Sciencemadness Discussion Board - glycine nitrate

glycine nitrate

Rosco Bodine - 4-10-2004 at 15:21

While browsing PATR , I found an item
of interest which appears to be a compound similar to urea nitrate , only
more sensitive and powerful . The compound is aminoacetic acid nitrate ,
or glycine nitrate , evidently a simple
acid salt formed by direct combination
of dilute nitric acid and glycine . The
compound is described as a powerful explosive resembling picric acid in its properties . The chemical formula is
H2N-CH2-COOH + HNO3 , mw 138.08 ,
mp ca 145 with evolution of gas .

The detonation proceeds according to
the equation H2N-CH2-COOH-HNO3 ---->
2CO + 3H2O + N2 , releasing significant
amounts of carbon monoxide .

See PATR vol. 1 page A178

Has anyone ever experimented with
glycine nitrate ? It would seem to have
usefulness because of its relatively easy
and cheap manufacture , and may be of
interest in eutectic nitrate mixtures with things like urea nitrate or ammonium nitrate , methylamine nitrate , calcium nitrate , ect .

chemoleo - 4-10-2004 at 15:50

Funnily enough I recently thought about this, too... but discarded the idea thinking that it probably wouldn't be powerful, but more importantly (to me), hard to detonate.

From my experience with other amine-nitrate salts, I wouldn't think this one is easier to detonate. I guess it has to be tried. Do you have more info on impact sensitivity?

Another interesting amino acid nitrate may be that of arginine, - as it may form a di-nitrate, or even tri-nitrate. (I.e. Arg. is (H2N)CH(COOH)(CH2-CH2-CH2-NH-(H2N)C=NH)
Availability may be more an issue here though.

Rosco Bodine - 4-10-2004 at 16:12

There is no further information I have
except the brief PATR article which does
give a few references . However if the
properties resemble picric acid , then the
material is not going to be very hard to
initiate in particulate form . It would
likely be similar to picric acid or TNT ,
sensitive as pressed charges , insensitive
when cast . This compound would be more powerful and sensitive than the
glycine - ammonium nitrate double salt ,
which might also be a component in some
sort of cast composite . The material would most likely be acidic similarly to
urea nitrate .

chemoleo - 4-10-2004 at 16:29

Putting this to the test:

0.5 mole glycine (28.5 g) was dissolved in 150 ml water (its solubility isn't very high), and 0.5 mole HNO3 (48.5 g of 65%) was added slowly, while keeping the solution on ice. Both reagents are analytical.

The solution warms up slowly. As I did previously with other amine nitrates, I added 2 ml of this solution either to acetone, or absolute alcohol. UNLIKE with previous amine nitrates, no precipitation occurred.

This is unfortunate, as I am not really keen on boiling the solution to dryness (apart from HNO3 fumes that might be liberated).
I guess I will just put it on a plastic plate, and let it evaporate over the next few days. Hmm. Outside I guess....

Any thoughts?

Rosco Bodine - 4-10-2004 at 16:51

AW NAW ! not another "ghost in the beaker" reaction ! or "Where's the compound I'm supposed to see" mystery

I have no idea what is going on there unless it is affected somehow by order of addition , concentration of acid and
solutions . You could try adding the
powdered glycine to stirred cold undiluted acid and see what happens . Or you might try making a paste of the glycine
with a smaller amount of water and very
slowly adding the d 1.4 nitric acid to the stirred slurry .

Would have to go to the original references from PATR and see what the
journals say about the synthesis .

It may be that the product is there , but
highly soluble , and the only way of getting the solid is by evaporation .

Rosco Bodine - 5-10-2004 at 06:29

chemoleo ,

A couple of thoughts . As you added the nitric acid , did the glycine then dissolve much more easily , resulting in a rapidly clearing solution ? Was the warming effect
greater than would be expected from an
ordinary dilution of the acid , as would be
an indicator of a chemical reaction ? Have you tried a heat assisted concentration until any crystals appear , and then chilling
to increase the precipitation ? If this acid salt behaves similarly to urea nitrate , being stable and highly soluble in hot solution , and much less soluble in cold ,
then the direct precipitation could be done
by working with a hot concentrated reaction mixture , from which the crystals
begin to precipitate just after the temperature begins falling away from the
boiling point . Precipitation could be completed in the cold , and evaporation
of the residual solution should provide recovery of any remaining product .

The crystals of glycine nitrate should be rhombic plates or needles . The material was prepared in 1820 by Braconnot ,
E.N.Hornsford , Ann. 60 , 26 (1846)
mp given by A.P.N. Franchimont, Rec. 2, 339 (1883) , other references are
Beil 4 , 340 and Thorpe 2 ( old edition 1917) , 467

Let us know what develops after the solution evaporates .

PATR also lists the dehydrated form of glycine nitrate , which it calls "nitroglycine" , and this would appear to be analogous to nitrourea and
nitroguanidine , as the product obtained
when the ordinary nitrate is dehydrated
by dissolving in cold concentrated sulfuric acid and then dumping the solution into cold water . But PATR does not specify the
method used to obtain the "nitroglycine"
as being analogous to that method for
nitrourea and nitroguanidine . PATR does
state that nitroglycine forms explosive salts and specifies that the silver salt of
nitroglycine is explosive . I speculate that
metallic salts of nitroglycine would likely be powerful primary explosives , and this
is very interesting for experimentation , since so far as I am aware anyway , such
compounds have not been mentioned in
online discussion and are pretty obscure
curiosities in the literature , which would seem worthy of examination .

[Edited on 5-10-2004 by Rosco Bodine]

[Edited on 5-10-2004 by Rosco Bodine]

chemoleo - 5-10-2004 at 07:40

Well I am certain a reaction should take place, why shouldn't it? The reactions between amines and strong acids is normally straightforward.
Apart from that - nitric acid normally smells quite distinctly. However, the glycine nitrate solution is DEVOID of any smell whatsoever.
Regarding solubility, it's probably just that the resultant nitrate is highly soluble. Which is unfortunate, because it almost certainly means it is nice and hygroscopic, so 1) difficult to keep dry 2)tricky to make it dry (due to its energetic nature).

Anyway... I will do it again (while I let the original solution evaporate), and this time with very little water. Hopefully the nitric acid will dissolve any undissolved glycine. I will try and aim for a solution that effectively contains 75% water and 25 % HNO3. This worked nicely when I tried to precipitate other amine nitrates with ethanol. Although I am pretty convinced I won't be able to precipitate it. Lets see

PS I am not really keen on hot evaporation, as I just don't know the properties of the stuff. If you found a reference that cited that GlyNitrate was obtained by boiling down a solution thereof, that would help

Rosco Bodine - 5-10-2004 at 08:27

Urea nitrate is extremely soluble , but
the dried crystals are absolutely *not*
hygroscopic , so we cannot be too hasty
in expecting a direct relationship between
solubility and hygroscopicity to hold , even though it often does parallel , it is not an absolute rule . Guanidine nitrate
is similarly highly soluble , but also non-hygroscopic , and hopefully the same may
apply to the related compound , glycine nitrate . Also it is typical for such salts
to be stable in hot solution . But just
the opposite will be true for the dehydrated forms which will be gradually
decomposed by boiling water uneventfully
via hydrolysis . I understand your caution
when heating an unknown solution , but
it is likely that it is relatively safe to boil
a solution of glycine nitrate until crystals just appear and then allow the concentrated solution to cool . Alternately
the glycine could depart at escape velocity
and warp speed its way returning home
to the interstellar regions of the distant
Saggitarius galaxy , leaving a mile wide
crater sans one very surprised researcher

So you toss a coin and go for it

chemoleo - 5-10-2004 at 08:57

I guess you are right about the safety (or unsafety) of boiling it down. It's just that I had unpleasant past experiences where logic demanded it should be safe, and suddenly it turned out it wasn't.

Anyway... I wouldn't quite compare it ot urea nitrate.
Unlike what you say, urea nitrate isn't very soluble at all, in fact, you can use nitric acid to purify urea from urine ( http://www.sciencemadness.org/talk/viewthread.php?tid=2415 , last post). There, one achieves a 97% yield from 14g urea in about 50 ml of 33% dilute HNO3. Hardly a high solubility, if only 3% (0.5 g UN) dissolve in about 50 ml!
Anyway... this doesn't really matter wrt glycine nitrate. All I am saying it may be dangerous to extrapolate. I will test it anyway...

Rosco Bodine - 5-10-2004 at 09:11

I have kilos of urea nitrate on hand ,
and it is definitely very soluble except
in the cold , very cold .

Another thought relates to the possible
reaction of the nitroglycine with hydrazine sulfate , to possibly form a "nitroaminoglycine" compound similar
to the known reaction for producing nitroaminoguanidine from nitroguanidine .
Such a "nitroaminoglycine" compound , if
it exists , could also form a series of explosive metal salts , possibly having
useful properties .

Any of the three compounds , glycine nitrate , nitroglycine , or nitroaminoglycine
might give products of interest when diazotized with sodium nitrite . So there
definitely are a few experiments which
could be done involving glycine nitrate and
its possible derivatives .

[Edited on 5-10-2004 by Rosco Bodine]

[Edited on 5-10-2004 by Rosco Bodine]

Rosco Bodine - 5-10-2004 at 14:38

Philou Zrealone where are you :-) We have an experiment, yeah baby..... a science experiment made just for you :-) nitroaminoglycine , does it even exist??

Sorry , I just had to say that again :cool:

Update

chemoleo - 6-10-2004 at 05:26

Last night I boiled down the glycine nitrate solution to about half of its original volume (100 ml). At that point, the vapours that came off started to smell of HNO3, so I had to stop. To cool, this was placed into the -20 deg C freezer. Tiny needle like crystals could be seen if one looked closely... but they didn't become more after an hour.
50 ml of this was mixed with EtOH (96%), or acetone, and (both 500 ml), and placed in freezer for 10 hours. No crystallisation. At least I am convinced now that the glycine nitrate is truly soluble in these two solvents.
Lateron I shall see what happens if a 25% glyc. nit. solution is placed into the -20 deg C freezer.
If this doesn't work, then I will truly start to wonder how the GN was prepared. Particularly as boiling doesn't seem to work. Oh... I guess one thing I could try is to freeze dry it. BUT... with a potential explosive, and equipment that isnt my own? Hmmm...

Rosco Bodine - 6-10-2004 at 07:09

Yeah , this is a peculiar result for what should be a simple salt forming reaction ,
and I don't understand the result either .

The original journal articles probably would shed some light on what is needed
to get the desired product . I have encountered these sort of reactions before which would seem so simple and then prove to be just the opposite in a way that challenges the confidence one has that any proposed synthesis is "simple" just because it seems like it should be . There is probably some factor of temperature or pH or some variable to
which the reaction is sensitive , or some
competing side reaction which is complicating things . I don't know what
to suggest , and for guessing , well your guess is as good as mine . I have a list
of "reactions to do" longer than my list
of experiments done and reagents on hand , but this reaction is getting added to my list of "mystery" reactions to study
further and see what's up with the
"anomalous" results . Nothing like a mystery for curious minds .

neutrino - 6-10-2004 at 13:22

Have you tried salting the stuff out? That should be much safer than boiling it.

Rosco Bodine - 6-10-2004 at 14:23

Salting out is a good idea , but the most
likely candidate would be ammonium nitrate , and there is the potential then
of forming the glycine - ammonium nitrate
double salt , or a ternary complex , which
is an interesting possibility unto itself .

Calcium nitrate is another possibility , but
has the same potential .

Given the isolation difficulty, I think when I try this I will likely just make a paste of a portion of the glycine , add the nitric acid
dropwise to get a warm slurry for a small working volume , and then concurrently
add the remaining glycine in small portions
keeping pace with the addition of nitric acid . If some crystallization can get started in the more concentrated mixture
as it cools , then the mixture can be poured into a large pyrex casserole tray
in a shallow layer for evaporation of the
remaining water . A heating pad for low
heat and a fan blowing air across the tray
should speed the drying .

Success!!

chemoleo - 6-10-2004 at 17:35

I now have ± 30 g of glycine nitrate!

Indeed, it was all a matter of temperature and concentrations.

0.5 mole glycine (28.5 g) was added to 30 g of water, and to this 0.5 mole HNO3 (48.6 g of 65%) was added.
Of course the glycine didnt dissolve in the 30 g of water, but as soon as I started adding HNO3, the undissolved glycine would literally disappear where I added the HNO3 (indicating of course that a reaction was taking place).
The solution also heated up rapidly, to about 70 deg C. Once all the HNO3 was added, all the glycine was dissolved. Then this was put on ice, and then into the -20 deg C freezer. Crystallisation ensued! Lots and lots of it. The crystals are kind of squarish flat, and reflect light nicely. About the size of sugar grains by the end of it.

This was filtered off, and the crystals collected. Of course I had to test it with ethanol - and surprise surprise, no dissolution! I guess this is because previously I always had a fair amount of water present, preventing crystallisation.
Anyway, the crystals were washed with ethanol, and now they sit in a plastic container, still sort of moist. It will be kept outside... just in case.

Hygrocopicity: NOT really noticeable! a spatula of cyrstals actually dried, rather than getting wetter.

Friction test: No effect, when putting the moist stuff onto a metal plate and scraping it.
A few crystals were put onto the hotplate, and heated a bit... so that it was just too hot too touch. Crystals are definietley dry. Rubbing them onto the plate with a metal spoon didnt do anything (good!), and neither did the heat. Tapping it hard with the spoon didn't do anythign either - also good.
At last, under the flame (on a spatula), it would melt, and then decompose, leaving a black residue. No obvious flame.

It's all good, it seems easy & safe to handle (which was my main worry).

What to do with it now? From previous experience with amine nitrates, they are damn hard to initiate, even with several grams of HMTD. In fact I cannot report success.

Hmm, anyway, will try to melt a small amount and see whether thats possible without decomposing it. But this is stuff for the weekend. I might subject it to a bit of thermite, maybe heatshock does the job

PS yields are not ideal... but i didnt bother concentrating the mother liquor, plus lost lots during filtering/handling. Clumsy me

[Edited on 7-10-2004 by chemoleo]

Rosco Bodine - 6-10-2004 at 18:00

Hot Damn ! That is good news . I was worried for awhile there that this might be a bust , and thinking WTF is wrong , there should be an avalanche precipitation
of crystals dropping out of this reaction , almost like a setup of expanding plaster
threatening to crack the beaker , and yet you were getting only a whole lot of nuttin' instead , for all my headscratching
and wondering . Okay I'm feeling better now

Have you tried putting some of the crystals on an "anvil" or equivalent and
giving it the old hammer test ? Not necessarily a definitive test but a good
snap or bang can be a good sign of easy
detonability .

I have successfully detonated urea nitrate
which is likely less sensitive than will be the glycine nitrate . My experience with
urea nitrate is that a threshold amount
of HMTD is 2.5 grams , 9mm diameter column hand pressed in a polypropylene
5ml culture tube 12mm OD X 75mm L .
3 grams HMTD would be about right for
sure detonation of urea nitrate . A good
compound detonator with 2.5 grams of
picric acid or equivalent base charge gives
guaranteed success . The glycine nitrate
should be more easily detonated than urea nitrate , and about a third more powerful , perhaps a rough equivalent to
TNT or a little better

and a whole lot
cheaper and easier to produce . Hmmm ,
this really could have interesting possibilities .

[Edited on 7-10-2004 by Rosco Bodine]

Rosco Bodine - 6-10-2004 at 22:01

chemoleo ,

This material is pretty unknown so regard
all of this as theoretical and experiment
with caution .

There is an idea for what you could do with a small sample of your glycine nitrate . Try to convert it to nitroglycine , which should be soluble in acetone .

Since there is no method described ,
possibly use the same method as for
nitrourea or nitroguanidine . Dissolve
the glycine nitrate slowly , added gradually in portions to stirred *ice cold*
concentrated H2SO4 and pour the cold , probably milky solution over crushed ice
to precipitate the nitroglycine .

See if dripping in a concentrated solution
of silver nitrate or lead nitrate into an
acetone solution of nitroglycine results
in a product that is a primary explosive .
Some water may be needed to be added
to the acetone solution of nitroglycine to
create a "solubility interface" to bring about this reaction . Or a plain aqueous
solution may work at moderate temperature , but not too warm or the
nitroglycine will possibly be decomposed .
Nitroguanidine can actually be recrystallized from boiling water for example , but nitrourea is decomposed ,
and what stability nitroglycine would
have in hot water is absolutely unknown .

Nitroaminoglycine and its salts could be
a further experiment .

[Edited on 7-10-2004 by Rosco Bodine]

Axt - 7-10-2004 at 02:25

Quote:

Originally posted by Rosco Bodine
Since there is no method described...

Might mean more to chemoleo then us --> <a href="http://ww1.altlist.com/~58717/pulse.altlist.com/images/nitroglycine-german.jpg">nitroglycine</a>

Translation?<br>

Rosco Bodine - 7-10-2004 at 06:17

Good link , translation of interest indeed .

also called nitroaminoacetic acid or
perhaps ? nitraminoacetic acid , so
that is the stuff .

My German is humiliatingly poor so I
would pick at that article for days to get the gist of it .

Is Rhadon around ? He has a talent
for these translations .

[Edited on 7-10-2004 by Rosco Bodine]

Translation

chemoleo - 7-10-2004 at 11:54

The first paragraph goes on about nitramine acetic acid ether - but as I don't quite know what it is, I shall refrain from translating it. It seems though that nitramino acetic acid is prepared from the ether. Any ideas? Unfortunately, no mention is made of the procedure to add the glycine nitrate to conc. H2SO4.

Then, starting from nitramino acetic acid ("Nitraminessigsaure"

:

Nitramino Acetic Acid (NAA, HOOC-CH2-NH-NO2) crysallises in long needles, melts & decomposes at 103-104 deg C, is not much soluble in cold, but easily solubilised in hot water; it is also soluble in EtOH, diethylether and acetone, but not much in chloroform, benzene and ligroin (don't know what that is). It's a double basic acid (?).
Salts of NAA: The potassium salt explodes mildly upon heating, and it precipitates with Pb and Hg salts, which redissolve in the presence of more nitramine salt.
The corresponding Ag salt turns dark in light, decomposes in boiling water while producing a silver mirror, and explodes upon heating (the dry substance presumably).
The copper salt precipitates when boiling up a solution of NAA with copper carbonate, in the form of very beautiful blue crystals. It is not much soluble in water, acidic, and turns green when heated (it forms the dihydrate). The salt cannot be turned into the anhydrous form via heating due to concomittant decomposition.
Both free NAA and the salts produce a red colour with iron chloride (it doesn't state which, i.e. II or III chloride).
Heating NAA on its own up to 125 deg C leads to its decomposition, partly into CO2, NOx, CH3OH and an unidentified liquid residue.

Looks like, whoever is to make this, won't have trouble identifying it. But by this description it doesnt look like that NAA could be used for more than primaries.

Rosco Bodine - 7-10-2004 at 12:38

The described properties seem to indicate
nitroglycine is more comparable with nitroguanidine than nitrourea , because
nitrourea is not heat stable and decomposes even in warm water .
Nitroglycine could actually be a stronger high explosive than nitroguanidine ,
with heat stability better than nitrourea ,
but somewhat less than nitroguanidine .

The dibasic acids are neutralized by two
+1 valency alkali atoms , for example
styphnic acid is dibasic , picric acid is
monobasic .

The lead salt or other heavy metal salts
may be interesting , and it looks like
such salts could be formed in aqueous solution with no problem .

[Edited on 7-10-2004 by Rosco Bodine]

Nitramino acetic acid ?

chemoleo - 7-10-2004 at 17:23

Ok, 11 g of dry glycine nitrate was slowly added (30 min) to 23 ml of 98% H2SO4. The nitrate seemed to dissolve, the first few additions left the solution clear. Lateron, it turned milky-clear, but I am not sure whether these were tiny bubbles.
After all was dissolved, this was put into 150 ml ice water. No immediate crystals

.
It's now in the fridge, let's see what it looks like tomorrow ...

PS proportions of H2SO4 over crushed ice are roughly those of COPAE

[Edited on 8-10-2004 by chemoleo]

Rosco Bodine - 7-10-2004 at 19:18

That should be more than enough H2SO4 .

I extrapolated the proportions as compared with the COPAE description for
nitroguanidine to apply to nitroglycine .

And for your 11 grams of glycine nitrate ,
considered on a molar basis , you would
have required 12.2 ml H2SO4 , and then
after dissolving that amount of glycine nitrate in the cold acid , kept below 10 C ,
dumped it over about 75 grams of crushed
ice in a prechilled beaker . Those are more economical quantities for larger batches if the solubilities and other factors permit .

I made nitroguanidine once many years ago , and I don't recall for certain but IIRC
the precipitation of product was fairly rapid when the mixture was dumped over the ice .
I do recall that I recrystallized
the product from boiling water , and that
the nitroguanidine crystallized out as long
hard , but tough and flexible needles , having a distinctly springy plastic quality like hard nylon bristles which had been pulled from a scrub brush . The peculiar material was a very bright glistening white color . Such a crystalline form is
undesirable for press loading , and I hope the crystals of nitroglycine are a more
usual and compact geometry . Sometimes
a subsequent crystallization from a different solvent is used to get crystals
in a form that is desirable .

chemoleo - 7-10-2004 at 20:16

Yes, I know I used more H2SO4 than in COPAE.
I did it mainly because I wanted to have a large excess of it, to make sure its dehydrating power comes to full force. Also, because the mixture became rather thick. At last, I reasoned an excess shouldn't matter as the amine nitrate is added in small portions... indicating that the reaction isn't really stoichiometric in the sense that precisely one molecule of H2SO4 is needed, no more and no less. I can't see why an excess of H2SO4 could hurt basically.
The description of the German article says it's not much soluble in cold water. I thought, at least when the reaction mix is slowly layered into the the H2O, I should see preciptiation / crystallisation at the interface, regardless... but I didn't.

I will try it again, with much much less water next time. But I don't think it will work... but lets see first.

Another problem is, as long as it doesn't crystallise, it will prove rather hard to show that I really did obtain nitramino acetic acid. Regardless of the cation I add (Fe, Cu, Ag, Pb), it will first react with the remaining H2SO4, forming precipitates (or not), thus interfering with determining whether I got NAA or not.

Let's see, shall try it again with extremely restrictive conditions. If it doesn't work then... I will give it a rest, and play abit with the glycine nitrate itself.

Rosco Bodine - 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

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]

Axt - 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>

Rosco Bodine - 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]

DeAdFX - 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

DeAdFX - 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?

K9 - 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?

Rosco Bodine - 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 .

K9 - 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.

DeAdFX - 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]

chemoleo - 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.

K9 - 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]

DeAdFX - 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

chemoleo - 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]

Rosco Bodine - 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]

franklyn - 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.

.

not_important - 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..

K9 - 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?

Glycine Nitrate

dascrazyhungarian - 22-11-2008 at 13:09

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

Formatik - 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.

chemoleo - 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

dascrazyhungarian - 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]

chemoleo - 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.

K9 - 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?

Axt - 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]

Axt - 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

497 - 9-1-2009 at 17:54

Only part in Kirk-Othmer that mentions nitration:

"Several electrophiles, such as acetic anhydride, nitric acid or alternative nitrating agents, such as ammonium
nitrate in trifluoroacetic anhydride (41), or sodium hypochlorite, react at N-1, which is followed by
reaction atN-3 under suitable conditions."

chemoleo - 9-1-2009 at 20:01

Very interesting, that glycine H2N-CH2-COOH reacts so readily with urea to form hydantoic acid.
Structure (simple condensation product):

It should give interesting products with other amino acids, such as serine or threonine,

and introduce another OH group. Unless condensation occurs with the urea on the OH. Regardless, the products should give an interesting compound.
Nitration thereof should give a nice mixed nitramide/nitrate ester/nitrate.

Hydantoin,

which can be quite readily obtained by intramolecular cyclisation/amide bond formation (amidation) (see Axt's post above) is again interesting, not only in the case of glycine as a starting compound, but for higher amino acids as well, all of which should give interesting nitration products. I imagine using phenylalanine for condensation with urea, and subsequent cyclisation with HCl, to give the cyclic phenylalanine hyantoin derivative, should give a very interesting and powerful nitration product.

I just wanted to point out the possibilities in this.