazolate Anion.pdf (551kB)
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The diazonium salt of carbamoyl azide may be an interesting cation to examine as a possibility of a non-metallic cation forming energetic salts with various triazole or tetrazole anions. A diazonium azide nitrotetrazole .....yeah riiiight :D
Sounds like it should be right in Klapotke's territory.

http://www.sciencemadness.org/talk/viewthread.php?tid=1987&a...

[Edited on 2-10-2013 by Rosco Bodine]

snooby - 8-10-2013 at 09:49

I'm trying to use my NaCuNT (copper salt of sodium-nitrotetrazolate) instead of toxic lead-azide. My NaCuNT is a light-blue, chalky powder. If heated on a spoon for like 2 seconds, it detonates violently. But when I put it in a drinking-straw for example and press it, it does NOT detonate when it comes in contact with a fuse or some blackpowder.

Some other facts: when I hit some loose powder with a hammer (very strong blow requierd) it detonates. When I put a lighter against it, most of the time the detonation of some of the powder just blows away the rest of the powder. I was wondering if there are some guys (or mayb girls) who are using this primary in their dets and if they can give some advise aabout it

snooby - 8-10-2013 at 09:49

I'm trying to use my NaCuNT (copper salt of sodium-nitrotetrazolate) instead of toxic lead-azide. My NaCuNT is a light-blue, chalky powder. If heated on a spoon for like 2 seconds, it detonates violently. But when I put it in a drinking-straw for example and press it, it does NOT detonate when it comes in contact with a fuse or some blackpowder.

Some other facts: when I hit some loose powder with a hammer (very strong blow requierd) it detonates. When I put a lighter against it, most of the time the detonation of some of the powder just blows away the rest of the powder. I was wondering if there are some guys (or mayb girls) who are using this primary in their dets and if they can give some advise aabout it

Rosco Bodine - 8-10-2013 at 18:09

Azole-Based Energetic Salts, Chemical Reviews, Gao and Shreeve

Attachment: Azole-Based Energetic Salts, Chemical Reviews.pdf (1.6MB)
This file has been downloaded 8105 times

Boffis - 9-10-2013 at 09:30

@ Rosco I posted this reference a year ago and picked out a few do-able syntheses in it but it didn't stir up any meaningful response. Its a great reference, full of data and interesting ideas but some of the statements about methods of synthesis are wrong and you need to refer to the original papers (many of which I have requested through the references section).

Hope you get a better response!

Rosco Bodine - 9-10-2013 at 17:46

@Boffis, are you talking about your post in another thread?
http://www.sciencemadness.org/talk/viewthread.php?tid=21743&...
I missed it but above is the article, since the reference was posted,
Dany sent me a link for the article, and then I reduced the file size enough for it to attach.

You were experimenting with the dicyandiamide, aka cyanoguanidine, so I thought the summary of interesting copper compounds I posted last week
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...
may rouse your curiosity, with regards to the guanazole synthesis involving cyanoguanidine being boiled with hydrazine dihydrochloride. Given that in my improved hydrazine sulfate synthesis using pool hypochlorite and urea, there are modifications possible where the end product desired is not hydrazine sulfate, it had occurred to me that a modification might be chosen such as formation of methyl ethyl ketone azine, separating and hydrolyzing the azine with hydrochloric acid, and distilling off the MEK, leaving hydrazine dihydrochloride for use as a precursor for boiling with cyanoguanidine where the ultimate end product would be guanazole. It could of course also be possible to first obtain the hydrazine sulfate in the usual way and convert it to the hydrazine dihydrochloride using calcium chloride, filtering out the sulfate value and concentrating the filtrate in preparation for reaction with the cyanoguanidine.

Thereafter, the guanazole would be nitrosated by one method to the dinitrotriazole, or the nitrosation under Sandmeyer condition would provide the mixed result where half the product is dinitrotriazole and half the product is nitrotetrazole.

Cyanoguanidine is actually a slow time release nitrogen fertilizer which is sold as 66-0-0 and is stocked in 25kg bags but it is an obscure product probably not widely used or commonly found stocked because it is an expensive specialty product and special order ag product for professionals. One brand name is Guardian-DF for the cyanoguanidine crystals.
A bag of the stuff could set a golf course landscaper back a couple of hundred bucks easily, but hey golf is important :D

[Edited on 10-10-2013 by Rosco Bodine]

snooby - 13-10-2013 at 22:42

http://www.youtube.com/watch?v=wu9Y1OCXXO0

Here's a vid of some of the NaCuNTZ i made. I think its behaviour in a detonator is the same as lead-azide. Difficult to detonate from a single spark. Since I have no visco at the moment I cant test a det with visco; only with a straw filled with blackpowder (but i cant get detonation, only some crackling.

Rosco Bodine - 17-10-2013 at 11:24

Here are a couple of additional articles. These look familiar so they may have been posted before, but I haven't found where so here they are.



Attachment: Insensitive high-performance replacements for RDX, Klapotke ADA466070[1].pdf (926kB)
This file has been downloaded 1385 times

Attachment: Green Pyrotechnics, A Chemists Challenge, Klapotke.pdf (842kB)
This file has been downloaded 1542 times


[Edited on 17-10-2013 by Rosco Bodine]

DubaiAmateurRocketry - 21-10-2013 at 07:45

Just curious, what is the toxicity or LD50 of tetrazole compounds ?

5 aminotetrazole for example ?

DubaiAmateurRocketry - 24-10-2013 at 12:27

Quote: Originally posted by Axt  
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]


It is possible to hang a nitro group there ?

snooby - 31-10-2013 at 12:34

We all know that a very important substance is Sodiumnitrotetrazole or NaNTZ! We can all make this easily from the acid salt of cuppernitrotetrazole. Just neutralize it with NaOH and distinguish the CuO leaves u a yellow solution of NaNTZ! Put a CuNO3 solution in it to get the NaCuNTZ....

But this is not the case. The obtained product (see my video http://www.youtube.com/watch?v=wu9Y1OCXXO0 ) is NOT suitable for using in detonators! It wont detonate simply by fuse! After reading a lot, I discoverd that this so called 'raw solution' of NaNTZ must be purificied. This can be done by evaporating the raw NanTZ solution and then extract the pure NaNTZ. BUT this proces is dangerous. After NaNTZ recrystalize from aceton it easily forms anhydrous NaNTZ wich is very very dangerous. There are some case where the stuff exploded without reason....

So, my idea: Slowly evaporate your raw NaNTZ solution, wich will give you the monohydrate of NaNTZ and some contamination. Then extract the NaNTZ with an excess of hot aceton. Instead of evaporating the stuf just pour it in distilled water. Then boil the water until the aceton is removed. Now you have the pure solution

Davin - 31-10-2013 at 17:34

Quote: Originally posted by snooby  


After NaNTZ recrystalize from aceton it easily forms anhydrous NaNTZ wich is very very dangerous. There are some case where the stuff exploded without reason....



Do you have a reference for this? I have never seen or heard of the the anhydrous coming out of acetone...

Dany - 31-10-2013 at 18:41

Quote: Originally posted by Davin  
Quote: Originally posted by snooby  


After NaNTZ recrystalize from aceton it easily forms anhydrous NaNTZ wich is very very dangerous. There are some case where the stuff exploded without reason....



Do you have a reference for this? I have never seen or heard of the the anhydrous coming out of acetone...


Best reference until now :)

http://onlinelibrary.wiley.com/doi/10.1002/zaac.201300010/ab...

Dany.

Davin - 31-10-2013 at 20:31

Thanks for the compliment Dany, I do believe that method of NaNT dihydrate synthesis to be the best one out there, with the addition rate and temperature control tuned perfectly to avoid microdetonations prior to the isolation in high yield of perfect crystals of the dihydrate. :D ;)

But what I was wondering about was if there was a NaNT reference somewhere indicating the loss of hydration waters of NaNT during recrystallization from acetone as snooby has mentioned. I have never came across any mention of this, and certainly have not had it occur myself.


snooby: If your NaNT solution is coming out yellow you have a temperature control or pH control issue.

[Edited on 1-11-2013 by Davin]

Dany - 31-10-2013 at 20:43

Davin, i want to take advantage of your presence to see what are the progress in TKX-50? does the team plan to perform in depth studies on this important HEDM like cylinder expansion test? i would like to know how it will perform in metal acceleration ability and if the Dcj prdicted by EXPLO5.05 is realistic. I also would like to know the value of the constant (alpha, beta, kappa and tetha) used in the BKW EOS in EXPLO.05 for performing detonation performance calculation in your articles.

Dany.

[Edited on 1-11-2013 by Dany]

snooby - 1-11-2013 at 09:34

And what about my idea of putting the aceton/NaNTZ mix into water and let evaporate the aceton?? Then you avoid the step with working with the pure NaNTZ..?


Engager said......
And one more thing, BE AWARE that separation of NaNT from solution in acetone IS very dangerous, and i know people from sciencemadness forum who taken serious wounds and injuries during this process, when product spontaneously exploded during crystallization. This could be attributed to formation of very hazardous anhydrous salt, but that is not quite clear in conditions then that happened. So you must consider this proces as very dangerous and take appropriate safety measures/precautions. I'm persistently encourage you to leave separation of pure solid compound and use it only in form of pure AQUEOUS solulitons, prepared by separation of Cu salt and reaction with corresponding ammount of sodium hydroxide (and heat/filtering as written). Remember, clever people learn from mistakes of others, stupid learn on their own. Be smart and cautious, and you will be alive long enough and still be in good health to tell about your beautiful chemical adventures



Btw: a solution of NaNTZ SHOULD be yellowish.. right

snooby - 2-11-2013 at 05:43

Okay today i did it again! I made a solution of (so called RAW) NaNTZ out of acid CuNTZ. You can use this solution to make AgNTZ yes, but no, it will not be pure. You can also make NaCuNTZ (the famous primer) from it, just by puting an solution of CuNO3 in some raw NaNTZ solution, boil it, cool it, filter it, done. See the youtube link for the raw NaCuNTZ! It is not suitable for detonators! In the video it looks like it is! But I need to put a flame against it for like 1 second, and that is just too long. In a det, it wont work, all because of the NaNTZ solution whas RAW.

://www.youtube.com/watch?v=wu9Y1OCXXO0

Today I boiled the raw NaNTZ solution on a waterbath, until cristals apeared. This is your NaNTZ, but with a lot of junk in it. I trew hot aceton over it and decanted the aceton, which turned yellowish. Evaporating the aceton can be dangerous because of anhydrous NaNTZ can form (I red this and also Enger confirmed it.) And btw,,, I had an accident with 200 mg, blowing my eardrums.

So after the aceton dissolved the NaNTZ, there still was a lot of undisolved stuff in my glass. This shows that the NaNTZ solution whas deffinitly not pure! All the stuff that doesnt dissolve is not NaNTZ, and this stuff makes the NaCUNTZ not suitable for detonators of course.

So then I putted the aceton into water, and let the aceton evaporate. After there were no signs of aceton I got a yellowish solution of Pure NaNTZ! I tested this and made some NaCUNTZ and AgNTZ with, wich shows clear colores. Its drying right now, and I will post the results of it! I think this is an safe method of making pure NaNTZ solution, amen

Davin - 2-11-2013 at 14:04

Quote: Originally posted by Dany  
I also would like to know the value of the constant (alpha, beta, kappa and tetha) used in the BKW EOS in EXPLO.05 for performing detonation performance calculation in your articles.



version: alpha: beta: kappa:theta
5.03: 0.5:0.176:14.71:6620
5.04: 0.5:0.96:17.56:4950
At home right now and cannot find 5.05 or 6.01 yet. Will let you know.

Dany - 2-11-2013 at 23:30

Davin, i'm very grateful to you for providing me this informations.

So the version 5.03 (i think this is the first version) of EXPLO5 uses the sets of constant of the well known BKWN which is published by M.Suceska. In his paper [1] M.Suceska compared the BKWN output to other well known BKW EOS variant (BKWR, BKWS and BKW TNT/RDX). Suceska found that BKWN give the best overall agreement between the calculated and experimental values of detonation parameters.

[1]M.Suceska, EXPLO5-Computer program for calculation of detonation parameters (in International Conference of ICT Held in Karlsruhe, Federal Republic of Germany on July 3-6, 2001. Energetic Materials: Ignition, Combustion and Detonation)

http://oai.dtic.mil/oai/oai?verb=getRecord&metadataPrefi...

Dany.




[Edited on 3-11-2013 by Dany]

Gargamel - 4-11-2013 at 05:40

I only have experience with NH4NTZ, but my experience is similar to snoobys.

I made NH4CuNTZ, als well as NH4NiNTZ.

Both perform nicely, stunning - once you get em going ;)

They are both very stubborn to ignite via flame, almost impossible. The only viable setup for me was putting a thermite layer upon the copper salt - the nickel salt failed even with that.


Am I the only guy experiencing this problem?
Does somebody have an opinion on that?

snooby - 4-11-2013 at 05:53

@ Gargamel: The NaCUNTZ is very powerfull but not easy to use in detonators indeed! Not flamesensitive enough! Can you please explain which kind of thermite you are using!? And how you use it in a det? Must be a metal cap right?

The silversalt I made with my pure NaNTZ is very flamesensitive but also very impact-sensitive, so I dont want to use the silversalt! Also sent you a PM!

Gargamel: for the best peforming/most flamesensitive NaCUNTZ:

- Reflux the NaNTZ and CuNO3-solution! Or at least boil it. The liquid must get colorless, if not, you added to much CuNO3 for the amount of NANTZ. So dont put to much CuNO3 (its difficult to calculate the amount of NaNTZ in your solution right). Afterwards, cool it and filter it. Then washing with ethanol and water of course.

- Raw NaNTZ solution is not enough, make it pure by evaporate the solution (not to fast).Do this in different steps! So for example portions of 30 ml NaNTZ solution. Then youre sure you dont have to work with more then 1 gram at most. When Crystals appears, put boiling aceton in it. The decant the hot aceton and put it in distilled water. Do this with al your portions. Then boil the solution to evaporate the aceton. Then let the NaNTZ further evaporate leaving you a really pure solution of NaNTZ.

- use distilled water and in the last step, make sure your NaNTZ solution is PH 4

[Edited on 4-11-2013 by snooby]

Gargamel - 4-11-2013 at 09:48

Quote:

Can you please explain which kind of thermite you are using!? And how you use it in a det? Must be a metal cap right?


Simple iron oxide stuff. Only with pyro aluminium to make it sensitive. Maybe CuO or Bismuth based stuff would be better, but I don't like it anyway.
BP never worked.

I did not use it in any det, I find it useless. A primary should be fuse sensitive. The green primaries I tested aren't.


This whole thing was interesting for me because I wanted a primary insensitive to friction and ESD. And as far as I read myself through this whole thing, that applies only to the NH4 salts.





edit:
No metal cap, it was just a parallel wound paper tube, 6mm inner diameter, 1mm walls.
Confinement is not the issue here, like with mercury fulminate, HMTD and so on. If it ignites, DDT comes extremely fast, practically immediate. A small crumb maybe a millimeter long made a little crater in my working plate. Superb!
But before it went, I could push it around over the table with the flame of my little torch...

[Edited on 4-11-2013 by Gargamel]

magneet - 4-11-2013 at 11:52

Witch synthesis did you use for your NH4NT? I'm interested in NH4CuNT as well, but I stumble upon the invest of bariumhydroxyde and such for the synth mentioned bij Engager, did you use the direct method with ammonia soln?
I've experience with AgNT, but I find it rather too sensitive to my tasting, its initiating propperties however are unbeatable IMO.
Quote:

Am I the only guy experiencing this problem?


Could it be something with purity of your reagents or purification steps in between synthesis?
I tried NaCuNT a long time ago and it was just like crackling when lit in a pile, in a cap it just didn’t do anything.
I always blamed myself for bad, or no purification of the 5-ATZ, CuNT, and NaNT between synthesis, after that I abandoned further research into it because reliability was a main factor.

Other thing that came to mind was too much energy dissipating thorough the mass before going high order.
I can’t remember if I tried loosely packed NaCuNT but it would need bigger confinement if it didn’t work I thought, raising scrapnell levels.
There is always a grey area around people going public with practical experience with this kind of stuff, even with lots of easy to prepare primairy’s and its synthesis to be found everywhere.

If thermite is a key factor to get it to work I would be very satisfied, giving up AgNT for thermite => NH4CuNT.

snooby - 5-11-2013 at 08:12

Today I did some tests on the sensivity of NaCUNTZ. Blows with a hammer were positive, about 25% less sensitive in comparisson with dextrinated lead-azide but friction-tests almost were al negative. This NaCUNTZ is relatively flame-sensitive but not reliable in a detonator.. So, with the positive hammertests, I am sure my NaCUNTZ is the right stuff, however it is yet not suitable in a det.. I think this was the last time I've made NaCUNTZ.. (btw also made the purple Nickel-salt with it, was even worse!).

The AgNTZ however (yellowish Crystals) are interesting for in detonators, but they are quite sensitive. So, then I would rather stay with the Azo-Clathrate from Mr. anonymious then with the AgNTZ.

Rosco Bodine - 5-11-2013 at 13:15

Well tickle me tweeters and bump my subwoofers :D
http://www.youtube.com/watch?v=O6kSEqnDoLE

<iframe sandbox width="640" height="480" src="//www.youtube.com/embed/O6kSEqnDoLE?rel=0" frameborder="0" allowfullscreen></iframe>

DubaiAmateurRocketry - 7-11-2013 at 11:17

Quote: Originally posted by AndersHoveland  
I think the most promisting energetic compound may be dinitromethyl tetrazole.
“Syntheis of 5-Dinitromethyltetrazole”, A. V. Shastin, B. L. Korsunskii, T. I. Godovikova, V. P. Lodygina. (2009) Russia

The structure of this compound has resemblance to another well-described insensitive energetic compound, diaminodinitroethylene (Fox-7).

Dinitromethyl tetrazole is somewhat acidic and can form salts.

Measurements of the explosive properties of dinitromethyl tetrazole have not been reported, but I think it would have an excellent combination of explosive performance and stability.

The aromatic nature of the ring would stabilize the nitrogen atoms, while the two NH groups be electron-donating toward the geminal nitro groups, stabilizing them. Many energetic tetrazole compounds have lower sensitivities than RDX, and Fox-7, which also contains the gem-dinitro functional group, is roughly twice as resistant to impact as HMX.


[img]http://www.sciencemadness.org/talk/files.php?pid=233635&aid=17226[/img]


This thing is actually interesting. I got the papers down there.
Quote: Originally posted by The_Davster  
http://onlinelibrary.wiley.com/doi/10.1002/prep.200900049/ab...

"Dinitromethyltetrazole and its salts: A comprehensive study"


Paper in the uploads

And in the paper, the Di-ammonium cation of the Dinitromethyltetrazole, is it possible to use the nitronium cation ?

http://onlinelibrary.wiley.com/doi/10.1002/poc.3197/abstract





Attachment: Synthesis of 5-Dinitromethyltetrazole.pdf (235kB)
This file has been downloaded 1013 times



[Edited on 7-11-2013 by DubaiAmateurRocketry]

Attachment: phpFvHU8l (744kB)
This file has been downloaded 849 times

Rosco Bodine - 13-11-2013 at 23:58

Here are some of the aforementioned DBX-1 related references attached along with a related patent

Attachment: Preparation of High Purity Sodium 5-Nitrotetrazolate (NaNT)-An Essential Precursor.pdf (697kB)
This file has been downloaded 1106 times

http://www.navsea.navy.mil/nswc/indianhead/TEWPresentations/...

Attachment: DBX-1 A Lead Free Replacement for Lead Azide.pdf (393kB)
This file has been downloaded 2285 times

Attachment: US8440008 Cuprous Nitrotetrazolate - Fronabarger and Williams.pdf (579kB)
This file has been downloaded 1132 times

Attachment: Williams-Mike-DBX-1-A_Potential_Drop-In_Replacemen.pdf (1.3MB)
This file has been downloaded 2350 times

Attached also is a google translation of a German patent and on page 12 of the pdf are examples of some other copper complexes of interest

Attachment: Patent DE102010036950A1 - New metal-tetrazole complex useful as initiating e.pdf (155kB)
This file has been downloaded 1284 times

Thanks to Dany and solo for the journal articles

[Edited on 15-11-2013 by Rosco Bodine]

Rosco Bodine - 15-11-2013 at 00:40

As was pointed out earlier in the thread there has already been worked out at LANL a method for isolation of 5-nitrotetrazole that is analytically pure

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

The method of Gilligan and Kamlet was patented in US4093623
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

quote: Ammonium nitrotetrazolate was prepared by diazotization of 5-aminotetrazole in the presence of excess nitrite followed by extraction as the tri-laurylamine salt and displacement by ammonia. Upon addition of stoichiometric amount of ammonium hydroxide, sodium nitrotetrazolate forms quantitatively and is analytically pure.

See US7498446 page 4 column 3 line 53 Attached

An idea was described previously for what may be an alternative method for conditions for the Sandmeyer reaction or for adjusting the reaction system thereafter to obtain a more easily filterable crystalline material, which in retrospect
may also be a useful intermediate for DBX-1.
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

It is possible that other low solubility salts of 5-nitrotetrazole may facilitate purification of the nitrotetrazole needed in pure form for successful preparation of cuprous nitrotetrazolate in the desired crystalline form. Or it may be found schemes for precipitating or decomposing the impurities and leaving the purified nitrotetrazole value in solution. Unreacted aminotetrazole impurity may be reduced by improvement of the nitrosation method.

Attachment: US7498446 Primary Explosives of Tetrazole Moiety.pdf (58kB)
This file has been downloaded 746 times

A spontaneous explosion of sodium nitrotetrazole dihydrate during drying has been reported. See page 8 of the attached document.

Attachment: ADA137898.pdf (1.1MB)
This file has been downloaded 992 times

To revisit the earlier aspect of an alternative route for isolation of the nitrotetrazole as a variation on the method of Gilligan and Kamlet see US4552598 attached

Attachment: US4552598 Ethylenediamine salt of 5-nitrotetrazole and preparation.pdf (767kB)
This file has been downloaded 1064 times

Further refinement of the process for DBX-1 has been reported by Klapotke and others having parallel research.

Edit: Per request of the inventor presently involved in business negotiations related to the technology, a delay of discussion of some proprietary details of this technology is being effected. Respect for the inventors explains the edits and missing posts in this thread about process details for which discussion can wait awhile yet until the corporate attorneys are satisfied the art originators interests are secured. Putting a lid on this discussion for awhile until given the "all clear" to proceed with further discussion.

Sufficient to say the technology is in part originating from this forum. No more speculation about coincidental discussions and professional publications need be indulged about where the overlap occurs for amateur experimentalism and the formal literature and ongoing current research. For this forum we are already there and have been there awhile.

[Edited on 16-11-2013 by Rosco Bodine]

snooby - 15-11-2013 at 08:23

Thanks for noticing the '' A spontaneous explosion of sodium nitrotetrazole dihydrate during drying has been reported. See page 8 of the attached document ''. I was not able to find it anymore in the shitload of patents that are written about nitrotetrazoles, but it's something to keep in mind!

Like I said I will try the DBX-1 and post results

The_Davster - 15-11-2013 at 12:31

Snooby, from that article:
"In the light of this incident, doubt must be cast on the stability of NaNT.2H20 although it should be stressed that we have prepared many batches in the past without any similar problems. A further batch of NaNT.2H20 was subsequently prepared without incident."

This looks like a one-time thing. I have prepared NaNT.2H20 many times and never with any spontaneous explosions. Considering the authors mention it was exposed to zinc/acid spray, a lot more could be going on here than simple NaNTX.

Rosco Bodine - 15-11-2013 at 13:56

Maybe it only happens once in a thousand times, it just somehow goes wrong.
Statistically, then there is exactly the same chance of the anomaly if this is the
first of a series of one thousand experiments, or it is the next experiment following 999 which have gone before without incident. So there should be remembered that there are three kinds of lies; there are lies, damn lies, and statistics. :D Murphy's law may not be the unvarying and inviolate supreme law of the land or universe, but too often it does seem close enough for government work.

That gel formation intermediate reported during the formation of DBX-1 is possibly analogous to the remarkable effect that also occurs for lead styphnate under very specific conditions.

http://www.sciencemadness.org/talk/viewthread.php?tid=25035&...

http://www.sciencemadness.org/talk/viewthread.php?tid=2827&a...

With regards to my post yesterday being edited,
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...
my apology to snooby for our interrupted discussion.
I apologize for the temporal disconnect and temporary constraint placed upon discussion of quoted material not yet fully approved for publication.

I think an earlier post which I made some years ago may have usefulness in the reaction sequence algebra being applied to development of DBX-1

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

However, I am not sure how useful that idea could be for not having tried it, converting the first obtained acid copper salt gotten via Sandmeyer to a neutral mixed sodium copper salt. I never contemplated this idea as anything potentially useful except as a shortcut that may produce a more useful product directly with little additional manipulation, or as a filtering aid for the isolated material which would then be subjected to similar further workup, being digested with sodium hydroxide, but requiring less base for complete conversion to the sodium salt, than would the acid copper salt ordinarily gotten from the Sandmeyer reaction unmodified, or not subsequently further reacted in the same pot.

(Na)2[CuII(NT)4(H2O)2] may possibly be convertible to DBX-1 by sequential reaction with AcOH and/or HCl followed by subsequent treatment with a mixture of Cu(OAc)2 and Na ascorbate.

[Edited on 16-11-2013 by Rosco Bodine]

DBX

snooby - 17-11-2013 at 05:19

Did some homework 2day. This stuff should be DBX-1. I have used the synthesis without NaNTZ but only acid CuNTZ and sodium-ascorbate. I cannot post the synthesis again because it is patented at the moment.

DBX.jpg - 106kB



[Edited on 17-11-2013 by snooby]

DBX-2.jpg - 106kB

Rosco Bodine - 18-11-2013 at 03:17

Earlier in the thread was mentioned a reference by Glligan and Kamlet that was an inaccesible paper. Attached is that file.

Also is an interesting microprocess continuous reaction scheme which gets around the need for a Sandmeyer reaction and produces sodium nitrotetrazole directly.

Attachment: Gilligan and Kamlet 1976 research ADA036086.pdf (1.2MB)
This file has been downloaded 1075 times

Attachment: US7253288 Continuous microreactor process for sodium nitrotetrazole.pdf (1.2MB)
This file has been downloaded 1179 times

[Edited on 18-11-2013 by Rosco Bodine]

snooby - 18-11-2013 at 05:11

Interesting! In the article continuous microreactor.... they mention a synthesis for pure NaNTZ which should be even more safe and easy.. why all the effort for NaNTZ with purifying etc in other articles :(

@ Rosco: this DBX looks like the right color right? Think I made a little to much at once. Is it advised to separate the stuff into 0.5 grams portions or even less? Don't really know what to expect of it when it's dry!



[Edited on 18-11-2013 by snooby]

Naamloos.jpg - 78kB

snooby - 22-11-2013 at 08:58

As promised. In the middle is the DBX-1. However it is still drying! Think it is almost totally dry. How much of the stuff will set of PETN? I red 40 mg did the job but I am not sure anymore.

derritaves.jpg.png - 752kB

snooby - 22-11-2013 at 10:14

I managed to make 2.8 gram of pure, extracted NaNTZ! It is slightly yellow colored. Should I be concerned that the stuff is going to dehydrate? What is the best way to store the stuff in your opinion?

Same for the AgNTZ, can it be stored under some distilled water or something else?

The DBX-1 seems to be dry, though it is still not as reactive as for example AgNTZ. Quite sensitive towards impact though..

[Edited on 23-11-2013 by snooby]

Dany - 25-11-2013 at 08:15

generally, if the product crystallize with water molecule it is difficult to dehydrated. When water molecule crystallize with your product it is now a part of this substance and not like a wetted substance that will dry with time. A simple example is crystalline CuSO4.5H2O which stay hydrated at room temperature. dehydration occur at elevated temperature. So maybe if you heat your synthesized EM to hundred of degrees you will dehydrate it (with probably a decomposition). of cours this is not the case since you will store your EM at room temperature.

Dany.

recent patent applications

Rosco Bodine - 5-12-2013 at 17:23

US20130317232 MTX-1 Tetrazene Derivative Having Improved Stability

US20130204005 DBX-1 related patent

Attachment: US20130317232 Alternative to Tetrazene.pdf (748kB)
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Attachment: US20130204005 Lead Free Primary Explosive.pdf (1.5MB)
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Ragnar - 22-12-2013 at 16:14

I would have expected the DBX-1 you synthesized to be a little more redish. I would not keep for long term storage. However, I doubt that you would. Any excess can be rendered inert by combing it with 10% sodiumhydroxide. This is an extremely interesting compound and is being sought as a replacement for Lead Azide for military applications. Based on former life, I have learned that the military is always trying to find ways to be more earth friendly. They don't care about what they blow up, but heaven forbid if there are heavy metals left behind.

snooby - 23-12-2013 at 06:23

The DBX-1 turned almost black in the end. When dry it became little chunks of DBX-1 who where impossible to be powdered. They were quite sensitive for impact but did not work when ignited by fuse unfortunately. The synth I used was whithout the use of NaNTZ. Maybe this synth was not so good after all. I now have an amount of cupric(II)cloride and I will try the synth again in a while. I indeed decided to put away the stuff. Have you tried DBX-1 yourself btw?

snooby - 23-12-2013 at 06:57

Btw im trying on BNCP. But first I want to do the synth of mono-(5-nitro-H-tetrazolato-N)triammine copper(II) perchlorate (MNCuP). In the synthesis Engager says:

'To solution of 40 ml 70% HClO4 in 100 ml of water, 3.5g (0.01379 mol) of carbonato triammine copper(II) nitrate in 30 ml of water is added with stirring. Deep blue color of copper carbonate complex quickly turns to transparent sky blue. Resulted mixture is heated to 60 ± 10С and left to stand at this temperature for half of hour and heated to ~80C, then concentrated solution of sodium 5-nitrotetrazolate (0.00689 mol) is added by drops with stirring'.

I have no idea how much (0.00689 mol) of sodium 5-nitrotetrazolate is! Don't know the moll mass of the stuff. Anyone got an idea?

Dornier 335A - 24-12-2013 at 01:45

Sodium 5-nitrotetrazolate has the formula NaCN5O2, so the molar mass is 137.033 g/mol. (dihydrate: 173.063 g/mol)

snooby - 24-12-2013 at 03:03

Thanks for information.
100% / 1 mol = 100*0.00689 = 0.689
173/100 = 1.73*0.689 = only 1.191 grams of NaNTZ for every 3.5 grams of carbonato triammine copper(II) nitrate. Seems to be a little less for that amount of HCLO4 also:(

franklyn - 5-2-2014 at 21:54

High energy tetrazole-based compounds as lead replacement explosives
www.chemikinternational.com/year-2013/year-2013-issue-1/high-energy-tetrazole-based-compounds-as-lead-replacement-explosives-wojewodka-a-witkowski- t

That article here _
Attachment: High energy tetrazole-based compounds as lead replacement explosives.zip (840kB)
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snooby - 1-3-2014 at 08:49

Soooo ppl! Hello again. I have great news! I have made (in steps og 1 grams) superpure NaNTZ! About 7, dissolved in deminiarlised water. (what should the PH be btw?P

I want BNCP: I got sodium perchlorate and coblat sulfate , ammoniumcarbonate and H202 30%!


BUT i only got 5% ammonia.. insead of 25.

So I got everyting except 25% ammonia..My question, can i use Household ammonia and do it like this: inseatd of 250 ml 25% ammonia i will use 1150 ml 5% ammonia. And then put 14 ml h202 30% and then eveporate till 300 ml. Whil this work ?

500 ml H2O + 250 ml 25% ammonia solution. Resulted dark violet solution is oxidised by addition of 14 ml of 30% hydrogen peroxide. Solution is allowed to sit for 30 minutes, after that period it is placed on boiling water bath and is evaporated to 300 ml volume.

1. Preparation of [Co(NH3)4CO3]2SO4*3H2O complex. 47g CoSO4*7H2O is dissolved it 125 ml of water and is added to solution of 100g (NH4)2CO3 in 500 ml H2O + 250 ml 25% ammonia solution. Resulted dark violet solution is oxidised by addition of 14 ml of 30% hydrogen peroxide. Solution is allowed to sit for 30 minutes, after that period it is placed on boiling water bath and is evaporated to 300 ml volume. During course of the concentration process, solid ammonium carbonate (25 g) was added in installments. Solution is filtered from unsignificant ammount of precipitated black cobalt oxide and is further concentrated to 200 ml volume. Solution is slowly cooled to room temperature, product precipitates as small deep-red prisms. They are filtered out from the solution and allowed to dry at room temperature. Yield is 16 g of pure product, mother liquer can be further concentated with addition of ammonium carbonate to get more 16 g of complex, but it is less pure.

2. Preparation of [Co(NH3)4CO3](ClO4) complex. 16g of complexed synthesised on first stege is dissolved in 320 ml of water. Solution is filtered and 16g of sodium perchlorate in 40 ml of water is added with stirring. Mixture is cooled on ice (or in freezer) for 3-4 hours. Product precipitates as small, lustrous, sharp violet prisms. Crystalls are filtered off, washed with small ammount of ice cold water and dried at room temperature. Yield is about 14 gramms.

3. Preparation of BNCP. 14g [Co(NH3)4CO3](ClO4) is dissolved in 140 ml 10% perchloric acid, and solution of 26.5g of sodium 5-nitrotetrazolate dihydrate in 450 ml of water is added with stirring. Solution is placed on boiling water bath, and allowed to sit there for 4 hours. Solution is slowly cooled to room temperature and then cooled in freezer to 10°С, precipitated crystalls of BNCP are filtered of, washed with cold water, and recrystallised from 1% perchloric acid. Yield is 12.9g.

Photos of reaction products: first is tetraminocarbonato cobalt (III) sulphate trihydrate (product 1), second is tetraminocarbonato cobalt (III) perchlorate (product 2), third is crystalls of BNCP.

snooby - 21-3-2014 at 04:13

I managed to make some very nice Orange Red Crystals of BNCP. When ignited by a flam the result is flashy cracklings! I saw a video of engager who was able to use it in a detonator.

Is it nessecary to grind the BNCP fermly before using it!? It is not was sensitive toward flame as I was hoping.

snooby - 28-3-2014 at 10:19

Ok I was succesful in detonating BNCP in a plastic tube! But, sensitivity for friction should be low.. but with hammer scratching causes detonation rather easy (3.2KG should be the standard). For PETN this is 6 kg, but I dont get it going how hard I try. Is this normal for BNCP? My advise for BNCP, still stay safe with it...

The test was as follow: I took a sample of BNCP on a brick, very sandy and irregular surface. Then scratching with hammer with some pressure. Almost immediately detonation.

Dornier 335A - 28-3-2014 at 13:34

Using a surface like a brick or concrete drastically decreases the weight needed for in impact and friction tests. My nano-Armstrong's mix is very difficult to set off steel against steel, much easier with steel against concrete.

snooby - 28-3-2014 at 13:44

I thought BNCP was the BEST and safest primer nowadays. Is it no surprise I can detonate it with en moderate hamerstrike? It is like 3 times less senstive then AgNTZ for example. But still, it is farrr more senstive then PETN!

snooby - 17-4-2014 at 04:54

This is BNCP detonating aboout 30 mg!

Attachment: bncp video.MOV (1.9MB)
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Pure BNCP and detonator picture

BNCPd 3.jpg - 71kB

[Edited on 17-4-2014 by snooby]

[Edited on 17-4-2014 by snooby]

det 1 BNCP.JPG - 56kB

snooby - 19-4-2014 at 01:25

synth of mono-(5-nitro-H-tetrazolato-N)triammine copper(II) perchlorate (MNCuP). In the synthesis Engager says:

'To solution of 40 ml 70% HClO4 in 100 ml of water, 3.5g (0.01379 mol) of carbonato triammine copper(II) nitrate in 30 ml of water is added with stirring. Deep blue color of copper carbonate complex quickly turns to transparent sky blue. Resulted mixture is heated to 60 ± 10С and left to stand at this temperature for half of hour and heated to ~80C, then concentrated solution of sodium 5-nitrotetrazolate (0.00689 mol) is added by drops with stirring'.


So: Sodium 5-nitrotetrazolate has the formula NaCN5O2, so the molar mass is 137.033 g/mol. (dihydrate: 173.063 g/mol)

So I calculated:

100% / 1 mol = 100*0.00689 = 0.689
173/100 = 1.73*0.689 = only 1.191 grams of NaNTZ for every 3.5 grams of carbonato triammine copper(II) nitrate. Seems to be a little less for that amount of HCLO4 also.

Is this calculation correct?? Because in the synth of BCNP, you need to add 2.6 grams of NANTZ for every 1.4 grams of cobaltperchlorate stuff! So I think 1.191 grams NANTZ is very litle for 3.5 grams carbonato triammine copper(II) nitrate.

So is this correct, or am I making a mistake?

The_Davster - 23-4-2014 at 15:31

You are all welcome....OTC aminoguanidine :D
http://www.worldantiagingstore.com/brands/profound-products/...
http://www.supersmart.com/en--Blood-Sugar-Glycation--Aminogu...



[Edited on 24-4-14 by The_Davster]

Microtek - 24-4-2014 at 12:58

30 dollars for 7.5 grams... A little steep.

The_Davster - 24-4-2014 at 15:31

For sure, especially if you have seen alibaba prices :o

But those 7.5g, turned into a nitrotetrazolate primary would last...if you have a secondary in mind, not so much.

snooby - 29-4-2014 at 09:30

Can someone plz check my calculation I mentioned 3 posts above, since I dont want to waste a lot of holy grale chems!!

Dornier 335A - 29-4-2014 at 10:03

Engager stated 0.00689 mol NaNTZ. The molar weight of NaCN5O2*2H2O is 173.06 g/mol. 0.00689 mol*173.06 g/mol = 1.192 g.

The molar ratio of the copper complex to sodium nitrotetrazolate is 2:1, which I don't really see the point of. But I think you should follow Engager's instructions.

snooby - 2-5-2014 at 11:17

Well I calculated the same tnx: 3.5 grams of carbonato triammine copper(II) nitrate for every 1.91 grams of NANTZ.

With BNCP it is the opposite: 1.4 grams of cobalt stuff for every 2.6 grams of NANTZ.

Since NANTZ is harder to make, maybe the copperstuff is better variant to make! You need a lot less of NANTZ!

snooby - 3-2-2015 at 02:17

I made BNCP and NaCUNTZ. I was able to set off BNCP with a relatively simple primer such as mealpowder. However, NaCUNTZ seems to need a hotter primer. I think I can get 5/10 in my blastingcaps with NaCUNTZ. So, I am looking for a decent priming composition. I have tried 80 leadtetroxide/20 silicon and this one burns veryy fast (flashpowder like). Mayb you guys have some suggestions for a very hot primining composition.

Dornier 335A - 6-6-2015 at 08:53

I synthesised a small amount of C2H4N14 bis-diazotetrazolylhydrazine, or as I prefer to call it, ditetrazolylhexaazadiene.
When I dripped almost colourless diazotetrazole solution into hydrazinium chloride solution, it turned pink and then a fluffy yellow precipitate formed. It hydrolyzed again before I could vacuum filter it. After a few days tiny dense grains of a yellow compound had precipitated. A single of those grains, approx 50 micrograms detonates violently enough to rip a hole though aluminium foil when heated slowly. Still, it's not the unequivocal primary I though it would be. A few milligrams only puff and spread out the pile when ignited. Strongly pressed it is extremely brisant.

Density was calculated to approx 1.75 g/cc by group addition method, similar to 5-azidotetrazole (1.72 g/cc), 1-diazidocarbamoyl-5-azidotetrazole (1.72 g/cc) and 1,1'-azobis(tetrazole) (1.77 g/cc). Enthalpy of formation is most likely between +1300 and +1500 kJ/mol based on its structure and similar compounds. This gives it a detonation velocity of around 9300 m/s.

Here's my video about it: https://www.youtube.com/watch?v=qVZT5aR3ih0

DBX-1

Rosco Bodine - 4-9-2015 at 15:34

One of the inventors passed this along to me. Sharing is caring. :D


I get a real chuckle knowing that some of the leading high technology contributors of this world are associated with this ..er ..uh .."amateur" science forum. :cool:


Attachment: US20150239910A1 METHOD FOR PREPARATION OF A LEAD-FREE PRIMARY EXPLOSIVE.pdf (46kB)
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Jimbo Jones - 5-9-2015 at 03:52

Quote: Originally posted by Rosco Bodine  
One of the inventors passed this along to me. Sharing is caring. :D


I get a real chuckle knowing that some of the leading high technology contributors of this world are associated with this ..er ..uh .."amateur" science forum. :cool:


You can bet on it...;)

guanazole reaction revisited

Rosco Bodine - 24-9-2015 at 14:45

From about 7 years ago to again about 4 years ago and later a couple of years ago the subject of guanazole has received some attention. This post by Engager links back to the original discussion in another thread which is continued here in this thread.

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

I have some additional information snippets which are tending to support my earlier idea of synthesizing guanazole using the patent process of US2648671 which is reaction of molar equivalents of cyanoguanidine with hydrazine dihydrochloride in aqueous suspension to provide a quantitative yield of guanazole.

US3054800.bmp - 160kB

I still speculate it may be possible to proceed without isolation of the guanazole to diazotize and produce the dinitro derivative,

US3054800 dinitro.bmp - 165kB

or to produce the 50/50 mixture of the dinitro derivative with 5-nitrotetrazole via Sandmeyer reaction condition.

I think this may possibly be the easiest route to a tetrazole or more precisely to a mixture or possible double salt that is 50% 5-nitrotetrazole with the other 50% being 3,5-Dinitro-1,2,4-triazole according to the method of US3054800.

The best strategy for accomplishing this synthetic route is not yet identified and there would seem to be variations on the approach possible, which could involve isolation of a guanazole derivative as an intermediate, either a guanazole double salt complex with copper sulfate, or if it exists even better would be a double salt complex of guanazole with copper nitrate.
An additional possibility is the formation of a guanazole nitroso derivative which may be a not previously identified intermediate for either 3,5-Dinitro-1,2,4-triazole, or possibly an intermediate in the patent process leading to the 50/50 mixed product. I believe that a possible isolation of the copper salt or ammonium complex copper salt, or double salt could be done. Or it may be possible to separate the 50/50 mixture into its components, depending upon how the process is done.

Does anyone have any information as to whether or not guanazole forms a double salt with copper nitrate as does form with copper sulfate? Further, does anyone have information about the nitroso derivative of guanazole, which would possibly be guanazole oxime? See the article attached page 518.

Also attached is an abstract for a Russian article which is not available online, but which may be helpful.

I am still studying and reviewing what are available references so I am sharing what I accumulate on this potentially useful synthetic route and its possible products. The silver and the copper salts would seem to be of interest. And of course there are many possible double salts not yet identified.

Attachment: from JCS page 517 guanazole.pdf (215kB)
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Attachment: rjapchem0839_abstract Synthesis 3,5-dinitro-1,2,4-triazole, Russian Journal of Applied Chemistry, Vol. 73, No. 5, (2000) (3kB)
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Attachment: guanazole pages from PATR Vol. 5 D(cont.)-E.pdf (148kB)
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Attachment: guanazole page PATR Vol. 6 E(cont.)-G.pdf (92kB)
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Attachment: US2648671 PREPARATION OF GUANAZOLE.pdf (84kB)
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Attachment: US3054800 50-50 mixture of dinitrotriazole and 5-nitrotetrazole via Sandmeyer reaction on guanazole.pdf (130kB)
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Attachment: preparation and characterization of 3,5-dinitro-iH-1,2,4-triazole.pdf (1.5MB)
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Attachment: Synthesis, Properties and Performance of the High Explosive ANTA.pdf (555kB)
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Attachment: Pages from dubious Ledgard.pdf (203kB)
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There has been other interest in guanazole conversion to
3,5-Dinitro-1,2,4-triazole

https://www.youtube.com/watch?v=IxEpkA1V46k

<iframe sandbox width="640" height="360" src="https://www.youtube.com/embed/IxEpkA1V46k?rel=0" frameborder="0" allowfullscreen></iframe>

[Edited on 9/25/2015 by Rosco Bodine]

Mr.Greeenix - 26-9-2015 at 01:00

Quote: Originally posted by Ragnar  
I would have expected the DBX-1 you synthesized to be a little more redish.

Quote: Originally posted by snooby  
The DBX-1 turned almost black in the end. When dry it became little chunks of DBX-1 who where impossible to be powdered. They were quite sensitive for impact but did not work when ignited by fuse unfortunately. The synth I used was whithout the use of NaNTZ. Maybe this synth was not so good after all. I now have an amount of cupric(II)cloride and I will try the synth again in a while. I indeed decided to put away the stuff. Have you tried DBX-1 yourself btw?


I tried recently it. With the method Rosco Bodine posted here http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

The synthesis worked just fine even when I haven't reach the temp. of 100°C at the end (had about 80°C)

My DBX-1 was first reddish but finally after it was fully dry it also gets its almost black apperance. These chunks were
difficult to powder but possible. I broke them up carefully. Finally I got the rusty colour stated in the literature. Also much more flame sensitiv and gives a greenish flame when ignited.



____
Only fictive!


[Edited on 26-9-2015 by Mr.Greeenix]

Mr.Greeenix - 21-10-2015 at 07:39

I synthetised 5-Aminotetrazole two times now.
The first time small scale with the method posted by Engager. The yield was ok and the product was very pure.

But now I scaled it up a little bit.
Approximately 10g Aminoguanidin bicarbonat ; 200ml 15% sulfuric acid ; 10g Nano2
and much sodium carbonate for the PH.

The problem is that I had a massiv yield of about 100g. I suppose that this is too good to be true:(
After cooling there were only crystals left in the beaker no more fluid, so I guess that all impurities also crystallized.
The Ph of my "5-Aminotetrazole" is neutral.

Is someone able to explain this yield?
Does someone know how to remove the sodium carbonat or sodium sulfat (Cause I neutralized with sulfuric acid) in my 5-Aminotetrazole. Suitable Recrystallization?

(Video to this method: https://www.youtube.com/watch?v=oTjgHo-EdXY) he also had a massiv yield but I halved the amount of chemicals used.
Thank you :)

Boffis - 21-10-2015 at 10:01

@Mr.Greenix it sounds like you have much sodium sulphate hydrate in there! 5-aminotetrazole crystallises as the monohydrate so you should get about 7.5g at 100% yield but you usually only get about 75% with the Thiele method.

Try treating the product with dilute HCl to ensure that it is the free tetrazole derivative, then leach with water until you have got rid of most of the sodium salts and then recrystallise from water. 5-aminotetrazole is very soluble in hot water but sparingly soluble in cold water and salt solutions so the recovery during recrystallisation is usually good.

By the way, always allow the filtrate to stand for several days or a week in contact with a few grains of the initial product and also stir occasionally making sure you rub the vessel walls occasionally. 5-aminotetrazole has a terrible tendency to supersaturate.

PS just because somebody makes a youtube video it doesn't mean they know what they are doing!

Rosco Bodine - 26-3-2016 at 07:29

Here is a doctoral dissertation of interest

694 pages - 35.1 MB

Advanced Energetic Materials Based on 5-Aminotetrazole - Synthesis, Characterization, Testing and Scale-up - Stierstorfer_Joerg.pdf

https://edoc.ub.uni-muenchen.de/12994/1/Stierstorfer_Joerg.p...

http://www.hedm.cup.uni-muenchen.de/personen/staff/stierstor...

http://www.hedm.cup.uni-muenchen.de/index.html

Also another interesting and more recent doctoral dissertation for which a link was posted earlier, and then disabled temporarily due to a confidentiality about a pending patent application, is again available for download since the patent has issued for the DBX-1 process described therein.

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

The dissertation is
Advanced Energetic Materials - Piercey_Davin.pdf

linked here again

https://edoc.ub.uni-muenchen.de/15389/1/Piercey_Davin.pdf





[Edited on 3/26/2016 by Rosco Bodine]

octonitrocubane - 27-3-2016 at 06:01

Anyone for 1,6-ditetrazolylhexaaza-1,5-diene? Dornier335A has it on Youtube. VoD 9300 ms. Sensitivity is, of course, just about unparalleled. Formula C2H4N14 - it contains 87.5% nitrogen by weight.

Rosco Bodine - 27-3-2016 at 09:18

Quote: Originally posted by octonitrocubane  
Anyone for 1,6-ditetrazolylhexaaza-1,5-diene? Dornier335A has it on Youtube. VoD 9300 ms. Sensitivity is, of course, just about unparalleled. Formula C2H4N14 - it contains 87.5% nitrogen by weight.


Here's the video

https://www.youtube.com/watch?v=WowrwV-0ca8

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https://www.youtube.com/watch?v=qVZT5aR3ih0

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[Edited on 3/27/2016 by Rosco Bodine]

Dornier 335A - 27-3-2016 at 11:50

The first link in Rosco's post shows its properties very well, but I'll provide some more information here.

Ditetetrazolylhexaazadiene is described in Engager's Energetic Derivatives of Tetrazole with the name bisdiazotetrazolylhydrazine and briefly in Fedoroff. It's synthesised by mixing diazotetrazole solution with a solution of hydrazinium chloride and sodium acetate. My product immediately dissolved/decomposed after forming though, probably due to too basic conditions. Replacing the hydrazinium chloride with hydrazine sulfate worked well, and sodium acetate buffer doesn't seem necessary, although the product is whiter without.

The product seems stable after drying but rapidly dissolves in basic solutions to give a strongly yellow solution. It hydrolyses slowly in water to give gas bubbles (nitrogen?) and 5-azidotetrazole. My product is stable in acidic solutions though.

Now comes the fun part: it's more explosive than anyone has probably ever dreamt of. My calculated performance at the measured density 1.8 g/cm3 is 9700 m/s and 420 kbar.
In addition, it's critical diameter is microscopic. I played around with tiny grains under a microscope, trying to make as small flakes as possible. I got an 18 micron thick flake, approximately 0.4 micrograms, to detonate (it put a dent in the aluminium foil).

This performance is not without downsides of course; it is exceptionally sensitive. Filter papers covered with ditetetrazolylhexaazadiene explode if ripped (something I discovered without protection...) Light tapping with a hammer sets it off, as does pressing. More videos will come in the future!

[Edited on 27-3-2016 by Dornier 335A]

Rosco Bodine - 27-3-2016 at 13:49

Regarding the aminoguandine bicarbonate precursor for aminotetrazole

A point of interest is a second independent confirmation regarding the pyrolitic decomposition of calcium cyanurate to pure calcium cyanamide. I think Davin first reported this does in fact work even as a "campfire" cyanamide produced in the hot coals of a wood fire kind of adapted process so long as there is venting of the byproduct gases from the heated to orange heat container allowed, but not allowing air ingress into the reaction mixture.

It looks like maybe a hacksaw cut was made to defeat the sealing of the threads and allow controlled venting for the "bomb" used for the pyrolysis which is good technique. A small press fit "freeze plug" type of safety overpressure blowout plug is a good idea also in the top end cap for a reactor like this in case venting is ever obstructed to prevent pressure buildup in the reactor. Probably a good easy safety vent providing a "gravity seal" would be to use a 3/8" clevis pin dropped into a 3/8" hole drilled into the end cap, with the loose seal at the shoulder being sufficient. The shaft of the clevis pin could be scored with a diagonal groove cut using a hacksaw, and if pressure from venting raised the clevis pin to the cut groove it should regulate there by gravity like a pressure cooker regulator, and function as a loosely fitted check valve and regulator.

https://www.youtube.com/watch?v=AF11Xuh0SaQ

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[Edited on 3/27/2016 by Rosco Bodine]

octonitrocubane - 27-3-2016 at 14:09

Having just synthesised five grams, its safe to say that I will never touch it again. One flake on the floor nearky gave me a heart attack. 4 grams contained with aluminium foil within a plastic bag lit at the bottom of the water bottle absolutely shred it. Despite being able to isolate ~10 micron flakes, it has yet to not detonate...

early thread missing images archived

Rosco Bodine - 27-3-2016 at 18:45

Some of the early pages of this thread have dead linked missing images so attached is an old backup pdf which has viewable most of the missing files

Attachment: Tetrazole thread archival images.pdf (2.4MB)
This file has been downloaded 1496 times

Erwinol - 10-4-2016 at 06:40

http://www.wydawnictwa.ipo.waw.pl/cejem/2-2010/full/Sabate.p...

NeonPulse - 24-4-2016 at 01:54

Ok so it has been quite a journey from pool chemicals, urea, sodium bicarbonate and hydroxide , ammonia, hydrochloric, sulfuric, nitric acids copper sulfate sodium nitrite and anything else I had forgotten but finally I got to make some of the copper nitrotetroazolate primary I had aimed for.
All components were OTC or made from OTC components except the 70% nitric acid( which could easily be synthesised OTC anyway) including the ammonia which I made from NaOH and ammonium sulfate, the hydrazine, the cyanamide ( my method was shown in video above) which all together formed the basis of the 5-ATZ and finally the CuNTZ.
Basically I had followed Engagers work here. It's his legacy here it would seem...
I must say though I'm pretty impressed by this compound although it is not the best initiator made from the 5-ATZ and really want to attempt the silver variant and the Mercury variant especially. This particular salt gave me no troubles synthesising it and I was expecting the micro explosions I had read about but luckily for me none happened. The only problems were the NOx fuming and thevery slow filtering of the ultra fine green mud.
It seems to have a tiny critical diameter and minute grains go off with a crack when heated on foil putting pin holes in it but with confinement in foil and heated it gives a pretty loud report and sends silver foil confetti flying. I want to test it a little more but so far I can see why primaries based on 5-ATZ and its salts are of interest as green energetic materials.

image.jpeg - 1.6MB

Rosco Bodine - 24-4-2016 at 07:41

Voila! ..... Verdigris Patina Terribilis :D

seafoam green with attitude :P

The color reminds me of the patina on roofs and statuary



[Edited on 4/24/2016 by Rosco Bodine]

roof

Laboratory of Liptakov - 24-4-2016 at 11:42

Oh my God. On roofs I see Neon - Cu NTZ compounds! Is not necessary huge a complication of synthesis. Much easily is scratching from the roof. Without acid and others chemical tools. I seems, that only what you needed is knife and ladder. Thanks for info...:cool:...LL

Dornier 335A - 24-4-2016 at 13:53

NeonPulse, is that Cu(NTZ)2 or is it the acid copper nitrotetrazole salt? Because that one is supposed to be very sensitive.

Liptakov, I climbed my local church's roof and found this:

HXS18pP.png - 927kB
It turned out to be copper(II) 5-azidotetrazolate though! Be careful!

NeonPulse - 24-4-2016 at 22:51

It's the acid copper salt. It's colour is much paler than the picture portrayed but the camera seem to get it right. It would be much better if it had a higher density like crystals rather than the fine fine powder. It doesn't seem overly sensitive but a lot of care is still taken while handling the dry product. Once it had been dried for weighing I have sprayed a mist of water to dampen it and put it in a container till it's needed.
Is it right that being stored underwater will slowly decompose it? I think I read that in some PowerPoint presentation about green initiators some time ago.
Wet storage is much preferred to missing fingers and I can easily see a small amount doing a lot of damage to a careless handler.

I know it seemed overly complicated but it's not really.Basically I wanted to see if this could be done using all OTC chemicals and it seems that with a bit of work and effort it can. However for all that work put in over a few weekends the end result was only a few grams of the green stuff. But that's enough since a little bit goes s long way.Most people would probably say it's hardly worth the time but hey, I think it's time well spent. I'll Give the photo another go:

image.jpeg - 2MB
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