Sciencemadness Discussion Board

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

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PHILOU Zrealone - 25-4-2016 at 04:52

To those who really think verdigris is Cu(NTAz)2, Cu(NTAz)2.HNTAz or HO-Cu-NTAz;
--> no its just the colour of women jealous from envy to NeonPulse's compound :D :)

or more seriously a similarity of colour between the beautiful pictures of NeonPulse's compound
and
Cu(OH)2.CuCO3 (from the old french vert-de-Grèce (green from Greece) or vert-de-gris (green of grey))

[Edited on 25-4-2016 by PHILOU Zrealone]

roof

Laboratory of Liptakov - 26-4-2016 at 00:32

Of course, for everybody. On roofs is NOT! Cu (NTAz) 2 as energetic materials. On copper roofs is nothing explosive material. It is only joy and joke during comunication in this thread. And of course jealousy that someone managed to synthesize it. From available compounds. ( However, I keep thinking, that the energetic materials NeonPulse always scratches from himself the roof )....:D...LL

a nitrogen rich explosive - 26-4-2016 at 09:02

NeonPulse has excelled himself. From OTC materials and a church roof...

No, seriously. How the hell did you do this??

Dornier 335A - 26-4-2016 at 13:37

This thread might contain some clues...

a nitrogen rich explosive - 3-5-2016 at 04:55

bis(5-nitrotetrazolylazide)? I'm not very experienced in tetrazole chemistry, but I think that is what it would be.
Let me elucidate...
A 5-aminotetrazole ring, with the NH2 group at 5 substituted with an NO2 group.
By the action of HNO2, the NH group at 4 ridded of hydrogen and with an extra nitrogen double-bonded outwards (like diazonium compounds.) Another 5-nitrotetrazole group with only a nitrogen atom at the fourth position bonded to the diazonium group of the other complex. 252g/mol. Wow.

[Edited on 3-5-2016 by a nitrogen rich explosive]

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PHILOU Zrealone - 4-5-2016 at 07:38

Quote: Originally posted by a nitrogen rich explosive  
bis(5-nitrotetrazolylazide)? I'm not very experienced in tetrazole chemistry, but I think that is what it would be.
Let me elucidate...
A 5-aminotetrazole ring, with the NH2 group at 5 substituted with an NO2 group.
By the action of HNO2, the NH group at 4 ridded of hydrogen and with an extra nitrogen double-bonded outwards (like diazonium compounds.) Another 5-nitrotetrazole group with only a nitrogen atom at the fourth position bonded to the diazonium group of the other complex. 252g/mol. Wow.

[Edited on 3-5-2016 by a nitrogen rich explosive]

NOPE as explained elsewhere!
-N3 is monovalent so you can't bridge 2 things with it.
-N=N- is bivalent (AZO) and with it you may bridge.
ex: azomethane is CH3-N=N-CH3 (dimethyldiazene)

a nitrogen rich explosive - 4-5-2016 at 08:56

So diazobis(5-aminotetrazole) would exist?

a nitrogen rich explosive - 4-5-2016 at 09:15

Also, by the way, I just put up my findings on my hands-on crash course on tetrazoles up on Prepublications, with syntheses of the 5 most explosive tetrazoles I have done yet.

Dornier 335A - 4-5-2016 at 10:21

Too bad your "findings" are full of errors and plagiarised material. I brought up some of them in your thread.

a nitrogen rich explosive - 4-5-2016 at 13:30

I'm not plagiarising. It was, as clearly stated, a write-up rather than a new synthesis method.

PHILOU Zrealone - 5-5-2016 at 05:48

Quote: Originally posted by a nitrogen rich explosive  
So diazobis(5-aminotetrazole) would exist?

Make a drawing of it first, post it and we discuss!

About your screenshot (retaken here as a jpeg picture for convenience purpose):
nitrogenrich molecule mistakes.jpg - 13kB

You will notice that you have a lot of mistakes...usually N is trivalent in organic chemistry; in your drawing
-if it is tetravalent, then it must display a charge like ammonium for example (NH4(+)) (cf. A and B)
-if it is pentavalent then it should display a double charge (cf. C)

--> You made a molecule charged with 4(+) charges and no balancing so repulsion forces will be against its existance.

The position C is even more concerning because you are able to put a N atom in sp conformation (180° linear):
1°) with an extra lateral sp3 bond
2°) into a ring with angle strain 109°

Try to buy a ball and sticks molecular model and do a first test with it.

a nitrogen rich explosive - 5-5-2016 at 08:30

Sorry about my +- mistakes - this is new software, and I don't know how to operate it properly.

Rosco Bodine - 5-5-2016 at 11:09

Quote: Originally posted by a nitrogen rich explosive  
Also, by the way, I just put up my findings on my hands-on crash course on tetrazoles up on Prepublications, with syntheses of the 5 most explosive tetrazoles I have done yet.


People at this forum don't need any of the dubious value of your own findings from a personal journey that is your own (hands-on) ??? (I doubt it) ....bullshitter's "crash course" in energetic tetrazole chemistry, which is a subject matter you 100% evidently do not regard seriously or would not be making unreferenced hypothetical "presentations" like you have done which amounts to a list of proposals or hypotheses not even decribed for what they are.

You wander into an area of chemistry that is unsurvivable to the foolish and do so with a cavalier attitude and approach that is dangerous.

What you are doing is not contributing or helpful and is dangerous.

I made a suggestion you stop this approach and posting activity which went ignored. Keep going with it and we are going to all see you sent back to school before coming to an advanced topic discussion as a place for a beginning of knowledge you don't yet have.

What you have continued to do is pin the needle over ranging the bullshit detector

I look for one reference or evidence that you have a clue and such reference or evidence or is not found

Edit to add links to avoid repeating myself:
http://www.sciencemadness.org/talk/viewthread.php?tid=23573&...

http://www.sciencemadness.org/talk/viewthread.php?tid=65807&...

http://www.sciencemadness.org/talk/viewthread.php?tid=65807&...

To the 4 possibilities stated by Bert in the linked post could be added the deficient masonry example, where there are evidently a few bricks missing what would be the number needed for having a complete patio

[Edited on 5/5/2016 by Rosco Bodine]

hissingnoise - 5-5-2016 at 11:31

Quote:
What you are doing is not contributing or helpful and is dangerous.

Rosco, this young idiot is the banned EatsKewls ─ he's like that occasional turd in the bowl that just won't cooperate!

If we ignore him he might just fuck off!



[Edited on 6-5-2016 by hissingnoise]

a nitrogen rich explosive - 5-5-2016 at 11:58

I am EatsKewls???? WHAT THE FLYING FUCK?
Look at all my posts! In not one of them have I ever flamed. I have bullshitted, but I haven't flamed. I don't have the same language quirks, I am interested in different things, and I have a totally different attitude. Why do you think this?
EatsKewls must have been mentally ill. He was permanantly, uncontrollably angry. I am not. Where is your proof, or is it just you thinking the worse?

hissingnoise - 5-5-2016 at 12:04

Quote:
EatsKewls must have been mentally ill.

Indeed, a few bricks short of a patio, as Rosco succinctly put it . . . ?


Rosco Bodine - 5-5-2016 at 12:04

bullshitting in the energetics section should get you banned period

a nitrogen rich explosive - 5-5-2016 at 12:12

Fair enough. Sorry about this.

Rosco Bodine - 6-5-2016 at 07:10

In the civilized world there is a concept that applies to human interactions of any sort,
that is actually a fundamental concept of ethics, morality, and law, and it can be called an
implied covenant of good faith and fair dealing. This is an alien concept for the dishonest.


a nitrogen rich explosive - 6-5-2016 at 16:06

That was thinly veiled, even by your standards. If you think that it's BS, say so, rather than talking of my covenant of honesty.

Rosco Bodine - 7-5-2016 at 08:11

When you want to conduct "thought experiments" be very sure you identify clearly what it is you are presenting is NOT reality based observation or tested process, or don't bring it here to this board.

a nitrogen rich explosive - 7-5-2016 at 14:00

That's fine.

Bert - 8-5-2016 at 06:30

a nitrogen rich explosive is banned from posting. Perhaps if he swears on a dead tree volume of Tadeusz Urbanski to cease from BS and CLEARLY identify speculations as such, rather than actual procedures and/or personal experience, that ban might be lifted.

Or maybe not. My back hurts, and I am very cranky.

aga - 8-5-2016 at 07:01

Quote: Originally posted by a nitrogen rich explosive  
I don't have the same language quirks,

Thinking about 'language quirks' is not something anyone would do, or even imagine a need to do, unless engaged in an activity that required it.

Rosco Bodine - 8-5-2016 at 07:59



Hmmm..........

I watched a rabbit running through the woods

I'm a wolf ;)

https://www.youtube.com/watch?v=br4ES2JDu-k

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Laboratory of Liptakov - 8-5-2016 at 12:30





gone.jpg - 27kB

OneEyedPyro - 8-5-2016 at 16:33

That's a relief to see him gone, spreading misinformation in the energetics section could get people killed!
I noticed a lot of what he said implied that he had physically made certain compounds yet at the same time lacked a basic understanding of those comounds properties. Anyone else think he seemed like a complete poser?

NeonPulse - 8-5-2016 at 16:48

Indeed. I'm surprised he lasted this long. The rant in the prepublication thread was a bad move. He did have an air of arrogance and tried to play everyone for fools
but it was easy to see through. I'm sure He will be back reincarnated though. People like that always seem to like having the final say and can't help themselves. - unless he copped an IP ban that is. Check for similar attitudes and post structures.

Bert - 8-5-2016 at 20:26

I will give this person a second chance...


Quote:
Certainly, I will need something first, though.

1: Find a print edition of ANY of the several volumes of Tadeusz Urbanski: Chemistry and Technology of Explosives. As you are licensed for explosives chemistry work and have friends and mentors in the art, this will present little difficulty.

2: Take a picture of the book, your right hand on the cover, not obscuring title- And also in field of view, the front page from a (local to your home) newspaper, clearly showing the locality and the same date as this picture's posting date. You need not show your face or any other identifying features, and may wear gloves if you wish.

3: Start a new account under the name: a Nitrogen rich material and post this picture as your first post under that name in the "beginnings" forum, along with your oath to post righteously in the future. I will then IMMEDIATELY restore your posting privileges under your original screen name.

After that, you will post some links or other verifiable references showing your sources of information on ANYTHING in the energetic materials fields you choose to ask questions about.

State your informational sources, and explicitly say " I speculate" or "I have personally observed" as appropriate. In the case of original work, actual lab notes, including some pictures of apparatus, operations and products, along with any test data derived and balanced equations for all reactions.






Quote:
I swear that I will stop bullshitting. It hasn't got me far yet, because everybody else is too experienced to see through it. Now, I have heptanitropentane with photos of explosion. Please don't ban me.


a nitrogen rich explosive - 8-5-2016 at 23:28

Why the local newspaper?
Anyway, I'll do what I can.

I haven't been banned from posting!!

Bert - 9-5-2016 at 04:32

Erm. I apologize for that, and have made the needed change. Please proceed as directed above...

aga - 9-5-2016 at 11:09

ROFL

Bert - 13-5-2016 at 05:12

A Nitrogen rich material may be mere animal byproduct in origin, but that is no shame- a smelly mess in the barn can be a valuable fertilizer on the back 40...

DubaiAmateurRocketry - 15-5-2016 at 14:40

I thought I was leading the bullshit in this forum until reading nitrogen rich explosive's posts lol

PHILOU Zrealone - 16-5-2016 at 04:52

Quote: Originally posted by DubaiAmateurRocketry  
I thought I was leading the bullshit in this forum until reading nitrogen rich explosive's posts lol

No you are not bullshitting Troll at all!
You usually give good, realistic ideas and references.

Rosco Bodine - 12-6-2016 at 07:35

1,5-Di(nitramino)tetrazole: High Sensitivity and Superior Explosive Performance


This is an interesting report about a green energetic initiator. The synthesis appears to be complex in comparison with the potassium salt of DDNR which would have similar properties.

I think this energetic tetrazole compound should be compared with the potassium salt of DDNR which is gotten much more easily and economically to see if there is a favorable comparison in properties and performance. The economics for the easier gotten DDNR compound could cause it to be a better choice.

Attachment: Fischer_et_al-2015-Angewandte_Chemie_International_Edition.pdf (1.1MB)
This file has been downloaded 726 times

nitro-genes - 12-6-2016 at 12:02

Was wondering, I've seen very crude calcium cyanamide is available here as fertilizer. If one would be interested in cyanoguanidine: what if you would blend diammoniumsulfate/phosphate salts (very cheap) with the impure fertilzer and add to 40-70 deg C water, filter the solution hot and let the cyanoguanidine precipitate (maybe some calcium as well). Was thinking by some trial and error, mixing in the right proportions and taking into account solubilitites of all components, it could be a very cheap and OTC possibility.

I've also seen some people use the calcium cyanurate route for calcium cyanamide. What exactly is this calcium cyanurate? Ca(Cyanuric), Ca(Cyanuric)2, Ca(Cyanuric)(OH)? If you could make the latter, would there be no loss of cyanic acid during pyrolysis and higher yield? Sorry if this has been explained before


Rosco Bodine - 12-6-2016 at 13:05

Commercial fertilizer grade cyanamide can be worked up to produce cyanoguandine or 25 Kg bags of pure cyanoguanidine are available as a soil treatment slow release nitrogen but it is moderately expensive, maybe $10 per Kg.

I suggest the UTFSE approach to references on calcium cyanurate as a pyrolysis conversion precursor for calcium cyanamide. Since I gleaned that information from patents and other references....it involves a shortcut for the urea and lime process by jumping to the intermediate in that process that would otherwise be formed in situ in a less pure form. Cyanuric acid is easily made from urea and ammonium chloride or can be obtained commercially as chlorine stabilizer, rendered moderately soluble in boiling water neutralizing with sodium bicarbonate as the disodium salt and further reacted with a solution of calcium chloride to precipitate calcium cyanurate, which will pyrolytically convert entirely to pure calcium cyanamide at a low red heat, if air is excluded. First comes off cyanic acid as the calcium cyanurate decomposes first to calcium cyanate, and then CO2 comes off leaving pure calcium cyanamide.

nitro-genes - 12-6-2016 at 14:26

Fair enough, wasnt aware cyanoguanidine was available as fertilizer, haven't seen it anywhere though. And yes, I've seen sulfuric acid neutralization of calcium cyanamide to produce cyanamide and dicyandiamide (local low pH, expensive), CO2 (Needs rigorous stirring and gassing to complete reaction), acetic acid (expensive, usually low concentration), all producing low yield (IIRC). The synthesis of dicyandiamide from free cyanamide is usually performed under basic conditions. From what I've read preferably ammonia and not strong alkali since the alkaline earth metal salts are not stable from what I've read. So combining all of these, the neutralization of calcium cyanamide with cheap ammonium salts forming strongly insoluble calcium salts (mono-di ammonium phosphates, sulfates or maybe even ammonium or sodium bicarbonate) would possibly yield ammonia and cyanamide, which upon condensing would possibly yield dicyandiamide in high yield and I haven't seen this particular route mentioned before.

I've made cyanuric acid from urea before using a bit of (185-210C) boiling paraffin oil as dispersant (OTC candle oil). IMO, there is no other use for the ammonium chloride than for dilution and to make elimination of NH3 from the viscous melt (which could form amelide and amelidine) more easy. So I was now contemplating the synthesis of calcium cyanurate you posted, starting from 2 moles of NaOH, cyanuric acid and calcium chloride posted here: https://www.sciencemadness.org/talk/viewthread.php?tid=2762, which mentions (HOCN)3 + 2 NaOH + CaCl2 ---> CaH(OCN)3 + 2 NaCl + 2 HOH. Just wondering if that second OH of cyanuric acid is deprotonated completely and solubilities of hydroxide double salt may be causing a basic calcium cyanurate to be formed or even if some complex is formed containing additional sodium. I havent seen any mention of a patent here, nor yields of aminoguandine from someone or analysis of the cyanamide produced. It is not criticizing just curiosity.

[Edited on 12-6-2016 by nitro-genes]

Rosco Bodine - 12-6-2016 at 15:53

Yeah there was a couple of ways to do the stoichiometry and I described the one I think that applied to an experimental I performed. This linked post should take you to other pages that follow up with other ideas.

http://www.sciencemadness.org/talk/viewthread.php?tid=2762&a...

There was an alternative hypothetical possible I think where perhaps there would not be lost anything but CO2 ...but the more straightforward approach seemed to be just to let one cyanic acid burn off to form the calcium cyanate.

[Edited on 6/13/2016 by Rosco Bodine]

ShotBored - 19-5-2017 at 07:24

Hey Fellas,

I'm relatively new to the pyrotechnics field, but my education background is in chemistry, namely inorganics, coordination chem, catalysis etc. I'm going to be fairly active in my forays into tetrazole chemistry, mostly in pursuit of blue, smokeless, perchlorate-free comps (the pyro quest for holy grail, I know). I was curious if any of you had delved either:

1) 3,6-dihydrazino-1,2,4,5-tetrazine (DHT); or
2)Triazoloaminotriazinyl-1,2,3,5-tetrazine (TATT) salts

TATT was mentioned by Klapotke/Steinhauser as being investigated by Koppes et al, but they never reported on flame colors of any of the salts, which included Al, Co, Ni, Cu, and Ba. My particular interest in the Cupric complex. However, the current synthesis pathway includes the use of cyanogen bromide which makes me tremble a little at the the thought of using.

DHT has many obvious applications in pyro and Klapotke called it "one of the most promising materials for smokeless colored pyrotechnics". Naturally, I have a few reservations in working with hydrazine, plus DHT has hydrazine functional groups that I'm sure make it toxic as all hell. I'd be interested in any light you guys could shed if you've done any research in this area yourselves.

P.S. Enjoy this awesome new article on the effects of adding NQ to your 5-AT propellant mixes! Cheers

pubs.rsc.org/en/content/articlepdf/2017/ra/c7ra01607g


PHILOU Zrealone - 21-5-2017 at 04:16

Quote: Originally posted by ShotBored  
Hey Fellas,

I'm relatively new to the pyrotechnics field, but my education background is in chemistry, namely inorganics, coordination chem, catalysis etc. I'm going to be fairly active in my forays into tetrazole chemistry, mostly in pursuit of blue, smokeless, perchlorate-free comps (the pyro quest for holy grail, I know). I was curious if any of you had delved either:

1) 3,6-dihydrazino-1,2,4,5-tetrazine (DHT); or
2)Triazoloaminotriazinyl-1,2,3,5-tetrazine (TATT) salts

TATT was mentioned by Klapotke/Steinhauser as being investigated by Koppes et al, but they never reported on flame colors of any of the salts, which included Al, Co, Ni, Cu, and Ba. My particular interest in the Cupric complex. However, the current synthesis pathway includes the use of cyanogen bromide which makes me tremble a little at the the thought of using.

DHT has many obvious applications in pyro and Klapotke called it "one of the most promising materials for smokeless colored pyrotechnics". Naturally, I have a few reservations in working with hydrazine, plus DHT has hydrazine functional groups that I'm sure make it toxic as all hell. I'd be interested in any light you guys could shed if you've done any research in this area yourselves.

P.S. Enjoy this awesome new article on the effects of adding NQ to your 5-AT propellant mixes! Cheers

pubs.rsc.org/en/content/articlepdf/2017/ra/c7ra01607g


Thank you for the article.

Such rich nitrogen and endothermic compounds tends to burn with a bright or purple-lilac flame (typical example is cyanogen or diamino-tetrazine).

The effect of the cation will thus be visible as an addition colour only if the burning heat is not too strong (otherwise all will shift to bright light (white/silvery/gold).
Cu(2+) will add some blue-green
Al(3+), Ni(2+) or Co(2+) shouldn't give a specific color
Ba (2+) may give a green color.

Would be interesting to test:
Li(+), Sr(2+) for red color,
Ca(2+) for orange/pink color
and B(3+) or BO3(3-) for green color.

ShotBored - 24-5-2017 at 05:11

Sorry, I said "flame colors" but meant "flame characteristics". I have an understanding of the color emitters down, with the exceptions of some of the newer, rare earth metal emitters such as yttrium, etc. My concern is more so aimed at the established synthesis pathways: it seems self-defeating for me to be aimed at "green" chemistry, yet use such nasty synthesis components such as hydrazine or cyanogen bromide. I was curious if any of you had synthesized DHT or TATT or if you all had used different pathways. I can post the current
general synthesis pathways for each if that would help.

I would agree, though, that forays into those other color emitters could prove fruitful. I know the Klapotke paper talked about some great red-emission from Sr-DHT and Sr-TATT complexes, but I didnt see anything about B, Li, or Ca. I'll have to let you guys know how the research plays out once my lab is done being built =)

PHILOU Zrealone - 25-5-2017 at 11:56

Quote: Originally posted by ShotBored  
Sorry, I said "flame colors" but meant "flame characteristics". I have an understanding of the color emitters down, with the exceptions of some of the newer, rare earth metal emitters such as yttrium, etc. My concern is more so aimed at the established synthesis pathways: it seems self-defeating for me to be aimed at "green" chemistry, yet use such nasty synthesis components such as hydrazine or cyanogen bromide. I was curious if any of you had synthesized DHT or TATT or if you all had used different pathways. I can post the current
general synthesis pathways for each if that would help.

I would agree, though, that forays into those other color emitters could prove fruitful. I know the Klapotke paper talked about some great red-emission from Sr-DHT and Sr-TATT complexes, but I didnt see anything about B, Li, or Ca. I'll have to let you guys know how the research plays out once my lab is done being built =)


You may always post synthetic pathways...for informational purpose and to see evolution of technics upon time...

Be careful...greener explosive is not per se related to greener chemistry...it may but it is not mandatory.
Greener explosive means an explosive that is less dangerous/detrimental to the environment...but on its practical use...and mainly focussing on less remanent toxic compounds and heavy metals like Hg, Pb (Quicksilver and Lead) by reference to old timers detonators/ignitors primaries for ammunitions....

It has little to do with the making/fabrication process...
Maybe to include this into a larger ecological view we should speak of "Greenest explosives" or "Enviro-friendly explosives" instead of "Green explosives".

On the other hand Green Chemistry focuses onto the process of making...but not onto the product...actually it may be possible that the resulting product of a green chemistry reaction is a treat to the environment...thus very toxic, remanant, carcinogen, teratogen, ...

ShotBored - 26-5-2017 at 05:06

Yeah thats true. In my industry, we speak of green chemistry as being comps that do not release toxic byproducts. For example, I have a composition that would be greatly improved by the addition of oxamide right now, however its evolution of cyanogen during combustion makes oxamide pretty much unusable for most of our comps. At the same time, I personally am concerned with the reactants being safe as well for my own personal wellbeing. I'll post a synthesis pathway later today and see if anyone has some ideas on how to do it differently, even if it adds a few extra steps.

nitro-genes - 29-7-2017 at 10:52

Aminoguanidine from calcium cyanamide and hydrazine sulfate:

Out of curiosity I tried a modification to Engager' s original aminoguanidine synthesis to try and make this synthesis easier and less prone to swings in pH during the simultanous additions of the calcium cyanamide /hydrazine sulfate and sulfuric acid by adding an acetic acid/acetate buffer component. All hydrazine sulfate can be added at once and only calcium cyanamide needs to be added , simplifying the synthesis and make it more suitable to perform using only pH paper to measure pH. Wasn't sure about including the presence of acetic acid/acetate due to possible condensations with hydrazine and aminoguanidine, leading to heterocycle formation, acetylhydrazides and disproportionations to diacetylhydrazides resulting in a loss of hydrazine during the reaction. I suspected though that at this pH/and concentrations , these would represent only very minor side reactions. The aminoguanidine obtained this way dissolved to a clear solution in acid (no calcium contamination) and seems to convert to 5-ATZ hydrate in a normal 74% yield using Thiele method. The only difference noticed during diazotization of the aminoguanidine was that there seemed to be just slightly more gas production (nitrogen, hydrazoic?) and a slightly greenish tint at the end of nitrite additions instead of yellow/orange for the aminoguanidine produced by Engager's method., after refluxing, both solutions were slightly yellow.

Procedure:

Outside and wearing two pair of gloves:

- To a 600 ml beaker was added 400 ml ~10% household acetic acid, 19 grams of NaOH was added at once and stirred to dissolve.
- To the quite warm solution was immediately added 55 grams of hydrazine sulfate and stirred briefly, untill
almost all hydrazine sulfate was dissolved. The pH of the solution tested with pH paper at this point was around 4.
- The beaker was added to a cold water bath (tap water) and allowed to cool down to around 20 deg C.
- 40 gram of calcium cyanamide was weighed out and added in small portions to the acetic acid/hydrazine sulfate solution, while keeping temperature around 20 deg C. throughout the additions. The pH was kept between 5-7. After adding about 20-25 grams of calcium cyanamide, additions of cold 50% sulfuric were needed to keep the pH lower than 7.
- When nearly all calcium cyanamide was added the pH was adjusted to 7 using the last bit of calcium cyanmide. The beaker was covered in plastic wrap and kept steering strongly for 1.5 hours at 20 deg C. The pH was checked every 30 minutes or so and 50% sulfuric sulfuric acid added to keep at 7. The pH didn't seem to increase much further anymore after 1 hour.
- After stirring for 1.5 hours, the pH was measured one more time (this one is most crucial!) and carefully adjusted to a pH of 7.
- The contents of the beaker were transfered to a wide neck , 1 liter erlenmeyer flask,. This was covered with a single layer of plastic wrap. and a 500 ml beaker filled with ice was put on top of the flask to keep air out and all hydrazine in the flask.
- The solution was heated slowly and temperature kept between 80 and 90 deg C for two hours. (150-160 deg C setting on my hotplate)
- Allowed to cool down to 60 deg C and filtered off the calcium sulfate. The filtered off calcium sulfate was added to the beaker again and 100 ml of hot water was added, stir redfor 5 minutes and filtered again. Both filtrates combined, pH adjusted to 6.5-7, (pH after heating was somewhere between 7 and 8) and cooled down to 40 deg C.
- 40 grams of sodium bicarbonate were added in small portions over 15 minutes . The aminoguanidine bicarbonate began to precipitate after only a few minutes. Cooled down to 10-15 deg C overnight and filtered, washed thoroughly with ice cold water and dried for 48 hours, yield 39 grams of aminoguanidine bicarbonate.

The simultaneous addition method gave me 22 grams yield and was a lot more hassle to keep track of the pH and temperature at the same time, overshooting temperature to 45 at one point at a pH higher than the pH paper could tell me. This method seemed advantagous since cyanamide solutions are most stable between pH 3-5, maybe even more acetic acid could be used to a starting pH of 3 and keeping temp down even more would minimize losses even more.
Also, my cyanuric acid was made from urea, I suspect yields were still a lot lower than theoretical since the cyanuric acid may not have been completely pure. Calcium cyanurate also seems to react with CO2 from the air to form calcium carbonate and cyanuric acid, which wouldn't form cyanamide during pyrolysis at 800 deg C. I think it may be advantageous next time to dry the calcium cyanurate ASAP.

[Edited on 29-7-2017 by nitro-genes]

Boffis - 29-7-2017 at 14:45

@nitrogene; interesting work. Were you working with homemade calcium cyanamide (Engeger style) or using a commercial product. Commercial 55% calcium cyanamide is now readily available in Europe and dirt cheap.

nitro-genes - 29-7-2017 at 15:41

Not sure how easily other some other triazoles would form when acetic acid/acetate is present during the heating step. From what I've read, acylhydrazides need higher temperatures and anhydrous conditions to form (STUDIES OK THE FORMATION OF 4-AMINOTRIAZOLE DERIVATIVES FROM ACYL HYDRAZIDES, ROBERT M. HERBST AND JAMES A. GARRISON).

I've seen the cyanamide fertilizer bags for sale, just more fun going all the way from urea though. :P Cyanamide was homemade by pyrolysis of calcium cyanurate at 800-1000 deg C. Used a welded 150mm diameter stainless steel container with 5 cm of 20 mm stainless tubing protruding from one end by which it could be filled and emptied. A conically shaped stainless steel weight was placed on top of the 20 mm tubing so that when fired, gasses could escape by lifting the weight up, closing it again when no more gas is produced. Worked nicely and gave abundant amounts of silvercyanamide on testing (can this be used for quantification of purity?). Yield was 90% of theory from calcium cyanurate and got 360 grams calcium cyanamide in total from 2 firings, which is more than I need anyway. The original goal was to make dicyandiamide, but decided a small amount of 5-ATZ would also be nice.

NeonPulse - 31-7-2017 at 17:22

Using the silver cyanamide method can be used to calculate purity. In engagers work he mentioned how he done this. I can't remember exactly where I saw it but it is in there. He used the measurements to calculate the N%.
Your method sounds like it's worth a shot. I have had lowered yield in a few of my AQB preparation attempts due to the PH issues. I have finished my furnace so I can heat the calcium cyanate to the exact temperature needed rather than put it in a fire like I have done previously.

I recently did a synth of CuNTZ this was quite nerve racking since I experienced the micro detonations this time around. Quite scary. I recrystallised the product this time from hot water. The colour difference is clear with the refined product being a sky blue rather than the green. It also seems much more flame sensitive too.
I want to attempt DBX-1 again. The last time I tried I suspect the purity of my starting product NaNTZ was not sufficient to get any product to form. I'm trying to get the best possible start to try again.

nitro-genes - 1-8-2017 at 13:48

Nice channel on YT, some clean looking EM chemistry video's there! The sythesis of CuNTZ was nice to see, some balls to produce it at this scale though, micro dets. and all. A vid on DBX-1 would certainly be cool as well! :)

Not sure what temperature range is acceptable for the pyrolysis of calcium cyanurate to calcium cyanamide indeed. Since the latter is produced commercially by reaction of nitrogen with calcium carbide at 1100 deg C or so, it would seem that at least the calcium cyanamide itself is reasonably stable at these higher temperatures, although this may be different for the pyrolysis reaction. For the pyrolysis I just used an airblown coal furnace from a hairdryer and a 10 liter old SS waste bin with lid that I dug into the ground for insulation. I did give the pyrolysis vessel some "legs" to keep the calcium cyanurate away from the really hot zone at the bottom of the can (where the air is blown in) and eyeballed for a red to dark-orange colour through a peakhole in the lid. Added a small amount of the calcium cyanamide to an excess of 10% HCl, which dissolved it completely and produced only very little gasses or smell, further did a qualitative test with silver nitrate as Engager desribed. The silver cyanamide does have a very low solubility, even from very dilute solutions of cyanamide and ammoniacal silver nitrate (~less than 0.1% for both) a strong yellow colour is obtained, even though it would probably be rather difficult to use the silver method as a really accurate purity assessment.

Also not sure what the exact purity of the AQB is from the acetate/acetic method. I did test the AQB melting/dec. point and the 5-ATZ of both methods, having roughly (together on hotplate test) same melting point, going from tranlucent to matt white at around 100 deg C, same decomposition temp (right after melting with many small bubbles forming) and similar crystal morphology (long glassy plates). Comparing the more energetic copper(II) salts of both batches would be most conclusive, but right now I have no direct plans for the 5-ATZ anyway, so some time perhaps. I did diazotize about 50 mg of the 5-ATZ (of the simultaneous addition batch) as a 0.7% solution and added some 1:1 hydrazine sulfate/NaOH solution to produce some ditetrazoylhexazadiene, truly amazing stuff but also indicative of how dangerous some of these tetrazoles can be.

physics inclination - 1-8-2017 at 19:22

Ok I know this is really tangential post, but copper nitrotetrazolate has possibly the best acronym for an explosive Ive seen so far, maybe barium nitrotetrazolate could compete with it though (BaNTZ i.e. of the dank persuasion) :P

Dornier 335A - 2-8-2017 at 13:19

NeonPulse, when you write CuNTZ, do you mean Cu(NTZ)2 or Cu(NTZ)2*NTZ? The second being the intermediate in NaNTZ synthesis.

I synthesised DBX-1 with really good yield a few months back but didn't have time to record a video. It's a really nice primary in every way though so I really should do some tests with it. I also have a small sample of pure 5-nitrotetrazole drying over concentrated sulfuric acid. It was made by extracting an acidified solution of NaNTZ with diethyl ether.

nitro-genes - 3-8-2017 at 14:26

Made an inquiry at Gaylord chemical, said I was looking for CuNTZ, but just got an angry reply back. :D

Do you guys know how stable 5-ATZ is on prolonged storage? An MSDS I found mentioned that it should be kept in an airtight container? Also said it has a distinct smell ( I smell nothing), does it react with oxygen/moisture/sublimate or something? Dangerous?

[Edited on 3-8-2017 by nitro-genes]

JJay - 3-8-2017 at 15:07

Quote: Originally posted by nitro-genes  
Made an inquiry at Gaylord chemical, said I was looking for CuNTZ, but just got an angry reply back. :D



I'm pretty sure their major product is DMSO... probably not a good place to source CuNTZ....

NeonPulse - 6-8-2017 at 17:17

Quote: Originally posted by Dornier 335A  
NeonPulse, when you write CuNTZ, do you mean Cu(NTZ)2 or Cu(NTZ)2*NTZ? The second being the intermediate in NaNTZ synthesis.

I synthesised DBX-1 with really good yield a few months back but didn't have time to record a video. It's a really nice primary in every way though so I really should do some tests with it. I also have a small sample of pure 5-nitrotetrazole drying over concentrated sulfuric acid. It was made by extracting an acidified solution of NaNTZ with diethyl ether.




It was the second one which I did need for the Na NTZ. When I first saw the acronym for the copper II NTZ I got a laugh out of that too. I did a little experimenting with recrystallising some and found the colour changed dramatically to a sky blue with a majority of the green being insoluble and removed by filtration. The junk left in the filter was Kahki green and when I attempted to light it up it was not very explosive and kind of crackled with green flames. The resulting filtrate was allowed to cool slowly in an attempt to grow crystals but they were tiny and there seemed to be an avalanche precipitation. The product was also much more flame sensitive than before. I wondered why Engager never mentioned this in his publication.

A sample of pure 5-NTZ would be great to have. I wanted to attempt it in the future- once I get enough of the sodium salt to experiment with. These compounds take quite some work to make as you know. It's extreme sensitivity and being very hygroscopic is a bother though. I don't want a repeat of the incident I had when trying to make the ditetrazoylhexazadiene. That shook me up good. I still haven't attempted to make it again since that. One day I am going to make it though. I'm fairly sure what went wrong for me there.

As for the 5-Aminotetrazole having a smell, I have not noticed any odour at all in my samples made from both methods. In solution they have a distinct smell though. As far as I know It is quite stable in storage under ambient conditions and slightly elevated temperatures too. I keep mine in an amber jar airtight in a normal temp range 15-30c.



[Edited on 7-8-2017 by NeonPulse]

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Dornier 335A - 7-8-2017 at 12:13

You hydrolyse the copper acid salt during your recrystallisation! You end up with the pale blue Cu(NTZ)2 and 5-NTZ solution.

CuNTZ.PNG - 376kB

The picture is from Primary Explosives by Robert Matyas. There's more information about the salt on pages 201-203 but it's not as good as lead azide and not a very interesting primary.


PHILOU Zrealone - 7-8-2017 at 12:51

Quote: Originally posted by Dornier 335A  
You hydrolyse the copper acid salt during your recrystallisation! You end up with the pale blue Cu(NTZ)2 and 5-NTZ solution.



The picture is from Primary Explosives by Robert Matyas. There's more information about the salt on pages 201-203 but it's not as good as lead azide and not a very interesting primary.


I wonder how is it possible to have a copper acid salt with NTZ (nitrotetrazole) what has only one proton?...
Usually acidic salts are possible with diprotic or multiprotic acids...typical example would be H2SO4
==> Na2SO4 (neutral)
==> NaHSO4 (acidic)

It is more complex with some metallic salts that can hydrolyse if too diluted
CuSO4 would be a neutral salt
Cu(HSO4)2 would be an acidic salt
Cu2(OH)2SO4 would be a basic salt

In the case of NTZ...
Cu(NTZ)2 would be neutral
Cu(OH)NTZ would be basic...

I suspect you meant this last one (the basic salt)...because
Cu(NTZ)2 + H2O <====> Cu(OH)NTZ + H-NTZ
The basic salt will indeed be less energetic because the proportion of metallic dead weight % by weight is higher into this than into the neutral salt (what contains more explosive counterpart).

Maybe there was a confusion with tetrazole (and not nitrotetrazole)?
==> Tetrazole contains 2 H that may display acidic properties and what is thus a diprotic acid...but that express only into strongly basic conditions...

nitro-genes - 7-8-2017 at 16:53

Probably all very dangerous and stupid ideas ...but...

Could you perform VNS using hydroxylamine on 5-ATZ or 5-NTZ?
Could 5-hydrazotetrazole react with nitrite under almost neutral conditions to form a pentazadiene bridge or would only 5-azidotetrazole be produced?
What would be the products if diamino tetrazole would couple with a solution of 5-diazotetrazole? Same for di/triaminoguanidine?
Same if 5-nitraminotetrazole or the dinitramine would be reduced with hydrazine?
Would it theoretically be possible to attach a tetrazine-N,N-1,3 dioxide ring to a tetrazole ring, analogous to the already synthesized TTTO? (8 nitrogens in row, so probably not)


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

Dornier 335A - 8-8-2017 at 07:52

No Philou, "copper acid salt" is just an old name for the intermediate in nitrotetrazole synthesis, Cu(NTZ)2*HNTZ *(H2O)4. It's a pretty accepted term though. So you can see how this could decompose into Cu(NTZ)2 and 5-NTZ. The dibasic salt (Cu(NTZ)2*2Cu(OH)2) exists too but it lacks the properties of a primary.

PHILOU Zrealone - 8-8-2017 at 11:54

Quote: Originally posted by Dornier 335A  
No Philou, "copper acid salt" is just an old name for the intermediate in nitrotetrazole synthesis, Cu(NTZ)2*HNTZ *(H2O)4. It's a pretty accepted term though. So you can see how this could decompose into Cu(NTZ)2 and 5-NTZ. The dibasic salt (Cu(NTZ)2*2Cu(OH)2) exists too but it lacks the properties of a primary.

Thank you for the infos and explanations :-).

[Edited on 8-8-2017 by PHILOU Zrealone]

NeonPulse - 8-8-2017 at 16:48

Despite hydrolysis of my product I still got nice yield of NaNTZ crystals upon reacting the copper NTZ with NaOH reducing the solutions volume and cooling. Maybe a little lowered yield but 10-15g. Certainly Enough to experiment further.

nitro-genes - 9-8-2017 at 08:54

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]

Attachment: 200 ug of Cu(II)(NATZ).avi (3.6MB)
This file has been downloaded 730 times


DBX-1

NeonPulse - 25-8-2017 at 03:45

after thinking about my first attempt and failure of synthesizing DBX-1 last year i realized my problem was mostly due to the poor quality of copper I chloride i had used. it was old and there was far too much copper II present for it to work n this intended use.
So I made a fresh batch CuCl by reducing a fresh batch of CuCl2 with Na2SO3 and keeping it un exposed to oxygen as possible before use. satisfied with the result i set about making DBX-1 by using the preparation outlined in example 2 of the US patent No:2013/204005A1

0.9g CuCl was put into a 100ml RBf with a small oval stir bar added and 20ml distilled water was also added to suspend the CuCl. next a solution of 2.08g of NaNTZ in 30ml Dist H2O was added to the flask all at once. the resulting solution was at first an olive colour which quickly changed to light brown and then to orange upon heating being applied.
the flask was fitted with a reflux condenser with cold water running and heating was applied to the flask to bring the temp up to a steady reflux.
i had a worry about the contents being very thick and not stirring properly so i added more H2O to help it stir.
this was kept up for just short of an hour and heating was removed.
the result was a rust coloured precipitate in a fairly clear solution which was filtered on a buchner funnel, rinsed with portions of water and finally with Anhydrous IPA and left to dry overnight. the weight of my yield was exactly the same as the patent example- 1.12g.

upon testing my product i was surprised to find that when lit it flashed off very fast similar to mercury fulminate. i was expecting a sharp snap and torn foil like with it's silver counterpart. when heated from below though the story was different.
it's brisance was clear. it is a high performer.
with some impact testing it did not seem overly sensitive when hit between steel surfaces, taking a light blow to fire it - this changed to a minimal tap when hit on concrete though. same with a friction test- it barely crackled on steel when rubbed hard with a ball hammer but on concrete it went off with just dragging the weight of the hammer itself over the sample.
for some final testing though i plan to test a tiny amount of DBX-1 on top of well pressed 200mg samples of TNT,PETN,ETN and MHN.
quite happy with this stuff so far though.





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Laboratory of Liptakov - 25-8-2017 at 12:00

DBX 1 is very sofistics energetic material. I am curious on compare testing with ETN...The Hat down....thanks for description. Dr.....:-)
Password of the day: Is there Copper? So it hit ...:cool:...Dr.

greenlight - 25-8-2017 at 21:16

Nice work NP!

I don't have any experience with tetrazoles but I know DBX 1 is going being looked at as the main replacement for lead azide being with it being non toxic and not heavy metal salt.
It seems that green explosives is the way for the future commercial research.

I look forward to seeing how it performs with initiation of secondaries.

[Edited on 26-8-2017 by greenlight]

PHILOU Zrealone - 26-8-2017 at 17:24

Quote: Originally posted by greenlight  
Nice work NP!

I don't have any experience with tetrazoles but I know DBX 1 is going being looked at as the main replacement for lead azide being with it being non toxic and not heavy metal salt.
It seems that green explosives is the way for the future commercial research.

I look forward to seeing how it performs with initiation of secondaries.

Paradoxally when analysing soil for heavy metals (at least here into Europe)...
==> Copper (Cu) is into the list of the dozen of requested metal quantification...
==> Green explosive maybe refer to the color ;):P:D:) and not to the enviro-friendlyness :cool:

Better switch to Na, K, Ca, Fe, Mg, Al, ... NH4, N2H5, guanidinium, ...

[Edited on 27-8-2017 by PHILOU Zrealone]

nitro-genes - 27-8-2017 at 15:45

Very nice! How sensitive is DBX-1 to flame or a glowing splint? Do the properties change upon storage? IIRC DBX-1 was sensitive to moisture upon storage, does DBX-1 itself also slowly oxidize to Cu(II) in contact with air?

After some reading... (:D) solutions of Cu(II) and salts of NATZ form Cu(NATZ)2, which is a hydrate and unsuitable as a primary. It seems water of hydration is the main problem with salts of NATZ, while its difficultly obtained anhydrous salts (such as the calcium salt ) seem more useful and even been suggested as a lead azide replacement. Tried to make a putative Ni(II)(hydrazine)2(NATZ) salt to see if this would increase flame sensitivity. Its a lilac in colour (like NHN) but similarly insensitive to flame as the copper salt, and even more reluctant to make DDT upon heating. Wonder if potential double salts/complexes of 5-NATZ and styphnates or trinitrophloroglucinates would exist and be more interesting. Since most of these form hydrates itself, probably not, but who knows?

[Edited on 28-8-2017 by nitro-genes]

NeonPulse - 2-9-2017 at 01:59

Quote: Originally posted by nitro-genes  
Not sure how easily other some other triazoles would form when acetic acid/acetate is present during the heating step. From what I've read, acylhydrazides need higher temperatures and anhydrous conditions to form (STUDIES OK THE FORMATION OF 4-AMINOTRIAZOLE DERIVATIVES FROM ACYL HYDRAZIDES, ROBERT M. HERBST AND JAMES A. GARRISON).

I've seen the cyanamide fertilizer bags for sale, just more fun going all the way from urea though. :P Cyanamide was homemade by pyrolysis of calcium cyanurate at 800-1000 deg C. Used a welded 150mm diameter stainless steel container with 5 cm of 20 mm stainless tubing protruding from one end by which it could be filled and emptied. A conically shaped stainless steel weight was placed on top of the 20 mm tubing so that when fired, gasses could escape by lifting the weight up, closing it again when no more gas is produced. Worked nicely and gave abundant amounts of silvercyanamide on testing (can this be used for quantification of purity?). Yield was 90% of theory from calcium cyanurate and got 360 grams calcium cyanamide in total from 2 firings, which is more than I need anyway. The original goal was to make dicyandiamide, but decided a small amount of 5-ATZ would also be nice.[/



I Managed to find that reference where Engager tested his product for purity using this method: from his post in the prepublications:'ve managed to preform quantitative analysis of product produced as described above. 1g of product was added to 150 ml of cold water and stirred for several minute, 2-3 ml of 70% HNO3 is added and mixture is stirred until all solid is dissolved and transparent solution is obtained. After this solution is complemented with 4 ml of 25% ammonia, and solution of 4.5g of silver nitrate in 50 ml of water with stirring. On addition of ~40 ml more of 25% ammonia silver cyanamide is precipitated as pale yellow mircrocrystalline solid. Mixture is stirred for 10 minutes, precipitate is filtered off, washed with water and alcohol and dried. Silver cyanamide is weighted and checked against theoretical of 3,197g for 100% calcium cyanamide. Analysis for my sample shown that is gives 2.85g of silver precipitate, indicating that sample contained 89.15% of pure calcium cyanamide, corresponding to nitrogen content of 31.2% (vs 34% calculated for formula CaNCN)

Also in reference to the DBX-1 I had made recently,?i tested its sensitivity to an ember on a splint and it is very easy to set it off this way. Flame is the same. Holding the flame just away from the sample also sets it off but with a slight delay. It has the characteristic whump of mercury fulminate or DDNP leaving a small patch of copper metal as a residual coating on the surface it was on before igniting. I'm just waiting for my new .001 scales to accurately measure amounts I'm working with. It is pretty snappy and I could easily see a small amount doing nasty damage if an unwanted detonation did occur so using small amounts Is a wise choice. I should have results of further tests in the next week or so, once I get rid of this rootkit on my PC which is consuming what little time I have spare lately. Darn computers. I'd have thrown it out the window if it didn't cost so much.

nitro-genes - 3-9-2017 at 03:23

Sounds like DBX-1 is even more flame sensitive as lead azide and pretty friction sensitive as well, crystal shape probably being an important factor.

Considering the reaction is a pyrolysis at ~1000 deg C, a product of 90% purity in 90% yield is still amazing. ;) Dilute solutions of calcium cyanamide in cold water and precipitating the silvercyanamide as a more course crystalline solid would help. Due to it's very low solubility it seems to form a really fine precipitate, easily partially escaping the filter. Been wondering if you could precipitate silvercyanamide as an extremely fine precipitate in very dilute solutions, maybe light extinction of the suspension could also be measured somehow.

PHILOU Zrealone - 4-9-2017 at 03:03

Quote: Originally posted by nitro-genes  
Sounds like DBX-1 is even more flame sensitive as lead azide and pretty friction sensitive as well, crystal shape probably being an important factor.

Considering the reaction is a pyrolysis at ~1000 deg C, a product of 90% purity in 90% yield is still amazing. ;) Dilute solutions of calcium cyanamide in cold water and precipitating the silvercyanamide as a more course crystalline solid would help. Due to it's very low solubility it seems to form a really fine precipitate, easily partially escaping the filter. Been wondering if you could precipitate silvercyanamide as an extremely fine precipitate in very dilute solutions, maybe light extinction of the suspension could also be measured somehow.

Did you test the same procedure onto the "unburned" original product of Ca cyanurate?

This to exclude the fact the precipitate could be Ag2SO4, AgCl, Ag2CO3 or Ag2O/AgOH.

If it is just a precipitation reaction between cyanamide and Ag(+)... why did you add HNO3 and NH4OH?
==> The NH4OH may react with the Ag(+) by compexing (solubilising) it or by forming a precipitate of AgOH/Ag2O
==> The HNO3 may reduce the precipitation of Ag cyanamide

nitro-genes - 4-9-2017 at 11:27

This might be something to test indeed, whether silver cyanurate is soluble in ammonia, although any possible cyanuric acid should mostly precipitate upon acidification of the calcium cyanamide (when not too dilute solutions are made that is, solubility is 0.3g/100ml at 25 deg C) and result in a cloudy solution of cyanamide. (Didn't notice this during my simple add-calciumcyanamide-to-cold-HCl-test) Some like dicyandiamide, guanidine, cyanides and cyanates may also form insoluble silver complexes/salts. Don't know their solubility, but if less soluble than the generally very soluble Ag-NH3 complexes of most simple anions, these could precipitate as well, along side the silver cyanamide. The latter two could interfere even though the calcium cyanamide solution is acidified, some HCN,HOCN and CO2 may still be present in the cold acidified and dilute cyanamide solution. Not sue about the solubility of silver carbonate in ammonia, supposedly it is a yellow salt was well, similar to silver cyanamide.

It's still a reasonable approximation probably, but due to the very fine precipitate of silver cyanamide, side reactions of calcium cyanamide when added to water and upon acidification (to free all cyanamide from the nearly insoluble calcium salts), possible precipitation of other silver complexes/salts and without a reagent grade calcium cyanamide as a positive control, it seems more of an expensive rough indication than accurate quantitative test.

[Edited on 4-9-2017 by nitro-genes]

Rosco Bodine - 30-9-2017 at 19:36

Simplified method for NaNT

US9598380

Attachment: US9598380 Facile method for preparation of 5-nitrotetrazolates using a batch system.pdf (614kB)
This file has been downloaded 722 times

Tdep - 1-10-2017 at 02:04

That's a great find Rosco, seems like a large improvement over the current method for both industry and amateur, if it does indeed work as described. Improvements to the speed of the synthesis as well as the safety, seems great.

Dornier 335A - 1-10-2017 at 11:58

That is fantastic! Twice the yield, quick and safe process and everything in a single step. This used to be the bottleneck in nitrotetrazole production so I think we'll see more of that ion in the future!

Rosco Bodine - 1-10-2017 at 13:37

For these type of slow additions, rather than making the addition "dropwise" from an addition funnel, it is a more precise method to use a very low flow rate metering pump like a syringe pump or similar low flow pump to slowly inject the reactant solution through a capillary or a small gauge cannula with the discharge below the surface in the stirred reaction mixture.

The injected reactant is sheared away as a continuous mix injected in the current of the liquid swirling past the injection point, so there is no cyclical impulse for the reaction waiting for each drop to grow and fall by gravity as an addition in much larger droplet sized increments. Infusion by precision method would be completely controllable and repeatable, and should also be safer when scaling up the batch size.

PHILOU Zrealone - 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]

Rosco Bodine - 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.

Rosco Bodine - 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&...

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&a...

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&a...

[Edited on 10/3/2017 by Rosco Bodine]

nitro-genes - 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?

Rosco Bodine - 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&a...

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.

Rosco Bodine - 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 635 times

A related developmental history patent is US7253288

Attachment: US7253288 Process for preparing substituted tetrazoles from aminotetrazole.pdf (900kB)
This file has been downloaded 602 times



[Edited on 10/5/2017 by Rosco Bodine]

NeonPulse - 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&... 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

nitro-genes - 25-11-2017 at 11:39

It seems guanylazide picrate is only mentioned few times in literature indeed, couldn't find anything either. Nice video on DBX-1 btw! :)

Tried the batch 5-NTZ production process from US9598380 today, the reaction went exactly as mentioned in the patent, no hard to filter, sticky, explosive CUNTZ, copper oxides or m(i/a)cro explosions during the additions, hooray! :D

I did downscale the reaction to 0.5 grams of 5-AT monohydrate instead of 1 gram, keeping the reaction volumes similar (Don't have <20 ml beakers) so not sure if this affected the end product somewhat. Still wonder how this reaction can supposedly produce such good yields, as I would have guessed the pH during the early additions would be too high to form the diazonium precursor in the first place and OH- or even water would be competing with nitrite.

Reaction:

1.18 grams of sodium nitrite in 10 ml distilled water were added to a 20 ml beaker, temperature was kept at 65 deg C. using a waterbath. To another 20 ml beaker, 0.73 grams of 98% sulfuric was added to 5 ml of water. Then 0.5 grams of 5-AT*H2O was dissolved in the dilute sulfuric and put next to the other beaker in the waterbath. The 5-AT/SA solution was added in the smallest increments possible, using a pipette, over the course of 45 minutes. The effervescence was only slight and proceeded steadily. There was a very noticable decline in effervescence with the addition of the last few drops of the 5-AT solution. After the effervescence had mostly stopped (another 5-10 minutes of stirring), the beaker was removed from the waterbath and allowed to cool down. As indicated in the patent, the reaction mixture had attained a very slight yellow colour and total volume (due to evaporation) was around 10 ml, end pH was between 2 and 2.5.

Sodium bicarbonate was added to bring the pH up to around 7, then a slight excess of calcium nitrate added and the calcium sulfate filtered off. The solution attained a noticeably darker yellow colour upon neutralization. A few mg's of silver nitrate in disitilled water was used to precipitate some silver 5-NTZ, which precipitated as a slightly beige coloured product. I was unable to remove the beige colour by washing with water as the silver salt of 5-NTZ should be completely white. It does behave very flame sensitive, detonates in microscopic amounts, blackens at around 240 deg C and explodes only when dropped on a hotplate >300 deg C, so probably reasonably pure silver salt of 5-NTZ. Yields were not determined due to small scale.

[Edited on 25-11-2017 by nitro-genes]

Rosco Bodine - 25-11-2017 at 13:36

No more sloppy wet CUNT for you guys except maybe on special occasions :D:P;)

Hennig Brand - 25-11-2017 at 19:37

NeonPulse, I like your electric furnace seen in the sulfuric acid distillation video. Some interesting looking videos.

Hello Rosco, good to see you on here. Glad to see you still find chemistry sexy. ;)

Rosco Bodine - 26-11-2017 at 04:08

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]


Working from the diammonium 5-nitraminotetrazolate precursor you may be getting ammonia complexation in situ for the reacting Cu or Ni or Ag salts and this may be a partial complexation in absence of sufficient ammonia.

The nickel(II) NATZ salt being very soluble is interesting as a potential opportunity for that solubility to be upset by complexation with hydrazine and to form a Nickel tris-Hydrazine NATZ analogue of NiNHN. Also suggested is the possibility of a double salt with the NiNHN analogue where a mixed solution of nickel nitrate and nickel NTZ is treated gradually with hydrazine to coprecipitate a possible double salt of NiHN and NiNTZ. I think the NTZ compound has more promise than the NATZ compound for such a coprecipitation scheme if the solubility of NiNTZ is good also, but could react with hydrazine to form a low solubility complex.

A nickel hydrazine azide is also reported so it provides another possibility as a candidate in a double or multiple complex salt scheme where a coprecipitation may occur. Such schemes have the potential of enhancing the properties of NiHN.

Ethylene diamine has interest as a complexation agent as well as interest in double salt formation due to reported ability to undergo a half neutralization by one acid reacting with one of its amines and completion of neutralization by a second different acid reacting with the second amine.

Glycine is known to complex metals and might have interest particularly for the Cu salts or potential double salts. Methylamine is another candidate for potential Cu complexation schemes.

It is impossible to really predict what sort of solubility driven interactions may lead to formation of what complexes that may occur for resulting materials that could be complexed and or multiple salts having synergistic properties. This is an area of pure research and experimentation for compounds that may be possible but are undiscovered or unreported.

The half neutralization scheme for ethylene diamine being completely neutralized by a second different acid, may likewise be possible for basic salts of one acid which are half neutralized by formation by first one acid and then converted to neutral complex salts by a second acid.

Regarding the silver salts, excess ammonia may dissolve and allow for purification by reprecipitation on neutralizing the ammoniacal solution of the silver salt.

[Edited on 11/26/2017 by Rosco Bodine]

Tdep - 29-11-2017 at 05:31

I also tried the batch 5-NTZ production process from US9598380 yesterday, but on a 0.75g 5-ATZ scale. I made the silver salt, and it iss good, very similar to silver fulminate really, but what really blows me away is just the power of this reaction mix.

Ok, so the pH for me ended up at around 9... I might not have scaled the nitric exactly correctly (it was a weird concentration in the patent). But here's a video showing....

Firstly: The raw reaction mix. It's very hard to dry, but when I stick it in the freezer, the whole lot turns into a sticky mass of crystals. The water boils off, and everything detonates violently.

Next, what I did was try to recrystallise from acetone. When a lot didn't dissolve, it turned more into an extraction. The yellow solid left behind (i'd say like 90% of the mass of the reaction mix?) after the acetone extraction is not energetic. When put over a flame, it simply evaporates away, calmly, not even burning like 5-ATZ does. The acetone used to extract the mix though.....

The next two clips are me heating (or accidentally setting fire to) the acetone solutions. The acetone boils/burns off before the solid explodes, but when it does, it's phenomenal. Look how it shreds that aluminium foil......!

So... is this the sodium salt of nitrotetrazole? I mean it has to be, because the pH of the mix is basic, but gee, it goes hard. The sodium salt seems to outperform the silver salt almost... whats up with that?

VIDEO: https://youtu.be/j3ulrXukg6o

nitro-genes - 3-12-2017 at 11:35

Ooops, just noticed I got the ratios of sulfuric and nitrite wrong for the batch 5-NTZ proces...:o Shouldn't be doing this stuff late at night (or at all:D)

The potassium salt might be interesting as well, it doesn't form hydrates like the sodium salt. Read somewhere that the main reason it is unsuitable as a primary is it's "low" decomposition temperature of 195 deg C, although couldn find any sensitivity data.

Some interesting paper about DBX-1

Attachment: Development of a Lean Process to the Lead-Free Primary Explosive DBX-1 (929kB)
This file has been downloaded 550 times

[Edited on 3-12-2017 by nitro-genes]

NeonPulse - 3-12-2017 at 22:04

Had a go at making mercuric Nitrotetrazolate according to the synthesis depicted in this document: http://www.dtic.mil/dtic/tr/fulltext/u2/a036086.pdf
I did it at 1/10th the scale - making large amounts of such a powerful primary makes me nervous. Followed the synthesis to a T including preparing the Mercury nitrate solution from HgO. The Solutions of HgNO3 and Sodium Nitrotetrazolate were mixed at 75c as directed and were left at a slow stir speed until 30c. Shortly after mixing not much seemed to be happening but at about 55-50c there was a gradual precipitation of the product in a microcrystalline snow in The beaker. Once it got to about 30c which was also the temp in my lab I left the solution for a few mins before gravity filtering and rinsing several times with ice water and finally with a small portion of Dichloromethane.

Now I must say that I was very impressed by this stuff. It flashes off with a dull thump like its fulminate cousin but a bit faster, with a white orange flash. when confined in foil I had perhaps a few Mg in a bit of foil and held it over my alcohol burner and the report was loud. It actually shocked me. The foil was atomised shiny glitter and my ears were ringing. I don’t recall the DBX-1 being quite as powerful. It’s also not super impact sensitive or friction sensitive but enough to be useful as a primer. Obviously a drawback is that it contains mercury. The little squares of foil that I lit it on showed the signs of amalgam formation in the way of the tiny fibers that formed when mercury is in contact with Aluminium.

A26D8224-538C-41F7-BA26-454E06F5996E.jpeg - 2.8MB

[Edited on 4-12-2017 by NeonPulse]

B6933215-77E7-4552-B766-9F67F1DE293B.jpeg - 1.4MB

snooby - 30-11-2018 at 08:45

When I made the raw NaNTZ mix, and I put aceton in the mix to extraxt the pure NaNTZ from the crude crystal mix I end up with unknown amount of NaNTZ dissolved in the aceton.

To use the pure NaNTZ to make BNCP I need to know how much NaNTZ I have made. So, I need to evaporate the acetone and wheigh the NaNTZ. This part i really dont like, because of the power and sensitivity of pure NaNTZ. Just 0.5 gram CAN turn u deaf.

To avoid contact with the stuff, I wheigh the empty can, then let the aceton evaporate, and wheigh the can again. Then I just put the right amount of distilled water over it to get a useable solution of nantz in water.

I would like to know, how do you guys handle crude and pure NaNTZ?

Is there a reason to be so scared of it?

[Edited on 30-11-2018 by snooby]

Dornier 335A - 2-12-2018 at 04:15

NaNTZ crystallizes from water as a dihydrate which is quite insensitive. It requires pretty strong blows with a hammer to go off.

Acetone on the other hand may or may not give you the dihydrate so I would be very careful, the anhydrous salt is very sensitive!

snooby - 3-12-2018 at 05:21

That is excactly what concerns me. The aceton step is very important to remove impurities from the NANTZ mixture. I did the whole process 5 times with about 3 grams of raw NaNTZ and never had problems. Still I dont feel very comfortable with it. Are there any guys that did NaNTZ purification?

Edit: I remember following thing. When i had the pure nantz in the aceton dissolved, i poured distilled water in this mixture. Then I would heat the liquid untill no acetone smell was obtained anymore. I then simple let the water evaporate. Quite time consuming however

[Edited on 3-12-2018 by snooby]

nitro-genes - 3-12-2018 at 11:54

No experience with recrystallization from acetone, though recrystallizing NANTZ from hot methylethylketone (MEK) definitely resulted in a hydrate (melted and boiled first when heated, only then exploded). Even though this was tested at small scale first, I still added a few drops of water to the MEK for the main batch as a psychological reassurance. :o Wondered if MEK would not be an even better solvent for NaNTZ recrystallization, since it is more hydrophobic than acetone and has a higher boiling point, so maybe less likely to crystallize an anhydrate and better recovery efficiency?

Thinking some more about the patented batch process...what would be the most prominent impurities? I've noticed that a dark yellow impurity is formed along with the colourless NANTZ. The yellow impurity darkens in colour when basified further, so my guess would be that this would be mostly 5,5'-diazoaminotetrazole or 5,5' azotetrazole? Maybe the reaction is so fast that upon adding the 5-ATZ/Acid solution to the nitrite solution, the mixing efficiency becomes limiting in how much self-coupling takes place? The same thing applies for the reaction of hydrazine and nitrous acid to from hydrazoic. Apart from really strong mixing, would further dilution of the 5-ATZ/Acid solution not be more beneficial?

Also noticed that insufficiently purified NANTZ, immediately produces a fine green haze when cupric salts are added. IIRC, the solubility of the cupric salt of 5-NTZ is much higher than those of unreacted 5-ATZ, 5,5'-diazoaminotetrazole or 5,5' azotetrazole. Wonder if a first NANTZ enrichment step using cupric salts woudl be feasible. Don't know the exact solubility of all the cupric salts though, or if they even are all known...


[Edited on 3-12-2018 by nitro-genes]

Hex - 6-12-2018 at 04:25

Been a long time (12 years maybe?!) since I last posted on here, still some familiar names from back in the day though...PHILOU, Roscoe, hello! I'm still working in energetics and rediscovered the forum searching for anything new on DBX-1...some of the skills and improvisations in this thread are really impressive!

A couple of things that I don't think have come up in the previous 20 pages, apologies if I missed them on scanning through.

1) The "acid copper salt" actually turns out to have about 4% sodium in it (when using sodium hydroxide to neutralise, obviously). It's defied recrystallisation so I don't think anyone's got an X-ray structure yet.
2) If your "DBX-1" is brown and a nightmare to collect in a filter, it's probably not DBX-1. No-one is 100% sure what the brown, "gel-like" intermediate is that forms on ascorbate reduction of NaNT/Cu(II), but it's very difficult to convert to DBX-1 without having DBX-1 crystals to seed the reaction with...chicken and egg. Apparently the transition from gel to DBX-1 is quite obvious visually when it happensand the product is visibly crystalline and reddish, unlike the brown sludge. I had a few goes (without seed) and isolated the products...they were all energetic and flame sensitive, but the DSC peak exotherm varied across a range of around 80C depending on the batch.

I've got some nice NaNT.2H2O in hand, made by an adaption of the Fronabarger filter reactor method for making NaNT solution, but as I was going for purity I evaporated it, Sohxleted the solids and recrystallised by slow evaporation from acetone (some of the rhombic crystals are 40x40mm plates!) and have slight yellowish tinge, I'm going to try the Cu(I) method next, it seems to be less seed dependent...looking back over the thread I see Neon's tried this method and it's no surprise that his product looks much more like DBX-1 - nice job!!


nitro-genes - 6-12-2018 at 12:06

It seems very difficult to get good DBX-1 crystals. The "gel" is a weird thing indeed... I remember trying some alternative synthesis schemes using the cupric/ascorbic method, and in one instance (using much lower temperatures during the synthesis), the entire solution became like a solid gelatin pudding. What I found really strange is that boiling this gelatin mass in some instances still refused to produce DBX-1. :o The gel doesn't form from the CuCl synthesis indeed, though even then the product seems a mix of well formed crystals and almost amorphous stuff. Could be the simultaneous presence of cupric and cuprous results in this gel (The cupric may allow more ligand binding, forming almost a polymer) and/or could relate to the ascorbic, though both would seem easy enough to exclude. Alternatively, the DBX-1 forms as very small crystals, and the formation of DBX-1 crystals from this colloid depends on a poorly understood self-assembly process maybe?

Rosco Bodine - 13-12-2018 at 03:30

There is a strange gel formation that can also occur for lead styphnate. So it may be a clue what is occurring there has a physical chemistry parallel. It seems like the gel could be exploited, perhaps as a method of formation for double salts which might be gotten by mixing one gelled system with another gelled system where the two could interact and form a product from the gel precursors.

nitro-genes - 13-12-2018 at 12:23

Interesting idea, using these gels to produce double salts...:) Strange phenomena these gels, noticed there was a paper posted on SMDB about the lead styphnate jelly, from what I read it seems to be controlled by pH mostly, so maybe is determined by how coordinated water interacts with the Pb2+ and styphnate to produce some hydroxide containing complex, though cannot picture how this would look like.

Can DBX-1 be produced at slighty lower pH? What happens if ascorbic acid is used instead of sodium ascorbate?

[Edited on 13-12-2018 by nitro-genes]

Dornier 335A - 13-12-2018 at 14:15

I have used ascorbic acid instead of sodium ascorbate! It worked perfectly; the DBX-1 was reddish and settled quickly on the bottom.

nitro-genes - 13-12-2018 at 15:14

Seriously? Nice!!! Any microscopy pictures? :D Does the DBX-1 produced dissolve in HCl as a clear solution, no copper particle residual? Is it actually soluble in HCl?

5-NTZ is a very strong acid, coincidentally about as strong as picric (:D) at a pKa of 0.8, so after performing the picric reductions using cupric/ascorbic I was contemplating before if a pH of about 2 would interfere with the formation/complexation of 5-NTZ to the cuprous salt indeed. Performing the entire reaction in dilute acetic might be even more beneficial. Similarly, the picramic and styphnamic complex of Cu(I) is only displaced at very low pH and high concentrations of competing ligands such as Cl- or NO3- (but not sulfuric), so was wondering if the same would apply for DBX-1 indeed. The reduction of picric/styphnic might be interesting for the production of DBX-1 as well, as it is sort of an optimized procedure for the steady production of Cu(I).

One of the important differences would be the question how hard that Cu(I) is "gripping" the 5-NTZ? Is there some measure or definition for that? Reading IIRC that DBX-1 is easily hydrolysed by water, my first guess was that it was a rather weak interaction. Silver azide is another surprising example, forming almost a completely ligand coordinated polymer that precipitates even from very acidic solutions, despite the azide ion being a rather weak base.

[Edited on 14-12-2018 by nitro-genes]

snooby - 19-12-2018 at 06:14

Anyone with a decent dbx1 synth? The one with ascorbic acid gave me brown chunks wich where not usable as a primary. I hope someone can post another synthesis or some advise about that.

Also a question: when purifying crude NaNTZ crystals I do an extraction with aceton. Since I dont want to evaporate the acetone (to exclude forming of anhydrous nantz) I mix the aceton with demi water. Then I let the aceton evaporate on a hot water bath, so only water remains. Is this a good thought?

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