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Rosco Bodine
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[*] posted on 7-10-2004 at 21:11


There should be no problem caused by your using more of the acid , unless the
solubility / concentration problem should
do an encore :D That was the only thought I really didn't want to say at this
point ;) But I also have some reservation
that the same scheme for dehydration can
be used as was straightforward for nitroguanidine or nitrourea . It may not work regardless of proportions . But it
seemed worth a try . And even if the
dehydration experiment should fail to
produce the nitroglycine , the original
glycine nitrate should itself still have value .

Copper sulfate might give a precipitate
from the greatly diluted mixture . A partial
neutralization with ammonia might be helpful there if the possible nitroglycine
remains in solution .

But I agree it seems logical any nitroglycine present should have precipitated on dilution , so it doesn't appear likely that the desired compound was produced , or that changing proportions would fix that problem in this type reaction .


[Edited on 8-10-2004 by Rosco Bodine]
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[*] posted on 8-10-2004 at 22:12


The extract I uploaded was the reference given in Fedoroff, which supposedly gives its syth from its ammonium salt. Maybe I cut something out, so <a href="http://pulse.altlist.com/banners/nitroglycine.zip">heres</a> the whole article.<br>
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Rosco Bodine
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[*] posted on 9-10-2004 at 06:19


chemoleo ,

Because no precipitate immediately appeared when the solution of glycine nitrate in sulfuric acid was diluted with water , it would seem that the reaction between the sulfuric acid and glycine nitrate most likely simply displaced the
nitric acid from the glycine nitrate and
converted it to glycine sulfate which remained dissolved in the mixed acid
resulting . If that is what did occur ,
then the glycine nitrate may have value
as a solid nitrate useful as a nitration agent , giving a glycine sulfate byproduct which does not thicken the
acid mixture so greatly as does potassium or sodium nitrate . It seems also possible
that perhaps a proportion of glycine nitrate in admixture with other nitrates
used in such nitrations might result in
a thinner mixture , where the mixed
sulfates produced may have a lessened
tendency to solidify and thicken the mixture . I have often wondered if there
is possibly some advantageous mixture
of different nitrates in certain proportions
which would be most favorable in its usefulness as a source of nascent nitric acid when added to sulfuric acid , and
have speculated that such a mixture may
have advantage over the use of a single nitrate . Possibly glycine nitrate may have value in such a nitration scheme ,
either useful alone , or as a modifier in
mixture with other nitrates . Always I
try to make some observation of this sort
to try to glean any information of value which may be provided , concerning an
experiment which fails to produce an intended product , and yet may produce
information of value otherwise .

The use of fuming nitric acid of near anhydrous concentration would probably be required for conversion of glycine nitrate to nitroglycine , but this would not
be a desirable method as a lab method .
There is a patent for nitroguanidine which
describes such a method having validity ,
but the dangers and difficulty do not commend that process for lab scale work .

So at this point I would suppose that the
glycine nitrate itself definitely still has interest , but the difficulties attendant nitroglycine and its derivatives rules out my own interest in pursuing experiments with them .

Because of the simple and safe synthesis
of the glycine nitrate , and its properties
being reported similar to picric acid , the plain glycine nitrate is certainly still interesting for experiments . If it has
sensitivity to initiation similar to picric acid , then glycine nitrate could be used
as a base charge in detonators if it is
chemically compatable with initiators ,
among other uses . Glycine nitrate could
also be useful as an easily and cheaply made booster , or as a component in
mixtures . There are only a few explosives
which closely approach or surpass TNT
equivalency in power , and are able to be
made easily and handled with economy and safety . Glycine nitrate could prove to be one of those very few materials which have that value .

Plain glycine has been specified as a detonation catalyst in ammonium nitrate explosives sensitized by nitroaromatic compounds , especially with
nitronaphthalene containing compositions , where glycine in small amounts causes a marked improvement in sensitivity and brisance over compositions without glycine . It seems likely that glycine nitrate would also function as a detonation catalyst in such mixtures , but this is untested . A patent
regarding this has been issued .

GB497145

See page 2 line 36

[Edited on 9-10-2004 by Rosco Bodine]
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[*] posted on 2-7-2005 at 13:26


Hello. Sorry for bumping an old thread...

I have attempted to snythesize Glycine nitrate through HCL/Ammonium nitrate/Glycine as can be seen on powerlabs http://www.power-labs.com/forum/viewtopic.php?t=587 (read my post for further detail) The reason for this post is to recieve more feedback and prehaps have others confirm I have synthesized Glycine nitrate. The product is still wet so I cannot see if it burns.

Here is a picture of my product. I resized the picture so it might be a little blurry...
http://img139.imageshack.us/img139/6727/unknown3205fx.jpg
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[*] posted on 8-8-2005 at 18:27


Alright i tried doing this procedure again at 50% scale with nitric acid instead. When i added the nitric acid at a slow rate part of the glycine dissolved[not all]. I am confused as to why the glycine didnt dissolve?
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[*] posted on 16-6-2006 at 11:23


I just got some glycine and I wanted to try out glycine nitrate.

Would this work if I used NH4NO3 + H2SO4? The ratios I worked out are 53 g glycine to 80g NH4NO3 and 106 ml H2SO4 (allowing for 30% excess nitric acid). Though I guess I would have to use a bit more H2SO4 just for volume.

Does this sound about right?
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Rosco Bodine
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[*] posted on 16-6-2006 at 12:57


It likely won't work . If you read the earlier posts
where already formed glycine nitrate was being
dissolved in sulfuric acid as an experiment attempting
to dehydrate it , the material was decomposed by
the excess of sulfuric acid . So it follows that any
attempt at a double decomposition using an acid
and AN is a scenario where you would want the AN in excess , and no excess of acid . Also , a similar method
for producing urea nitrate from urea works better
using HCl and AN than using H2SO4 for the acid ,
and for good yields the proportions and procedure
are carefully controlled . Glycine is a much more
expensive starting material than urea , so the economics
favor simply making a paste by dropwise addition of
nitric acid with stirring , regulating the addition to
keep the mixture hot but not quite boiling so that
the neutralization proceeds to completion when the
equivalent of HNO3 has been added and stirred into
the mixture . Alternating additions of glycine and
then acid to a small starting mixture should keep the volume of the mixture and excess liquid minimized ,
while still keeping the mixture stirrable . On cooling
and evaporation of the moisture , there should be only pure crystals of glycine nitrate as the product .
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[*] posted on 19-6-2006 at 18:53


Well after attempting a synthesis using ammonium nitrate and HCl, I've come up with this - http://img.photobucket.com/albums/v78/wolfhound/myst.jpg

Nothing was crystallizing so I left it in the fridge overnight and found this today. It air-dried extremely quickly once filtered. The large crystals definitely look interesting.
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[*] posted on 20-6-2006 at 21:27


Wow your really lucky your stuff air dried quickly. The stuff I made took forever to dry and when I left it in the sun to speed things up it started to fume a brown gas:( [I am under the assumption I did a really lousy job and removing the last bit of acid]

[Edited on 21-6-2006 by DeAdFX]
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chemoleo
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[*] posted on 21-6-2006 at 05:22


How do you know it isn't ammonium sulphate? Did you test it? The glycine nitrate should fizzle in the flame.



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[*] posted on 24-6-2006 at 21:07


I don't really know what the crsytals are of, but I don't see how they could be ammonium sulfate when there was no sulfate involved in the reaction.

The crystals melted into a black liquid when heated with a butane torch lighter. Maybe something like this - https://sciencemadness.org/talk/viewthread.php?tid=5583#pid6... ?

[Edited on 25-6-2006 by K9]
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[*] posted on 24-6-2006 at 22:34


I noticed that when you add a small amount of charcoal (5grams of glycine nitrate double salt with .5grams of charcoal) the mixture decomposes and emits a dim flame with some sparks. The addition of .5 grams magnesium makes the mixture decompose even quicker.

I assume if you obeserve the same phenomenon then you probably have fairly pure sample of glycine nitrate
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[*] posted on 25-6-2006 at 15:20


I was referrring to this:
Quote:
Would this work if I used NH4NO3 + H2SO4? The ratios I worked out are 53 g glycine to 80g NH4NO3 and 106 ml H2SO4 (allowing for 30% excess nitric acid). Though I guess I would have to use a bit more H2SO4 just for volume.


Anyway, by your black liquid description, it doesn't sound like that it is ammonium chloride (if you made it from ammonium nitrate and HCl). Maybe it is glycine chloride?

The reason why I doubt you have glycine nitrate is because the crystals I obtained are really fine (a powder essentially), and not translucent chunky blocks. Why don't you try it with HNO3 on its own? You can always distill it. Or maybe glycine sulfate and ammonium nitrate work, forming ammonium sulphate and glycine nitrate (assuming that ammonia is the stronger base, and also because ammonium sulphate is much more soluble than the glycine nitrate)

[Edited on 27-6-2006 by chemoleo]




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Rosco Bodine
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[*] posted on 25-6-2006 at 17:11


When working with precursors which are highly soluble
and attempting to produce products which are also highly soluble by double decomposition , isolating one
by crystallization while leaving the other in solution ....
is definitely a process which requires an artful bit of
physical chemistry and experimentation to arrive at
the optimum conditions . Just because this can be
done for urea and ammonium nitrate using HCl does
not necessarily mean that the process is easily adaptable
or adaptable at all to other scenarios using other materials as some of these schemes are workable ,
but others are not . Actually it took a lot of experiments
to work out that urea / AN / HCl procedure and get it to
work predictably well so it is definitely not any general method , and was only considered because of the cheapness of the precursors making it acceptable even
with 16 % ( IIRC ) penalty compared to a straightforward titration using nitric acid to produce a quantitative yield of
perfectly pure product . Given the much greater cost of glycine , that loss is unacceptable so what chemoleo is
saying is absolutely correct ....just neutralize the glycine
directly with HNO3 instead of attempting double decomposition by a method parallel to the urea / AN / HCl method .

If a double decomposition is contemplated for avoiding use of HNO3 , then it might be better to use a solution
of glycine sulfate and react with a solution of calcium nitrate , filter out the CaSO4 and evaporate the solution
but the losses will be significant , and there is also the
potential for double salt formation with any of these
double decompositions .

Glycine perchlorate would possibly be more worthwhile
if experimentation along this line was to be done . What I am thinking here is that perhaps ammonium perchlorate
solution could be converted to calcium perchlorate solution by boiling several hours with hydrated lime , driving off the ammonia and filtering out unreacted lime .
Titrate an equivalent of glycine using dilute H2SO4 and
then mix the hot solutions , filter out the CaSO4 and
evaporate the solution to get the glycine perchlorate .

I just had another thought that glycine permanganate may
possibly be interesting also by way of the same method as
betaine permanganate . That patent has been posted and
it may be worth an experiment since stable organic permangantes are rare , and they are energetic materials .

[Edited on 26-6-2006 by Rosco Bodine]
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[*] posted on 6-8-2006 at 01:13


Somewhat naively it seems to me
Glycine and Oxalic acid warmed in water should make Glycine Oxalate
adding Calcium Nitrate to this should by double replacement precipitate
Calcium Oxalate leaving the Glycine Nitrate in solution.
Also
What about compounding this further with methanol to eliminate acidity.

.
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[*] posted on 6-8-2006 at 02:32


Decent idea, although there are a few potential problems.

Amino acids bind to calcium oxalate, and modify its crystallization behavior, how significant this would be I can't say.

Amino acid oxalates don't look to be very soluble in alcohol, perhaps a few grams per 100 cc. Tests are needed.

Does sound worth a small scale test. The bis salt, with two glycines per oxalic acid, might be more soluble in alcohol than the mono salt..
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[*] posted on 18-12-2006 at 13:32


I just finished making some glycine nitrate with HNO3 (definitely a fine powder and not chunky blocks), and I was wondering if anyone has had any luck with nitroglycine?
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[*] posted on 22-11-2008 at 13:09
Glycine Nitrate


Hello Everyone

I made some glycinitrate today

The only information i found where on k9s experimental page

http://www.geocities.com/houseofK9/gn.htm

I searched google but found nothing
does someone have any data about this compound?
I am mainly interestet on data about Vod and solubility

Btw sorry for my poor english
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[*] posted on 22-11-2008 at 17:38


According to this glycine nitrate has a heat of formation of -1257 cal/g. The PATR-cited Beil. 4, 340 might have some basic solubility info.
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[*] posted on 22-11-2008 at 20:58


Merged thread with an existing one.
There's also some more info on double salts here
https://sciencemadness.org/talk/viewthread.php?tid=5583




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[*] posted on 23-11-2008 at 08:24


Today i had the first sucess with the glycinnitrate i made yesterday.
I pressed 10gr of glycinitrate into a pvc-tube an initiated it with 1gr petn and 0,3gr of silveracetylit.
it gave a extremly loud report an made an crater with 10cm Diameter
maybe i will make some photos tomorow

Thanks for merging the threads i found most of the data i searched in it

[Bearbeitet am 23-11-2008 von dascrazyhungarian]
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[*] posted on 23-11-2008 at 18:09


I think for anyone to believe this you'd have to compare it to a control, i.e. the same thing but without the glycine nitrate.



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[*] posted on 5-1-2009 at 17:02


I keep forgetting what an interesting compound glycine nitrate is and I'm glad I thought of it again. In the near future I'm hoping to try production of nitroglycine, but there is still such a shortage of information about it and its synthesis. Has anyone had any further luck with this?
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[*] posted on 8-1-2009 at 23:47


"The fact that the condensation of unsubstituted glycine with urea and sulfuric acid leads to the formation. of a hydantoin (X) in high yield" DOI: 10.1007/BF00635948

It seems possible that this product would form a nitramine on nitration. Though I cant acces the article. It shouldn't be too hard to find a nitration product of hydantoin to run an analogy off.

[Edited on 9-1-2009 by Axt]
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[*] posted on 9-1-2009 at 00:44


Heres what I could find, from british patent.

I didn't find any convenient nitration reagents, NH4NO3 with trifluoroacetic anhdride in nitromethane gives the dinitramine according to Synthesis (1988), (9), 743-5. That should be a dense and powerful explosive though unstable to hydrolysis which may be the reason for the exotic nitration reagents.

If someone could check "Hydantoin and Its Derivatives" in Kirk-Othmer it seems to have a section on its nitration, evidenced by its google cache.

Nitration of hydantoic acid itself I suspect will just give the primary nitramine, though perhaps if one could condense 2 mol glycine to 1 mol urea followed by nitration to secondary dinitramine and hydrolysis you'll get nitroglycine. I couldn't find any reference to this though.

The nitration of N-phenylsulphonylglycine gives nitroglycine (Zhurnal Organicheskoi Khimii, 19(4), 761-6; 1983), so maybe condensing sulphamic acid with glycine will give a route to nitroglycine as well. Though the only prep for this I could find was condensing sulphamic acid with chloroacetic acid.

[Edited on 9-1-2009 by Axt]

nitrohydantoin.jpg - 45kB
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