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Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
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[*] posted on 25-7-2010 at 04:52


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

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

Any suggestions/ideas?
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[*] posted on 25-7-2010 at 15:11


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

Attachment: Chemistry_of_Aminoguanidine_And_Related_Substances.pdf (975kB)
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[Edited on 25-7-2010 by Engager]




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[*] posted on 25-7-2010 at 23:33


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

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

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

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



[Edited on 26-7-2010 by Taoiseach]
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[*] posted on 31-8-2010 at 09:12


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

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



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






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


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[*] posted on 31-8-2010 at 12:28


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

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

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

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

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

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



[Edited on 31-8-2010 by Engager]




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[*] posted on 31-8-2010 at 23:05


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

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

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

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

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


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

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

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

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

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

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

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

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

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

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

[Edited on 2-9-2010 by Rosco Bodine]
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biggrin.gif posted on 2-9-2010 at 10:00
Triaminoguanidine nitrate synthesis kinetics


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

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

Kinetics of triaminoguanidine nitrate synthesis

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

Attachment: Kinetics of triaminoguanidine nitrate synthesis.pdf (770kB)
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[*] posted on 2-9-2010 at 13:32


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

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

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

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

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

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

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

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

mgdatz.jpg - 10kB

[Edited on 2-9-2010 by Taoiseach]
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cool.gif posted on 2-9-2010 at 18:16
Here's an interesting paper


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

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

Note:
Azidoformamidinium Perchlorate = Guanyl Azide Perchlorate

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

Attachment: Aminoguanidine Perchlorate, Triaminoguanidine Perchlorate, Guanyl Azide Perchlorate.pdf (316kB)
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[Edited on 3-9-2010 by Rosco Bodine]
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[*] posted on 3-9-2010 at 01:27


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


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

[Edited on 3-9-2010 by Engager]




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[*] posted on 19-9-2010 at 17:59


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

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


5-atz.bmp - 697kB
keep in mind that is only 350mg.
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[*] posted on 29-9-2010 at 05:07


Quote: Originally posted by Rosco Bodine  
Quote: Originally posted by The_Davster  
About the azidotetrazoles and ethyleneditetrazyl azide mentioned in the early parts of this thread. Looks like the old patent made something else or, they the patent made an impure oil of a product. The following paper states the ethylene bridged azidotetrazole to be a solid.
http://www3.interscience.wiley.com/journal/122512017/abstrac...

(This is not the first instance of something being discussed on this board being published a few years later...:P :o )


If you have the complete article please post it. It could be the temperature is low for which crystal data is referenced, or it could be a different isomer, or something different entirely from the material referenced in the patent.

Edit: Thanks to solo for the article attached


@The Davster

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

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

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

Attachment: US3151935 Thermal Conversion of Sodium Chlorate to Perchlorate.pdf (243kB)
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[Edited on 29-9-2010 by Rosco Bodine]
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[*] posted on 7-10-2010 at 13:32


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

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

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

[Edited on 8-10-2010 by Rosco Bodine]
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[*] posted on 17-10-2010 at 12:43


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

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

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

[Edited on 17-10-2010 by AH-Poster]
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[*] posted on 21-10-2010 at 09:04


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


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

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



[Edited on 21-10-2010 by Rosco Bodine]
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[*] posted on 21-10-2010 at 13:01


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



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

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

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

[Edited on 12-6-2008 by Engager]


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

Interesting file for test data from the following link

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

See US7592462 attached

See Hirlinger research paper attached

See essay explosives attached

Diaminotetrazole Chloride article attached

Attachment: essay explosives.pdf (1.2MB)
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Attachment: US7592462_Explosive_complexes.pdf (142kB)
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Attachment: Hirlinger research paper.pdf (789kB)
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Attachment: Diaminotetrazole Chloride.pdf (283kB)
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[Edited on 22-10-2010 by Rosco Bodine]
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[*] posted on 21-12-2010 at 08:30


Obviously what as a result of reaction cyanamide and hydrazine -reaction product aminoguanidine. But i have in its dictation dicyandiamide and hydrazine sulphate. How, in what way you out of dicyandiamide and hydrazine sulphate prepare aminoguanidine bicarbonate? publish the reference.
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[*] posted on 6-1-2011 at 13:47


<b> The Usage of 5-ATZ as a nucleophile </b>

Having kept an eye on the topic concerning 5-ATZ, I have been wondering, has anyone tested the strength of 5-ATZ as a nucleophile? For example, I have been looking at the possibility of using it in a nucleophilic substitution with chloromethane.
Has anyone attempted any similar procedures?
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[*] posted on 23-2-2011 at 02:24


:mad: 擦的 果然是疯狂的东西 5AT硝酸盐不可小视……



擦的……英文水平太低 有中国的疯子们么?
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[*] posted on 23-2-2011 at 11:29




"英文水平太低 有中国的疯子们么?"


保留尝试! 某人将回答。我们有中国成员。




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[*] posted on 23-2-2011 at 23:47


Quote: Originally posted by Hydrazinium  
<b> The Usage of 5-ATZ as a nucleophile </b>

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


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

Ethyl bromide does similar.




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Rosco Bodine
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[*] posted on 24-5-2011 at 01:23


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


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

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

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

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

[Edited on 24-5-2011 by Rosco Bodine]
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[*] posted on 29-5-2011 at 01:46


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

P.S.

By the way Rosco, is it safe to perform your hydrazine sulfate synthesis under ordinary kitchen aspirator?
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Rosco Bodine
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[*] posted on 29-5-2011 at 11:26


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

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

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

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

[Edited on 29-5-2011 by Rosco Bodine]
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[*] posted on 30-5-2011 at 00:21


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

P.S.

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