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Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
The_Davster
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[*] posted on 15-11-2006 at 19:36
5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends


There has been talk of tetrazoles and precursors in several threads, usually as off-topic discussion, I thought it would be an idea to do a bit of a collection of some of this into a single thread.

The 'My favorite Primary Explosive' thread on E&W, where the nitrotetrazoles are first mentioned.
http://www.roguesci.org/theforum/other-explosives/3158-my-fa...
Ironically, I found this thread after I had done all my research, which as Rosco posted all the patent refs in that thread, would have made my life much easier had I found that thread before I dug through the literature looking for refs to the patents.

5-ATZ
US patents 5424449 and 5594146 detail the synthesis of 5-ATZ from hydrazine, cyanamide, nitrite and ammonia, but as aminoguanidine is an intermediate in the synthesis, one can start with it. I have read that aminoguanidine hydrochloride is used in some pills that are supposed to make you live longer, and in my opinion is much preferable to the use of hydrazine:P. I have not looked further into the use of such antiaging pills as I have reagent aminoguanidine. I had worked out the ammounts of aminoguanidine needed to pick up the procedure in the middle, but I lost my calculations, and then found what Microtek had already done it, so from there on I used his numbers. (Much thanks, I hope you do not mind me posting your procedure)

Quote:


- 6.45 g aminoguanidinium bicarbonate was suspended in 7 mL H2O and neutralized with 5 mL 30 % HCl ( dropwise addition although it cooled down rather a lot during addition ).
- pH was checked with universal indicator strips and adjusted to ca pH 4.
- Another 5.3 mL 30 % HCl was added all at once.
- A soln of 3.5 g NaNO2 in 7.5 mL H2O was added from an addition funnel while stirring vigorously and keeping temp at 17-20 C with an ice bath ( no salt ). Addition proceeded smoothly with negligible evolution of NOx ( not visible and only just detectable by smell ) until the very last drops which gave the evolution of NOx which is typical of nitrite with acid. This likely signified that all the aminoguanidine had been diazotized.
- Stirring was continued for 20 minutes at 20 C after addition was completed.
- 4.9 mL 25 % ammonia soln was added all at once ( pH was measured at this point and was found to be ca 6-7 ), the flask was equipped with a condenser and the mix was heated to beginning reflux. It was held there for 2 hours.
- While still hot, pH was adjusted to ca 4 with HCl and ammonia water; ca 1.8 mL 30 % HCl was required.[I found I actually had to basify instead at this step]
- Mix was allowed to cool very slowly by turning off the hotplate but letting the flask stay on it. Once it had cooled to room temp, it was placed in the refridgerator until a temp of 10 C had been reached.
The product crystallized in very well defined plates beginning from ca 40 C.
- Almost all the mother liquor was easily decanted from the dense crystal mass, and 12 mL of H2O was added to remove co-precipitated chloride.
- Mix was heated to 45 C with stirring and was then allowed to cool to 10 C.
Not all of the product was dissolved in this operation.
- Product was removed by filtration and washed several times in the filter with cool water.


Works Great! Even did a melting point(or rather, decomposition point). The crystals are quite nice, but the solution tends to super-saturate(4/5 times), so introduction of a seed crystal at around 50C is a good idea. I added one at 60-70C once, and the resultant crystals looked different, but still had the same melting point. The crystals formed when a seed crystal is introduced at this temp do not look as pretty, and they hold more water taking longer to dry, so 40-50C seems ideal.

Nitrotetrazole(ate)
US patents 4093623 and 2066954 describe the prep of acid copper nitrotetrazolate from 5-ATZ, which can then used to make other nitrotetrazolate compounds via metathesis. Example 6 of 4093623 was carried out on a scale just slightly greater than testtube scale, giving a precipitate of CuHNT(NT)2, I did not let this dry as it is said to be sensitive to shock and electrostatic discharge, and my winters are very dry. The acid copper salt was reacted with NaOH solution as per example 8 in the same patent, however I am simply using a slightly acidic solution of NaNT (pH=4, as per patent directions) instead of evaporating to get sodium nitrotetrazolate crystals. However the solution has turned a light yellow/green over a couple days, so it may be advantageous to keep it basic and then acidify before using the sodium salt to make other metal nitrotetrazolates.
Speaking of which, I prepared a very small ammount of silver nitrotetrazolate, which simply leaves me in awe. It reminds me of silver fulminate in terms of how small an ammount of it will go DDT, even when wet. (used flame to do this). Something silver azide does not do as well. I believe Rosco calls this an "unequivocal" primary. Sensitivity is said to be relatively low, but I have done no testing of this, and likely will not. This was more of a long wonderful chemical adventure than a search for an ideal primary.:P I just decided to expend so much effort into getting to this point as I really adore the structure of tetrazoles.:D



Others which I have no experience with to date
Azidotetrazole:
https://sciencemadness.org/talk/viewthread.php?tid=5129
JoPEP,30, 2005, page17
Looks like crazy stuff, I should try it sometime

Nitraminotetrazole:
Can be done with either making the nitrate of ATZ, then dehydrating, or by using nitraminoguanidine in the tetrazole reaction. Unfortunatly nitraminoguanidine requires hydrazine.
Thermochemica Acta 384 (2002) 113-120

ATZ-nitrate:
PEP, 30 (2005) No3 191

5-halotetrazoles:
Been meaning to research these, I want to make iodo and bromo


I intended to write more under this section, but I am tired now, more later perhaps. There is also a complete route from cyanuric acid(pool chlorine stabilizer) to tetrazoles, I know Rosco is doing some work on this as well, but I intend to put a bunch more annoying steps in to avoid the use of hydrazine. But really I have only started this part, and that would be for another thread.

I tried to attach a big review of tetrazole chemistry, but it is too big, and rapidshare is full curently. I'll post it when there is more room on rapidshare



[Edited on 16-11-2006 by The_Davster]




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[*] posted on 15-11-2006 at 21:55


Phenyl cyanide + NaN3 + NEt3-HCl is supposed to yeild phenyl tetrazole. Since I do not know of good place to upload stuff I will send you the link discussing the synthesis.



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[*] posted on 17-2-2007 at 18:51
Tetrazylazides


Liquid or plastique primaries are virtually unknown .

Ethyleneditetrazylazide is reportedly a way to do this .

I do not know of any information available concerning
synthesis of these tetrazylazides .

Attachment: US2170943 Tetrazylazides.pdf (80kB)
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[*] posted on 18-2-2007 at 00:19


Is that archaic nomenclature? Could tetrazyl be the old name for tetrazoyl? Making the compound in question an 'ionic liquid' of whatever 2 molecules of 5-ATZ linked through nitrogens to the NH2s on ethylene diamine is called, then protonated somewhere and the azide salt formed?

Or it could be a di substituted tetrazole ring...but I can't imagine a bridging ethylenediamine stabilizing any azotetrazole.

Really, I am very intrigued!




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[*] posted on 18-2-2007 at 00:50


I don't understand the term tetrazyl either ....

wonder if it is equivalent to " tetrazolyl " ?

The germans used a different nomenclature
and it is a bit confusing . The same thing occurs
with regards to some of the other tetrazole patents .
IIRC there are a few lines in COPAE about some
of the different synonyms used for the same groups .
Defintely encounterd this nomenclature confusion before ,
and it seems that it was Axt or Nick F who was good at sorting these out .

Anyway , those are reputable names on the patent ,
company and inventor alike ....so there is likely something
to this group of compounds , which they aren't saying
too much about with regards to synthesis .

The attached file sheds some light on this ......
whew what a synthesis , reserved for the skilled
and not squeamish about toxic materials ....

[Edited on 18-2-2007 by Rosco Bodine]

Attachment: US2179783 Tetrazylazide and Salts.pdf (103kB)
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[*] posted on 18-2-2007 at 01:13


Here is more information expanding on that first patent

Attachment: GB510992 Tetrazylazide Priming Explosives.pdf (155kB)
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[*] posted on 18-2-2007 at 12:07


From what I gather...The first German patent is only claiming an improved process for mass production of the azotetrazole...For which there are other known routes too, not involving cahones as big as would be necessary for that patent:P

So now we are definatly getting somewhere...it is an azotetrazole. Excellent. Those are not impossible. However the ethylene part of the molecule is still confusing.
Unfortunatly, due to the standard synths of disubstituted tetrazoles, azotetrazole probally cant be used as the starting material. Unless its an ethyl-azo disubstituted tetrazole, in which silver azotetrazole and ethyl iodide should give the product.

I wish the patent had a molecular structure for the compound...




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[*] posted on 18-2-2007 at 12:47


Looks to me like all that is required for the ethylene derivative is to react ethylene dichloride with 2 equivalents of sodium tetrazylazide .

The basis for these salts is Tetrazylazoic Acid ....
which seems to be hydrazoic acid which has
been combined with a tetrazole ring ......
now that should enhance the already incredible
energy and also lend a greater stability if my guess
is correct .

I have to wonder if the sodium tetrazylazide could be substituted for sodium azide in the azo-clathrate synthesis leading to a series of tetrazylazo-clathrates which would tame the overly sensitive straight lead tetrazylazide ...while manifesting extraordinary power .

My guess would be that the critical diameter on these tetrazylazides would be extremely small ....capillary sized
det cord anybody ? Did somebody ask for explosive paint ?
This stuff should do the trick :D

[Edited on 18-2-2007 by Rosco Bodine]
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[*] posted on 18-2-2007 at 13:11


Oops, yeah, meant diiodoethane last post.

I don't know, I am a bit unsure whether what bridges the two tetrazoles is a -CH=CH- or a simple -CH2-CH2-. Archaic nomenclature can be a bit strange for such things. Either way, makes me very curious about what would happen with the -C(triplebond)C- variant, but dichloroacetylene as a starting point is...:o. Diiiodo would also probably work...

Hmm, I have some sodium nitrotetrazole crystals lying around, and diiodoacetylene is easyish to make(but rather toxic for my tastes)...I might just have a go on a variant like this...
Should be safer than azotetrazole variants, as I have heard horror stories about azotetrazole. NaNT at least turns to a liquid before it dets with surprising violence.

(Rosco, thanks for bringing these up from obscurity, I had been in a chemistry slump and nothing was really catching my attention, these brought me out:D)

As for a substitute for NaN3 in the azo-clathrates...Why not use both azotetrazole, and azide. :D With some nitrotetrazole added to taste:P

[Edited on 18-2-2007 by The_Davster]




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[*] posted on 18-2-2007 at 13:24


A cauldron full of complexes
is kind of like
a saucer full of secrets .....

What you get
might even trump
old Forrest Gump

with life that's like
a box of chocolates

You never really know
exactly what you are going to get :D

I would add that a healthy dose of paranoia
would not be out of place concerning this class
of energetic materials ....I'd definitely keep quantities
very small , recognizing that this sort of material is
right up there among the most energetic materials
known to science . It wouldn't take much of this stuff
doing the unexpected to do a lot of damage .

[Edited on 18-2-2007 by Rosco Bodine]
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[*] posted on 18-2-2007 at 22:57


I was right in thinking this " tetrazyl " prefix is perhaps equivalent to " tetrazolyl " , and have been able to further clarify exactly what it is , as well as a possibly easier method of synthesis .

The same compound having the following *six* synonymous designations is described in PATR Vol.9 , T-124, 125

5 - Azido Tetrazole , Tetrazolyl Azide , 5 - Triazo - Tetrazole ,

Diazotetrazolimide , Tetrazylazoimide ,

[ Tetrazolyl- (5) ] - azoimide

It is also item #2 on page 2 of the attached patent .

In COPAE , page 447 , Davis describes in more detail the method mentioned in the patent , using tetracene as the precursor , hydrolyzed using NaOH , to form an intermediate triazonitroso-aminoguanidine which is isolated by addition
of copper acetate producing a precipitate of bright blue colored explosive copper salt . This salt after filtering and washing and treatment with acid ( probably HCl ) gives
the Tetrazolyl Azide .

So essentially , Calcium Cyanamide , Hydrazine Sulfate ,
and sodium nitrite ......or Aminoguanidine Bicarbonate and
sodium nitrite are the precursors for tetracene , and this
eliminates the need for more extreme and toxic cyanogen and azide reagents proposed by the Friedrich patent .

Davis cites a reference providing more on this and I will be requesting it through channels here .

The Chemistry of Aminoguanidine and Related Substances ,
G.B.L. Smith , Chem. Rev. , 25 , 214 (1939)

Attachment: GB185555 Tetrazole Initiator Compounds.pdf (286kB)
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[*] posted on 19-2-2007 at 01:16


There is also a route from 5-ATZ to azidotetrazole, I have it hardcopy and will dig it up hopefully. Just need to find my folder on the tetrazoles...its around here somewhere.
Looks fun: https://sciencemadness.org/talk/viewthread.php?tid=5129

I also have JoPEP,30, 2005, page17 written down as a ref for them.

But for now, uploaded is the chemistry of aminoguanidine file you wanted:


I should move this out of the complex thread and into the tetrazoles thread I started a while back. Fine with you? These arent really complexes....

EDIT: Crap, too big to attach here, I rapidshare.COM ed it
http://rapidshare.com/files/17182917/The_Chemistry_of_Aminog...



[Edited on 19-2-2007 by The_Davster]




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[*] posted on 19-2-2007 at 02:05
The Chemistry of Aminoguanidine and Related Substances


Here's a smaller file .....

Thanks to kmno4

And yes any alternate routes are of interest .

Actually there are only a few of these
tetrazoles of particular interest as most of them
have been evaluated and ruled out for
oversensitivity or other reasons .

Funny you should post that link for the thread
about the acetic acid ....and yeah I was thinking about
what was mentioned about the incompatability ,
realizing that the copper precipitate of the nitroso
derivative of tetracene must be formed in alkaline solution ,
and then separated from the sodium acetate in alkaline
supernatant and filtrate , carefully rinsing out any acetate
from the copper precipitate , *before* acidifying .....
or else a nasty surprise awaits :P

It would really be nice to have a more forgiving method ,
which doesn't involve copper salts ....maybe a calcium salt
for example .

[Edited on 19-2-2007 by Rosco Bodine]

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[*] posted on 3-3-2007 at 20:04
5-azidotetrazole via Ba(OH)2 hydrolysis of tetracene


Thanks to Joeychemist and solo for this helpful reference .

See the last paragraph on page 5 ,
Alkaline degradation of IX (tetracene monohydrate) .

Evidently simply boiling tetracene with a base hydrolyzes
it with the expulsion of one ammonia , and leads to
ring closure and formation of 5-azidotetrazole .....perhaps
(hopefully) being present as the soluble 5-azidotetrazole salt of sodium , in the case where the base used for the hydrolysis is sodium hydroxide . This should simplify greatly
the synthesis of 5-azidotetrazole where it is needed as
an intermediate which will not be isolated , knowing
that it is produced *directly* by the alkaline hydrolysis of
tetracene .

This finding is in contrast with what Davis reported on COPAE concerning the incorrectly alleged intermediate triazonitroso-aminoguanidine identified mistakenly by Hofmann via elementary analysis , whose composition was actually identical with the monohydrate copper salt of
5-azidotetrazole .

An interesting side note concerning the related derivative
of tetracene , 5-aminotetrazole . I have read in PATR ,
tetracene quietly decomposes / converts completely to
5-aminotetrazole by nothing but gentle heat being applied to the sample of tetracene for several days ,
@90C less than 3 days .


[Edited on 4-3-2007 by Rosco Bodine]

Attachment: The Structure of Tetracene.pdf (778kB)
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[*] posted on 4-3-2007 at 00:04


Excellent!

For the aminotetrazole though....90C for 3 days? Reflux diazotized aminoguanidine in ammonia for 3h...82% yields. Tried and true.




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[*] posted on 4-3-2007 at 01:11


Yeah it is in PATR under " Tetrazene " , an Australian
government study found that stab detonators containing
tetracene would fail to function after storage at elevated temperatures because of the tetracene slowly changing to
5-aminotetrazole by thermal decomposition . They stated
complete conversion at 90C in less than 3 days .

With regards to the reaction of the 5-azidotetrazole sodium salt with methyl or ethyl sulfate or chlorides ,
I wonder if other esters such as the nitrate or nitrite
esters would work as well , or if the nitrite ester might
lead to something different . I especially wondered about the reaction possibility for the nitrite esters since they are so easily made .
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[*] posted on 8-3-2007 at 18:47


There is probably a workable general route to the useful energetic tetrazoles and related materials
which uses OTC precursors .

The production of Calcium Cyanamide or Zinc Cyanamide
or Magnesium Cyanamide ....or perhaps some mixture
of these cyanamides which might form more readily by
pyrolytic decomposition of their cyanurate precursors ,
could then be reacted with Hydrazine Sulfate to form
aminoguanidine as the intermediate ....which is then
reacted with sodium nitrite or perhaps nitrosated ,
" diazotized " by other methods , and depending upon the
pH at which this is done , the product is guanyl azide ,
or tetracene , or 5-aminotetrazole ......by variations upon
the process .

Guanyl Azide Picrate is itself another useful , stable and powerful energetic material
which is satisfactory for use as a base charge in detonators .

To any of these products then can be applied subsequent treatments
to obtain the desired tetrazole compound .

IIRC , the Zinc Cyanurate is the material which is converted at a somewhat lower temperature
to the desired cyanamide . It still requires a low red heat ,
but this should be reachable without too much difficulty ,
in a rudimentary sort of furnace , or even in an open
fire or over a burner .

A preliminary experiment I did seemed to produce the desired cyanurate precursor ,
but I haven't yet fired this material to see if the cyanamide is produced as expected ,
however it should work as this reaction is mentioned in several patents .

https://sciencemadness.org/talk/viewthread.php?tid=2762&page...

Tetracene can be produced from the reaction of the
alkaline earth cyanamide and hydrazine sulfate ,
without isolation of the aminoguanidine intermediate ,
by treatment of the reaction mixture with NaNO2 .
I have a patent concerning this and I will find it
and attach it later .

I expect there are perhaps a dozen different energetic materials which are of reported value ,
maybe half of those of special interest among this class of compounds .

[Edited on 8-3-2007 by Rosco Bodine]
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[*] posted on 8-3-2007 at 19:26


I actually made a dozen grams or so of the calcium cyanurate. In another post you say it decomps to HOCN. That should instantly combust at the required temps hopefully right? No toxic death cloud?:P

[Edited on 8-3-2007 by The_Davster]




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[*] posted on 8-3-2007 at 20:18


Right ...cyanic acid should burn off , and then extinguish as
the excess cyanic acid comes off at a lower temperature stage of the decomposition where the cyanurate
is probably converted first to a straight cyanate .

The evolving cyanic acid vapor might not ignite within an
electric furnace being gradually heated ....but it should ignite in a flame fired environment for sure . If you are using a
metallic vent line , simply discharging it onto the flame of a small burner used as a pilot light should flare it off okay .
If you wanted to bubble any offgassing into alkaline water
you should use a trap or checkvalve to prevent any suckback of the liquid when the rate of gas evolution slows .

IIRC , The cyanuric acid is actually a trimer of cyanic acid ,
thermally decomposed .....a parallel sort of material
as is trioxane and formaldehyde . Anyway , after the
alkaline earth cyanurate is decomposed to its normal
cyanate ....the "extra" HOCN is gone ....and further
decomposition as the material reaches red heat ,
evolves only CO2 ....and when it finishes offgassing
CO2 .....all that should be left is pure white Calcium Cyanamide .

Of course this would not be a commercially viable process because it is counterintuitive to sort of reverse engineer
the usual products of a process along a tangent to get back to an intermediate :D ....
in our case the alkaline earth cyanamide .

But for a lab scale approach to how easiest to take an
OTC material like chlorine stabilizer , cyanuric acid , and
produce pure calcium cyanamide or other pure cyanamides from it ....this would seem the most probable
candidate as a method , doing a straightforward thermal
decomposition of an intermediate which should produce
nothing else but the desired product .

Attached is a patent describing the conditions for reaction
of calcium cyanamide with hydrazine sulfate to form aminoguandine in solution , and a filterable form of
calcium sulfate residue by control of pH which influences the
crystalline form of the of the calcium sulfate byproduct .

The aminoguanidine solution in this patent process is
then neutralized with H2SO4 to form a solution of aminoguanidine sulfate , to which is added baking soda
to precipitate insoluble aminoguanidine bicarbonate which
is filtered out .

But you see at the point where the aminoguanidine freebase
or sulfate is available in aqueous solution , other things can be done to obtain different products if aminoguanidine bicarbonate is not the desired end product .

Guanyl Azide or its salts , or tetracene , or 5-aminotetrazole ,
or other materials may be obtained by further reactions upon the aminoguanidine intermediate without any need for its isolation .

[Edited on 9-3-2007 by Rosco Bodine]

Attachment: US3673253 Aminoguanidine Bicarbonate via Calcium Cyanamide and Hydrazine Sulfate.pdf (385kB)
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[*] posted on 9-3-2007 at 21:18
5-Nitroaminotetrazole from 5-Aminotetrazole


The 5-aminotetrazole nitrate dehydration to form
the 5-nitroaminotetrazole has been described as
a somewhat analogous reaction to the dehydration of
guanidine nitrate to form nitroguanidine . The conditions must be carefully controlled and the temperature kept low due to instability of the amino group of the amino tetrazole , which will be oxidized under too severe conditions . The free acidic 5-Nitroaminotetrazole should
probably not be isolated as the dry material but left in solution , or converted to one of its more stable salts .

There are a few ways of doing the conversion directly
from 5-Aminotetrazole , not requiring its nitrate as
an intermediate . Attached is a patent which describes
5-Aminotetrazole being dissolved in concentrated H2SO4
and then nitrated with fuming (90%) HNO3 added dropwise @20-25C , the mixture drowned over crushed ice and then neutralized with NH4OH to precipitate the
diammonium ? salt of 5-Nitroaminotetrazole . Other salts
can be made from this . See page 4 , Column 5 ,
Example 1 .

Alternately to using the mixed acid , a Japanese patent
JP11279164 describes that the nitration can be accomplished by addition of NH4NO3 to the solution of
5-Aminotetrazole in concentrated ? H2SO4 . Since I
am unable to read Japanese ....the details of the method
are unclear . But it appears that the process is otherwise
similar .

According to the reactions shown in the Japanese patent
and also other English language references , the free acidic 5-Nitroaminotetrazole is obtained in solution by treatment of the ammonium or sodium salt with HCl .

The potassium salt is the salt specified for use in the reaction for producing " Stabanate " , the double
lead salt of 5-Nitroaminotetrazole and Styphnic Acid ,
which is a patented US3310569 initiator having superior stability and 50% higher brisance in the sand test than lead styphnate . It is reportedly satisfactory for use as
an initiator in detonators , although its performance in that regard is not disclosed .

[Edited on 15-3-2007 by Rosco Bodine]

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[*] posted on 9-3-2007 at 22:01
Here's an older related journal reference


The Nitration of 5-Aminotetrazole

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[*] posted on 10-3-2007 at 08:43


I have prepared 7.25g nitroaminoguanidine as follows: (Patent US2617826)

(hydrazine sulfate was made with Mr. Anonymous's recipe, nitroguanidine was made from homebrew guanidine nitrate)

200ml water was heated to 60�C and 11g NQ were added while stirring. 15.3g hydrazine sulfate, 100ml water and 6.90g NaOH were mixed and stirred until everything had gone into solution. This solution was slowly poured into the agitated and heated NQ-solution/suspension. Heating (60�C) and stirring was continued during half an hour. After 15 minutes all the NQ had dissolved. The liquid turned orange and during the experiment I smelled ammonia:
HN=C(NH2)(NHNO2) + H2N-NH2 ---> HN=C(NHNO2)(NHNH2) + NH3

So after these thirty minutes, the solution was neutralised with concentrated hydrochloric acid (approx. 6ml HCl 29% was used). The liquid was allowed to cool to 5�C (fridge) and was left so for one hour for full precipitation of the NAQ (the colour... how should I say: slightly pale yellow - "blanc cass�" - light off-white colour?), . It was then filtered and washed with two portions of 15ml cold distilled water. Dried at 80�C. Yield: 7.25g or 57.6% yield.
:)

BTW: I added two teaspoons of sodium nitrite and 10ml GAA to the filtrate. A very light foaming occurred (no smell or colour, I gess it's nitrogen) and after a few hours I noticed a white somewhat fluffy precipitate. I filtered it, washed it with some water and let it dry. Unfortunately it only burns (no deflagration or something energetic). Does anyone have an idea what this stuff is?

Now, can someone give some help for the synthesis of nitroaminotetrazole and nitroguanyl azide (starting from NAQ off course). The only documents I found was Reaction of nitrous acid with nitroaminoguanidine and Ultraviolet absorption of 5-NATZ and it salts but as can be seen no specific reaction conditions, weights, procedure, ... are given. PATR (page A259-260) is not very helpfull too :(.


[Edite le 10-3-2007 par Sobrero]
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[*] posted on 10-3-2007 at 13:08


Quote:
Originally posted by Sobrero
Now, can someone give some help for the synthesis of nitroaminotetrazole and nitroguanyl azide (starting from NAQ off course). The only documents I found was Reaction of nitrous acid with nitroaminoguanidine and Ultraviolet absorption of 5-NATZ and it salts but as can be seen no specific reaction conditions, weights, procedure, ... are given. PATR (page A259-260) is not very helpfull too :(.
[Edite le 10-3-2007 par Sobrero]


(Edit)
Nitroaminoguanidine is evidently an alternate precursor for nitroaminotetrazole .
The other path would be to reduce the nitroguanidine using zinc , to get aminoguanidine , and then nitrosation , followed by cyclization to 5-aminotetrazole and nitration as described earlier .

The entire article may provide some additional information
concerning the alternate route described in the abstract
which you just linked for nitroaminotetrazole from
nitroguanylazide . I will request that article .
( Edit : See complete article attached in following post )

Nitroaminoguanidine can be nitrosated to form nitroguanylazide .....by a similar method as is used
for conversion of aminoguanidine to guanyl azide .

The following excerpt US6350307 , page 9 , column 15 ,
line 30 , concerns guanyl azide

Preparation of Guanyl Azide

An initial charge of technical grade hydrochloric acid and distilled and demineralized water is indirectly cooled down to about 0.degree. C. Aminoguanidine bicarbonate is subsequently added at about 10.degree. C. in the course of about 30 minutes. Thereafter, the batch is indirectly cooled down to about 0.degree. C., and sodium nitrite solution is added up to max. 15.degree. C. in the course of about 3 hours. This is followed by stirring with nitrite excess for 15 minutes. Directly prior to transfer of the azo groups, the nitrite excess is removed with amidosulphonic acid.


A Ukranian patent (attached) describes this , including isolation of the product . There is an English summary on page 2 .

Abstract of UA16960U

A method for producing nitroguanilazide and derivatives thereof comprises nitrosation of N-nitro-N'-aminoguanidine (NAG) in the aqueous medium in the presence of sulphuric acid by potassium nitrite at a molar ratio of and providing water excess of 1.48 l H2O/mole of NAG at the temperature of with subsequent keeping the reaction mixture at the room temperature during specified time, evaporation of reaction mass during a long time at the same temperature, three-stage extraction of solid remainder by anhydrous diethyl ether at the amount of 1.2 l (C2H5)2O per 1 mole of output NAG, evaporation of ether remainder and obtaining nitroguanilazide (NGA) with an output of 77 %. At that for nitrosation nitrites of alkaline andalkaline-earth metals - MNO2 (M=Na, Li, K, 1/2Ca, 1/2Mg, 1/2Ba, 1/2Sr) are used at a molar ratio of as acid H2SO4, HNO3, H3PO4, HBr are also used, it is carried out at cooling, the reaction mass is filtered and cooled, keeping it in these conditions for 5-10 hours, the residue is filtered, dried and nitroguanylazide is obtained with an output of 40-55 %, and aqueous solution after filtration of NGA is extracted by diethylether at an amount of the extract is evaporated and additional amount of NGA is obtained (15-40%).

But I would not recommend isolation of
the nitroguanyl azide , as much as I would personally
have interest in the possible picrate , given that the
analogous (non-nitro) guanyl azide picrate is already known
and has been observed to be stable , and useful as a base charge for detonators . The possibility exists that the
Nitroguanyl azide picrate , having its additional nitro
group would also be interesting , and hopefully have adequate stability along with greater power than the
already known " ordinary " guanyl azide picrate .

[Edited on 15-3-2007 by Rosco Bodine]

Attachment: UA16960 Nitroguanylazide Ukranian patent.pdf (279kB)
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[*] posted on 10-3-2007 at 20:07
Nitrosation products of Nitroaminoguanidne


The Reaction of Nitrous Acid with Nitroaminoguanidine

Here is the entire article associated with that
single page linked above .

Attachment: The Reaction of Nitrous Acid with Nitroaminoguanidine.pdf (435kB)
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[*] posted on 13-3-2007 at 22:21


Here's an aminotetrazole related primary

Attachment: US3663553 Di-Silver Aminotetrazole Perchlorate.pdf (101kB)
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