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quicksilver
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Guanadine nitrate, etc
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?
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Swany
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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.
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Chris The Great
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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.
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Axt
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| 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]
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quicksilver
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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!
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Axt
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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
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Chris The Great
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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...
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quicksilver
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Thank you all so very much!
The azide->tetrazole material is getting me further along. You guys are a real help.
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]
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Axt
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| 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.
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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]
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quicksilver
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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
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Axt
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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>
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Madandcrazy
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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]
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quicksilver
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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.
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Madandcrazy
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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.
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quicksilver
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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.
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Swany
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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]
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quicksilver
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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.
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SAM4CH
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How can I seperate guanidine nitrate in urea/ammonium nitrate process "Patent 4535185"?
Sam
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Eclectic
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http://v3.espacenet.com/textdoc?DB=EPODOC&IDX=GB923272&a...
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SAM4CH
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I like to get ammonium nitrate/guanidine nitrate solubility vs. temperature (-10 to 150 degree)..
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deiki
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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]
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quicksilver
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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.
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chemoleo
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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?
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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SAM4CH
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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.
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SAM4CH
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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??
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