Sciencemadness Discussion Board

C.T.M.T.N.A (R-salt)

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PerFecTioNisT - 22-2-2005 at 12:09

I.m intresting about this HE, and maybe there are people who did this explosive by this recept?

**********************

This is R.D.X., but missing three oxygen atoms (one from each NO2 group). It uses no concentrated nitric acid. The only acid used is hydrochloric, and it doesn't even have to be very concentrated. This explosive is carcinogenic and toxic, contact should be avoided. However, this is perhaps the best explosive to make at home since it is easy to produce and powerful. The reason it's not used militarily is the low yield of 30% (I have seen 50% stated, but this means that the weight yielded is 50% of the weight of hexamethylenetetramine used, e.g. 3.5 grams of C.T.M.T.N.A. from 7 grams of hexamethylenetetramine.)
VoD is 7800 m/s at 1.57 g/cm3. Relative briscancy is 1.17. Lead block expansion is 370 cm3. At this density 2.5 grams of Mercury Fulminate will cause detonation, at 0.85 g/cm3 a mere 0.3 grams of Mercury Fulmiate will suffice!


You will need:


7g of hexamethylenetetramine,
60mL of 15% hydrochloric acid,
10.5g of sodium nitrite,
Distilled water,
50mL of 10% sodium carbonate solution,
20mL of acetone,
1g of sodium carbonate,
An ice bath,
A 150mL beaker,
A thermometer,
A filter funnel,
Three filter papers.


1) Dissolve the hexamine in 25mL of water and add the hydrochloric acid in the 150mL beaker.
2) Cool this to 0*C in the ice bath, and add a solution of the sodium nitrite in 50mL of water, while stirring.
3) Leave the solution to react overnight at 5*C, and then filter out the crystals.
4) Wash them with 200mL of water, then the sodium carbonate solution, then another 200mL of water.
5) Dissolve them in the acetone at around 40*C, add the 1 gram of sodium carbonate, and stir for 5 minutes.
6) Filter the solution
7) Dump the filtrate into 100mL of cold water in the other 150mL beaker to precipitate the crystals.
7) Filter them out, and leave them to dry in a warm, dry place in a thin layer.

Who had try to do this?

Mumbles - 22-2-2005 at 15:14

I've tried it and gotten shit for results. I keep the temp low, but it started bubbling. It's definatly not ammonia, or formaldehyde or HCl. It's hard to explain. It smells kinda like warm bread if that makes any sense.

After maybe 45 minutes this foamy stuff on top forms. I think this is the R-salt. I let it react for the time recomended by Mr. Cool, and by morning the foam was all but just about gone. I don't like it. I would be willing to try if I found a better method.

Federoff R-Salt Preparation

chemoleo - 22-2-2005 at 15:16

Well I didn't realise how remarkably simple the synthesis is. Indeed, acc. to Federoff, only the pH seems to influence nitrosylation. The lower, the better essentially, else one gets di-nitroso products. At pH 1, one exclusively gets the trinitroso form.

In fact, this is the optimised prep in Fedoroff:

Bachmann & Deno (Ref 6) added simultaneously a soln of NaNO2 in 6M HCl,
at a rate required to maintain a pH of 1, to a solution of hexamethylenetetramine in ice & water. The mixture was held at 0° for 30 minutes. The yield of practically pure product was 50% (mole for mole basis)

Maybe this ought to be done that way instead.

[Edited on 22-2-2005 by chemoleo]

No product..... :(

PerFecTioNisT - 23-2-2005 at 06:38

I didnt keep the temperature when added NaNo2 soak, when I added it, all stuff started bubling and was brown fumes, its no2 if I dont wrong.But tomorow i did not saw any cristals.....What was wrong?NO product?

[Edited on 23-2-2005 by PerFecTioNisT]

Mumbles - 23-2-2005 at 19:50

Is that reference saying a solutions of NaNO2 and 6M HCl added simultaniously, or a solution of NaNO2 in 6M HCl. The simultaniously would make me think that it is 2 separate, but it mentions a singular solution and uses "in".

I may try out the ice directly in solution next time. It seems that would work a lot better for cooling.

chemoleo - 23-2-2005 at 20:10

Well I copied it straight from Federoff, no rewording. If you really want to be sure, I guess you ought to get that reference.
The way I understood it is that you mix NaNO2 with HCl, icecold, so as to prevent NOx evolution. This you add to the hexamine.

PerFecTioNisT - 24-2-2005 at 01:40

Yesterday I did one more.I cooled my stuff to -2C and added nanao2.The highest temperature was 10C, al stuff bubling and I let him to stayed in the yard over night.And this morning i didnt find the product :( I dont know what to do......
And what is the Federoff?Maybe there are several recept to do this R-salt?



[Edited on 24-2-2005 by PerFecTioNisT]

stygian - 24-2-2005 at 08:06

To me it's saying the hexamine and HCl are in one beaker, cooled to 0c, then NaNO2 solution is added.

referencing

J_O_H_N_Q - 1-3-2005 at 23:59

Hey Perfect, nothing personal man, but, shouldn't you at least tell people that you quoted Mr Cool's webpage?
He did go to all the effort to write that stuff up, at least give him credit for it.

[Edited on 2-3-2005 by J_O_H_N_Q]

PerFecTioNisT - 2-3-2005 at 01:51

Yes this is from MR.COOL web , soory...I think that all peoples knows.

Oxidize R-Salt!

SAM4CH - 18-3-2005 at 11:33

Can I convert R-salt to RDX?! more details!

C.T.M.T.N.A (R-salt)

Pyro_boy - 26-4-2005 at 09:54

C.T.M.T.N.A (R-salt): Actually the yields can be much better if your using Muriatic Acid, 31.5% HCl and potassium nitrate.

I've gotten up to the high 60% yeilds with this method. i'm going to tweek the formula and see if 80% is possiable.

chemoleo - 26-4-2005 at 12:14

Potassium NitrAte?? :o:o

Pyro_boy - 26-4-2005 at 12:40

yeah, It was suppose to be Nitrite, but I used Nitrate instead. I worked, oddly. NO3 instead of NO2..

The_Davster - 26-4-2005 at 12:47

You probally just have HDN...

Esplosivo - 26-4-2005 at 21:26

I don't understand the exact mechanism by which this reaction proceeds, but mixing a nitrite with hydrochloric acid clearly indicates the formation of nitrous acid. I would say that what occurs is a sort of nitrosylation, but I am not sure. If this is so, it surely would not give the same results if the nitrite is replaced with a nitrate.

sparkgap - 26-4-2005 at 21:32

Just my two cents, but the guy made no mention of testing his purported product chemically to verify it was the subject explosive. So we can't really say if it was. Most likely, however, would be that something structurally different, but just as explosive as the original, was made.

sparky (^_^)

Axt - 17-7-2005 at 04:07

Quote:
Originally posted by Rosco Bodine <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=3033">here</a>
Also hexamine or hexamine dinitrate or even HMTD could form R-salt or a similar derivative . (from NOx)


I'd previously tried to get R-salt by bubbling N2O3 through 20g hexamine, 100ml 32% HCl and 150ml water, cooled to 5°C. A precipitate did seem to form (solution turned white/turbid) but temperature gets out of control and solution fumed off as you get if r-salt is added to hot acid (its not stable in acid solution, far worse if its hot). If one was going to attempt this you will need to use a slurry of crushed ice, external cooling wont work.

Anyway, heres conventional r-salt through NaNO2/HCl/hexamine. Three solutions were made, one containing 60g 35% HCl in 100ml water, one containing 40g NaNO2 in 80ml water and one containing 20g hexamine and 60g HCl in 100ml water. The NaNO2/HCl solutions are combined, producing blue solution of nitrous acid. This is then added to the hexamine/HCl <0°C. The foam filtered off, dried. Yield was just over 50% right on the documented yield. Melting point on rapid heating was 110°C, close enough to documented temp of 106-7°C. The other possible product (dinitrosopentamethylenetetramine) melts at 207°C so easy to tell apart.

By not mixing the up the nitrous acid first, theres a lot more foaming and heating and often I end up with nothing at all.

R-salt burns easily with soft orange flame leaving residue, with noise but not as vigourously as RDX. Ive never tried to detonate it.

<center><img src="http://www.sciencemadness.org/scipics/axt/rsalts.jpg"></center>

^ I dont think all of the pics above are from the same batch.

R-salt / RDX eutectic

Rosco Bodine - 17-7-2005 at 06:37

R-salt forms a relatively low melting eutectic at about a 50/50 mix with RDX which results in a very high energy composition . PATR mentions a minor proportion of a third material used in the composition . Possibly the ethylene or propylene pseudo-nitrosite could also be useful in such a meltable composition .

With regards to use of N2O3 for R-Salt ,
some means of pH control might give better yields . For example , dissolving
hexamine in white vinegar ( 4 or 5% acetic acid ) in excess and then adjusting
the pH if necessary with HCl , chilling very cold and nitrosating , could give better yields than using HCl alone as the acid as when sodium nitrite is used as the nitrosation reagent . When the solid nitrite is used it would tend to buffer the reaction pH by virtue of the sodium it contains . But the use of N2O3 would
be absent that buffering effect which
would cause the reaction mixture to become more and more acidic as the nitrosation proceeds . The effect would be lessened in a reaction mixture which
is mainly acidified with acetic acid and where HCl is present in lower amount .
There is also the possibility that this approach would not work at all , especially if the acetic acid itself should be nitrosated , or if the dilution is too great for the reaction mixture of this sort to react as wished .

Axt - 17-7-2005 at 23:59

I'm attaching the article referenced in PATR 2700, which gives the desired pH, takes a ratio of 6M HCl to 1M hexamine to give the trinitroso product. It mentions that the use of acetic acid alone will produce the dinitroso product, then it shows a less then convenient route from this to HMX.
Quote:
Originally posted by SAM4CH
Can I convert R-salt to RDX?! more details!


It is mentioned in PATR 2700 that r-salt can be nitrated to RDX with H2SO4/AN in >90% yield. If N2O3 drawn off H2SO4/AN/starch was to work it could be a convenient way to RDX, requiring no nitric acid or nitrites. Note that 50% R-salt yield is based on 1M hexamine creating 1M R-salt, with RDX theoretically 2M are created for every 1M hexamine in ammonium salt is used. This means, through this route, at best you can expect a 25% yield of RDX from hexamine.

[Edited on 9-12-2005 by Axt]

Attachment: nitrosation of hexamine.pdf (395kB)
This file has been downloaded 3316 times

Rosco Bodine - 18-7-2005 at 07:03

From the information in the Bachmann & Deno article it appears that use of acetic acid takes the pH too far in the wrong direction for R-salt and leads instead to the DPT material which is primarily useful as a precursor for HMX . The DPT is obtained in better yield more cheaply by simply using less HCl to raise the pH of the
reaction mixture , so acetic acid offers no advantage .

PATR states that a mixture of R-salt and NG kept at 90C for 5 days showed no apparent decomposition ? Possibly a misprint , because that would seem to indicate stabilizing properties for R-salt towards nitroesters which if true is very interesting . If this is general , R-salt could possibly have value as an energetic stabilizer as well as filler for ETN melt and other low melting compositions , and possible usefulness in many other nitroester containing compositions .

Rosco Bodine - 24-11-2005 at 19:33

Urbanski describes 84% yields of R-salt reported by Aubertein giving detailed instructions for synthesis

P. Aubertein , Mem. Poudres 33 , 227 ,
( 1951 )

Also in the same journal a method for production on a semi-commercial scale is reported by Ficheroulle and Kovache

H. Ficheroulle and A. Kovache , Mem. Poudres 33 , 241 , ( 1951 )

These would be interesting references if anyone has access and may share these articles .

halogen - 26-11-2005 at 04:22

You bubbled N2O3 through hexamine/hydrochloric acid? Why would you need HCl? Just to keep PH down? Why the -NO replace Cl. Is nitrous acid stronger?

Axt - 26-11-2005 at 18:01

Quote:
Originally posted by halogen
You bubbled N2O3 through hexamine/hydrochloric acid? Why would you need HCl?


In aqueous solution:

N<sub>2</sub>O<sub>3</sub> + HCl → NOCl + HNO<sub>2</sub>
NOCl + H<sub>2</sub>O → HNO<sub>2</sub> + HCl

And acid conditions are needed to form R-salt opposed to the dinitroso derivative.

halogen - 27-11-2005 at 08:12

I N2O3 was nitrous anhydride. If not, what is?

Axt - 28-11-2005 at 01:20

You will get HNO2 from water + N2O3, which then decomposes from the exotherm. You'll get some from N2O4 as well.

R-Salt needs concentrated acid solution @ pH1, HNO2 is a weak acid. R-salt is also decomposed by strong acid solutions, thus the reaction isn't as merry as it first looks.

[Edited on 28-11-2005 by Axt]

Rosco Bodine - 28-11-2005 at 08:06

R-salt reportedly has 125% the output of TNT and yet it is made under fairly mild conditions . That alone makes it interesting and even better if the yield could be increased over the 50% without too much added difficulty . I hope someone will get a look at those 1951 articles in Memorial of the Powders .
The reference in PATR to the 90C heat test
for an R-salt and NG mixture is also intriguing , and it makes me wonder what may be the result of mixtures with other nitroesters like ethylene glycol dinitrate ,
and erythritol tetranitrate , IF of course the information in PATR is accurate and
not a misprint like some others we have seen .

In the thread about HMX there was a high yield reported for DNPT by a reaction scheme which may be adaptable to R-salt using different proportions and pH . An experiment by a forum member BASF was unable to confirm the method for DNPT ,
which seemed to be a low temperature variation on something similar to the
K process for RDX , but intended for a nitrosamine product . Such a
" no hexamine " method for R-salt from
reaction scheme which proceeds from a mixture of NH4 and CH2O providing
" nascent hexamine " as the precursor for the nitrosamine would be an interesting simplification , similarly as is the case for those of us who make out own hexamine anyway and never drop it out of solution as hexamine free base , but rather as the dinitrate .

R-salt is a chemically reactive material and
I have wondered also what is its reactivity towards an organic peroxide , such as MEKP , or a liquid MEKP / AP mixture , or in an AP melt :D

K9 - 4-12-2005 at 09:14

Just to clarify, the "60g 35% HCl in 100ml water" would be ~51 ml of the HCL in 100 ml water to give ~12% HCl in solution? Thank you in advance.

Axt - 4-12-2005 at 09:57

Yes 60g 32% (actually checking bottle, its 32% not 35 as I previously said) HCl was added to 100ml H2O, which makes it 160g of 12% HCl. I hate volume measurements of impure liquids.

This has been a bit touchy, and it may be advantageous to lower the HCl percentage making sure to keep the HCl:hexamine ratio >6:1 & pH ~1.

K9 - 4-12-2005 at 10:24

Ok then one more thing. At 160 grams of 12% HCl, that works out to 0.526 moles (unless I screwed that up somewhere) to 0.14 moles of hexamine - or a 3.75:1 ratio which wouldn't be 6:1. Did I just screw that up somewhere or was that right?

I've tried adding NaNO2 at the end twice before resulting in total loss of product. I'm planning now to attempt this method with 17 grams KNO2 in 30 ml water, 7 grams hexamine, and I guess whatever concentration I dilute my 31.45% HCl down to.

EDIT: From here - http://www.basf.de/basf/img/produkte/farbmittel/leder/pdf/pb... 31.45% HCl is at a density of 1.1600 g/ml. So if I were to go with 12% I guess I would be using roughly 21g HCl in 35g H2O or 18.4 ml HCl in 35 ml water.

[Edited on 4-12-2005 by K9]

Axt - 4-12-2005 at 10:43

OK, you scared me there for a while. Punching buttons on the calculator scratching my head :o You forgot the other HCl/hex solution.
Quote:
Three solutions were made, one containing 60g 35% HCl in 100ml water, one containing 40g NaNO2 in 80ml water and one containing 20g hexamine and 60g HCl in 100ml water


Its 120g 32% HCl all up, so ~7.5 HCl to 1 Hexamine. This was done before I read that article, so dropping it back to 6:1 may prevent the decomposition that sometimes occurs.

K9 - 4-12-2005 at 21:15

Oh whoops I completely forgot that. Sorry.

Now after reading the article, it seems that their preferred method of reagent addition is of HCl and NaNO2 to a hexamine/water solution in one instance and addition of NaNO2 solution to a hexamine/HCl solution in another. But from what I understand the order makes no difference at all, just the pH.

There is also the matter of the ratios. From what I can understand, the best ratio seems to be about 1:6:4.3 of hex:HCl:nitrite.

As for the order of addition, I guess I'll go with adding HCl/NaNO2 to the hexamine/water solution since that seems to give good yields unless there's some reason that I'm missing for which the hexamine should be dissolved in HCl first. Again, I know that all that really matters is the pH level maintenance, but I don't quite know how well I will be able to control the pH during reagent addition.

Aside from the addition discrepancy (which again as far as I know makes no difference) I'm prepared for this procedure to finally work after the failures. I'll report back with the results which will probably be nearer the end of the week.

Thanks again for all the help.

[Edited on 5-12-2005 by K9]

K9 - 6-12-2005 at 16:54

Sorry for the double post but here's the results. Finally a success!

First I added 30 ml of 31.45% HCl to 50 ml water and this was mixed with 18 grams KNO2 in 30 ml water. I then added 7 grams hex to 50 ml water.

http://img.photobucket.com/albums/v78/wolfhound/ct1.jpg

At < 0C I added the nitrous acid to the hexamine solution. At first I thought nothing was happening but then it foamed up quite a bit, almost to the top of the reaction vessel. Then the foam went down as the gas escaped.

http://img.photobucket.com/albums/v78/wolfhound/ct2.jpg
http://img.photobucket.com/albums/v78/wolfhound/ct3.jpg

This was then filtered and now it's drying. I don't know how great the yield is since it's a big air filled blob of wet product still, but I'll measure when it's dry. Either way I'm just happy that it worked.

http://img.photobucket.com/albums/v78/wolfhound/ct4.jpg

I think the first time I tried it I actually did get something but it was an uncontrolled foaming with lots of NO2(?) coming off. So now all that's left is drying and weighing. Just one more question, is there any reason to wash the product to neutralize it? Thank you for the help and I appreciate any input.

[Edited on 7-12-2005 by K9]

HMMM

chloric1 - 6-12-2005 at 19:38

Hey I cannot wait until I can do the experiment! That nitrous acid solution looks pretty, kind of like blue koolaid.:P:D

Deceitful_Frank - 7-12-2005 at 01:56

Well done! This is also on my to-do list, I beleive that this CTMTNA has a density of around 1.6 and velocity in the order of 7800m/s, stablises NG and forms a more powerful composition due to synergy of oxygen balance. Toxic but an excellent explosive

I wanted to make it as I saw it as a potentially easy route to RDX though I am aware that the overall yeild from hex to RDX will be no more than 25% of theory.

I posted a thread about converting this to RDX both on totse and on APC but without alot of interest. If you were to try to do this would you be using the xNO3/H2SO4 bath to nitrate or to oxidise? Ime not sure how the reaction would procede even after etensive searching on the net. It would be good to know the correct ratios of reactants to use if only to increase that abbysmal yeild though I fear you may end up having to just use a large excess just to be sure.

EDIT:

Just walked my GF to work and upon walking back in the freezing foggy air, I've had a couple more thoughts regarding the above.

At first I assumed that CTMTNA would be VERY oxygen defficient... in the order of TNT and PA but it seems that It has the same theoretical detonation products as HMTD... CO, N2 and H2, some carbon would obviously form but I would not expect to see black smoke upon firing. More a grey mist like from HMTD.

Also I remember reading that CTMTNA forms a low melting point and easily castable eutectic in a 50:50 ratio with RDX though I'm not sure what defines a "low melting point" IMO this would be have slightly more power than composition B and be of similar balance.

Also, if your nitration/oxydation to RDX is not to be and you can perfect your yeild and ecomany when synthesising CTMTNA, you could try plastisisng it with a 20% mix of 4:1 by mass NG/MHN. Although the heat output would be lower than than RDX/NG/MHN plastique I'd bet the velocity would still be around 7800m/s for a fully plastisised though TOXIC mass... (gloves)

[Edited on 7-12-2005 by Deceitful_Frank]

K9 - 7-12-2005 at 09:04

I think I do want to try the conversion to RDX just to see if it does work and I would be using xNO3/H2SO4. I'm not really sure how to figure out what the ratios should be (any help would be appreciated there) but I wouldn't be using a very large amount now anyways.

Rosco Bodine was the one that mentioned the mix (in page 1 of this thread) with RDX. That too sounds interesting. And the plasticized CTMTNA also sounds good.

As far as improving the yield, I don't really know how I would go about that. I still have to weigh my yield but whatever I do get, lowering the HCl concentration to allow better formation of nitrous acid (which is what I'm told would help it) might possibly increase my yield. In the paper they also mentioned allowing about 1/2 hour time to pass before filtering. I let about 15 minutes go by before filtering off the foam. That may help too. But it just seems like anytime the yield increases by a considerable amount it is simply due to having more dinitroso product.

EDIT:

Just weighed the dry product. Bang on at 50% yield.

[Edited on 7-12-2005 by K9]

Rosco Bodine - 7-12-2005 at 12:00

The conversion of R-salt to RDX is an idea which seems
to offer no advantage over the usual nitrolysis of HDN ,
and is much more dangerous . The Simecek article which
describes the reaction conditions is covered in the thread
started by BASF about HMX without acetic anhydride .

Axt - 16-1-2006 at 23:23

Quote:
Originally posted by Rosco Bodine <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=4937#pid57468">here</a>
Anybody have access to these R-salt articles ?

P. Aubertein , Mem. Poudres 33 , 227 ,
( 1951 )

H. Ficheroulle and A. Kovache , Mem. Poudres 33 , 241 ,
( 1951 )


The second one is attached. Wait a <i>little</i> longer for the first.

Attachment: R-salt-Mem Poudres 33 241.pdf (823kB)
This file has been downloaded 1831 times

Axt - 1-2-2006 at 14:47

Heres the first.

http://ww1.ft100.net/~64671/xfiles.ft100.net/images/rsalt_me...

Rosco Bodine - 1-2-2006 at 20:08

Excellent get . Thanks for these references Axt .
These articles are another first on the web ,
so far as I know anyway .

Now pdb has something worth the work :D

From what I can understand of it the H2SO4
appears to be producing the increased yield .

pdb - 2-2-2006 at 13:26

I might help if you wish, provided I could access the document, but the server is out of reach. Is it so big that you can't attach it to your message ?

Rosco Bodine - 2-2-2006 at 14:42

The server is blocking the unsplit file so I have
split it up into four files attached in sequence .

[Edited on 2-2-2006 by Rosco Bodine]

Attachment: Pages 1 thru 4 from rsalt_mem_poudres_33_277.pdf (715kB)
This file has been downloaded 1820 times

Rosco Bodine - 2-2-2006 at 15:29

Here's the second file .

Attachment: Pages 5 thru 7 from rsalt_mem_poudres_33_277.pdf (891kB)
This file has been downloaded 1592 times

Rosco Bodine - 2-2-2006 at 15:30

Here's the third file .

Attachment: Pages 8 thru 10 from rsalt_mem_poudres_33_277.pdf (595kB)
This file has been downloaded 1482 times

Rosco Bodine - 2-2-2006 at 15:31

Here's the fourth and last file .

Attachment: Pages 11 thru 13 from rsalt_mem_poudres_33_277.pdf (687kB)
This file has been downloaded 1600 times

Memorial des Poudres (vol 33) - in English

pdb - 3-2-2006 at 06:18

Here you are...

Attachment: TRIMETHYLENE TRINITROSAMINE - (Memorial des Poudres - vol 33) (english).pdf (87kB)
This file has been downloaded 3658 times

Rosco Bodine - 3-2-2006 at 07:35

Thank you for the excellent translation of this important
and enlightening reference . More productive experiments
are foreseeable having this reference as a guide .


There are a couple of ideas which I have considered with
regards to the production of R-salt . I always make my
own hexamine from the reaction of paraformaldehyde mildewcide crystals and 28% ammonia blueprint developer
in excess , bringing the completed reaction to boiling after
all is in solution to drive off any unreacted ammonia and
leave a strong solution of pure hexamine in nearly quantitative yield , based on the 96% purity of the paraformaldehyde crystals used for the synthesis .

The solution may be boiled down until crystals of hexamine
just appear and then the heating stopped . Upon cooling the hexamine will redissolve due to the inverse solubility
curve of hexamine with regards to temperature , leaving
a cold saturated solution . Hexamine dinitrate can be
precipitated from the freezing cold solution by just neutralizing with HNO3 in no great excess . The residual
solution contains some dissolved hexamine dinitrate which
is generally lost since the solution cannot be evaporated
by boiling at ordinary temperature . But the solution
from filtration of HDN can be further used directly in synthesis instead of simply being discarded as waste .
The HDN solution can be mixed with a 15% excess of theory
of hydrogen peroxide and kept in the freezer for the precipitation of HMTD which is complete after a couple of days . And it seems likely that the cold HDN solution could also be used for the production of R-salt by reducing the amount of H2SO4 somewhat for one of the Aubertein
syntheses , to adjust the pH accounting for the HNO3 present in the HDN which is in solution . A useful byproduct
would thus be salvaged from a waste solution from the
synthesis of the HDN precursor for RDX , improving the economy of the process . Also the R-salt produced would
be of value because of its ability to form useful eutectics with
any RDX ultimately made from the HDN which was recovered
as crystals earlier in the process . This production of R-salt
as a byproduct would offset the losses which are inherent in the relatively inefficient nitrolysis of HDN to RDX . A further
improvement in efficency may be obtained by using the diluted nitrolysis mixture from filtration of the RDX , which
contains fairly concentrated HNO3 , for neutralization of
subsequent batches of concentrated hexamine solution to
produce more HDN and R-salt . By this scheme otherwise
wasted byproducts are recycled in the process , which would be of significant value in any large scale production .

Fulmen - 3-2-2006 at 08:54

Wonderful work guys, this really seems like a real alternative to the much more complicated RDX-synthesis. And wouldn't you know, I found both hexamine and sodium nitrite in the basement the other day :-) But I would like to know more about the toxisity before I start, I don't have a real lab and toxic materials give me the heebies-jeebies. Like the kilo or so of DNT I have, I'm sure it would be a valuable compound if I only could bring me to ever use it...

Douchermann - 6-7-2006 at 09:41

Sorry to bring up an old thread, but I can not find a reaction diagram for this for the life of me. All of the reactions I thought of did not give 11.6grams of theoretical yeild for 7grams of hexamine (as in Mr. Cool's procedure). Does anyone know it, or can they figure it out? It would be interesting to see it.

Rosco Bodine - 7-7-2006 at 16:42

Quote:
Originally posted by Douchermann
Sorry to bring up an old thread, but I can not find a reaction diagram for this for the life of me.


Now that I think about it , I have never seen the reaction stated either , so here is what I suppose is most likely .

(CH2)6N4 + 3 HNO2 ----> (CH2)3N6O3 + NH3 + 3 CH2O

m.w. 140.19 hexamine --------- m.w. 174.13 TMTN

100% yield of TMTN would be 1.2421 grams
per each 1 gram of hexamine .

The best yield reported by Aubertein in Experiment 19 was
64.9% of theory which amounts to .806 grams of TMTN
per each 1 gram of hexamine .
Quote:

All of the reactions I thought of did not give 11.6grams of theoretical yeild for 7grams of hexamine (as in Mr. Cool's procedure). Does anyone know it, or can they figure it out? It would be interesting to see it.


The equation I provided above is probably correct .

Evidently the yield figure of 84% attributed to Aubertein by Urbanski on page 122 of volume 3 , is an error .

It may be worthwhile also to experiment with nitric acid
as the acid used in whole or in part in the process for producing TMTN , and using Hexamine Dinitrate as the form of hexamine . My first experiment for TMTN will likely be
of that nature , simply to satisfy my curiosity . I have a
hunch , an intuition that this could work fine also , and it would be interesting to discover what the effect would be on the yield .


[Edited on 8-7-2006 by Rosco Bodine]

Douchermann - 9-7-2006 at 14:02

That would make sense. The by products would then react producing 1/4 mole of hexamine for ever mole of hexamine used previously (ammonia as the limiting reactant). So if 10 grams of hexamine is used initially, 2.5 grams will be produced (theoretically) from the by products.

Rosco Bodine - 9-7-2006 at 15:01

It would be nice if it went that way , but no such luck .

The acidic conditions prevent the recombination of
the byproduct ammonia and formaldehyde to reform
the original hexamine and this parallels the situation
for RDX . You see the formation of hexamine only
occurs in alkaline reaction medium where the ammonia
can be free and the formaldehyde is also reactive .
In acidic systems there is a different reaction which
leads to methylamine derivatives and di and tri-methylamine derivatives instead of the hexamethylene
cyclisation favored in alkaline systems .

Even for the case where it was once believed that
an additional yield of RDX could be gotten from the
reforming of hexamine from the decomposition products , this has been proven to be untrue , but involves some
complex intermediates of a different nature which form
in the extreme nitration mixtures for RDX , and then are converted to RDX by a series of reactions .

That is unlikely to be possible in the aqueous system
used for producing TMTN .

One thing that could be done is to use the waste filtrate
from TMTN for production of formite . Adding the proper amount of ammonium nitrate and urea would cycle the waste formaldehyde to methylamine nitrate and the di and trimethylamine nitrates also in lesser amount . These products along with additional AN and urea ,
could be mixed to form a melt castable which would be a high energy composition nearly equivalent to TNT and probably cap sensitive . If not , the TMTN could be used
as a booster for it .

Douchermann - 9-7-2006 at 19:45

Could just AN be used to convert the waste formaldehyde into Methylamine nitrate?

4CH2O + 5NH4NO3 = 4CH3NH2 + 6HNO3 + H2O
CH3NH3 + HNO3 ----> CH3NH2*HNO3

Or would that reaction not progress.

Rosco Bodine - 10-7-2006 at 21:32

A simultaneous reaction is not practical because the
methylamine formation is favored by high temperatures ,
while the TMTN formation requires low temperatures .
It goes something like you have it but the reaction is more complex with secondary reactions and byproducts which are reduced and involved with yet another reaction with urea . There are a couple of patents concerning this . I can't dig them up right now as I am salvaging what I can from about four years worth of data loss after the main drive has failed in my computer , which should keep me busy for weeks trying to get a fraction of the data restored from what part of it was backed up . The drive failure sneaked up on me with read and write errrors that have corrupted everything pretty badly that was a larger file . A lot of the small pdfs. I may get back but that is about it .

Everybody who has a burner should burn backups and
keep docs properly archived . I used to do it regularly , but have gotten distracted lately and didn't know that
a lot of the data I was backing up was already corrupted .

Douchermann - 12-7-2006 at 06:21

Oh okay, thanks. I'll see if I can find the patents myself.

Rosco Bodine - 12-7-2006 at 06:56

With regards to utilizing the waste solutions , it is something mainly pertinent to industrial scale production which would seem worth the trouble for economic and environmental considerations . For lab scale syntheses it is hardly worth the trouble . This process would also be predicated on the
success of using nitric acid instead of the sulfuric or hydrochloric acid as has been described for TMTN , so that
there would only be nitrates in the final mixture . This is part of my interest in seeing if the TMTN can indeed be made
from HDN as a starting material , and using nitric acid to
achieve the pH 1 reaction condition , not only to see if the
yield of TMTN may be improved , but also because the value
of the waste solution for further reaction may be improved ....
not only for potential value in regards to formite which may or may not proceed well , but simply knowing that neutralization with ammonia and evaporating would lead
to a useful residue of nitrates and hexamine , so that there
would be no waste output from the TMTN production .
Efficiency is everything with regards to chemical plants ,
so zero waste is an important goal for the economic and environmental concerns ......waste not , want not :D

The two " formite " ( formaldehyde / AN reaction mixture ) patents that I know about are

EP0037862

GB1548827


Patent related to such mixtures value in cast melts

US1968158

Related reaction under alkaline conditions which
produces hexamine instead

US3660182

Slurry related hexamine containing AN composition

US3496040

[Edited on 12-7-2006 by Rosco Bodine]

SAM4CH - 13-11-2006 at 07:23

I prepared 150 R-salt and I tried to detonate 50g and it exploded nicly, after few months (6 month) I tried to detonate the other 100g with primer and poster but it did not explode!! what's happen to my r-salt?

quicksilver - 13-11-2006 at 07:47

What conditions was it stored under? And what were the specifics of the attempt at detonation? - In other words, if something funtions at one time and then at another time the SAME thing does not funtion, the question one asks is "what changed?" This is the way computer code is debugged & the same methodolgy works for a variety of issues.

SAM4CH - 13-11-2006 at 12:29

it kept in empty aerosol can "semi tight", and about detonation there is no sign for explosion of r-salt and I am sure because I could see the traces of powder and the explosion sound was weak!!?
Note: I kept it as a block "I melt it before"...

Kray - 30-11-2006 at 05:40

How I know need make all reaction by all rules if you want to make r-salt.Whats was the temperature when you was making it?

DeAdFX - 28-12-2006 at 20:25

Quote:
Originally posted by Mumbles
I've tried it and gotten shit for results. I keep the temp low, but it started bubbling. It's definatly not ammonia, or formaldehyde or HCl. It's hard to explain. It smells kinda like warm bread if that makes any sense.

After maybe 45 minutes this foamy stuff on top forms. I think this is the R-salt. I let it react for the time recomended by Mr. Cool, and by morning the foam was all but just about gone. I don't like it. I would be willing to try if I found a better method.


Hmm I got the same results[shit] as you but I only let my stuff settle for 6 hours instead.


Probable reasons for shit yeild. I was only able to keep the temp between 10-15C through most of the synthesis[getting as high as 17-20C. The thermometer was difficult to read as the foam was blocking the #'s. I also waited to damn long to purify the "product". As mentioned in this .pdf http://www.sciencemadness.org/talk/viewthread.php?action=att... it says that you should only let the product react for 20 minutes to get the greatest yeild. Does this mean the moment you add the acid or the moment you are done adding the acid?

Hmm its a little difficult to maintain the temperature @0C than I though. I guess I could use more ice, cool down the Nitrous acid before addition, or slow down the acid addition[nitrous to hex/hcl]. I guess these are the only easy ways to maintain the temperature?. .


Stupid question but since I failed in the synthesis.... Are the CTMTNA crystals suppose to perciptate[95% of them] within the first 10 minutes with the other 5% in the next 10 minutes? Or is your product the foam shit because looking at Axt's pictures my foam is yellow and his product is yellow?

SAM4CH - 4-5-2007 at 14:04

I need a perfect procedure for oxidation of r-salt to RDX using AN/H2SO4 or H2O2 or hypochlorite!!!

quicksilver - 1-10-2007 at 11:21

In an attempt to re-energize discussions on energetic materials here I was wondering anyone continued any of the experiments dealing with R-SALT and reached any conclusions outside of the quoted material re:
*R-SALT as a "gateway" to RDX synth,
*R-SALT yields (influences) and conclusive stats on R-SALT - it's VoD & uses in industry or the military......anyone(?)

[Edited on 1-10-2007 by quicksilver]

The WiZard is In - 1-5-2010 at 08:17

Quote: Originally posted by PerFecTioNisT  
I.m intresting about this HE, and maybe there are people who did this explosive by this recept?



I have eye-balled this in the obvious books. The Book sez —

It do be/can be made from formaldehyde, ammonium hydroxide, and sodium nitrate.

Köhler and Meyer note that ... although easily prepared and
powerful, the explosive has not been used in practice owing
to its limited chemical and thermal stability.

They note the hexa. / alkali metal nitrite / dilute acid method
of synthesis.

PATR2700 C630-31

It was Bachman & Deno who discovered that the chief factor
that determines the nature of the product is the pH of the soln.

WE Bachmann & NC Deno, The Nitrosation of Hexamethylenetetamine
and Related Compounds, JACS 73, 2777-79 (1951).

quicksilver - 1-5-2010 at 09:36

Quote: Originally posted by The WiZard is In  


PATR :D



Wooo... you hit an old thread; cool.

I hit the PATR first thing.
I did find some material from a text written in German (don't have it near this station) at or around the time of the War.

They experimented with it but dropped it as it had a low shelf life (needed seriously strict conditions to maintain itself) & reacted poorly to compaction & or a eutectic w/ what little TNT was available at the time of writing. The idea was to stretch the TNT supply as well as heighten it's brisency. It made more sense to adulterate the TNT with ammonium nitrate rather than R-Salt and most likely the heat (even as low as 80 C) disagreed with it's (R-Salt's) longevity.

Back some years ago when I really did look into this; mostly it was European material that had any info. The important elements to the synthesis are temperature control (cold) and maintaining ph. It's a easy lab but it's a curiosity as a practical expls. it's not really appropriate.


edit:
Bachman was a real RDX fan. Much of his professional published stuff was RDX this and that. Most likely, the REALLY interesting stuff he did is still tough to get due to the nature of government patent disclosures.



[Edited on 1-5-2010 by quicksilver]

The WiZard is In - 1-5-2010 at 10:04

Quote: Originally posted by quicksilver  

They experimented with it but dropped it as it had a low shelf life (needed seriously strict conditions to maintain itself) & reacted poorly to compaction & or a eutectic w/ what little TNT was available at the time of writing. The idea was to stretch the TNT supply as well as heighten it's brisency. It made more sense to adulterate the TNT with ammonium nitrate rather than R-Salt and most likely the heat (even as low as 80 C) disagreed with it's (R-Salt's) longevity.



The Book sez

Eutectic Composition With TNT
42% Cyclo....
58% TNT

Rate of detonation 7 000 m/sec

hiperion42 - 4-5-2010 at 07:05

necromantic :(

gnitseretni - 20-5-2010 at 12:12

Just re-read the whole thread and noticed there was no mention of recrystallization. Is it just not necessary or is there a different reason?

quicksilver - 20-5-2010 at 13:20

Quote: Originally posted by gnitseretni  
Just re-read the whole thread and noticed there was no mention of recrystallization. Is it just not necessary or is there a different reason?


I think that's a very good question. In literature (especially from Germany) there had been no specific mention of re-crystallization. It may be that R-Salt is a delicate material & recrystallization may not be the best idea from a stability stand-point. It apparently does not have a great shelf-life in any event (narrow temp sensitivity). The solvent may be too expensive to make that an industrialist effort worth the money (Ethel Acetate was mentioned). But I see no reason why a less expensive material couldn't be used. Lab-grade acetone is NOT what is bought at hardware stores and the impurities associated with less expensive materials may be the real reason. R-Salt was an effort to save money.

gnitseretni - 20-5-2010 at 15:31

I can't find any useful information on R-salt, let alone anything on recrystallization :(
I suspect the low yield is to blame.

gnitseretni - 22-5-2010 at 09:10

Made some R-salt. Used the same amounts Axt did but yield was (as usual) crappy. Only a measly 5 grams :(

I took a teaspoon R-salt and dissolved it in 10ml denatured alcohol. It dissolved easily. Then I added it to an ounce of cold water. Nothing happened. I thought maybe I didn't have enough water so I doubled the amount of water... still nothing. Then 250ml water... STILL NOTHING!! What the hell!
I thought adding more water would probably be a waste of time so I flushed it down the drain. Then I tried it with methanol(HEET). Same thing.. nothing!!
Then before I got a chance to try it with MEK, a windgust came and blew the rest of my R-salt all over the lawn :o And I was like.. F U then.. I don't like R-salt anyway :P No really.. I won't make this shit again, I had enough of the crappy yields.




RDX easy synthesis

Anders2 - 17-9-2010 at 13:28

I wonder if H2O2 can oxidize this nitrosamine to the nitramine, potentially forming RDX?

I read in the literature that nitrosobenzene can be oxidized to the nitro by bubbling in NO2, so presumablym adding a small ammount of nitrate salt to the nitrite used in the reaction for making CTMTNA, would allow formation of RDX, not CTMTNA. Since HNO2 + HNO3 <--> 2NO2 + H2O

Rosco Bodine - 17-9-2010 at 21:25

No, there won't be any "RDX easy synthesis" via the method you are proposing.
IIRC there is a conversion of R-salt to RDX possible using H2O2 and high concentration HNO3, but the overall yield is inferior from the same starting materials to the conventional nitrolysis of hexamine dinitrate using highly concentrated HNO3, so the economics are unfavorable for the R-salt route.

quicksilver - 18-9-2010 at 08:40

Absolutely. One of the simplest direct nitration is in use in a plant in the mid-west US (the USA's largest) & in fact does use hexamine di-nitrate. It's a straight nitration and has been in operation for decades. So the likelihood of another technique superseding it is very unlikely.
This has been demonstrated as an entrenched production method in industry magazines and even television shows like Discovery because in the final analysis the cost factor is really only the higher percentage acid.

AndersHoveland - 21-9-2011 at 22:04

Quote: Originally posted by Anders2  
I wonder if H2O2 can oxidize this nitrosamine to the nitramine, potentially forming RDX?

I read in the literature that nitrosobenzene can be oxidized to the nitro by bubbling in NO2


Although nitroso groups can usually be easily oxidized, oxidizing nitrosamines (where the -NO group is connected to a nitrogen atom) is much more difficult. Plain H2O2 is unable to oxidize nitrosamines, such as CTMTNA.

For oxidizing CTMTNA into RDX:

Peroxytrifluoroacetic Acid. I. The Oxidation of Nitrosamines to Nitramines
William D. Emmons. J. Am. Chem. Soc., 1954, 76 (13), pp 3468–3470 (1954)

Peroxytrifluoroacetic does not seem to oxidize organic chlorides,
"Anhydrous solutions of peroxytrifluoroacetic acid in methylene chloride can be prepared..."

however, peroxytrifluoroacetic has been shown to oxidize off tert-butyl groups, but not methyl or ethyl groups,
"The trifluoroacetic acid-mediated removal of t-butyl groups in protected amino acids leads to the formation of t-butyl trifluoroacetate"

Peroxytrifluoroacetic acid can be prepared by reacting 90% H2O2 with pure trifluoroacetic acid.


Other possible methods of oxidation

Peroxytrifluoroacetic acid is also mentioned in the literature as being used to oxidize pyridine to pyridine N-oxide. Oxidizing pyridine in this way must be very difficult, otherwise such an obscure regent would not have to be used. Any other regent that is capable of oxidizing pyridine to its N-oxide also probably has a high likelihood of being able to oxidise nitrosamines to nitramines.

So here is a list of the other methods that can be used to selectively oxidize pyridine:

Titanium "zeolite" catalyst
Selective mono N-oxidation of substituted pyrazines in good yields using 30% dilute H2O2 as an oxidant with a specially prepared titanium silicate catalyst is possible.
Preparation of the Catalyst:
Add a solution of titanium peroxide to ethyl silicate (with or without an organic solvent) to obtain a gel. Hydrolyze the homogeneous gel previously obtained, by adding an organic base to the gel. The ammount of organic base should be only 6-15% of the ammount of silica gel. Next, add deionised water after the yellowish-white color of the gel begins to turn into a greenish-white color. Stir the greenish-white gel for about 1 hour, then heat the gel in a pressure cooker at 100 -110 C. The gel must be constantly heated in this way for at least 20 hours. Further heating, up to 2 days, is preferable. This will result in a solid composite product. Separate out the resultant solid composite material, dry, and bake at a 350-500C temperature to obtain the final product. This is a catalyst and so only a small quantity need be prepared. The organic base should be an organic amine with lots of bulky organic groups on it, either a tri- or tetra-alkyl amine, such as tetrapropyl ammonium hydroxide. Alternatively positively charged coated silica particles can be used instead of the ethyl silicate. These can be prepared by mixing an aqueous colloidal silica with stabilized basic aluminum acetate. The aluminum composition is stabilized with a small quantity of boric acid, which controls the hydrolysis of the aqueous solution of basic aluminum acetate.
The catalyst produced above is known as TS-1 and is basically a porous titanium silicate crystal with a structure analogous to zeolite. TS-1 is not yet commercially available. It can also catalyze the oxidation by H2O2 of imines R2C=NH into oximes R2C=NOH.


Methyl Cyanide Activation
Methyl cyanide, also known as acetonitrile, can activate the H2O2 so that it can oxidize the cyclic nitrogen atom in pyridine.
At a pH of 8 , H2O2 reacts with CH3CN to form a peroxycarboximidic acid intermediate, with the structure,
CH3C(=NH)O--OH. This is unstable and immediately oxidizes whatever reducing agent is in solution. If no reducing agent is present, acetamide will result and oxygen gas will escape from solution. Other nitriles beside methylcyanide also will work, possibly even addition of threads of acrylic fabric (synthetic wool) will work. An alkaline solution of a nitrile and H2O2 can also oxidize an alkene to an epoxide.

Using H2O2 and Acetic Acid
This method initially sounds too easy to be true. But it may be possible that this simple method has been overlooked by researchers, in favor of the much more obscure/uncommon peroxytrifluoroacetic acid.

"Oxidation of 2,6-diamino-3,5-dinitropyridine by refluxing with a 30% solution of H2O2 in acetic acid produced 2,6-diamino,3,5-dinitropyridine-N-oxide in 80% yield."

R. Hollins, L. Merwin, R Nissan, Journal of Heterocyclic Chemistry 33, p895 (1996)

H. Ritter, H. Licht. Journal of Heterocyclic Chemistry, 32, p585 (1995)

So there you have it, three different methods that are likely to be able to oxidize CTMTNA into RDX, using readily available precursors.



[Edited on 22-9-2011 by AndersHoveland]

497 - 22-9-2011 at 03:25

The old french reference talks about getting over 20g R-salt from 28g hexamine using H2SO4 and NaNO2. Did they screw up or did the recent attempts at synthesizing it screw up?

Pretty much they say to dissolve 28g hexamine in about 400ml H2O, add 45g H2SO4 (about 100ml battery acid). Then immediately begin adding a solution of 70g NaNO2 in about 250ml H2O while keeping the temperature below 10*C and stirring, over 5 minutes. Continue stirring for another 10 minutes, then filter the precipitate. Wash the the precipitate with water. Dry at room temperature to get crude R-salt. They say the R-salt is pretty stable dissolved in hot 25% acetic acid, while the dinitrosated byproduct decomposes rapidly. Also recrystallization from methanol or acetone increases stability of R-salt. 33.4g R-salt dissolves in 100ml acetone at 15*C.
Pure R-salt melts at 105*C, 5-55% dinitroso impurity melts between 105*C and 100*C. Over 60% dinitroso impurity melts above 110*C.
Can anyone confirm this literature?

quicksilver - 22-9-2011 at 13:50

The PATR mentions somethings about this. The original patent is Swedish I believe and I have no access to either the language or their patent site. Acetone appears to be "too effective" of a solvent (255% !!! when @50-60C) and it's presented to achieve a better result using methyl alcohol. -{Similar to the ETN solubility issue}-
Quoting:
Melting point on rapid heating was 110°C, close enough to documented temp of 106-7°C. The other possible product (dinitrosopentamethylenetetramine) melts at 207°C so easy to tell apart.
Optimized prep in Fedoroff:

Bachmann & Deno (Ref 6 in the PATR) added simultaneously a solution of NaNO2 in 6M HCl, at a rate required to maintain a pH of 1, to a solution of hexamethylenetetramine in ice & water. The mixture was held at 0° for 30 minutes. The yield of practically pure product was 50% (mole for mole basis).
Another issue is the foam & pH; temp of the synth must be substantially controlled as when one approaches 20C you'll end up w/ DNTP. (this appears to be a stumbling block on occasion - temp has to be ridged at or BELOW 10). dry ice & acetone IS overboard but a small amount of dry ice & glycol will last long enough to keep you from ever going past 10C

Some have insisted that it is "RDX but missing three oxygen atoms" one from each NO2 group. However PATR reference (Bachmann?) insists this is not the case and sensitivity is quite different. Was presented as a carcinogen; recently OSHA (in Apache Powder Co.) found RDX to be "high risk" for what that's worth.

Failures in synthesis also appear due to use of solid alkali nitrates instead of HNO3; apparently the acid must be used for a success. The nitrite method does appear to be appropriate from what I could find. Experiment notes show that 0C (rather than 10) have a favorable effect on diminishing foam. The foam is almost a "red flag" that the temp is too high. Also, by not "mixing the up the nitrous acid first, there is a lot more foaming and heat" (this appears significant as it appears in several labs).
I can only confirm from my notes, the PATR and past posts. The best source (IMO) is to get the original Swedish patent(s).




I have some notes here but I can't find the Pat number. However I think one date was 1938.





[Edited on 23-9-2011 by quicksilver]

497 - 25-9-2011 at 12:58

Here is the paper I was talking about.


Attachment: TMTN synth.pdf (87kB)
This file has been downloaded 1385 times

oxidizing nitrosamines to nitramines

AndersHoveland - 23-1-2012 at 13:25

Here is another route that could potentially be used to selectively oxidize R-salt to RDX,
Quote:

A modified electrode comprising a film of mixed-valent ruthenium oxides with cyano cross-links on glassy carbon mediates the oxidation of N-nitrosamines. The oxidations are two-electron processes. Using N-nitrosodi-n-propylamine as a model compound, the mechanism of the oxidation was shown to involve a coupled protonation of the oxidized form of the mediating film. Bulk-scale controlled-potential electrolysis of N-nitrosamines yielded the corresponding N-nitramine; gas chromatography—mass spectrometry did not show any evidence of side reactions.
"Oxidation of N-nitrosamines at a ruthenium-based modified electrode in aqueous solutions", Waldemar Gorski, James A. Cox, Journal Electroanalytical Chemistry (1995)
Quote:

CTMTNA, also called R-Salt, is similar to RDX. The difference is that it has NO groups insteads of NO2 groups- making it a nitrosamine. Nitrosamines are known carcinogens so it has that drawback. Toxicity aside, CTMTNA is quite a powerful explosive with a VoD of 7800 m/s at 1.57 g/cm3, relative briscancy of 1.17, and a lead block expansion of 370 cm3. It can form a low melting eutectic with RDX at a 50:50 ratio. It can also be converted into RDX using xNO3/H2SO4. One other drawback of the explosive is that the yield is low, 50% being a good yield.

One other point about this explosive is that two forms can be produced - the dintroso product and the trinitroso product. The aim here is to produce the trinitroso form. This is accomplished by performing the reaction at a pH of 1. A higher pH will result in formation of the dinitroso product.

The required materials are HCl, hexamine, and a nitrite. The literature refers to NaNO2 use, but I used KNO2 because that is what I have. The ratio I use is 1:6:4.3 of hexamine to HCl to KNO2 as this seems to provide a good yield.
For this synthesis 7 grams of hexamine in 50 ml water, 30 ml of 31.45% HCl in 50 ml water, and 18 grams of KNO2 in 30 ml water were used. The HCl solution and KNO2 solution were mixed to form a blue solution of nitrous acid.

The solutions were cooled down to < 0C and the nitrous acid was added to the hexamine solution. At first nothing happened but then after a short while the mixture began to foam up, almost over the top of the reaction vessel. The foam went down as gas escaped and about 20 minutes later it was filtered.

The product was then dried and weighed. The yield is shown here and is just above 50% of theoretical. That works out to 4.4 grams for 7 grams hexamine used.


[Edited on 23-1-2012 by AndersHoveland]

C.T.M.T.N.A. attempts

Boffis - 15-2-2012 at 18:05

Following the purification of crude hexamine by recrystallization from 30% water and 70% isopropanol and the recovery of the isopropanol by gentle vacuum distillation (to avoid possible decomposition of the remaining hexamine) a small volume of saturated aqueous hexamine solution containing a little isopropanol remained. Rather than discard it I decided to try the preparation of trimethylene trinitrosamine by reacting it with sodium nitrite and sulphuric acid as discussed earlier in this thread.

In order to determine the concentration of hexamine in the residual solution one gram of the saturated hexamine solution was accurately weighed out onto a watch glass and evaporated to dryness on a water bath. The loss of weight gave 0.785g of hexamine. So 35.85g of the hexamine solution (approx. 0.2 moles) were weighed out and diluted to 200ml with de-ionised water. Next 150ml of 4M sulphuric acid (recovered from dehydration of guanidine nitrate experiment and standardised to this strength) were diluted to 400ml. Both solutions were placed in the freezer to cool while a solution of 69g (1 mole) of sodium nitrite was dissolved in 200ml of water; this solution does not need cooling since it is self cooling.

When the hexamine solution and the sulphuric acid had reached about -5°C they were mixed together in a 2L beaker and the addition of the sodium nitrite commenced at such a rate that all of the nitrite should have been added within 10-15 minutes. Vigorous, preferably mechanical, stirring is required as the mixture froths badly as the pale yellow product separates out Fig.2. After the addition of about three quarters of the sodium nitrite the solution had become difficult to stir and so was filter at the pump. The cake was left on the filter and the remaining sodium nitrite add to the filtrate but no further precipitate formed. It appears that only about 0.75-0.8moles of sodium nitrite are required. By the end the solution had warmed up to about 40°C.

The filter cake was washed with 100ml of water and sucked dry. It was dried at 40°C for about 10 hours to give 11.52g of pale yellow fine grained curd like solid (33.1% yield) Fig.2.

A second batch was run using 41.01g of the hexamine solution diluted to 150ml and 0.7moles of sulphuric acid diluted to 300ml. The two solutions were mixed and cooled to-12°C in the freezer. Only 60g of sodium nitrite in 200ml of water cooled to the same temperature was added with vigorous stirring fairly quickly. After the addition of about half the sodium nitrite the temperature had risen to +10°C so addition was stopped and the slurry placed in the freezer for 30 minutes to bring the temperature to below zero again and the addition continued. The yield of curd like pale yellow trinitrosamine this time was 18.34g after drying or 52.7% yield.

The two crops of product were combined (29.86g) and recrystallized from 300ml of methanol. In theory 180ml is sufficient (COPAE) but in practice it is not possible to filter the solution fast enough to prevent crystallisation in the filter and increasing the vacuum causes the filtrate to boil and therefore crystallise in the decreased volume. The recrystallized product takes the form of yellow bladed crystals to 30mm long Fig.3. They were stirred to break up the larger blades before filtering, filter at the pump, washed with a little cold methanol and sucked as dry as possible and dried (recovery 23g) Fig.4.

The filtrate was used to recrystallized the product from a third and final preparation and then reduce to half its original volume in a rotary evaporator and a final small crop of crystals recovered.

Discussion
The frothing is caused by the evolution of nitrogen and formaldehyde may be detected amongst the volatile product by its pungent smell but no brown nitrogen oxides were observed. The approximate reaction appears to be;

C6H12N4 + 4HNO2 = C3H6N6O3 +3CH2O + N2 + 2H2O

Hexamine + Nitrous acid = trinitrosamine + formaldehyde + nitrogen + water

It will be noticed that the ratio of nitrous acid to hexamine is 4:1 but since formaldehyde can react with nitrous acid the actual ratio may be higher. It appears from the experiments above that lower temperatures limit the side reactions and reduce the side reactions; however, the yields at the lower temperature were still only a little over 50%. It may be possible to improve things further by using crush ice from the deep freeze at about -20°C directly into the reaction mixture to provide more efficient cooling. Reducing the volume of solution and decreasing the nitrite added to something closer to the ideal 4:1 ratio does not appear to reduce the yield significantly. Temperature seems to be the main factor affecting yield in acid conditions.

How the hell do you get the pictures where you want them? Anyway the photos are the frothing mixture after adding half the nitrite. Second row left crude product; right, recrystalling from methanol. Bottom, Final product.

Trimethylene trinitrosamine end of addition.jpg - 58kB

[Edited on 16-2-2012 by Boffis]

Trimethylene trinitrosamine crude prod.jpg - 68kB Trimethylene trinitrosamine crystallising.jpg - 58kB

[Edited on 16-2-2012 by Boffis]

Trimethylene trinitrosamine fin prod.jpg - 69kB

[Edited on 16-2-2012 by Boffis]

[Edited on 16-2-2012 by Boffis]

[Edited on 16-2-2012 by Boffis]

quicksilver - 16-2-2012 at 09:24

Cute looking crystals! nice post.

You can only put your pics in order when you have all of the "Brows buttons" (sp?) out for the number of pics you have. So if you have 4: start by making 4 brows buttons in a Post Reply response, number the pics and place them in order you want. The reason I say number them is that I THINK that the sideways displays might occur from a naming convention in the software.

Ral123 - 18-2-2012 at 00:01

Quote: Originally posted by Axt  
Quote:
Originally posted by Rosco Bodine <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=3033">here</a>
Also hexamine or hexamine dinitrate or even HMTD could form R-salt or a similar derivative . (from NOx)


I'd previously tried to get R-salt by bubbling N2O3 through 20g hexamine, 100ml 32% HCl and 150ml water, cooled to 5°C. A precipitate did seem to form (solution turned white/turbid) but temperature gets out of control and solution fumed off as you get if r-salt is added to hot acid (its not stable in acid solution, far worse if its hot). If one was going to attempt this you will need to use a slurry of crushed ice, external cooling wont work.

Anyway, heres conventional r-salt through NaNO2/HCl/hexamine. Three solutions were made, one containing 60g 35% HCl in 100ml water, one containing 40g NaNO2 in 80ml water and one containing 20g hexamine and 60g HCl in 100ml water. The NaNO2/HCl solutions are combined, producing blue solution of nitrous acid. This is then added to the hexamine/HCl <0°C. The foam filtered off, dried. Yield was just over 50% right on the documented yield. Melting point on rapid heating was 110°C, close enough to documented temp of 106-7°C. The other possible product (dinitrosopentamethylenetetramine) melts at 207°C so easy to tell apart.

By not mixing the up the nitrous acid first, theres a lot more foaming and heating and often I end up with nothing at all.

R-salt burns easily with soft orange flame leaving residue, with noise but not as vigourously as RDX. Ive never tried to detonate it.

<center><img src="http://www.sciencemadness.org/scipics/axt/rsalts.jpg"></center>

^ I dont think all of the pics above are from the same batch.


I just got some nitrite and I tried this. First attempt-I added the HCl solution to the nitrite slowly for about two hours at temp near 0 degree. The NO2 was quite a lot but for 40g nitrite I guess it wasn't big loss. Then cooled it and added cooled hexamine/HCl. I got little foam and let it over night. The other day I could recover barely a gram. I didn't burn well and was leaving carbon residue.
Second attempt-the HCl and the nitrite was cooled to atleast -5 or -10. Still NO2. Cooled again and added the hexamine solution(also like -5). Very little foam that disappeared within like half and hour. Is there a noob proof way, with these yields even RDX seems somewhat cheap :D

Rosco Bodine - 18-2-2012 at 01:13

It has been six years, (link) http://www.sciencemadness.org/talk/viewthread.php?tid=3033&a... since I really thought about even in passing but had wondered if there may be a reaction between R-salt dissolved in methanol and trimeric acetone peroxide. Seeing the pictures by Boffis of the R-salt in methanol ....hmmmm I was thinking about this again, wondering if maybe a peripheral experiment could be done to see if a transnitrosation reaction or other reaction occurs between AP and R-salt. It would be good to know of any potential compatability / reactivity issues.

Adas - 18-2-2012 at 01:46

Reaction between TATP and R-Salt? Wow... You must consider that TATP is pretty chemically stable. I don't think any reaction will occur at all.

Rosco Bodine - 18-2-2012 at 01:58

Do you know?

Adas - 18-2-2012 at 02:09

I don't know, I am just wondering.

Rosco Bodine - 18-2-2012 at 02:16

Then that's two of us. Hey Boffis, while you're in the neighborhood :D MEKP is another potential transnitrosation
possibility.

[Edited on 18-2-2012 by Rosco Bodine]

Farnsworth - 21-1-2013 at 23:45

I apologize for the thread necromancy, but I have a relevant question.

According to

ENGINEERING DESIGN
HANDBOOK
EXPLOSIVES SERIES
PROPERTIES OF EXPLOSIVES
OF MILITARY INTEREST

R-Salts has a negative oxygen balance of 55%. Could it be combined with TNT in a manner similar to Comp. B, but adding AN to balance it better? Barring any unpleasant reactions it sounds like R-Salts could be used to greatly boost the effective power of an AN-heavy Amatol composition in something like a 50-30-20 composition of AN, TNT, and R-Salts respectively.

caterpillar - 22-1-2013 at 00:32

I wrote about unsuspected reactions at this forum. Never mix R-salt with AN!!! Trace amounts of nitric acid, presenting in AN will react with R-salt. Violence reaction began after some days since I made mixture of R-salt and AN. I thought about negative oxygen balance too. But at the first I noticed, that aforementioned mixture burns very fast, compared with another mixtures of AN with reducing agents. I did not suspect that something is wrong with that mixture and leaved 50-60 gr to stay at room temperature. As I said, violence reaction suddenly began. There was no flame, but clouds of gray smoke. Process continued no more than 1-2 seconds. Plastic vessel, where that mix was stored, had been melted. Fortunately, I was alone at my home and had enough time to remove all results of this incident before my parents went back to home.

Farnsworth - 22-1-2013 at 21:50

Interesting.... And this is why we ask questions before we go mixing chemicals together! ;)

May I ask if there is any known negative reaction with straight TNT (assuming the TNT has been very carefully washed and neutralized to eliminate that nitric acid residue)?

What I'm getting at is I wonder if R-Salts could replace RDX in a Comp. B type explosive. It would certainly be interesting if it can.

caterpillar - 23-1-2013 at 03:06

I do not know. Most likely, neutral compound like TNT will not react with R-salt at all. But I rather doubt, if such mix will have any valuable property.

Ral123 - 24-1-2013 at 06:25

From where do you plan getting TNT? You can surely make some mixed isomers of some nitroaromatics, it may be detonatable, but how do you plan separating isomers, lower nitration products? I made attempt to make TNT and I got something witch really looked like it. I mixed it with ETN and it still didn't go off with azide+etn/egdn. Also how is it possible to get decent yields of ctmtna? To me it's more expensive then RDX.

Motherload - 30-1-2013 at 07:19

It may seem more expensive but ... The OTCness of it is almost universal.
R-Salt
Hexamine - Cheap
NaNO2 - Cheap
HCl - Cheap

RDX
Hexamine - Cheap
WFNA - almost impossible to buy or stupid expensive or make your own.
Your still at about 60% yield
Add NH4NO3 (questionable availability) and AcAn (Forbidin) then you may get up to 80% yield.

R-Salt is pretty awesome. And the carcinogenicity .... I don't generally eat and snort my explosives and the usual gear ... Gloves, mask and glasses will protect me from the rest.

VladimirLem - 30-1-2013 at 09:19

Quote: Originally posted by Motherload  
It may seem more expensive but ... The OTCness of it is almost universal.
R-Salt
Hexamine - Cheap
NaNO2 - Cheap
HCl - Cheap

RDX
Hexamine - Cheap
WFNA - almost impossible to buy or stupid expensive or make your own.
Your still at about 60% yield
Add NH4NO3 (questionable availability) and AcAn (Forbidin) then you may get up to 80% yield.



yeah, that it :)

is there any good syn for making RDX from R-Salt?
I've read some syn making RDX with AN/H2SO4...BUT...RDX and H2SO4? the fuck?:o

Better for me would be a straight nitration with HOKO-YFNA...does that work?

Ral123 - 30-1-2013 at 10:36

RDX is so straight forward. H2SO4+nitrate salt. Distil that and nitrate your HDN. I did it with aluminium tube. The product RDX was great, yield as good as with my commercial WFNA.
I did several ctmtna attempts and my biggest batch of more then litre gave me less then two grams. However distilled water and recrystalizastion solvent are still the same price.
Can you post the synth. witch gives you decent yields?

Boffis - 30-1-2013 at 17:54

@Ral123

Read my post above; it contains details of several attempts. I can routinely get 50% yields. Just follow the details carefully!

...and you too can get 50% yields.

VladimirLem - 31-1-2013 at 10:06

hi

i have s short question about the syn of R-Salt/RDX


when nitration hexamine straight to rdx or if you make R-salt there are much Syn where there is more hexamine used than the final RDX/R-Salt is in wheight

im no chemical pro (obvisiously^^) but...if you nitrate some stuff (in this case hexamine) the ONO2/NO2 (are bound at the hexamine) so if you know that you have a Syn where you will get under good conditions 50g final produkt RDX, the WHY mixing, lets say 60 g in it...is seems (for me) just to delute the reaktion...letzs say 40g Hexamine will get full nitrated and the other stuff only to Di-Nitrate (shit) so why dont use just 45-50g Haxamine and get a fullnitration at the whole stuff and get 55g-60g final produkt...

does anyone knwo why?

Motherload - 31-1-2013 at 10:58

It's because nitrolysis of Hexamine to RDX isn't the only reaction taking place.
There are other side reactions occuring that use up reactants.

Farnsworth - 6-2-2013 at 21:44

So what would be the most useful means of binding R-salts in a useful form?

I'd make an educated guess at something like combining it with 5-10PBW of paraffin wax and pressing it into a small pellet?

With the acid reactivity issue and poor oxygen balance, it would seem the actual applications for the material would be somewhat limited.

Ral123 - 7-2-2013 at 01:36

I think you plasticise it with inerts, you would need like a half a kilo for reliable initiation by a booster. Someone have any idea of it's sensitivity?
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