RDX by the "N" Process...

[Mr Cool]

Here, "N" is standing for "Neglected", since I've never heard of anyone trying it, and have only seen the process mentioned twice.
I am referring to the nitration of potassium methyleneamidosulphonate by the common H2SO4/HNO3 acid mixture. Now, you might be thinking "Potassium what?", but it is easily made by condensing formaldehyde with sulphamic acid, which is easily bought as a limescale remover and can also be used to make dinitramides, as shown by Alchemist in his topic on that subject.

The reaction is outlined below:

HOSO2NH2 + KOH --> KOSO2NH2 + H2O (because zwitterionic sulphamic acid will not react as easily with formaldehyde)

KOSO2NH2 + CH2O --> KOSO2NCH2 + H2O

KOSO2NCH2 + HNO3 -(H2SO4)-> (-CH2NNO2-) + KOSO2OH

Where (-CH2NNO2-) consists of nitramine polymers, which will include HMX but also undesirable linear polymers...

So far all I've done is made, purified and dried the potassium sulphamate, and I'm about to try and react it with paraformaldehyde.
But I wanted to open up this topic to see if anyone has any info AT ALL on this process, before I blindly blunder forward...
Unless anyone suggests otherwise, the nitrating conditions used will be the same for those used when making dinitramides, but with proportionally less acid. Ie, very fucking cold.

So, does anyone know anything about this route?

[kabooom]

actually W process (W comes from wolfram the inventer)

[Mr Cool]

Ah, Wolfram! Excellent, maybe that will help my search for information. I got stuck at the first stage, forming the potassium methyleneamidosulphonate. I was expecting a ppte to form, but there was no sign of one, and I gave up until I got more information. Maybe now I will be able to find something useful...

[Mr Cool]

Thanks to Polverone for accidentally bringing espacenet.net to my attention in the censored patent thread, I've found a <a href="http://l2.espacenet.com/espacenet/viewer?PN=GB899692&CY=ch&LG=en&DB=EPD" target="_blank">Patent</a> that could be useful!
They claim 75% yield, which isn't too shabby!
Or near quantitative yield with SO₃!!
And they recommend either anhydrous HNO₃ or HNO₃ with SO₃, meaning that a conventional mixed acid could almost certainly be used, even if yields do suffer.
It does seem a bit heavy on acid usage, but still, it brings RDX into the "easy-as-TNP" category assuming that it works as described. No need to distil HNO₃, no need for Ac₂O :D .
I will definitely be trying this, following the patent but with NH₄NO₃/H₂SO₄ instead of HNO₃, at the weekend if not sooner.

<small>[ February 12, 2003, 02:01 PM: Message edited by: Mr Cool ]</small>

[Mr Cool]

Still having problems getting the condensation product with CH₂O to form. I thought I had some but it turned out to be just ammonium sulphamate that had ppted :mad: .
I really don't understand it. I depolymerise (CH₂O)_n with hot dilute aqueous NaOH to form a roughly 30% solution (35% in theory, but some will escape), and add this to cold conc K or NH₄ sulphamate in a 2:1 molar ratio, CH₂O:sulphamate. And nothing happens!
Huh, I'll keep trying...