Sciencemadness Discussion Board

Guanadine nitrate, etc

quicksilver - 27-5-2006 at 06:00

Are there other energetic material compounds utilizing Guanadine Nitrate aside from nitroguanadine and nitrosoguandine? I really want to learn more about this material and it's use in industry. Triple base propellents are facinating; I have always wondered if such could propell a rocket instead of a shell. TBSP have the ability to vary considerably their speed and the weight of the projectile. Thus far experiments with crude TBSP have prooved to me that it could be done by the hobby rocket fan. But my real question which I am having a tough time finding is this:
With the massive availability of guanadine nitrate from Degussa a friend of mine illustrated how to make aminogunadine bicarbonate. It was an easy task and illustrated in the COPAE. But from there I had wondered how to develop guanyl azide. Should be a step away but the concept eludes me; any ideas?

Swany - 27-5-2006 at 11:49

Other guanadine salts, such as the perchlorate, may also be interesting. I have 400g of GN, and have expiremented with NQ (nitroguanidine) and prepared some nitrosoguanidine (interesting stuff). I am not very familiar with this area of explosives, however they seem to be quite interesting.

Chris The Great - 27-5-2006 at 17:21

You need to react with a nitrite to get the azide.


Also, the reaction of guanidine nitrate with hydrazine gives triaminoguanidine nitrate in high yield.

Axt - 28-5-2006 at 03:40

Quote:
Originally posted by Chris The Great
guanidine nitrate with hydrazine gives triaminoguanidine


Triaminoguanidine + acetylacetone -> 6-Bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine
6-Bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine + hydrazine -> 3,6-dihydrazino-1,2,4,5-tetrazine
3,6-dihydrazino-1,2,4,5-tetrazine + HNO2 -> 3,6-diazido-1,2,4,5-tetrazine.

I think that will need nothing more elaborate then a glass jar, though the diazide (C2N10) is a hyperactive primary. The dihydrazine is a high explosive literature gives calc. VOD of >10000 which I dont believe at all.

Or make the diamino derivative then oxidise to LAX-112, not sure of its props but it looks good on paper. Theres a lot of other explosive tetrazines derivatived from 6-Bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine but the above seem to be the easiest to get to with common chems, while still having exceptional performance.

[Edited on 28-5-2006 by Axt]

quicksilver - 28-5-2006 at 07:05

Chris: do you remember where the nitrite info came from?

I just thought about that....A VoD of 10,000??? That just doesn't seem right. Anything over 8000 was ususally discussed on Usenet in the 1990's all the time and I don't rememeber anyone taking about something as mundane as a guanl derivitive at such speeds. I don't believe it either.

The tetrazine(s) were a breeze but the azide has me stumped in-so-far as any available patent literature, etc. [ Access to NaN3 but not hydrazine means that I need to think in that direction.] Has anyone seen any patents, etc. I tried the USPO but got a zero on all attemps; anything in German or French? I would really apprieciate any hints; I just can't find much outside of the older textbooks. And they typically use hydrazine instead of sodium azide.

Thank you all - I really apprieciate the input!

Axt - 28-5-2006 at 12:36

I just deleted this post, after posting that guanyl azide is not isolatable, as I found COPAE does actually say its isolatable as its salts so I know what your asking now, you want the azide salt rather then 5-aminotetrazole.
Quote:
Originally posted by quicksilver
The tetrazine(s) were a breeze


Not to be confused with tetracenes & tetrazoles, all different and the three major energetic routes out of guanidine.

Attach article on azide->tetrazole rearrangement, not sure if your answer is in there, havn't read it but the title sounded right.

[Edited on 28-5-2006 by Axt]

Attachment: Theoretical Study of the Azido-Tetrazole isomerization.pdf (507kB)
This file has been downloaded 1215 times

Chris The Great - 28-5-2006 at 20:05

There are also some very interesting propellants (specific impulse 235 with solid carbon in the exhaust, add an oxidizer and.... ) based on triaminoguanidine. I'll see if I can dig them up sometime, I have no clue were they might be...

quicksilver - 29-5-2006 at 06:47

Thank you all so very much!
The azide->tetrazole material is getting me further along. You guys are a real help.
:D
I really love crystaline structure, it's one of the things that continiuosly facinates me. The tiny needles from niroguanidine are some of the prettiest I have seen in a very long time and the yields are so damn high that this stuff will captivate me for several experiments to come. I really need to recommend that if you haven't made nitrogunadine and love crystal structure and enjoy using a microscope this one will floor you. I am really trying to rig up a camera to a large microscope I have been using. I wanted to have a small collection of the various crystals from assorted materials that are in common use. I will certianly post them what I do.
I saw the initiation of nitroguanadine just reciently and it's really unique. Virtually no flash, loud & powerful report, and a very clean det. This stuff has possibilities; I just know it. And the chemistry surrounding the various guanadines is quite enough to satisfy someone who is much further along than myself. It's a real challenge.

And you "hit the nail on the head" - It's Guanyl Azide that is my target. from what I understand this is a primary that was used in Europe for a time as an initiator in very sofisticated systems due to it's unique properties. One of which is low bi-products after detonation. It was used in very small applications where there existed electronics and optics which could be damaged by Pb etc. From the little I understand, it's a very clean initator; and it has low toxicity (within reason of course). The more I learn about it the better it sounds.

Axt's paper presents some profund issues I had not known perviously. That which Guanylazide hydrochloride is very stable & by that guanyl azide itself has sensitivity issues. This however may not be a great deal more than simple PbN6. The essence here is that most of the guandine materials are very well developed crystals and we all know that azides need to be dextrinated, etc to reduce crystal size to the point that well shaped crystals are not produced at any great degree. The paper is complex but has some good leads. What I am reading is that tetrazine is used to produce (via azide) a material somewhat similar to a cage-crystal lattice (clathrate) but in a form that limits crystal size and shape. This may be possible for the hobby experimentor. Tetrazine is a VERY easy thing to synth. It's actually a fun lab with guanadine nitrate available. The need for a hydrochloride and the addition of an azide is also a simple proposition. Unfortunatly the paper appears to be post-grad level material and I need to really study this thing quite slowly. I would be quite proud of myself if I could make a go of it.
But to finally have another clathrate....THAT would be excellent! However I am not convinced that I am on the right track here in making a jump that it is a cage-crystal lattice. A keynote here in this process is the role of the lone pair N which permits the formation of the bond and in re-reading that does not sound like the clathrate mechanism. But could a clathrate be produced outside the standard guanyl azide synth? If any experiment be attempted it would be done on a milligram scale as I know that the final result initially would be a well formed crystal if steps were not taken to stop that formation. And well formed azide crystals are not a good thing. :(

[Edited on 29-5-2006 by quicksilver]

Axt - 29-5-2006 at 09:16

Quote:
Originally posted by quicksilver
That which Guanylazide hydrochloride is very stable & by that guanyl azide itself has sensitivity issues


I still have not read it, but doesnt it say that guanyl azide is unstable rather then "sensitive" in that it cant be isolated rather wants to rearrange to 5-aminotetrazole. So you want its nitrate salt. Trying to "free base" the azide results in the rearrangement.
Quote:
Originally posted by quicksilver
Tetrazine is a VERY easy thing to synth.

Quote:
Originally posted by quicksilver
What I am reading is that tetrazine is used to produce (via azide)


Still confusing Tetrazine with tetracene and tetrazole. Unsubstituted tetrazine would be C2H2N4 where tetrazole is CN4H2 and tetracene is short name for a certain tetrazine hahah Well tetracene is sometimes called tetrazine which is probably more accurate, so just to confuse the issue a bit more tetracene is also C18H12. So I think for clarity in this context 1-guanyl-4-nitrosoaminoguanyltetrazine should be called tetracene .. hahah, cause the 1,2,4,5-tetrazines I refered to above have little to do with tetracene as in 1-guanyl-4-nitrosoaminoguanyltetrazine, cause thats just confusing right. ^ I'm not even going to read over that again godamnit hahah very annoying.
Quote:
<i>From US 6,350,307</i>

<u>Preparation of Guanyl Azide</u>

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.


Swap HCl for HNO3. Isolating the nitrate from its aqueous solution is the only issue I think..

See page 265 here, gives you the old german references needed for isolation of nitrate and perchlorate salts. Nothing in english though, and regarding the guanylazide picrate, sadly, as far as I know, Australian patents that old are not available online.

<a href="http://ww1.mytoplist.net/~64678/explofiles.mytoplist.net/banners/chemistry%20of%20aminoguanidine.pdf">The Chemistry of Aminoguanidine and Related Substances</a>

"Attempts to isolate free aminoguanidine result in the formation of s-diaminotetrazine."

Thats interesting as well, 'cause oxidation of that will give LAX-112, VOD 8300m/s.

[Edited on 30-5-2006 by Axt]

quicksilver - 30-5-2006 at 05:21

Axt: The link returned a "page not found" unfortunately.
But from what I have at this point I am ready to try the previous patent info above. My synth for Aminoguanidine Bicarbonate worked well so available is a substantial amount of that material. It was used for tetrazine (the one with a "z") successfully :) --from COPAE to make sure that it was the genuine article. The tetrazine synth was extrapolated due to Davis's use of expressions like "heated under steam" and no temp given. But it worked! We assumed it was above 40C and not above 60C. He goes on to say that the beaker be shaken to start the precipitation of tetrazine. The lab was crude but the precipitate was of a good quality.
Guanadine seems to be a whole world unto itself. So much research was done with it.

I took your excerpt from the patent and did some checking as well which lead to more material. I just ade a little text file-pdf so if anyone is interested they can have a look quite quickly.

[Edited on 30-5-2006 by quicksilver]

Attachment: Guanyl Azide.pdf (101kB)
This file has been downloaded 1696 times

Axt - 30-5-2006 at 06:54

Sorry, link is fixed.

Especially sorry if anyone ended up with shit on there computer from that 404 crap. Not going to be aqble to use that host anymore I think.

Well, maybe just once more.

<a href="http://ww1.mytoplist.net/~64678/explofiles.mytoplist.net/banners/nitroguanidines.pdf">Nitroguanidines</a>

Madandcrazy - 30-5-2006 at 08:03

Interested thread, also for some suggestions about
some amines (=NH2, ...) with the double binding and additional syntheses.

I mean some chemical are useful, maybe for some syntheses similar tetrazole derviates to bypassing maybe costly syntheses by substitutions, but easy ;) available.

2,6-dichlororquinone-4-chloroimide
dimethylglyoxime
diacethylmonoxime

Still some to many bleaching syntheses and the
ethylenediamindinitrate (NH2)2CH(NO2)2 and sensible
substitutions or diamin syntheses.

I think some chemicals are suitable, maybe to reacting with
trinitromethane or chlorotrinitromethane ...

n,n-dimethylenediamin
n,n,n`,n`-tetramethylehylenediamin

But is oxidation easy without destroying starting materials or nitrating bevor it oxidized ?

Interested more, is the nitrile group suitable for some of
this reactions ?

example is the
diaminomaleonitrile
CNC(NH2)=C(NH2)CN

[Edited on 30-5-2006 by Madandcrazy]

quicksilver - 2-6-2006 at 06:05

You have given me a wierd idea and I just wondered if anyone else thought about it: a direct synth of a "Guanidine Azide".
If CH5N3 -> NaN3 in a equa-molar weight similar to a transitional metal synth would there be any possibility of such a propellant being formed and if so would the gas level be richer than a simple NaN3 auto-air bag propellant? Or would the damn thing simply detonate....? Opinions, options, or is this too stupid an idea....?

If such were feasable the attempt at such an experiment would be under such minute quantities (milligrams at max) due to the structure of the crystals in certain examples. Nitroguanidine come to mind.

Madandcrazy - 2-6-2006 at 09:34

Surely a good idea, guanidine azide by the way of guanidine nitrate. But the problem are certainly what is the guanidine nitrate, from what prepared and some problems by extraction, solublity and forming out the crystals.

You mean shurely some interested compositions like

guanidine dinitrate HN=C(NHNO2)2 (carbamideamindinitrate)
nitroguanidine nitramideamin HN=C-(NHNO2)-(NHNHNO2)
cyanoguanidine nitrate (NHNO2)-C=NHN

But, are this components preapareable easy or do it exist in theory only ?

You mean shurely too some suggestions ;) for some substitution syntheses.

quicksilver - 6-6-2006 at 06:37

Indeed! My concept is that both are water soluable thus a subsitution of the guanidine nitrate for, say, silver nitrate (in a standard silver azide synth) in water brought to 0 C and then a dextrinated mixture of a sodium azide solution priciptating a (dextinated) guanidine azide. Crystals kept from growing via temp, magnetic stirring, and dextrine.
Could this be done on a milligram level for safety? Perhaps....It did work with nickel nitrate (water soluable) and cuporous nitrate (water soluable) but the sensitivity was so high as to be useless for any application. The real problem as I see it is the crystal growth. Nitroguanadine is a crystal-grower's drean. It sprouts needles so large and well defined that I fear it is not possible to control them. The nickel azide was close to usable but still sensitive enough that more than 20mg was far too dangerous. Copper azide is a touch explosive and not usable IMO. But gunanidine may just be less sensiitive; the crystal growth issue aside.

Swany - 6-6-2006 at 09:53

Hydrolysis of aminoguanidine yeilds semicarbazide, which in turn yeilds hydrazine, ammonia, and carbon dioxide. Oxidation of aminoguanidine with KMnO4 gives azodicarbondiamidine nitrate.

Source: http://encyclopedia.jrank.org/GRA_GUI/GUANIDINE_CN3H5.html

Today I prepare nitroguanidine to work on guanyl azide salts.

EDIT: I had a large post typed up, but then it managed to disspear when I clicked on Axt's link and it was quick-reply, so it was long gone. Re-reading the thread, I then noted that everything I had prepared to post had been extablished. Charming.


[Edited on 6-6-2006 by Swany]

quicksilver - 7-6-2006 at 06:28

I have worked with gunanidine for a time. I did get the aminogunaidine bicarbonate synth down and it is a "non-crystaline" affair. I suppose if I want to work with tetrazine that I could do that all day long as the yields are not all that bad from gunadine nitrate to the aminogunadine bicarbonate. I think it looks like CH6N4-CH2O3. But simply making nitroguanidine via guanidine nitrate +H2SO4 is a breeze and fun too. One trick is to re-crystalize with the hotest water available and to get that to cool to near ice as fast as possible....sounds unique but that is where the best crystals will be. I have seen crystals of alpha nitroguanadine 6mm in length. The yield is unquestionably in the 90% range also. The yield is such that drying is fast as it gets like wool the needles are so tightly packed. It also will pop at about 4500mps if conditions are right (Urbanski). But it's not considered an HE of any strength; but rather a unique one due to it's "cool" explosive properties.

SAM4CH - 13-10-2006 at 13:31

How can I seperate guanidine nitrate in urea/ammonium nitrate process "Patent 4535185"?

Eclectic - 13-10-2006 at 15:00

http://v3.espacenet.com/textdoc?DB=EPODOC&IDX=GB923272&a...

SAM4CH - 13-10-2006 at 19:03

I like to get ammonium nitrate/guanidine nitrate solubility vs. temperature (-10 to 150 degree)..

deiki - 14-10-2006 at 01:21

Less interesting than tetrazines but still worth mentioning in my opinion, nitroguanidine can be used to prepare 2-nitroimino 5-nitro hexahydro 1,3,5-triazine (patent 4,937,340)

The NTO sythesis using nitroguanidine instead of urea looks also possible to me:

http://img220.imageshack.us/my.php?image=nwyx9.jpg

Does anyone know if this had already been attempted ?

EDIT (to chemoleo): Ouch, my bad, I completely messed up the drawing, I should have done it more carefully since it was an old idea.

It starts form aminoguanidine instead of aminourea (not nitroguanidine instead of urea as I previously said) :

http://img517.imageshack.us/my.php?image=nwey4.jpg

[Edited on 14-10-2006 by deiki]

quicksilver - 14-10-2006 at 07:06

The link didn't funtion for me: is it still up there? I did a patent search and looked at some stuff I have and didn't see any reference to nitroguanidine in any NTO synth. Extrapolating from US4937340; could you explain why it seems possible? I'm looking at it and trying to figure why subsitution would work. I even started a Chem Office comparison as it seems like a unique idea (albiet a "longer way there"). It could still be fun.

chemoleo - 14-10-2006 at 08:38

Just copy and paste the *entire* link.
I wonder how the HCOOH is supposed to work there - there's one nitrogen missing in the imidazole ring, what is it provided by?

SAM4CH - 23-10-2006 at 00:59

I tried with ammonium nitrate/urea method using silica gel I dissolved the resulted molten mixture with water "800 mL water" and evaporate it to 400mL and I let it cool to 5 C, I got about 50g which i melts "melting point test" at 172 C, I boiled the remaing solution and got about 130g of unknown material for me which melts at 72C.

What happen in my experiment?
I used 228g NH4NO3, 125g urea, 50g silica gel and I heated this at 190-200C for 3.5-4 hours.

SAM4CH - 16-12-2006 at 01:59

I faced a problem in getting Tetrazine in the last step "aminoguanidine bicarbonate, acetic acid and sodium nitrite" by Megalomania's method, I can not get precipitate only yellowish liquid... What is the problem there??

quicksilver - 16-12-2006 at 06:06

forgetting "Megalomania's" method for a moment and returning to the COPAE for our common ground (I know that experiment well so it's easy to comment) - what is needed is an initial solution brought to about 70C - remember they said exposed to steam so they mean a hot solution - is then shook violently after a period the temp and the shaking is what starts the percipitation. HONESTLY, it has never failed IF the solution is hot and the shaking, strong. Percipitation of tetrazene starts at about 3-6 hours (the point wherein the temp will drop) and is complete at about 16 hours after initial formation. The experiment has been scaled up 50% with similar results. - Just my opinion, but typos can have a bad effect on experiments, so I try mine from source material even if another author like "Megalomania" is just fine in most every case, etc. But in this issue I think it's just a copy of COPAE. However get your temps to about 70-80 (damn hot solution) :D It will work!

franklyn - 4-8-2008 at 19:58

Mechanism of Guanidine Nitration
http://article.pubs.nrc-cnrc.gc.ca/ppv/RPViewDoc?issn=1480-3...

Synthesis of Substituted Guanidines
http://article.pubs.nrc-cnrc.gc.ca/ppv/RPViewDoc?issn=1480-3...

Crystallization techniques mongraph from GEA Messo GmbH
http://www.messo.com/mde/cmsresources.nsf/filenames/MESSO_Cr...

.

plante1999 - 18-9-2013 at 04:55

I received 100g of guanidine carbonate from an ebayer recently, and I'm very pleased with the product. I made some guanidine nitrate, and upon melting it suddently catch fire and burn rappidly. The guanidine will be perfectly suitable for my intended use.

I just specified that because I never saw anyone mentionning its flamability anywhere on SM.

PHILOU Zrealone - 18-9-2013 at 05:04

The perchlorate of guanidine is another more powerfull beast than the nitrate, it is also very flamable when dry...

With a friend we detonated like 5g inside a copper tube with a tiny silver acetylide -nitrato complex detonator.... it was hell powerfull detonation for such a tiny amount.


[Edited on 18-9-2013 by PHILOU Zrealone]

malford - 18-9-2013 at 05:39

Quote: Originally posted by PHILOU Zrealone  
The perchlorate of guanidine is another more powerfull beast than the nitrate, it is also very flamable when dry...

With a friend we detonated like 5g inside a copper tube with a tiny silver acetylide -nitrato complex detonator.... it was hell powerfull detonation for such a tiny amount.


[Edited on 18-9-2013 by PHILOU Zrealone]


Could you please reconcile your post with these? Specifically the flammability.

[Edited on 18-9-2013 by malford]