Sciencemadness Discussion Board - Trying for Keto-RDX

I dont want HDN cause of its toxicity

Then tell me what are you doing messing with N-N bonds?

DubaiAmateurRocketry - 8-1-2014 at 06:57

multi nitrogen bonds or compounds does not really mean toxic though, 5-Amino-Tetrazole have 4 nitrogen bonded together however its much much less toxic than Sodium azide.

underground - 8-1-2014 at 08:09

It is impossible to use just hexamine in case of HDN ?

Motherload - 8-1-2014 at 16:32

Using HDN has a few advantages.
Better yield, the exotherm is comparatively less and less WFNA will be required.
Do you know how toxic K6 is ?

Yes it is possible to use just Hexamine.

http://www.energetic-materials.org.cn/hnclen/ch/reader/creat...

[Edited on 9-1-2014 by Motherload]

underground - 8-1-2014 at 16:42

Using HDN has
Do you how toxic K6 is ?

I have to idea!! i guess it is not such, like RDX....

What it is a lot ? If it is i will abandoned it....

roXefeller - 8-1-2014 at 17:23

Toxicity is varying yes, and so is the probabilities of an uptake. Working with highly toxic gases is bad cause a flare up could come on you without intention. Working with somewhat toxic solids, not so bad unless you are planning to make breakfast of it or licking it off your fingers like rib sauce. Aspirin in high doses is bad, but you don't live in fear of the medicine cabinet because you know you'll only eat one dose. Most of chemistry is toxic, which is just a sliding scale between therapeutic and nerve-gas-evil. If you want to work with interesting/practical chemicals, you may have to accept some level of risk. There is an LD50 you could look up for much of this to determine what accidental uptake is tolerable. By the way, should things go wrong (or right on some) NOx is evolved which is very bad, even though the final product of the nitration isn't so bad.

underground - 8-1-2014 at 17:35

If just k-6 toxicity should be like PETN,ETN or EGDN it is ok, but if it is like HDN and tetrazoles i will not go for that

DubaiAmateurRocketry - 9-1-2014 at 09:00

If just k-6 toxicity should be like PETN,ETN or EGDN it is ok, but if it is like HDN and tetrazoles i will not go for that

Tetrazole is only moderate toxic, is does not accumulate in your body, is quickly eliminated if ingested, unless you eat more than a handful of it. According to most MSDS on 5-Amino-1,2,3,4-tetrazole, it has only a Health hazard of level 3, which means it is similar to the water chlorine they put in the swimming pools! eg: Calcium hypochlorite.

Even if it has a level 4 hazard, such as Sodium Azide, it still have a LD:50 of around 1.5grams for a normal adult. So if you just dont eat it, and just wash your hands after handling, you will be fine. If you ingest some thought, Sodium azide will cause negative effect on your kidney according to some MSDS.

In EM, I care more about the sensitivity, because you can take care in handling, however sensitivity do not give you a chance.

[Edited on 9-1-2014 by DubaiAmateurRocketry]

VladimirLem - 9-1-2014 at 10:16

If just k-6 toxicity should be like PETN,ETN or EGDN it is ok, but if it is like HDN and tetrazoles i will not go for that

do you want to eat them?

some rubber gloves and maybe some breathing protection will work great !
especially when you know some compound is classified as "toxic" you will handle it with care...

example: pottasium cyanide is classified as "very toxic" (T+) and you need to eat around (afaik) <150mg> of it, to die...thats A LOT...

you blow shit up but act like some pussy because you feel unable to handle some (most of them aren't THAT) toxic stuff?

underground - 9-1-2014 at 12:17

I just do not want to play with those chemicals for just a hobby, it is my choice...

roXefeller - 9-1-2014 at 15:30

Lincoln logs make a nice hobby too, nontoxic. I have some I could give you. 'course you could still choke on them if you ate them.

What's the LD50 for choking?

caterpillar - 9-1-2014 at 16:40

I dont want HDN cause of its toxicity

Who said this BS? How salt of relatively harmless hexamine (it is component of some usual medicine and addiction to spawn) could be more toxic that nitric acid??? If you are afraid of the last one, you should stay far away from explosives.

underground - 10-1-2014 at 02:30

I have seen almost everywere that when any conversation come into place about HDN, the first thing it is said is about the toxicity of HDN and the care that must be taken!

underground - 10-1-2014 at 04:14

By the way, i have seen a lots of conversations about HE but nowhere any preparation of them, except the used (NG,ETN EGDN...) For example K-6 looks easy to make from an experienced chemist but nobody ever try it!!

caterpillar - 10-1-2014 at 05:49

I have seen almost everywere that when any conversation come into place about HDN, the first thing it is said is about the toxicity of HDN and the care that must be taken!

Aristotel claimed, that a fly has eight legs and this nonsense was repeated by so-called "scientists" for many years. I made HDN and pressed filtered precipitate to remove as much water as possible (later I made some RDX from it). Most likely, I used gloves. I did not eat it nor inhale it, so I cannot say, if this compound is really toxic. But i do not think so.

underground - 10-1-2014 at 06:19

Ok... when i am going to have the necessary safety equipment, i will give it a try. I will give it a try first with just hexamine to see what happens... Also i am planning to use AN in case of HNO3, i guess it will work. We will see...

Pix - 10-1-2014 at 06:22

How can ı separate hexogen from octogen ? I have just acetone as a solvent
Hexogen more soluble in acetone thus after hexogen dissolved in acetone ı filter acetone from insoluble octogen then can precipitate it ?????

caterpillar - 10-1-2014 at 13:51

Ok... when i am going to have the necessary safety equipment, i will give it a try. I will give it a try first with just hexamine to see what happens... Also i am planning to use AN in case of HNO3, i guess it will work. We will see...

According to original article, mixed acid must be strong enough to insert two nitro-groups into urea. This might be a problem. I'd like to test this method myself, but currently I have no reagents at all- only few gr of KMnO4 and half of kilo of NaHCO3 (to say nothing about NaCl). Mixed acid can be prepared, using dry Ca(NO3)2 and sulfuric acid. During reaction, CaSO4 extracts some water from acid.

Motherload - 10-1-2014 at 21:45

I don't know how well Ca(NO3)2 will react with H2SO4.
Theoretically .... React the 2 and decant/filter of WFNA leaving behind CaSO4.
You will have to completely dry and dehydrate the Ca(NO3)2 from the Di hydrate.

From what I have read from others experiences ..... It turns into a thick viscous slurry. Kinda like plaster for arm casts etc.
The above works with Ba(NO3)2

NH4NO3 is probably best for making WFNA in situ.

caterpillar - 11-1-2014 at 01:00

I don't know how well Ca(NO3)2 will react with H2SO4.
Theoretically .... React the 2 and decant/filter of WFNA leaving behind CaSO4.
You will have to completely dry and dehydrate the Ca(NO3)2 from the Di hydrate.

From what I have read from others experiences ..... It turns into a thick viscous slurry. Kinda like plaster for arm casts etc.
The above works with Ba(NO3)2

NH4NO3 is probably best for making WFNA in situ.

Ca(NO3)2 is a tetrahydrate normally. Put it onto frying pan and heat. It boils, than converts into solid mass. if you want to get WFNA in that way, you'll surely get slurry. But if you want to get mixed acid (usual mix contents 40 % of nitric acid and 60 % of sulfuric one, in this particular case 50:50) you'll get slurry at the bottom of a reaction vessel and nice transparent layer above it. Decant and go ahead. Vacuum filtering will give you more mixed acid, if you do not want to waste reagents. Warning: do not use powder of Ca(NO3)2! it must be smashed to grains, but not to dust. 3-4 mm in diameter. Reaction between them and sulfuric acid goes slowly, I usually waited for day and night. It is useful to turn reaction vessel once in an hour upside down. I do not try to say, that it is the best choice in any event. I used this method, when I wanted to make NC or NG. But for preparation of TNP KNO3 (or NaNO3) is a better choice.

caterpillar - 11-1-2014 at 01:02

underground - 11-1-2014 at 01:02

That i was thinking also, dry AN for replacement of WFNA. Just place all chemicals into the desiccator bag and let them dry for 1-2 days. Caterpillar, it would be fine to give it a try, and not only you, but anyone who can. Maybe we will achieve something wonderful right here.

Also some calculations must be done cause the mixed acid is given on mls, we have to convert the mls to grams, and replace the moles of HNO3 with a nitrate salt...

[Edited on 11-1-2014 by underground]

underground - 30-1-2014 at 09:04

By the way, the pdf file it is said a 50:50 mixed acid, i juess it is on mls, for example it is said "65 ml of mixed acid (HNO3+H2SO4, 50:50%)" so i guess the mixed acid it is going to be 32,5ml of NA and 32.5ml of SA, that is correct ?

VladimirLem - 30-1-2014 at 09:59

By the way, the pdf file it is said a 50:50 mixed acid, i juess it is on mls, for example it is said "65 ml of mixed acid (HNO3+H2SO4, 50:50%)" so i guess the mixed acid it is going to be 32,5ml of NA and 32.5ml of SA, that is correct ?

yes, im pretty sure...

underground - 30-1-2014 at 10:33

Thanks!

caterpillar - 30-1-2014 at 13:23

Negative, in such texts weight is always used, but not volume. It means 100 gr of nitric acid and 100 gr of sulfuric one.

underground - 30-1-2014 at 15:59

Quote: Originally posted by caterpillar

Negative, in such texts weight is always used, but not volume. It means 100 gr of nitric acid and 100 gr of sulfuric one.

100g H2SO4 x (1 mL / 1.84g) = 54.35 mL H2SO4

100g HNO3 x (1 mL / 1.51g) =66.23 mL HNO3

Total = 120.58 mL so surely it is not 100gr of NA and SA

I also believe that it is by volume.

[Edited on 31-1-2014 by underground]

Rosco Bodine - 31-1-2014 at 00:02

This is something that caught my notice and I posted a link 9 years ago about the dinitrourea being of interest with regards to keto RDX.
http://www.sciencemadness.org/talk/viewthread.php?tid=4729&a...

The 50/50 mix of 95% H2SO4 and 100% HNO3 was by weight proportions, to clear up any question about that.

I suspect that the mixed RDX / keto RDX product may defy separation because it may be an adduct that is formed.

This process might be adaptable to use of a nitration mixture using a nitrate with H2SO4 either fully or in part. And I think adding the urea value as urea nitrate could be useful also.

underground - 31-1-2014 at 02:40

Quote: Originally posted by Rosco Bodine

This is something that caught my notice and I posted a link 9 years ago about the dinitrourea being of interest with regards to keto RDX.
http://www.sciencemadness.org/talk/viewthread.php?tid=4729&a...

The 50/50 mix of 95% H2SO4 and 100% HNO3 was by weight proportions, to clear up any question about that.

I suspect that the mixed RDX / keto RDX product may defy separation because it may be an adduct that is formed.

This process might be adaptable to use of a nitration mixture using a nitrate with H2SO4 either fully or in part. And I think adding the urea value as urea nitrate could be useful also.

Thanks for your informations Rosco Bodine. Indeed it is by weight. I am almost sure that some nitrate salts will do the job, as long as there are plentful out there, (kno3, nano3, nh4no3) and also i believe that K-6 is the only way for an amateur chemist for something more powerfull than RDX.

Surely when i have time i will give it a try, it looks the only way road energetic material in my opinion.
The use of urea nitrate in case of urea i also believe that it will improve the yelds of dinitrourea, and also the use of HDN in case of hexamine will be also fine to improve the yields of K-6

Here is also an another pdf file according to k-6. I upload it here to have them all together

[Edited on 31-1-2014 by underground]

Attachment: Synthesis+of+Keto-RDX+and+its+Characterizations+Calculation.pdf (1.1MB)
This file has been downloaded 970 times

caterpillar - 31-1-2014 at 06:36

Most likely, nitrourea would be better. But one question still remains: how strong sulfuric acid must be. Mixed acid must be strong enough to incorporate the second nitro- group into nitrourea. I suspect, that ordinary sulfuric acid cannot do it and oleum is a must.

underground - 31-1-2014 at 08:46

Surely oleum will increase the yields of dinitrourea but it looks like it is possible just with a NA/SA mixed acid.
An 95% SA and 100% NA is described in this pdf without actually any oleum, and as you said, if you replace the urea with nitrourea it would be even better.

[Edited on 31-1-2014 by underground]

Rosco Bodine - 31-1-2014 at 09:21

This is not a new idea. This was being discussed 10 years ago at the E&W forum and initial experiments reported that using NH4NO3 plus H2SO4 failed to produce dinitrourea. Experiments with H2SO4 plus other nitrates such as the anhydrous eutectic of 65% Mg(NO3)2 / 35% KNO3 were not investigated.

DubaiAmateurRocketry - 31-1-2014 at 11:38

Surely oleum will increase the yields of dinitrourea but it looks like it is possible just with a NA/SA mixed acid.
An 95% SA and 100% NA is described in this pdf without actually any oleum, and as you said, if you replace the urea with nitrourea it would be even better.
[Edited on 31-1-2014 by underground]

NH or Urea structure could be nitrated by Ac2O/HNO3, or HCl/Ac2O/HNO3 and some could be nitrated by HNO3/P2O5

[Edited on 31-1-2014 by DubaiAmateurRocketry]

Ral123 - 31-1-2014 at 12:01

I don't know about Keto-RDX that much, but can it be an accessible for everybody cap basecharge option for example? If one doesn't even have eritrithol but has hexamine?

underground - 31-1-2014 at 15:57

Quote: Originally posted by DubaiAmateurRocketry

NH or Urea structure could be nitrated by Ac2O/HNO3, or HCl/Ac2O/HNO3 and some could be nitrated by HNO3/P2O5]

The point is to make something really good that it does not need exotic chemicals like Ac20 / P205

caterpillar - 31-1-2014 at 19:26

P2O5 is exotic? That's interesting, because I had it when I was young. No problem, a special shop with chemicals. But I think, in this particular case anhydrous Ca(NO3)2 + H2SO4 will be better. I have a solid guess, that in such mixture CaSO4 extracts some water and increases concentration of mixed acid. Yeah, there is one disadvantage- white mess of small crystals of CaSO4. But upper layer is transparent and can be decanted. I used it for preparation of NG and NC.

underground - 5-2-2014 at 09:45

What is the difference between the 1,3,5-trinitro-1,3,5-triazacyclohexane-2-one and 2-Oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (keto-RDX) ? I guess it is the same. This is because in this abstract it is said that:

"Compound XIV (1,3,5-trinitro-1,3,5-triazacyclohexane-2-one), a powerful explosive, is stable under normal conditions but decomposes to 1,3,5-trinitro-1,3,5-triazapentane in dioxane and to methylene dinitramine salts in an aqueous medium upon contact with moisture, amines, bases, alkalis, metals, etc."

[Edited on 5-2-2014 by underground]

[Edited on 5-2-2014 by underground]

SM2 - 6-2-2014 at 08:37

I just do not want to play with those chemicals for just a hobby, it is my choice...

KCN's like KOH or NaOH. It's like lye. A little wetness (many cyanides are quite hydroscopic) and it will burn your skin like lye does. I'd think that it's horribly corrosive tissue effect is enough to command respect. Oh yeah, and don't dump a ton of it into an acidified toilet, close the bathroom door, turn off the fan, and sit on the throne, inhaling that remotely pleasant prussate smell - bad imitation of benzaldehyde smell.

Avoid - I said - AVOID the grape Kool-Aid at ALL costs.

underground - 9-3-2014 at 15:49

I can not understand exactly the procedure is described on this page about K-6 but it looks like it can be formed from nitroguanidine. So i was wondering if we can replace the urea with nitroguanidine from traditional K-6 proccess (with 50:50 ratio mixed acid) to form K-6 is going to work, as long as nitroguanidine is much more easier to form than nitrourea , and more stable also.

Motherload - 12-3-2014 at 21:20

The NTNHT intermediate itself in the above proposed reaction looks quite energetic.
I can't name it properly ... Google yielded nothing.
Anyone know it's proper name ?

underground - 14-3-2014 at 05:51

The NTNHT intermediate itself in the above proposed reaction looks quite energetic.
I can't name it properly ... Google yielded nothing.
Anyone know it's proper name ?

I found some info about NIHT.HCL
Go to page 71 at this file

NIHT.HCL may will be something useful for making some EM like K-6

I believe that replacing the hexamine with NIHT.HCL from RDX process with fuming nitric acid, it is going to form pure K-6

Attachment: NIHT.HCL.zip (259kB)
This file has been downloaded 645 times

[Edited on 15-3-2014 by underground]

Metacelsus - 14-3-2014 at 13:50

What is the difference between the 1,3,5-trinitro-1,3,5-triazacyclohexane-2-one and 2-Oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (keto-RDX) ?

None. They are just named differently.

underground - 17-3-2014 at 01:07

Will urea nitrate or nitrourea is going to react with hexamine with the presence of HCL, as nitroguanidine do ? Then, what this reaction is going to form ?

Is it possible to form something like that ?

[Edited on 17-3-2014 by underground]

1.jpg - 2kB

PHILOU Zrealone - 18-3-2014 at 02:29

Will urea nitrate or nitrourea is going to react with hexamine with the presence of HCL, as nitroguanidine do ? Then, what this reaction is going to form ?

Is it possible to form something like that ?

[Edited on 17-3-2014 by underground]

It needs to be tested, but while nitroguanidine is relatively stable towards hydrolysis as its dervivatives NIHT.HCl; the nitrourea and its putative derivative will be more prompt to hydrolysis... So you will probably get ring opening, decarboxylation to get O2N-NH-CH2-NH-CH2-NH2 wich should be unstable in HCl and the final product would then be hexamine dihydrochloride and depending on the condition methylamine, dimethylamine, trimethylamine hydrochloride and NH4Cl.

underground - 18-3-2014 at 08:05

So that it is why they use nitroguanidine and not nitrourea.
PHILOU Zrealone will just H2SO4/Nitrate salt (like dry AN) will yeld k-6 from nitrated NIHT.HCl or not?

Edit: Also K-6 is stable towards hydrolysis, as long as it also contains an urea group, or it is not ?

[Edited on 18-3-2014 by underground]

PHILOU Zrealone - 18-3-2014 at 11:57

Yep that is the reason why.
But in your scheme it is shown that 3 arrows uses Ac2O/HNO3 to give 2 different products...there must be different conditions and NNHT should also lead to NTNHT with Ac2O/HNO3.

I honestly don't know if NIHT.HCl and H2SO4/NH4NO3 will lead to k-6.

You last question is funny because a few post ago you wrote:
"Compound XIV (1,3,5-trinitro-1,3,5-triazacyclohexane-2-one), a powerful explosive, is stable under normal conditions but decomposes to 1,3,5-trinitro-1,3,5-triazapentane in dioxane and to methylene dinitramine salts in an aqueous medium upon contact with moisture, amines, bases, alkalis, metals, etc."
And this sentence fully reply to your question... moisture and aqueous imply water ... so k-6 is sensitive to water, bases and acids.

[Edited on 18-3-2014 by PHILOU Zrealone]

underground - 18-3-2014 at 13:06

This is because of my poor english.
So, the tendency to hydrolyzed really does not sounds good...

NTNHT looks more promising for many reasons (as Motherload said), but i can not found nothing about its properties and its manufacture process

PHILOU Zrealone - 19-3-2014 at 04:18

Hydrolysis is not always fast or critical; there are many hydrolysable compounds that are isolable and storable.
You simply have to wash-dry (with a volatile solvent - or with a sequence of volatile solvents that is/are unreactive towards your compound) them as fast as possible and avoid prolongated contact with the air or water. K-6 should be handlable and not so fast at hydrolysis if stored well.

Heat and pH are wel critical for such sensitive compounds during the solvent and water removal ... so better cool and at reduced pressure than warm and at atmospheric pressure.

NTNHT should be hydrolysable by water traces because it is a derivative of the putative very unstable N,N',N"-trinitroguanidine ... in their scheme they imply it turns into K-6 by splitting off the nitroimino moeity and replacement by an oxygen atom...this means:
O2N-N=C(Ring) + H2O --> O=C(Ring) + H2N-NO2 (nitramide)
H2N-NO2 --> H2O + N2O (*)

So traces of water will be reformed autocatalytically and traces of water will remain in a stationary state of concentration (one molecule of water is used and one is formed).

(*)H2N-NO2 also forms NH3, HNO3, HNO2, NH2OH, NxOy when in contact with water.

underground - 19-3-2014 at 10:29

Hydrolysis is not always fast or critical; there are many hydrolysable compounds that are isolable and storable.
You simply have to wash-dry (with a volatile solvent - or with a sequence of volatile solvents that is/are unreactive towards your compound) them as fast as possible and avoid prolongated contact with the air or water. K-6 should be handlable and not so fast at hydrolysis if stored well.

Heat and pH are wel critical for such sensitive compounds during the solvent and water removal ... so better cool and at reduced pressure than warm and at atmospheric pressure.

NTNHT should be hydrolysable by water traces because it is a derivative of the putative very unstable N,N',N"-trinitroguanidine ... in their scheme they imply it turns into K-6 by splitting off the nitroimino moeity and replacement by an oxygen atom...this means:
O2N-N=C(Ring) + H2O --> O=C(Ring) + H2N-NO2 (nitramide)
H2N-NO2 --> H2O + N2O (*)

So traces of water will be reformed autocatalytically and traces of water will remain in a stationary state of concentration (one molecule of water is used and one is formed).

(*)H2N-NO2 also forms NH3, HNO3, HNO2, NH2OH, NxOy when in contact with water.

I understand PHILOU Zrealone, thanks a lot for your precious help, i really appreciate that

underground - 23-3-2014 at 16:24

I was wondering, how H2SO4 can be used to make k-6, as long as H2SO4 destroy RDX and i guess it will do the same with K-6. Except that, also RDX participates through this process!

underground - 24-3-2014 at 04:19

Today i tried to make some k-6 but in case of urea, i used the same moles of UN, and in case of HNO3, i used the same moles of H2SO4/NH4NO3 and then i just follow the procedure according to the pdf.

I used 18.4gr of UN, 60gr H2SO4, for HNO3 i used 93.4gr H2SO4 and 76.67gr of dry NH4NO3 (total H2SO4=153.4gr) and 10.4 gr of Hexamine.

I mix 153.4gr of H2SO4 and 76.67gr of AN and let it to cool into an ice/water bath. When all of AN was dissolved i slowly add 18.4gr of UN and i let it at about 30minutes with addition stirring every 5 minutes. I then add the Hexamine and let it for more 30minutes with addition stirring every 5 minutes also.
I then just drop the mixture into 750ml of water and i saw something like it was going to form, but unfortunately i did not take nothing

[Edited on 24-3-2014 by underground]

VladimirLem - 24-3-2014 at 10:04

I then just drop the mixture into 750ml of water and i saw something like it was going to form, but unfortunately i did not take nothing

[Edited on 24-3-2014 by underground]

hi

i dont have much knowledge of chemestry, but i guess H2SO4+nitrate salt is too weak...this isnt crappy ETN...it seems to be too "exotic"/complex to be made with nitrate salts...i know this sounds weird, but the more powerful the most explosives are, the more you need high purity/dry chems (oleum, acetic anhydride, P2O5)

if you have a destillery, go for pure HNO3 and try the way of the pdf....im interested in that syn too

underground - 24-3-2014 at 10:53

Quote: Originally posted by VladimirLem

VladimirLem i do not have destillery, that is why i used this method.

caterpillar - 25-3-2014 at 03:47

What is the problem with distillator? Conc nitric acid do not react with steel. You may make distillator, using simple coffee pot. On the other hand, you can do without it, using nitrate salt + sulfuric acid. This mixture is more powerful nitrating agent, than usual mixed acid. I'm not sure about AN + H2SO4, but KNO3 or NaNO3 + H2SO4 works good. And you may use Ca(NO3)2- this salt has two advantages. CaSO4 is quite insoluble, therefore after reaction you'll get mixed acid. And most likely CaSO4 extracts some water from H2SO4 and therefore increases concentration of mixed acid.

underground - 25-3-2014 at 08:11

Why not AN ? There is not much difference between AN and KNO3 or AN and NANO3.

hissingnoise - 25-3-2014 at 08:27

Quote:

I mix 153.4gr of H2SO4 and 76.67gr of AN and let it to cool into an ice/water bath. When all of AN was dissolved i slowly add 18.4gr of UN and i let it at about 30minutes with addition stirring every 5 minutes. I then add the Hexamine and let it for more 30minutes with addition stirring every 5 minutes also.
I then just drop the mixture into 750ml of water and i saw something like it was going to form, but unfortunately i did not take nothing

That's because hexamine decomposes in H₂SO₄ . . .

underground - 25-3-2014 at 09:39

Quote: Originally posted by hissingnoise

Quote:

That's because hexamine decomposes in H₂SO₄ . . .

What about this paper

hissingnoise - 25-3-2014 at 10:37

Quote:

What about this paper

OK! It should've read; "Hexamine hydrolyses in sulphuric acid soln.."
The researchers used anhydrous mixed acid which is practically beyond the reach of the chemistry hobbyist . . .

underground - 25-3-2014 at 11:18

Quote: Originally posted by hissingnoise

The researchers used anhydrous mixed acid which is practically beyond the reach of the chemistry hobbyist . . .

My H2SO4 was boiled so the max concentrations could be achieved. Also the rest chemicals was dried into a desiccator bag with CaCl. More anhydrous can not be...

fredsci93 - 23-3-2021 at 20:59

Recently I made some K6 according to that Chinese paper, I am currently looking for the write up I did, what I do remember was I used equal parts by volume sulphuric acid and yellow fuming nitric acid plus some pentoxide (~2g) to account for any excess water however the necessity of this I think is dubious and not mentioned in the paper, then I added urea over ~30 minutes limiting the temp bellow 15C,

The next step entails adding the hexamine which is ridiculously exothermic, it took ~5h and 5+ kilos of ice to keep the reaction at ~0C (always <5C) and if the hexamine was added in too large a portion it would run away and kill the entire reaction by spraying the room with the reaction. but after the reaction, I cleaned it up, dissolved it up in acetone and crashed it out (I remember using to much solvent, oops) the final powder weighed 7.36g but I could have done better (crude yield from the paper adjusted for size was 12g), I have some photos as well.

The product detonates to shock with alot of effort and won't detonate to heat, because of this I don't think it could only be RDX (I have not been able to detonate it by shock before) or be a nitrourea. If I get the chance I'll do a proper test

The whole process is pretty great for nitric acid efficiency, you get similar efficiencies to the K process (if you get the reported 12g not 7.36g) only without the high operating heat and the explosive (its a 65/35 mix of RDX/K6) is superior to even the Bachman process product (5-10% HMX?), I recommend giving it a try (the link was posted u_underground in this thread)

btw: The first photo was from an accident I had while preparing the compound, this lead to no product just filled the room with deadly gas and got me really mad, also the hexamine contained 1% paraffin as it was unpurified and the urea was fertilizer grade (both were powdered in a blender before use)

[Edited on 24-3-2021 by fredsci93]

Attachment: Synthesis+of+Keto-RDX+and+its+Characterizations+Calculation (3).pdf (1.1MB)
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[Edited on 10-11-2021 by Polverone]

Nitrosio - 13-5-2021 at 23:48

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Synthesis repeated with a much larger scale plus (some) characterisations

fredsci93 - 3-9-2021 at 01:15

I decided to repeat the procedure for K-6 now that I have some ethyl acetate for separation. The synthesis went well however before I go into detail I will preface by saying I had a mishap during this particular reaction, during the addition of urea my ice bath was not salted enough and the temp was ~-2c, this was totally inadequate for stoping runaway reaction, my reaction mix reached 10C then would not stop slowly increasing in temperature and within 10 minutes the temp had reached 19C!

Large amounts of gases were being released, at this point, I made a new salted ice bath and was able to control the temp however during this transfer a small amount of water entered the reaction, along with poor stirring this contributed to my sub-par yield (stirring was totally manual which left periods of no stirring, however during hexamine additions the stirring was nearly continuous)

to 136.5mls of Anhydrous nitric acid ~140mls of technical grade 98% sulphuric acid was added on an ice bath

The mixture should be transferred to a salted Ice bath before 40g of ethanol recrystallized urea (MUST be finely pulverized) was added in ~400mg portions making sure the temp stays far below 10c.

The mix was aged on a new salted ice bath for 30 minutes, at this point, the mix was ~-6C. 20g of recrystallized DRY hexamine (MUST be finely pulverized) was added in very small quantities keeping the temp below 0c (make sure to essentially sprinkle the hexamine to avoid runaway) with strong stirring if any hissing noise is noted STIRR AS FAST AS POSSIBLE as if the hissing can continue the mix will runaway.

At this point, I needed to transfer the mix to another salted ice bath as the cooling rate was too slow, another 20g of hexamine was added in the same manner as before.

The mix was removed from the ice bath and placed on a warm water bath to raise the temperature to 10C, (temp was maintained below 12c with the aid of an ice bath and warm water bath (17c)) this mix was stirred for 30 minutes before being dumped into 2L of roughly crushed ice.

The mix was filtered and washed first with large amounts of water then with a ~1% bicarbonate solution then with large amounts of water (no decomposition from the bicarbonate is evident) after drying over 50h or so with the aid of a 150W ceramic heater and 50W halogen heater/fan the mix weighed 30.46g (about 55% of the claimed yield)

5g of the crude substance was dissolved in ~75mls boiling acetone leaving an inert off white residue (bellow measurement thresholds, looked like ~100mg) and a solution of k-6/RDX, this solution was filtered, reduced to 50mls by a 50W halogen heater/fan, cooled to room temp and placed in the freezer for 2 hours. the crystals were collected and the solution was further reduced to ~25mls before being chilled and filtered, this was repeated again to 10mls, the combined crystals weighed 3.97g

neither the crude mix nor pure mix was particularly shock-sensitive, however, I will note the crude mix SEEMED more sensitive (very relative)

The Crude mix smokes off leaving a small amount of residue in indirect flame and ignites and burns under direct flame with some residue, when the mix was purified the burning qualities increased significantly, it burns quickly (much faster than the crude in both cases) in direct or indirect heat and leaves nearly no residue.

Solubility characteristics were recorded by dissolving ~100mg of compound in ~10mls of room temp solvent and letting sit, heating if required, a soluble compound is one that I observed to dissolve quickly at room temp, a slightly soluble compound is one which dissolved some of the compound at room temp, or at boiling temp.

The pure mixture was soluble in acetic anhydride, acetic acid, acetone, DMSO, and MEK, it was partially soluble in ethyl acetate (only the k-6 dissolves) and methanol (took a very long time and heating), the mixture was insoluble in 99% ethanol, DCM, Chloroform and water.

There will be more to come on this as I need to wait for some solvents, however, I decided to post this now since it's been a couple of weeks since the solvents were supposed to arrive and I thought some of you might find it interesting in its current form.

notes (all very speculative):
1: I decided not to use HDN for multiple reasons, one it's highly hygroscopic so most likely I would introduce some water, and two the paper uses more nitric acid per gram of product when they employ HDN, I believe this is because HDN is more likely to become RDX in the given amount of nitric acid rather than k-6 in the reaction mix as it is less susceptible to total cleavage by nitrolysis (which is required for the reaction as the reaction proceeds as follows (TOTAL ASSUMPTION AND ONLY A PARTIAL REACTION) hexamine --> Iminodimethanol derivative HO-CH2-NH-CH2-OH (with varying levels of nitration), HO-CH2-NH-CH2-OH + O2N-NH-CO-NH-NO2 + xHNO3 ---> Keto-RDX).

2: I decided not to use urea nitrate one because of the hygroscopicity and also because from all the syntheses of dinitrourea I have seen no one uses urea nitrate, I assume this is because of either solubility reasons or because the urea nitrate is merely dehydrated to mononitrourea which precipitates.

3: I used equal VOLUMES of nitric acid and sulphuric acid based on the paper on which the synthesis is based, they give molar quantities that correspond to equal volumes, NOT masses (0.63mol H2SO4 to 0.8mol nitric acid), if you use masses the reaction will likely not work well.

4: My (slightly yellow) nitric acid was obtained by dehydration and fractional distillation of azeotropic nitric acid over an equal volume of sulphuric acid, the collection was stoped once the temperature dropped slightly and I obtained roughly the amount I was expecting ~half the original volume or a 70% efficiency.

5: It is not important to use white fuming nitric acid for obvious reasons as the urea will remove the excess coloration, however, this would slightly impact yield so you might want to decolor the nitric acid before use with dry air.

6: Phosphorus pentoxide was omitted and this appeared to have no negative impact on yield and the hexamine additions seemed to be tamer this time around, along with that during the previous run with pentoxide some dinitourea precipitated before hexamine was added whereas during this run the solution before hexamine addition was clear apart from a small number of bubbles. so I would recommend against using pentoxide.

[Edited on 3-9-2021 by fredsci93]

ManyInterests - 15-12-2021 at 12:09

I'm going to making my one and only Keto-RDX synthesis in a few days and I decided to bump this thread up to report on what I'm doing (this forum is officially my lab notes!).

I will be using HDN however. I made a dessicator with sodium hydroxide to draw off the moisture. My HDN is free of acetone as far as I know, so hopefully there will be no acetone induced runaways. I will do what I always do in nitrations... freeze my beaker in a solid block of saltwater ice. I will bring my mantle outside to use it to warm up the mixture to 10C when I am done with all additions.

I plan on using as much of my ~18 grams of HDN for this. Which seems mildly more sticky after I checked it just now. What could be happening?

fredsci93 - 15-12-2021 at 13:15

HDN should be dried with an acidic/neutral desiccator like calcium nitrate/chloride, it gets sticky over time because it absorbs water very easily even when semi sealed

ManyInterests - 16-12-2021 at 14:30

OK so after talking to fredsci93. I plan on using regular hexamine for my synthesis. I measured by entire yield of fuming nitric acid and it was 65ml with a weigh of 96.92 grams at around 30C (the temp I set my room to... so room temp) which gives it a specific gravity 1.491. I could be mildly off in how much I have, but that would be in the ~0.5 ml range, so it won't affected it that much.

My nitric acid is still quite red from nitrogen dioxide contamination. So I will need to bubble it out. I have a piece of polyvinyl tubing that I cut and I will bubble it out with my tiny little 12v bubbler (it's really cute, like palm sized!)

Edit: Maybe the bubbling is not necessary. fredsci93 did note note that nitric acid loses its color after sulfuric acid is added. I remember my ETN synthesis and this is true even when dealing with the azeotropic nitric acid. When I did my first ETN synthesis there was some yellowness/redness to my acid, but after adding the sulfuric acid it all disappeared in an instant. I will mix the acids outside and in a cold water bath to deal with any exothermic reaction.

Edit2: While the paper does state that the urea was added to the mixture at a temperature of 0-5C I will not be doing that. I will add it at the coldest possible temperatures. I know I probably will lose a bit of end-product for this, but I would rather not run the risk of a runaway reaction and instead keep things as cold as possible.

Assuming I get a max yield of 28 grams of end product. How much acetone will I need to dissolve all this in?

[Edited on 16-12-2021 by ManyInterests]

[Edited on 16-12-2021 by ManyInterests]

fredsci93 - 16-12-2021 at 16:25

For the temp, I went with 0-5C, I don’t blame you for wanting to go with a lower temp, it probably wont hurt much and will avoid runaway a bit so why not.

The recrystallisation doesn’t require much acetone IIRC, just heat it to 50C and add enough acetone to dissolve most of the product (some gunk is left over) and filter the solution, as for separating K-6 from RDX, it's very difficult, I think I managed to do it based off the crystal structure of two of my batches (RDX forms rhombic crystals keto-RDX forms more rectangular crystals, the mixed batch contained both types, the separated batch contained a higher amount of rectangular crystals), however ethyl acetate actually dissolves both substances to a degree, I might have gotten a pure product since I separated my crystallisation fractions, but it's hard to tell, so if you don’t have advanced tools to analyse the crystals it's somewhat pointless to try separate them, especially since the mix is already a very powerful explosive.

[Edited on 17-12-2021 by fredsci93]

ManyInterests - 16-12-2021 at 17:12

It's good that I don't need a lot of acetone. However, I don't plan on seperating the K6 from the RDX. Keeping them together in the mixture is OK with me. I probably will end up mixing the purified result with my ETN and to plasticize both (after taking out what I need from the ETN for my blasting caps). (although I can't remember if I filtered that dissolved ETN to get rid of the one hair bit and a small bit of pebbles, but I did test the result after and it was significantly more likely to pop and melt when subject to a flame. So the recrystalization did a lot to purify my result.

It'll be a while before I get a chance to set them off. I live in a crowded city and there isn't a place nearby where I can set off a crazy loud bang without anyone noticing. Thankfully I live in a fairly large country with vast swathes of wilderness. The problem with that is finding a place to trek that is also near a parking lot that is also not a known hiking trail. Parking a car at the side of the highway over here is illegal (and very conspicuous) except in the case of an emergency. Still, it can be done.

[Edited on 17-12-2021 by ManyInterests]

fredsci93 - 16-12-2021 at 17:32

yea, that's always the bottleneck in EM, it's very hard to do det tests, oh well just have to wait for an opportunity to present itself

Microtek - 17-12-2021 at 04:15

If you are satisfied with some of your tests being just 1-2 g of explosive, you should try Liptakovs method with coarse sawdust in a large bucket. The sound is like dropping a bag of cement on the ground, or closing a door somewhat forcefully. With this method I can do small scale tests on the ground floor without my kids noticing when they are upstair. Obviously, you need a lid for the bucket, or there will be sawdust everywhere.
Where I live, a suitable grade of sawdust can be bought in pet shops for rodents to nest in.

ManyInterests - 17-12-2021 at 09:55

I have cleaning grade sawdust that is quite thick and all.

But that being said. My keto-RDX synthesis ended in a massive runaway. It was my fault. I severely underestimated just how exothermic the final addition of hexamine was and I saw my glass thermometer fly through the roof. I immediately ran back into my apartment and closed the door, watching the massive cloud of gas emit and fly away. I hope no one noticed.

I will wait a while to let everything cool down before I can see if my beaker needs retrieving. I made several mistakes.

Firstly... holy smokes was it exothermic! I should used the quantities in the paper and not double it right away. The second thing is that I needed a larger beaker. I used my 250ml beaker when a 500ml would have been more appropriate. But I did not have my 500ml beaker with me so I had to transfer it from the 250ml to my 1000ml in order to prevent an early overflow. I made another regular ice bath, but the problem is I added too much water and the 1000ml beaker just bobbed around and it made stirring hard.

My thermometer was already busted due a previous runway that burned off the numbers except for one. So I was eyeballing it all the time. I wasn't entirely sure.

I also severely underestimated the amount of foaming it would make. I wasn't sure if would subside or what. It kinda looked like the ETN synthesis I had done several times before, but this was an entirely different beast. Even freezing my beaker in a solid block of ice was insufficient to keep the temperature in sub-zero ranges. While for my ETN synthesis it never broke loose from the ice block.

That being said. I am all out of fuming nitric acid and I am done with my experiments. I will be picking this hobby up for maybe another keto-RDX and CHP synthesis, but that'll be in a year from now.

And the next time I do it it will be HALF portions, a quarter of my attempt. I was too confident and it didn't work. And in a year from now.

I feel a bit disappointed ending my experiments without a bit of RDX. But hey, my first to attempts at freebasing hydrazine didn't work out. Failures happen. I learned. Next time I will succeed.

[Edited on 17-12-2021 by ManyInterests]

[Edited on 17-12-2021 by ManyInterests]

[Edited on 17-12-2021 by ManyInterests]

ManyInterests - 17-12-2021 at 10:45

Quote: Originally posted by Microtek

If you are satisfied with some of your tests being just 1-2 g of explosive, you should try Liptakovs method with coarse sawdust in a large bucket. The sound is like dropping a bag of cement on the ground, or closing a door somewhat forcefully. With this method I can do small scale tests on the ground floor without my kids noticing when they are upstair. Obviously, you need a lid for the bucket, or there will be sawdust everywhere.
Where I live, a suitable grade of sawdust can be bought in pet shops for rodents to nest in.

Yeah that's what I also planned on doing. I have a 5 gallon bucket full of sawdust. I also got a wooden block that I plan on inserting my blasting cap in to detonate. One other thing I can do is play ultra-loud music (it can reach 120 decibels) to muffle the sound even further.

Or I might carry that bucket to a park where no one can hear and set it off there. It'll be a bang, but no one will hear it due to the muffling and the distance.

Edit: I am curious as to how far I got in my synthesis. I had added all the urea, and while I did add most of the hexamine, I had one single (very level) spoonful left of the hexamine to put in. Maybe a few grams at the most.

The consistency of the solution was extremely milky white and very frothy, almost like a milkshake. Is this is supposed to happen? If I decided to not add the remainder and just let it sit in the icebath for however long would I still have ended up with some kind of yield? Assuming the temperature stabilized and dropped?

[Edited on 17-12-2021 by ManyInterests]

[Edited on 17-12-2021 by ManyInterests]

fredsci93 - 17-12-2021 at 15:38

haha, I'm glad someone else can attest to how ridiculously exothermic the reaction is, it took me a couple try’s to get the reaction to work, I would advise getting a k-type thermocouple in a one ended glass tube for temp monitoring it helped alot with making sure the reaction wasn’t going sour, but even with a k-type thermocouple it's super hard to control, I would also suggest a smaller scale, just to feel it out a bit before stepping it up to full scale (or in my case 4x scale), but even with my experience with the reaction I got shit yields and fucked up a bunch, so I wouldn’t be to discouraged, I might actually revist the keto-RDX synth myself, just to try get a more satisfactory yeild.

Also the nitration mix after a runaway didn’t seem to have any RDX/keto-RDX when I dumped mine into water, the high temps seem to cook the keto-RDX/RDX, but there’s no harm in dumping the mix into water just to see if anythings in it

I currently have 3 vials full of 3 of my K6/RDX samples in acetone evaporating (one I think is mostly RDX, one I think is mostly K6 and one is a purified mix) I'll send pictures of the vials and the samples in their respective bags once the acetone evaporates and gives some nice large crystals

For small tests I used to use a heavily insulated chilly bin, it worked ok, not great though, I have some det caps I need to test, so i'll try get some sawdusty for that

fredsci93 - 17-12-2021 at 15:46

The reaction mix is supposed to be milky and it does tend to take up alot of volume and froth, especially if the temp it to high since DNU decomposes exponentially faster at high temps into water and laughing gas which I think is the cause of the frothing(photo attached is just after some of the hexamine has been added from my old synth)

[Edited on 17-12-2021 by fredsci93]

ManyInterests - 17-12-2021 at 17:14

It's good that I didn't see anything I shouldn't. So everything was going well until I made the mistake of dumping the last remaining bit of hexmaine.

So the next time I will know (and review these posts). I will make sure I have a 500ml beaker. so I will have enough space for the expansion... or just halve my amount of acids and hexamine and call it a day.

Quote:

Also the nitration mix after a runaway didn’t seem to have any RDX/keto-RDX when I dumped mine into water, the high temps seem to cook the keto-RDX/RDX, but there’s no harm in dumping the mix into water just to see if anythings in it

Yeah but not with this runaway that I had! I noticed that the tempt went from what I assumed to be 15C to 50 C and it started to turn yellow and bubble. My spidey senses said 'this is going to blow!' and I immediately let go of the entire thing and fled. There was no explosion, but the resulting gas cloud was spectacular. I am pretty certain that if I caught even the smallest whiff of that stuff I would be in serious danger. Thankfully I got away and was completely safe.

The thing burned and boiled until there was nothing left was a black residue in the bottom. I guess that's whatever was supposed to be my RDX yield.

[Edited on 18-12-2021 by ManyInterests]

fredsci93 - 17-12-2021 at 17:29

wow, that's even more intense than my runaway, after the mix spewed gas and acid all over the walls (the gas was probably mostly N2O and nitric acid vapour rather than NO2 since it was uncoloured), a small amount of yellow liquid was left over, my runaway occurred ~1/2 way though my synthesis though, so it must have not generated enough energy to boil everything off since not all the hexamine was added

what sort of burning happened, just charing or full fledged flames?

ManyInterests - 17-12-2021 at 19:22

There was massive boiling and gasses spewing out. No flames, no lasting charring (my 1000ml beaker was 100% intact. You gotta love borosilicate glass!!) but imagine something boiling but in ultra fast-motion and it goes from full to empty in a few seconds. That was one hell of an ultra dramatic runaway and my single most dramatic runaway!

I did hear something popping, I thought my beaker busted, but what actually happened was my glass thermometer was what popped. I don't mind... that glass thermometer was already destined for the trash. The first runaway I had had worn out almost all of the numbers so I had no idea what it was indicating other than zero (which was the only number to survive). I had already ordered another 0-100C glass thermometer, but what I will be doing before continuing my experiments in a year or so is order a set of -30-100C thermometers from Aliexpress. They're not that expensive. I will have plenty of spares, and the greater range will tell me just how cold it is when I am at sub-zero temperatures.

This is a pity because based on what you said how the synthesis go, I was doing mostly fine until I dumped the remaining hexamine. The next time I do this if I feel like adding anymore is risky I will just call it a day. The one thing I learned about nitrating stuff is that you can undernitrate things, but you can't overnitrate something. This is why in my ETN synthesis I always put a little less erythitol to the nitrating mix. While this does mean I need to wash the end product more thoroughly, that is a small price to pay for a safer reaction.

fredsci93 - 17-12-2021 at 20:09

Right, I find the hexamine addition my first time around was super difficult, but on my last run it was much easier and the urea step was the awful part, not sure why, probably down to cooling, or any range of other factors, the reaction is pretty unpredictable and hard to tame, some time in a month or so I'll try another few synths at the scales quoted in the paper, this time with overhead stirring because I noticed there are alot of local heating maxima during the synth which will lower the yield alot.

MineMan - 18-12-2021 at 12:17

Fred? Why not use a slushy of dry ice and isopropyl or ethanol?

fredsci93 - 18-12-2021 at 12:50

The main reason I haven’t tried dry ice/ethanol is because where I live the only place to get dry ice is a BOC gas facility an hour away, it's inconvenient for me and salted ice baths are sufficient for the reaction so long as you replenish them often. It's an interesting idea, if I'm near the dry ice facility I'll grab a bit for a test run.

MineMan - 19-12-2021 at 19:59

Quote: Originally posted by fredsci93

The main reason I haven’t tried dry ice/ethanol is because where I live the only place to get dry ice is a BOC gas facility an hour away, it's inconvenient for me and salted ice baths are sufficient for the reaction so long as you replenish them often. It's an interesting idea, if I'm near the dry ice facility I'll grab a bit for a test run.

Doooooooooooo ittttttttttttt!

fredsci93 - 19-12-2021 at 20:39

I looked a bit, I’ll probably be a very long time before I try a dry ice reaction, the smallest amounts I can seem to find are 10kg boxes for nearly 90USD, which is a very frivolous purchase for a single reaction, which is a shame, I remember only 2 years ago they used to sell by the kilo :mad:

, oh well maybe they'll start selling by the kilo again soon (could have switched during covid?) or maybe I'll get some in a package.

ManyInterests - 20-12-2021 at 07:48

I didn't think of the dry ice and alcohol... I think I can get some in my area. I'll keep that in mind the next time around.

Microtek - 21-12-2021 at 05:04

Be aware that it is not always safer to cool a reaction excessively. It is possible to essentially stop some reactions if the temp is too low. This means that when you have added all of your reactants and at some point stop the cooling, the mix will heat up naturally. Then when it gets warm enough to begin reacting, the exotherm will warm it faster and faster --> runaway.

Also, don't freeze your beaker into a block of ice. A stirred cooling bath is much more effective for removing heat, even if the temp of the bath was higher than that of the block of ice.

fredsci93 - 21-12-2021 at 18:21

that's true, dry ice could be detrimental, the ideal reaction temp during urea additions is between 5C and 0C so dry ice could very easily be detrimental for making the DNU, however the hexamine additions should be done ideally between -5C and 0C and in that case dry ice/ethanol could be useful, but even then it could also lower it to low fairly easily, definitely worth a try if anyone has good access to dry ice.

[Edited on 22-12-2021 by fredsci93]

caterpillar - 8-1-2022 at 05:44

it seems to me that urea nitrate and hexamine dinitrate would be useful- the process won't be very exothermic. And these organic salts already contain some nitric acid.

Herr Haber - 8-1-2022 at 11:35

Quote: Originally posted by fredsci93

the hexamine additions should be done ideally between -5C and 0C and in that case dry ice/ethanol could be useful, but even then it could also lower it to low fairly easily, definitely worth a try if anyone has good access to dry ice.
[Edited on 22-12-2021 by fredsci93]

You can easily maintain -5 to 0c just with ice and salt. How long depends on how much ice you have and local temperatures.
You can get gel packs that freeze at all kind of temperatures to help manage your cooling. They are also very useful in distillations (just replace)
Check the different color / temperatures and check how low your freezer will go before purchasing.
Normal freezers will go down to -16c which for me is the blue gel.
That, and good brine can really help. Water will of course freeze around the packs.
They're a good alternative, are reusable (just rinse and put back in freezer).
Oh... and dont put them in acetone

Uriel - 3-4-2022 at 09:24

Hello guys,

I just fail to produce Keto-RDX via the 2008 Chinese paper route with H2SO4/NH4NO3 way :-(

1-I mixed 50g of 98% clear H2SO4 + 31g of recrystallized NH4NO3 and putted it in the freezer.
2-Then I've added 5.25g of urea to the cold mixture, unfortunately, I guessed the tiny pearls would dissolve... But don't all of them, 20% remain in pearls...
Probably the temperature was to far below zero...
The reaction is very strange, at first, the mixture is firstly like a soft past, and in 4 secondes, become hard like hard butter ! So strange ! And endothermic furthermore ! Then I managed to hit
this bloc and back it to soften butter with lot of efforts.
3- At -20°C the precedent paste is kneaded again to bring it to very thick slurry.
4- I've added 5g of hexamine wile the mixture was more easy to stir, like a hard paste. First by 0.5grams, then, like the temperature remain to -15°C, all the 5g of hexamine remained.
5- the temperature after 40 minutes was to -2°C (in a ice bath) then, I putted it in 20°C water and stir it again during 10minutes.
6- As the temperature was near 15°C, I poored it in 500mL 5°C water.
7- Almost nothing was precipitaed, only some pearls of urea wasn't still not dissolved...
Sad experiment, but cheap !

Conclusion: even the fact that the temperatures was not exactly the same than the paper, I guess that this route H2SO4/Nitrate is not a functioning way for RDX/K-6 BUT with a really strict method, maybe... Someone could succeed. Maybe.

(for example, I reach 95% yield for ETN since 7 years with this route (1/4/10) and 80% for ETN with 1/5/12 with KNO3)

[Edited on 3-4-2022 by Uriel]

ManyInterests - 16-7-2022 at 04:09

I did more reading from the paper, especially the last part where they discuss that Keto-RDX (K6) is more sensitive than RDX. I still have a hard time following on just how sensitivity scales work. I know that RDX is an exceptionally insensitive energetic material, but Keto-RDX being more sensitive than RDX means what? I assume it means more stable than PETN (which is quite stable) and ETN (not as stable as PETN, but still very safe to handle)?

I also read on a sciencedirect article (https://www.sciencedirect.com/science/article/abs/pii/S03043...) that it is only usable in phlematized form. Would that mean just mixing a bit of melted paraffin wax in it before using it or storing it?

Quote: Originally posted by Uriel

Hello guys,

I just fail to produce Keto-RDX via the 2008 Chinese paper route with H2SO4/NH4NO3 way :-(

1-I mixed 50g of 98% clear H2SO4 + 31g of recrystallized NH4NO3 and putted it in the freezer.
2-Then I've added 5.25g of urea to the cold mixture, unfortunately, I guessed the tiny pearls would dissolve... But don't all of them, 20% remain in pearls...
Probably the temperature was to far below zero...
The reaction is very strange, at first, the mixture is firstly like a soft past, and in 4 secondes, become hard like hard butter ! So strange ! And endothermic furthermore ! Then I managed to hit
this bloc and back it to soften butter with lot of efforts.
3- At -20°C the precedent paste is kneaded again to bring it to very thick slurry.
4- I've added 5g of hexamine wile the mixture was more easy to stir, like a hard paste. First by 0.5grams, then, like the temperature remain to -15°C, all the 5g of hexamine remained.
5- the temperature after 40 minutes was to -2°C (in a ice bath) then, I putted it in 20°C water and stir it again during 10minutes.
6- As the temperature was near 15°C, I poored it in 500mL 5°C water.
7- Almost nothing was precipitaed, only some pearls of urea wasn't still not dissolved...
Sad experiment, but cheap !

Conclusion: even the fact that the temperatures was not exactly the same than the paper, I guess that this route H2SO4/Nitrate is not a functioning way for RDX/K-6 BUT with a really strict method, maybe... Someone could succeed. Maybe.

(for example, I reach 95% yield for ETN since 7 years with this route (1/4/10) and 80% for ETN with 1/5/12 with KNO3)

[Edited on 3-4-2022 by Uriel]

I don't think that is going to work. RDX is not a simple nitrated ester like ETN or nitrocellulose. You need a very high concentration of nitric acid/HNO3 in order to get RDX or K6. Like WFNA at 98%+ or more.

[Edited on 16-7-2022 by ManyInterests]

[Edited on 16-7-2022 by ManyInterests]

Herr Haber - 16-7-2022 at 13:01

Unless you intend to subject the container of your energetic material to thousands of g's then it's doubtful you'll need to phlegmatize it.

And ugh...
RDX is a simple nitrated ester ? What is the nitro group attached to ?

Please comment on the image on the following webpage:
https://www.researchgate.net/figure/Molecular-structures-of-...

ManyInterests - 16-7-2022 at 13:50

Quote: Originally posted by Herr Haber

Unless you intend to subject the container of your energetic material to thousands of g's then it's doubtful you'll need to phlegmatize it.

And ugh...
RDX is a simple nitrated ester ? What is the nitro group attached to ?

Please comment on the image on the following webpage:
https://www.researchgate.net/figure/Molecular-structures-of-...

Arrrghh! I hate these embarassing typos (I corrected it) I mean that RDX is NOT a simple ester. My apologies.

Also that's good, so I don't need to do anything special in terms of handling or storage. I will, of course, treat K6 with the same utmost respect I treat any high explosive material. Just in case the gods of chemistry frown upon me and give that specific thing I am holding the stability of azidoazide azide...

KETO RDX FAILURE Via H2SO4+AN

Hey Buddy - 9-11-2022 at 11:20

Quote: Originally posted by Uriel

I also attempted this route of preparation using H2SO4 drain cleaner and NH4NO3. AN was recrystallized from agricultural AN prills, and was in a powdered form. Initial temperature was at min -5c and rose to max 5c during duration of whole experiment. Stirring was done with an overhead stirrer w/PTFE paddle stirrer.
H2SO4/AN mix was prepared and allowed to cool for 30min, Urea was added and allowed to react for 1 hour, then hexamine was added and reacted for 2 hours.

It "felt" promising but upon crashing into dH2O and filtering I was left with nothing.

ManyInterests - 9-11-2022 at 20:58

I just want to note that I made two attempts at producing Keto-RDX and both ended up with runaways. At this point I decided I will simply go to the simple method of making simple RDX (with adding a little bit of potassium nitrate to the fuming nitric to increase possible HMX yields) I had a successful RDX yield (very small, using HDN as a starting material) and I didn't find making RDX to be any more difficult than making ETN.

Maybe one day I will try to go with a Keto-RDX synth since I now have a electronic thermometer that will not have it's graduations fade away due to the fumes.

Hey Buddy - 16-11-2022 at 21:09

I just attempted this reaction per the Iranian paper. Imagine someone grabbing an industrial fire extinguisher, then discharging it into the air but it's all NO2. --The run away complaints are no joke. It is a deceptive reaction. I had massive cooling, -10 most of the time. Had teeny weeny run away for a few seconds on first additions of hexamine, easily controllable. Moved right along. When the temp climbed, I just took a break and let it cool. No big deal. A little over half way through hexamine addition, the temp climbed closer to zero and I got over confident. I heard a fizz for about three seconds, and the beaker just had foggy white haze, and then there was no recovery.

I could barely see the thermometer through the NO2 but it looked like one of those whack-a-meters at a carnival. I will reattempt this reaction with more tact, beware: do not let the temp go anywhere near zero. I use a PID overhead stirrer with paddle for this kind of stuff, and a sodium salt/ice bath, it stirs very strongly, I would have had difficulty managing the hexamine additions without automated strong stirring. My runaway began under 0 C or perhaps right at zero. It was not above zero though.

Honestly, if you wanted to impress someone on the dangers of runaways, this is the method to use. If you thought you knew what a good runaway was like, I guarantee you this is a good one.

[Edited on 17-11-2022 by Hey Buddy]

underground - 17-11-2022 at 06:35

Hey Buddy can you also try another synthesis of keto-RDX but this time use nitroguanidine instead of nitrourea ?

[Edited on 17-11-2022 by underground]

Hey Buddy - 17-11-2022 at 12:02

Hey Buddy can you also try another synthesis of keto-RDX but this time use nitroguanidine instead of nitrourea ?

[Edited on 17-11-2022 by underground]

Sure, with fuming nitric/ sulfuric 50:50? like the K-6 iranian paper? Sure. I will try it and record it for you.

--While we are talking about modified procedures, I should mention I tried a modification of the H2SO4 method of TMTN preparation, and added a molar equivalent urea to hexamine, and it precipitated a "keto-TMTN" version that was slightly whiter than TMTN. I have learned that Nitroso compounds introduce a yellow color and as you add oxygen to the molecule, it becomes whiter and whiter. TMTN is the most yellow, keto tmtn is a little whiter, NTNT is lighter whiter than keto TMTN. Furthermore, I believe I was able to oxidize the keto TMTN to keto RDX by using a glacial acetic acid/ammonium nitrate solution over about an hour, the yield is low but this oxidation solution turns from yellow on addition of TMTN to a fizzy foam when it converts with heat, and then becomes white. Im assuming the change in color is the oxidation taking place and it takes place with heat generation, typically from room temp to ~70c in a matter of 30 seconds or a minute. I have tried the same oxidation solution on an attempt to oxidize TMTN to plain RDX and it results in a foam volcano but at the end of the volcano, the solution changes from yellow to white, the beaker I was using is too small to contain the foam volcano, but a different method or a catch bowl around the beaker would contain it all. I also experimented with nitrite and nitrate and peroxynitrite oxidation attempts, and they resulted in volcanos as well, but it was a few years back and I took no notes. I think there is a route to Keto rdx through oxidation of keto-tmtn.

Additionally regarding this chinese/iranian synth in this thread on keto-rdx preparation, I believe this preparation is too long due to the sensitivities of hexamine addition, fredsci93 reprted an addition of 5 hours. If the hexamine could be added in a timely manner without runaway, then this preparation method would be really amazing.

I think the runaway probability is sensitized by climbing temperature, but the mass of reagents is too great to prevent runaway easily by the end of hexamine additions. I think this iran/china procedure could be potentially managed and runaway probability minimized by reducing reagents by one half and simply executing the reaction twice for the same yield. I suspect the addition of hexamine being halved would speed up the entire reaction duration. Other benefits, If there was a run away, losses would halved. --The beginning of the hexamine additions go smoothly and the problems only begin beyond half-way point of hexamine addition. In the prescribed procedure, The urea is already added before hexamine even begins. So by the time the runaway problem begins, the mass of hexamine and urea have already surpassed the would-be halfway mark of a theoretical version with half reagents. Of course there could be unforeseen complications by halving the reagents, but that seems to be an acceptable risk compared to 80% probability of outrageous runaway. If it worked, you could run the procedure cut down by one half, two times back to back, maybe even in the same amount of total time as the original procedure, and if you runaway your losses are only half.

Those are my thoughts on this issue, been thinking over since last night.

Hey Buddy - 17-11-2022 at 22:53