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Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
PHILOU Zrealone
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[*] posted on 2-10-2017 at 16:26


Yeah nice process ... thanks Rosco for that gem of a finding.

Very smart to work on unsensitive amino aromatic hard to diazotize and to use heat to make the substitution faster... such deactivated aromatic ring diazoniums resist wel to heating... this is the case of trinitroanilin... the electronegativity of the NO2 into the aromatic ring is comparable to the N into the tetrazole heteroaromatic ring...

Addition could also be made via gravity and capillarity fall through a fabric ribon coming from a reservoir and flowing near the surface or just below the surface onto the wall of the beaker via the ribbon...

So no drops and no big increase of reactant concentration, laminar flow agitation, no shock from falling drop...pretty reproductible and no need of electronic or pump...


[Edited on 3-10-2017 by PHILOU Zrealone]




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Rosco Bodine
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[*] posted on 2-10-2017 at 16:46


This particular synthesis for NaNT is a good example of how an exacting method can be very important in its details and small changes in method used can produce surprisingly large changes in the result. Chemical reactions that are sensitive to exacting process conditions required for process optimization are not unusual. This appears to be one of those fickle reactions where the optimum reaction condition is a fairly narrow window. There are many other examples of optimized chemical processes for manufacture of various materials where the process patented is a better way to skin the cat.
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Rosco Bodine
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[*] posted on 2-10-2017 at 16:59


Quote: Originally posted by nitro-genes  
Could only find some info on the diammonium, sodium, potassium and silver salt of 5-nitraminotetrazole, so I decided to make about 100 mg's of a copper(II) salt of NATZ by reaction of diammonium 5-nitraminotetrazolate and copper(II) sulfate, which precipitates a light green amorphous precipitate. Not sure if this would be Cu(II)(NATZ) or Cu(II)(NATZ)2, probably the former. It only crackles when touched by flame, but when heated over a flame it first turns brownish/black then detonates with great brisance at around 300 deg C. Also tried to make the Cu(I) salt by reduction with ascorbic, but just got some mustard yellow coloured gel-like crud that wouldn't filter, perhaps the Cu(I) salt is too soluble or too fine a precipitate.

It seems Cu(II)(NATZ) doesn't need too much to make DDT, has a Cu(II)(NATZ)(NTZ) complex ever been made? The nickel(II) salt of 5-nitraminotetrazole also seems very soluble, still would like to try if NATZ may form some more water insoluble and more flame sensitive complexes with nickel(II) nitrate and hydrazine. Are any of these already known?

[Edited on 9-8-2017 by nitro-genes]


It would be interesting to see if a nickel - potassium double salt would form. Gmelin has reported a double salt for the styphnate.

http://www.sciencemadness.org/talk/viewthread.php?tid=11105&...

Attachment: pages from Hand_book_of_chemistry 1857.pdf (392kB)

http://www.sciencemadness.org/talk/files.php?pid=162501&aid=...

Ethylenediamine nitrotetrazolate would probably be worth a look too. See US4552598 attached in an earlier post

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

Ethylenediamine nitrotetrazolate may form an interesting binary or double salt with Ethyleneditetrazylazide which was mentioned on page 1 of this thread

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

[Edited on 10/3/2017 by Rosco Bodine]
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nitro-genes
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[*] posted on 3-10-2017 at 16:00


A potassium double salt was also something I tried, though only in combination with Cu(II). Tried by slow addition of a strong copper sulfate solution to a near saturated solution of potassium NATZ in water and by cooling of a hot solution of both. Either way, the product seemed a mix of Cu(NATZ) hydrate (light green) and the potassium salt. The potassium salt washes out easily, so I'm quite sure it is a simple mix. NATZ being a diacid, the formation of these complexes can be difficult and highly depended on pH, though I doubt any more flame sensitive energetic complexes of NATZ have remained undiscovered. Something maybe worth mentioning is that instead of ether, NATZ can also be extracted using the more OTC solvents MEK and ethylacetate (from the diammonium salt after acidification with HCl).

That batch process for the nitrotetrazole synthesis would be really useful for small scale synthesis, give that no dangerous side products are formed such as azidotetrazole or something. Seeing it is absent from the patents, could HCl-NaCl-nitrite be a viable route to chlorotetrazole formation?
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Rosco Bodine
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[*] posted on 3-10-2017 at 18:16


The double styphnate of nickel and potassium also involves a dibasic acid (styphnic acid) so it caught my notice as a possibility likewise for nitraminotetrazole.

There was a patent US5516377 of interest attached to an earlier post
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&g...

It is possible you could get complexation of copper, nickel, or cobalt, probably zinc and silver also, by adding the respective nitrate to an ammoniacal solution of diammonium nitraminotetrazole.
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Rosco Bodine
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[*] posted on 5-10-2017 at 00:36


Here is a related recent patent US9718791

Attachment: US9718791 Facile method for preparation of sodium 5-nitrotetrazolate using a flow system.pdf (686kB)
This file has been downloaded 50 times

A related developmental history patent is US7253288

Attachment: US7253288 Process for preparing substituted tetrazoles from aminotetrazole.pdf (900kB)
This file has been downloaded 48 times



[Edited on 10/5/2017 by Rosco Bodine]
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[*] posted on 11-10-2017 at 16:42


Was wondering if anyone has more information on Guanylazide Picrate? (VOD, lead expansion,sand test,ect) All I have found is this : http://www.sciencemadness.org/talk/files.php?pid=131275&aid=... and a small paragraph in Federoff ‘s encyclopaedia I did expect to find a bit more info since there was a patent which would suggest that some tests were done.
Anyway I used this patent as a rough guide to synthesise some myself. Firstly I diazotised Aminoguanidine Bicarbonate as per a synthesis for 5-ATZ but instead of using base and heat to complete it I instead neutralised it with a hot sodium picrate solution. This formed an immediate precipitation of a bright yellow micro crystalline substance which I believe is the product. This was filtered off on a Büchner funnel, rinsed several times with ice cold water and set aside to dry. In a burn test it caught fire very easily and burnt much faster than picric acid alone with the trademark yellow smoke and carbon left behind. It is very insensitive and much like picric acid it needs to be wrapped in foil and belted very hard to get any visible result.

5C2F259D-5F73-4822-9E08-9590895212EC.jpeg - 506kB2D527D88-E354-4F4D-B684-DE03FB1410EF.jpeg - 983kB




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