Sciencemadness Discussion Board - Cyanogen nitrite/nitrate

Cyanogen nitrite/nitrate

Theoretic - 10-9-2003 at 04:44

I'm thinking about compounds-cyanogen nitrite and nitrate. I think they could be made by:
ClCN+NaNO2=NaCl+CNNO2
ClCN+NaNO3=NaCl+CNNO3
Both should be good explosives.

Knowing the toxicity of cyanogen chloride, I don't see why anyone would bother, anyway.

Would anyone be suicidal enough to try?

[Edited on 11-9-2003 by Theoretic]

madscientist - 11-9-2003 at 15:29

Another option for synthesis I thought of a while back that avoids use of the extremely toxic halonitriles:

NO2Cl + NaCN ----> NO2CN + NaCl

NO2Cl can be prepared by direct interaction of NO2 and Cl2 and condensing.

Performing the above reaction without intense cooling or a solvent of some sort would be idiocy on the order of suicide. I'm having trouble envisioning many suitable solvents, as anything organic is likely to react violently with NO2Cl, any chlorinated solvents will react with NaCN (assuming it's solvated in the first place), and plain water will hydrolyze NO2Cl. Perhaps liquid SO2? Not only should it function satisfactorily as a solvent, but it'd also ensure that the reaction remained cool.

And beware, that reaction would be sure to liberate some chloronitrile. Not necessarily in quantities that are going to affect yield to a noticeable degree, but certainly enough to cause a human to drop dead.

Theoretic - 12-9-2003 at 04:22

Thanks, that's quite useful (although I thought of NO2Cl too, I didn't know it could be made that way).
But don't worry about CNCl, it would react rather than escape (that's in a closed vessel).
Although I don't see why this reaction would be very exothermic, I suggest a solvent-liquid NH3. It's got about the same boiling point as Cl2, and the latter is liquefied at room temperature and 6 atm (lower pressure required with elementary cooling).

vulture - 12-9-2003 at 05:49

Cyanogen azide is known to be isolated.
Very sensitive material, I can't remember if it's toxic though.

It has a lovely formula: CN4

Nick F - 12-9-2003 at 06:31

Are you sure the monomer has been isolated, Vulture?
With all those multiple bonds around I'd expect it to trimerise quickly to cyanuric triazide.

madscientist - 12-9-2003 at 07:26

Unless the reaction vessel was airtight and/or you had excellent ventillation, it'd be dangerous. Not all ClCN is guaranteed to react, and even if it hydrolyzes on contact with atmospheric moisture on the way to your lungs, you've still got HCN, 50mg of which could easily kill you.

The problem with using liquid NH3 as the solvent would be this:

2NH3 + NO2Cl ----> NH2NO2 + NH4Cl

[Edited on 12-9-2003 by madscientist]

Iv4 - 18-9-2003 at 08:28

You could just do it outside.Like on your roof or something like that.

Just a thought but would HCN/NaCN with nitric acid do for this.

Theoretic - 17-11-2003 at 08:01

It doesn't seem that ClNO2 can be made by direct chlorination, my book states the opposite. But it can be made by:
1)SO3 + HCl => ClHSO3
2)ClHSO3 + HNO3 => ClNO2 + H2SO4.
HCN + HNO3 could work, just like HNO2 + ROH => RONO + H2O.
But since cyanide is much more basic, the reaction has to be carried out under more forced conditions. An option is preparing NO2HSO4 by SO3 + HNO3 and then:
HCN + NO2HSO4 => CNNO2 + H2SO4.
:cool:

Oh, and I doubt that NH2NO2 exists.

madscientist - 17-11-2003 at 08:54

NO2Cl can be prepared via direct chlorination. It's a reaction strongly defined by equilibrium, which would explain why your book may suggest that the reaction "goes the other way," so to speak.

HCN + HNO3 probably would yield highly exothermic oxidation.

I can't see HCN + NO2HSO4 yielding any NO2CN.

NH2NO2 does exist (known as "nitramine"

KABOOOM(pyrojustforfun) - 19-11-2003 at 15:00

name of the thread should is (obviously) wrong. it's nitro not nitrite.
<blockquote>quote:<hr>ClCN+NaNO3=NaCl+CNNO3<hr></blockquote>
nitrates don't participate in any nucleophilic substitutions as far as I know.maybe N2O5 could react with cyanuric acid to make the trinitrate. the result probably hydrolyzes in presence of moisture and is as unstable as carboxyl nitrates.
in my opinion cyanuric energetic derivatives ( cyclic (C(R)=N)3 )are far more interesting than the cyano ones. cyanogen chloride (readily?)polymerizes to cyanuric chloride...(read the following)
from Characterization, Crystal Structure of 2,4-Bis(triphenylphosphanimino)tetrazolo[5,1-a]-[1,3,5]triazine, and Improved Crystal Structure of 2,4,6-Triazido-1,3,5-triazine<blockquote>quote:<hr>2,4,6-Triazido-1,3,5-triazine: 3.1 g (16.8 mmol) cyanuric chloride in 30 ml of acetone; 5 g (77 mmol) of sodium azide. C3N12 (204.15) Yield: 3.29 g (96%), colorless needles, very sensitive to shock or heat, m.p. 94°C<hr></blockquote> :cool:

I found it on my hard. you can easily find the PDF by a google search.
COPAE gives alot more info its properties.

Theoretic - 1-1-2004 at 05:46

The reaction of NO2Cl on NH3 yields chlormaine and ammonium nitrite.
Why wouldn's nitryl bisulfate and hydrogen cyanide not yield the desired compound? The nitryl ion is the active component in nitration mixtures, separating it out would only ease the reaction (which is a nitration by the way).
I don't think that there would be an oxidation under controlled conditions, the triple bond is kinetically stable at room temperature.
By the way, Cyanogen chloride and NaNO2 would yield a mixture of cyanogen nitrite and nitrocyan, the nitration of HCN would only yield nitrocyan.

Help in finding info abou this compound

DubaiAmateurRocketry - 28-10-2013 at 08:11

Does this compound this exist?

N≡C-NO2

Can I see some synthesis or paper about it ?

Mant thanks.

Idk why i cant find any about it, but it seems interesting

vulture - 28-10-2013 at 08:26

http://www.sciencemadness.org/talk/viewthread.php?tid=925

DubaiAmateurRocketry - 29-10-2013 at 05:37

As the OP mentioned,

ClCN+NaNO2=NaCl+CNNO2

Does this method work? It seems pretty simple.

I dislike working with compounds so toxic, so is there a guide or any paper published about its synthesis and info ? Can someone share ?

For some reason the search engine is filled with CyanogenMOD,some android phone features, and overlaps my searches.

[Edited on 29-10-2013 by DubaiAmateurRocketry]

woelen - 29-10-2013 at 06:21

I have never seen this very old thread before, but one of the initial remarks that NO2Cl can simply be made from NO2 and Cl2 is not true. I tried that reaction myself and if you mix NO2 and Cl2 then nothing seems to happen. The mix remains dirty brown (mix of green color of Cl2 and brown of NO2). NO2Cl is a colorless gas and if a slight excess of Cl2 is added, then the mix should become very light green. NO2 and Cl2 may react, but then the reaction is very slow. If it is an equilibrium, then the equilibrium also may be strongly at the NO2+Cl2 side. I do not know, but in practice, NO2Cl is not easily made (a search on sciencemadness already tells enough, there hardly is any mention of NO2Cl. I wanted to make NO2Cl, I ordered chlorosulfonic acid for this purpose, but unfortunately, this chemical could not be delivered to me, due to REACH restrictions in the EU.

If CN-NO2 exists, then I think that it will be an amazingly toxic substance, probably as toxic as (CN)2, CNCl or HCN.

deltaH - 29-10-2013 at 06:37

I think I may have considered this compound myself a long time ago from a theoretical aspect. Possibly one has to be weary of the following equilibirum: CN-NO2 <=> CN^- + NO2⁺. When this occurs, I would imagine NO2+ would very quickly oxidise CN- to cyanogen and NO2, thus I believe this compound's production to be highly unlikely, all routes leading to NCCN and NO2!

I think this may be an interesting thing to consider from a thermodynamic perspective.

[Edited on 29-10-2013 by deltaH]

DraconicAcid - 29-10-2013 at 08:09

If copper(II) can oxidize cyanide to cyanogen, I'm fairly sure nitro derivatives will also do that.

woelen - 29-10-2013 at 10:09

Cyanide and NO2 are incompatible. That is a reaction which I have tried also. This leads to formation of a brown compound. The brown compound is paracyanogen, a polymeric form of (CN)2.

So, if NO2 can oxidize CN(-) to paracyanogen, then NO2(+) certainly must be capable of such an oxidation, or maybe it even goes further. I consider it very unlikely that CN-NO2 is formed and I have serious doubts on the existence of CN-NO2.

The compound ON-CN does exist (nitrosyl cyanide), it is a blue gas. I tried to make this gas by passing ONCl over humid AgCN, but did not succeed.

DubaiAmateurRocketry - 1-11-2013 at 01:48

Quote: Originally posted by woelen

Cyanide and NO2 are incompatible. That is a reaction which I have tried also. This leads to formation of a brown compound. The brown compound is paracyanogen, a polymeric form of (CN)2.

So, if NO2 can oxidize CN(-) to paracyanogen, then NO2(+) certainly must be capable of such an oxidation, or maybe it even goes further. I consider it very unlikely that CN-NO2 is formed and I have serious doubts on the existence of CN-NO2.

The compound ON-CN does exist (nitrosyl cyanide), it is a blue gas. I tried to make this gas by passing ONCl over humid AgCN, but did not succeed.

thanks. what about trinitromethyl cyanide ? N≡C-C(NO2)3 ??

deltaH - 1-11-2013 at 02:07

Quote:

thanks. what about trinitromethyl cyanide ? N≡C-C(NO2)3 ??

The problem may be cyanogen formation again:

? 2N≡C-C(NO2)3 => C2(NO2)6 + NCCN ?