Sciencemadness Discussion Board
Not logged in [Login - Register]
Go To Bottom

Printable Version  
Author: Subject: Nitroguanidine from Sulphamic acid and Urea
Axt
International Hazard
*****




Posts: 778
Registered: 28-1-2003
Member Is Offline


[*] posted on 31-7-2007 at 10:16
Nitroguanidine from Sulphamic acid and Urea


Nitroguanidine
from Sulphamic Acid and Urea

By Axt


Nitroguanidine is an explosive of some industrial and military significance, where its primary use is as an additive for propellants. The temperature of explosion for nitroguanidine is low, and when added to nitrocellulose-nitroglycerine powders it has the effect of both reducing muzzle flash and lowering erosion when compared to propellants of comparable power[1]. These are known as triple based propellants.

When used as a high explosive nitroguanidine detonates at a rate of 7650m/s at 1.55g/cm3 and its explosive power is relatively high, comparable to TNT[1]. Nitroguanidine is insensitive, failing to detonate from a 3.20m drop of a 2.5kg weight where TNT will detonate with a drop of 1.48m.[2]. It also has a low critical diametre of between 1.27-1.43mm[2].

While the toxicity of nitroguanidine is stated as being “high“ by Dobratz et al.[2], a study on its acute oral toxicity in mice by Hyatt et al.[3] placed it into the category of being practically non-toxic with a dose of 5000mg/kg producing less then 50% mortality .

The preparation of guanidine by fusing sulphamic acid and urea was patented by Mackay[4] and the mechanism was later studied by Boivin[5,6]. While no definite conclusions were obtained, the probable mechanism is shown in figure 1. The urea and sulphamic acid first fuse to form ammonium urea sulphonate, which dissociates into cyanamide and ammonium bisulphate which reacts to form guanidine bisulphate.


Figure 1: Preparation of guanidine bisulphate by fusing urea with sulphamic acid.


Nitroguanidine is prepared by dissolving guanidine nitrate in cold concentrated sulphuric acid (figure 2), then precipitating by pouring into ice water[7,8]. Though the yield obtained in this study was low, its an easy preparation and the precursors are both cheap and readily available.


Figure 2: Preparation of nitroguanidine from guanidine nitrate.


Precursors:

99% Sulphamic acid was sold in a hardware store as a descaler for removing calcium and rust deposits. Urea was also purchased from the hardware store in a 15kg bag for use as a fertiliser. Potassium hydroxide is available from hydroponics suppliers for raising pH.

Synthesis:

200g sulphamic acid and 124g urea were mixed in a shallow Pyrex bowl and placed into a fan forced kitchen oven. The mixture was left in the oven at 220°C for 2 hours, where it gave off some ammonia and melted into a clear liquid gradually thickening and forming a white semi-solid due to ammonium and guanidine sulphate separated of from the melt. This was then cooled and broken up to leave 302g of crude residue (figure 3).

The crude residue was then blended with 240g of potassium hydroxide in 1L of methylated spirits for 30 minutes (figure 3). This freed the guanidine and ammonia bases and precipitated potassium sulphate, 750ml of this free based alcohol solution was recovered by filtering the blended mixture.


Figure 3: Crude fusion product (left); Blending with alcoholic KOH solution (centre); Crude ammonium and guanidine nitrate salts (right).


The alcoholic solution of guanidine and ammonia was then neutralised with 70% nitric acid, this precipitated residual potassium hydroxide as its nitrate which was filtered out. On boiling down the alcohol to a concentrated solution, then evaporating dry, 84g of crude ammonium and guanidine nitrates was obtained (figure 3).

50g of the crude mixture of nitrates was directly converted to nitroguanidine by slowly dissolving small portions into 75ml of 98% sulphuric acid, the temperature was maintained from -5 to +10°C throughout the addition which took approximately 1.5 hours. The milky solution (figure 4) was left for 10 minutes at 10°C after the last addition then poured into 500ml of iced water. On standing the nitroguanidine precipitated as small crystals (figure 4) which were filtered and dried. Yield was 18.5g.


Figure 4: Guanidine nitrate dissolved in sulphuric acid (left); precipitation of nitroguanidine from 500ml water (right).


The nitroguanidine was recrystallised from boiling water to remove any nitrourea that may have been present, on cooling a mass of fine needles precipitated characteristic of nitroguanidine (figure 5).


Figure 5: 30x magnification of crystals of nitroguanidine from this study when crystallised from water (left); Nitroguanidine at 25x from the literature[7] obtained from rapid cooling of a water solution.


Explosive Properties:

The small fine needles obtained were pressed into a drinking straw, taped to a metal disk and initiated with 0.5g PETN under sand. The dent (figure 6) shows that the nitroguanidine did detonate however with low power. This low observed power can be attributed to the very low density at which the needles were pressed.

The nitroguanidine only deflagrated with difficulty when heated on a spoon over a gas flame, where it blackened, melted, emitted fumes then deflagrated leaving little residue. It would not deflagrate when held in the flame of a match.


Figure 6: detonation of low density nitroguanidine against metal plate.


References:

1] B.T. Fedoroff and O. E. Sheffield “Encyclopedia of Explosives and Related Items“. vol. 6; pg. G154. Picatinny Arsenal; New Jersey; USA (1960)

2] Dobratz, B and Crawford, P. "LLNL Explosives Handbook - Properties of Chemical Explosives and Explosive Simulants" Lawrence Livermore National Laboratory. California. (1985)

3] G. F Hyatt, S. K Sano, C. R Wheeler and D. W Korte “Acute Oral Toxicity of Nitroguanidine in Mice”; Letterman Army Institute of research Presidio of San Francisco, CA. (1984)

4] J. S. Mackay “Preparation of Guanidine Sulfates” US patent #2464247 (1949)

5] J. L. Boivin and A.L. Lovecy “Mechanism for the Formation of Guanidine from Urea and Ammonium Sulphamate” Canadian Journal of Chemistry; 33[7]; pg. 1222-1225; (1955)

6] J. L. Boivin and M. Tremblay “Synthesis of Guanidine from Urea, Ammonium Benzenesulphonate, and Ammonium Sulphamate” Canadian Journal of Chemistry; 36[2]; pg. 378-382; (1958)

7] T. L. Davis “The Chemistry of Powder and Explosives” Pg. 380; New York, John Wiley & Sons; London, Chapman & Hall. (1941)

8] G. B. L. Smith, V. J. Sabetta, and 0. F. Steinbach “Quantitative Study of the Preparations of Guanidine Nitrate and Nitroguanidine”; Industrial and Engineering Chemistry; 23[10]; pg. 1124-1129; (1931)

[Edited on 4-8-2007 by Axt]
View user's profile Visit user's homepage View All Posts By User
DeAdFX
National Hazard
****




Posts: 339
Registered: 1-7-2005
Location: Brothel
Member Is Offline

Mood: @%&$ing hardcore baby

[*] posted on 31-7-2007 at 14:33


Wow fucking awesome find Axt... I believe this method looks a lot more OTC than the ammonium nitrate + urea + silica gel method of producing G nitrate. Well except for the fact that my local hardware store only carries naval jelly or some sulfite mixture for rust removal :rolleyes:.

hmm... Say did you try mixing Metal+ NO3- and the guanidine bisulfate to produce Nitric acid, guanidine nitrate and Metal Sulfate? Or would other various nitrates result too(di/trinitrate)?

[Edited on 31-7-2007 by DeAdFX]
View user's profile View All Posts By User
guy
International Hazard
*****




Posts: 982
Registered: 14-4-2004
Location: California, USA
Member Is Offline

Mood: Catalytic!

[*] posted on 31-7-2007 at 14:43


Quote:
Originally posted by DeAdFX
Wow fucking awesome find Axt... I believe this method looks a lot more OTC than the ammonium nitrate + urea + silica gel method of producing G nitrate. Well except for the fact that my local hardware store only carries naval jelly or some sulfite mixture for rust removal :rolleyes:.

hmm... Say did you try mixing Metal+ NO3- and the guanidine bisulfate to produce Nitric acid, guanidine nitrate and Metal Sulfate? Or would other various nitrates result too(di/trinitrate)?

[Edited on 31-7-2007 by DeAdFX]


I found pure sulfamic acid in Home Depot; it was near the plumbing area. I never had a use for it.
View user's profile View All Posts By User
The_Davster
A pnictogen
*******




Posts: 2805
Registered: 18-11-2003
Member Is Offline


[*] posted on 31-7-2007 at 18:21


Haha....nice....just 4 days ago I worked on a similar pathway using the cyanamide(from pool chems as I posted in another thread) in molten AN with urea added to lower the melting point to 120or so celcius. Giving guanidine nitrate, and then after, nitroguanidine.
Interesting coincidence:P

(however I need the nitroguanidine for reduction, not for its energetic properties:))




View user's profile View All Posts By User
not_important
International Hazard
*****




Posts: 3874
Registered: 21-7-2006
Member Is Offline


[*] posted on 31-7-2007 at 19:01


And there is this thread from a bit over a year ago, references the same basic prep but starting with ammonium sulfamate, which may increase the yield in the first step - be an interesting experiment.

http://www.sciencemadness.org/talk/viewthread.php?tid=6111&p...
View user's profile View All Posts By User
Sauron
International Hazard
*****




Posts: 5358
Registered: 22-12-2006
Location: Barad-Dur, Mordor
Member Is Offline

Mood: metastable

[*] posted on 1-8-2007 at 16:37


Another use for sulfamic acid is the neutralization of strong caustic solutions such as gunsmithing "blueing" salts which are a mixture (highly concentrated) of ammonium nitrate and NaOH.

Nitroguanidine is the third main component in so called triple base propellants. As you know, a single base propellant is straight NC nitrocellulose. A double base propellant is NC/NG nitrocellulose/nitroglycerin.. When you get up into propellants for artillery, however, bore erosion becomes a serious issue that limits the life expectancy of the gun tubes (barrels) so nitroguanidine is added to reduce burning temperature and therefore bore erosion. That is triple base propellant.

Not normally encountered in small or medium caliber firearms applications.
View user's profile View All Posts By User
Axt
International Hazard
*****




Posts: 778
Registered: 28-1-2003
Member Is Offline


[*] posted on 2-8-2007 at 23:17


Quote:
hmm... Say did you try mixing Metal+ NO3- and the guanidine bisulfate to produce Nitric acid, guanidine nitrate and Metal Sulfate? Or would other various nitrates result too(di/trinitrate)?


I tried a few different ways before resigning myself to free basing the guanidine.

I tried dissolving the crude fusion product in water, filtering out the melamine (from trimerisation on cyanamide or decomp. of guanidine) then precipitating the sulphate with calcium nitrate. After filtering the calcium sulphate I then tried to boil cry to reclaim the supposed AN/GN but after a very large and volumous crystaline precipitate formed which near solidified the solution, possible a Ca double salt of sorts, I just chucked it out.

I also tried direct nitration of the crude fusion product with KNO3/H2SO4 to see if anything could be obtained via the simplest route possible, but I didnt recieve anything. In hindsight I think i disposed of it to soon as the NQ does take a little while to precipitate from the solution. Possibly worth another try.

I also tried isolating the ammonium urea sulphonate via lower temperatures following the procedure in the Canadian artilcle, same but with out the use of vacuum and only achieved a sticky resin with the consistancy of honey.

Quote:
I found pure sulfamic acid in Home Depot; it was near the plumbing area. I never had a use for it.


Sulphamic acid has many uses for energetic material synthesis, primarily nitramines via condensation with aldehydes and other amines. Its nitration itself forms dinitramide.

Quote:
And there is this thread from a bit over a year ago, references the same basic prep but starting with ammonium sulfamate, which may increase the yield in the first step - be an interesting experiment.


Yeh, thats the patent that the canadian article refers to. The article does say that yields are increased by use of ammonium salt however it only references to that patent. If you look at the patent, there is an example for fusing the acid with urea, and the yield based on sulphamate is practically the same. At least if the patent is to be trusted, as I recieve far lower yields then what they state.

[Edited on 3-8-2007 by Axt]
View user's profile Visit user's homepage View All Posts By User
Rosco Bodine
International Hazard
*****




Posts: 5248
Registered: 29-9-2004
Member Is Offline

Mood: analytical

[*] posted on 3-8-2007 at 09:26


Sometimes you need to be able to read between the lines a bit to get the whole story .

Anyway , if you have a pressure cooker ....
this patent US3009949 might be interesting

Attachment: US3009949_PRODUCTION_OF_GUANIDINE_PHOSPHATE_SALTS_.pdf (187kB)
This file has been downloaded 1119 times

View user's profile View All Posts By User
Eclectic
International Hazard
*****




Posts: 899
Registered: 14-11-2004
Member Is Offline

Mood: Obsessive

[*] posted on 3-8-2007 at 10:00


Very nice! Now we just need a preparation method for ammonium metaphosphate from monoammonium phosphate, and everything you need can be had from an agricultural supply house in 50 lb bags really cheap. :D
View user's profile View All Posts By User
Rosco Bodine
International Hazard
*****




Posts: 5248
Registered: 29-9-2004
Member Is Offline

Mood: analytical

[*] posted on 3-8-2007 at 14:00


Quote:
Originally posted by not_important
And there is this thread from a bit over a year ago, references the same basic prep but starting with ammonium sulfamate, which may increase the yield in the first step - be an interesting experiment.

http://www.sciencemadness.org/talk/viewthread.php?tid=6111&p...



Yeah here's the patent that chloric1 referenced
correctly " US2464247 granted to American Cyanamide Company in 1949 " but the number is incorrect in that
reference #4 which Axt gives above .

I think the yield is higher with the ammonium salt of sulphamic acid .

Another interesting patent is US2783276 , which shows that urea and ammonium chloride melted together with
silica gel as a catalyst , gives guanidine hydrochloride ....
but in the absence of the catalyst the product is cyanuric acid and dry ammonia as a byproduct . See US2527316

http://sciencemadness.org/talk/viewthread.php?action=attachm...

In the presence of the absorbent catalyst ....other guanidine salts are producible from urea and the corresponding ammonium salt ....particularly mentioned are the nitrate and phosphate as well as the chloride .

[Edited on 3-8-2007 by Rosco Bodine]

Attachment: US2464247 PREPARATION_OF_GUANIDINE_SULFATES.pdf (142kB)
This file has been downloaded 1060 times

View user's profile View All Posts By User
Axt
International Hazard
*****




Posts: 778
Registered: 28-1-2003
Member Is Offline


[*] posted on 3-8-2007 at 22:15


Quote:
Originally posted by Rosco Bodine
but the number is incorrect in that
reference #4 which Axt gives above .

I think the yield is higher with the ammonium salt of sulphamic acid .


Ahh yep sorry, I edited it. At a quick glance that 6 looks like a 5.

Nope the yields are the same, the patent is basing the yields on the urea used but the sulphamic acid is the most expensive so more practical to calculate the yields off it. Both examples 1 and 3 yield 0.4g of guanidine sulphate from 1g of sulphamic acid. They are using a 2x molar excess of NH4 sulphamate in examples 1 and 2, but not for the sulphamic acid.

The metaphasphate route looks interesting. Isn't that available as fertiliser, as is?

I think I read of a route through chloropicrin and aqueous ammonia somewhere as well, but cant find and other reference to it. This would be interesting if the needed pressures are low enough.


[Edited on 4-8-2007 by Axt]
View user's profile Visit user's homepage View All Posts By User
Rosco Bodine
International Hazard
*****




Posts: 5248
Registered: 29-9-2004
Member Is Offline

Mood: analytical

[*] posted on 4-8-2007 at 07:05


What caught my notice as interesting about the sulfamic acid plus urea reaction is the theorized *cyanamide* intermediate , and wondering if the process could be modified to favor cyanamide as the product , rather than guanidine .

The metaphosphate I'm not sure about the availability .

The normal othophosphate can be used with the silica gel catalyst .....but then less expensive ammonium chloride
would be make more sense . I have a string of patents
related to that silica gel catalytic process which would be the cheapest method . I wonder if it also works with ammonium sulfate .....since there are bagged fertilizers
which are 50/50 urea/(NH4)2SO4 sold very cheap and it appears to be a white very pure mixture .

The catalytic process works with NH4NO3 plus urea to produce guanidine nitrate directly ....but there is also the danger associated with heating that particular mixture .
IIRC there were strategies for handling that in the industrial methods , but it may not be so easy to implement for an improvised process .

Granulated silica gel is cheap OTC as a bulk dessicant for drying flowers , or keeping dampness out of gun cabinets . The more coarse material is even used as a
high end kitty litter .
View user's profile View All Posts By User
Eclectic
International Hazard
*****




Posts: 899
Registered: 14-11-2004
Member Is Offline

Mood: Obsessive

[*] posted on 4-8-2007 at 07:27


I've seen ammonium metaphosphate and polyphosphate listed as fertilizers, but the N-P-K numbers look squirrely. Pure metaphosphate should be something like 14-73-0, not 12-52-0.

My local supplier has mono ammonium phosphate (MAP) at 12-62-0 which is right on the money for 98%+ material. This can probably be dehydrated at 200-250 C, but it seems likely to form a viscous melt and loose some of the ammonia.

Anyone have numbers for the dehydration of MAP? Melting points for various intermediates?

[Edited on 8-4-2007 by Eclectic]
View user's profile View All Posts By User
Joeychemist
National Hazard
****




Posts: 258
Registered: 16-9-2004
Location: Canada
Member Is Offline

Mood: Sedated

[*] posted on 26-10-2007 at 04:14


Will this be made into a .pdf like the others anytime soon? It's been a few months...

Nice work btw, Axt. Sulphamic acid is becoming increasingly more useful. :)
View user's profile View All Posts By User
497
International Hazard
*****




Posts: 778
Registered: 6-10-2007
Member Is Offline

Mood: HSbF6

[*] posted on 9-4-2008 at 17:25


Guanidine nitrate is availabe easily and cheaply, you could use that instead of the sulphamic acid and urea. A little less OTC but easier and not much more expensive. Much easier than something like TNT at least.
View user's profile View All Posts By User
Sauron
International Hazard
*****




Posts: 5358
Registered: 22-12-2006
Location: Barad-Dur, Mordor
Member Is Offline

Mood: metastable

[*] posted on 9-4-2008 at 22:54


This procedure is here for those members who want an OTC method. It is not particularly efficient.

Guanidine nitrate is available, if you don't mind buying something so obviously explosives related these days.

Better to buy guanidine carbonate, cheaper and less conspicuous, and proceed from there.

I use this to make aminoguanidine, myself. For the purpose of making some pyrazoles and thiazoles.




Sic gorgeamus a los subjectatus nunc.
View user's profile View All Posts By User
franklyn
International Hazard
*****




Posts: 2553
Registered: 30-5-2006
Location: Da Big Apple
Member Is Offline


[*] posted on 15-8-2008 at 21:26


Analysis of the formation of Guanidine Sulfamate from Urea and Ammonium Sulfamate in a molar ratio
of 1 : 2 in a sealed container yielding equimolar amounts of Ammonium Sulfate and Guanidine Sulfamate
and subsequent conversion to Guanidine Nitrate is discussed at length here.
http://article.pubs.nrc-cnrc.gc.ca/ppv/RPViewDoc?issn=1480-3...
75 - 80 % yield is obtained at 30 minutes at 255 ºC at moderate pressure less than 200 P.S.I.G

.
View user's profile View All Posts By User
franklyn
International Hazard
*****




Posts: 2553
Registered: 30-5-2006
Location: Da Big Apple
Member Is Offline


[*] posted on 26-2-2010 at 20:06


Preparation of Guanidinium Sulfate from Sulfur Trioxide Ammonia Reaction Mixture and Urea

Download PDF fron this page _
http://www.journalarchive.jst.go.jp/english/jnlabstract_en.p...

.
View user's profile View All Posts By User
Bert
Super Moderator
*******




Posts: 585
Registered: 12-3-2004
Location: Blasted Hellish frozen Northern wastelands
Member Is Offline

Mood: Fridigidly frostily frozen

[*] posted on 31-3-2011 at 12:48


Quote: Originally posted by Axt  
Nitroguanidine
from Sulphamic Acid and Urea

By Axt


Nitroguanidine is an explosive of some industrial and military significance, where its primary use is as an additive for propellants. The temperature of explosion for nitroguanidine is low, and when added to nitrocellulose-nitroglycerine powders it has the effect of both reducing muzzle flash and lowering erosion when compared to propellants of comparable power[1]. These are known as triple based propellants.

When used as a high explosive nitroguanidine detonates at a rate of 7650m/s at 1.55g/cm3 and its explosive power is relatively high, comparable to TNT[1]. Nitroguanidine is insensitive, failing to detonate from a 3.20m drop of a 2.5kg weight where TNT will detonate with a drop of 1.48m.[2]. It also has a low critical diametre of between 1.27-1.43mm[2].

While the toxicity of nitroguanidine is stated as being “high“ by Dobratz et al.[2], a study on its acute oral toxicity in mice by Hyatt et al.[3] placed it into the category of being practically non-toxic with a dose of 5000mg/kg producing less then 50% mortality .

The preparation of guanidine by fusing sulphamic acid and urea was patented by Mackay[4] and the mechanism was later studied by Boivin[5,6]. While no definite conclusions were obtained, the probable mechanism is shown in figure 1. The urea and sulphamic acid first fuse to form ammonium urea sulphonate, which dissociates into cyanamide and ammonium bisulphate which reacts to form guanidine bisulphate.


Figure 1: Preparation of guanidine bisulphate by fusing urea with sulphamic acid.


Nitroguanidine is prepared by dissolving guanidine nitrate in cold concentrated sulphuric acid (figure 2), then precipitating by pouring into ice water[7,8]. Though the yield obtained in this study was low, its an easy preparation and the precursors are both cheap and readily available.


Figure 2: Preparation of nitroguanidine from guanidine nitrate.


Precursors:

99% Sulphamic acid was sold in a hardware store as a descaler for removing calcium and rust deposits. Urea was also purchased from the hardware store in a 15kg bag for use as a fertiliser. Potassium hydroxide is available from hydroponics suppliers for raising pH.

Synthesis:

200g sulphamic acid and 124g urea were mixed in a shallow Pyrex bowl and placed into a fan forced kitchen oven. The mixture was left in the oven at 220°C for 2 hours, where it gave off some ammonia and melted into a clear liquid gradually thickening and forming a white semi-solid due to ammonium and guanidine sulphate separated of from the melt. This was then cooled and broken up to leave 302g of crude residue (figure 3).

The crude residue was then blended with 240g of potassium hydroxide in 1L of methylated spirits for 30 minutes (figure 3). This freed the guanidine and ammonia bases and precipitated potassium sulphate, 750ml of this free based alcohol solution was recovered by filtering the blended mixture.


Figure 3: Crude fusion product (left); Blending with alcoholic KOH solution (centre); Crude ammonium and guanidine nitrate salts (right).


The alcoholic solution of guanidine and ammonia was then neutralised with 70% nitric acid, this precipitated residual potassium hydroxide as its nitrate which was filtered out. On boiling down the alcohol to a concentrated solution, then evaporating dry, 84g of crude ammonium and guanidine nitrates was obtained (figure 3).

50g of the crude mixture of nitrates was directly converted to nitroguanidine by slowly dissolving small portions into 75ml of 98% sulphuric acid, the temperature was maintained from -5 to +10°C throughout the addition which took approximately 1.5 hours. The milky solution (figure 4) was left for 10 minutes at 10°C after the last addition then poured into 500ml of iced water. On standing the nitroguanidine precipitated as small crystals (figure 4) which were filtered and dried. Yield was 18.5g.


Figure 4: Guanidine nitrate dissolved in sulphuric acid (left); precipitation of nitroguanidine from 500ml water (right).


The nitroguanidine was recrystallised from boiling water to remove any nitrourea that may have been present, on cooling a mass of fine needles precipitated characteristic of nitroguanidine (figure 5).


Figure 5: 30x magnification of crystals of nitroguanidine from this study when crystallised from water (left); Nitroguanidine at 25x from the literature[7] obtained from rapid cooling of a water solution.


Explosive Properties:

The small fine needles obtained were pressed into a drinking straw, taped to a metal disk and initiated with 0.5g PETN under sand. The dent (figure 6) shows that the nitroguanidine did detonate however with low power. This low observed power can be attributed to the very low density at which the needles were pressed.

The nitroguanidine only deflagrated with difficulty when heated on a spoon over a gas flame, where it blackened, melted, emitted fumes then deflagrated leaving little residue. It would not deflagrate when held in the flame of a match.


Figure 6: detonation of low density nitroguanidine against metal plate.


References:

1] B.T. Fedoroff and O. E. Sheffield “Encyclopedia of Explosives and Related Items“. vol. 6; pg. G154. Picatinny Arsenal; New Jersey; USA (1960)

2] Dobratz, B and Crawford, P. "LLNL Explosives Handbook - Properties of Chemical Explosives and Explosive Simulants" Lawrence Livermore National Laboratory. California. (1985)

3] G. F Hyatt, S. K Sano, C. R Wheeler and D. W Korte “Acute Oral Toxicity of Nitroguanidine in Mice”; Letterman Army Institute of research Presidio of San Francisco, CA. (1984)

4] J. S. Mackay “Preparation of Guanidine Sulfates” US patent #2464247 (1949)

5] J. L. Boivin and A.L. Lovecy “Mechanism for the Formation of Guanidine from Urea and Ammonium Sulphamate” Canadian Journal of Chemistry; 33[7]; pg. 1222-1225; (1955)

6] J. L. Boivin and M. Tremblay “Synthesis of Guanidine from Urea, Ammonium Benzenesulphonate, and Ammonium Sulphamate” Canadian Journal of Chemistry; 36[2]; pg. 378-382; (1958)

7] T. L. Davis “The Chemistry of Powder and Explosives” Pg. 380; New York, John Wiley & Sons; London, Chapman & Hall. (1941)

8] G. B. L. Smith, V. J. Sabetta, and 0. F. Steinbach “Quantitative Study of the Preparations of Guanidine Nitrate and Nitroguanidine”; Industrial and Engineering Chemistry; 23[10]; pg. 1124-1129; (1931)

[Edited on 4-8-2007 by Axt]




Boom.
The explosion removed the windows, the door and most of the chimney.
It was the sort of thing you expected in the Street of alchemists. The neighbors preferred explosions, which were at least identifiable and soon over. They were better than the smells, which crept up on you.
-Terry Pratchett, "Moving Pictures"
View user's profile View All Posts By User
Xenomorph
Harmless
*




Posts: 17
Registered: 23-4-2011
Member Is Offline


[*] posted on 21-6-2011 at 10:52


Unfortunatelly my local supplier have no sulfamic acid and I have never seen it also in hardware stores. However there is some viscous green stuff which smells like flowers and contains 10% sulfamic acid along with 75% phosphoric acid and 10% surfactants. Is there any cheap and easy way to extract sulfamic acid from it?
View user's profile View All Posts By User
White Yeti
International Hazard
*****




Posts: 816
Registered: 20-7-2011
Location: Asperger's spectrum
Member Is Offline

Mood: delocalized

[*] posted on 23-8-2011 at 11:29


Quote: Originally posted by Sauron  


Better to buy guanidine carbonate, cheaper and less conspicuous, and proceed from there.



In order to obtain nitroguanidine, what would you react the carbonate with? There are many different ways of making this explosive, but starting from a carbonate salt seems the most promising method for making nitroguanidine.
View user's profile View All Posts By User
watson.fawkes
International Hazard
*****




Posts: 2793
Registered: 16-8-2008
Member Is Offline


[*] posted on 24-8-2011 at 05:17


Quote: Originally posted by Xenomorph  
Unfortunatelly my local supplier have no sulfamic acid and I have never seen it also in hardware stores.
In the USA, it's available as TILELab brand "Sulfamic Acid Cleaner". Home Depot carries it in 1 lb. tubs. It's sold for removing grout haze from ceramic tile.
View user's profile View All Posts By User
ScienceSquirrel
Super Moderator
Thread Pruned
13-3-2012 at 05:41
franklyn
International Hazard
*****




Posts: 2553
Registered: 30-5-2006
Location: Da Big Apple
Member Is Offline


[*] posted on 16-10-2012 at 20:02


Reactions of Ammonium Sulphamate with Amides & Ureas
http://www.nrcresearchpress.com/doi/abs/10.1139/v56-214

* Side note :
On article page 1664 ( 3rd pg of pdf ) under the heading Alkylureas
" It was found that methylurea and 1,3-dimethylurea reacted with ammonium sulphamate
in a manner analogous to that of urea. Methylamine was isolated from the reaction mixtures."
This is also mentioned in the opening abstract , table IV does not show this perhaps an ommision ?

Table III
Guanadine .gif - 12kB

Attachment: Reactions of Ammonium Sulphamate with Amides & Ureas.pdf (358kB)
This file has been downloaded 580 times
View user's profile View All Posts By User
White Yeti
International Hazard
*****




Posts: 816
Registered: 20-7-2011
Location: Asperger's spectrum
Member Is Offline

Mood: delocalized

[*] posted on 25-11-2012 at 16:31


I didn't see anyone mention it here, but I found another post detailing the synthesis of nitroguanidine from urea, ammonium nitrate, and sulfuric acid as an intermediate for the synthesis of tetrazoles:
http://www.sciencemadness.org/talk/viewthread.php?tid=12938

This may potentially be an even cheaper and simpler method than with sulphamic acid.




"Ja, Kalzium, das ist alles!" -Otto Loewi
View user's profile View All Posts By User
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
*****




Posts: 1986
Registered: 2-3-2011
Member Is Offline


[*] posted on 12-1-2013 at 00:04


Here are some other interesting compounds that can be made from guanidine:

The di-nitrate salt of azobisformamidine, NH2C(=NH)-N=N-C(=NH)NH2, can be prepared by treating aminoguanidine nitrate, with excess dilute nitric acid, with a solution of potassium permanganate. The di-nitrate salt forms yellow plates, which explode at 180-184 °C.

2,5-dinitro-azobisformamidine, O2NN=C(NH2)-N=N-C(-NH2)=NNO2, forms redish to orangish-yellow crystals which explode at 165 °C. It is obtained by nitrating azobischloroformamidine* with 98.8% concentrated nitric acid and acetic anhydride. G.F. wright, Canadian Journal of Chemistry 30, 65-8 (1950). The compound was also prepared by oxidation of 1,6-dinitrobiguanidine with calcium permanganate, obtaining an orange-yellow product, melting point 171-172 °C with decomposition. R.A. Henry JACS 75, 958 (1953)

*Azobischloroformamidine, NH2C(=NCl)-N=N-C(=NCl)NH2, crystallizes in bright yellow needles or plates, melting at 152 °C when crystallized out of water, or 155.5 °C from ethyl acetate. The compound has toxicity and explosion hazards. Prepared by reaction of NH2C(=NH)NHNHC(=NH)NH2 with hypochlorite or chlorine gas. Alternatively, aminoguanidine may be oxidized to NH2C(=NH)N=NC(=NH)NH2, then chlorinated with NaOCl, giving a 42% yield of azobischloroformamidine, the product having a 96% purity.

[Edited on 12-1-2013 by AndersHoveland]
View user's profile Visit user's homepage View All Posts By User

  Go To Top