Sciencemadness Discussion Board

NOCl as chlorinating/nitrating agent?

ketel-one - 20-9-2009 at 11:49

For ethers R-O-R,

HNO3 + 3 HCl= Cl2 + 2 H2O + NOCl
NOCl + R-O-R = R-NO2 + R-Cl
Cl2 + 2R-NO2 = 2R-Cl + 2NO2

Would that work? What I'm really interested in is cleaving an ether to make two R-Cl s like with thionyl chloride.

[Edited on 20-9-2009 by ketel-one]

Picric-A - 20-9-2009 at 12:49

I cannot find any refs to the cleavage of ethers using Nitrosyl chloride. do you have any?
I though one of few reagents capable of this is HI.

ketel-one - 20-9-2009 at 15:09

Right, I've thought about HI it was one of my first posts on the short answers thread... but when cleaving R-O-R it gives R-I + R-OH, right? The HNO3 + HCl just seemed better because I can easily get both.

Also I think that NH4NO3 + HCl forms nitrosyl chloride to some extent because a mix of NH4NO3 + HCl will easily eat through copper to make CuCl2.
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I think those equations I put were correct. I mixed some NH4NO3 pellets with concentrated HCl. Stirred them, nothing happened as expected. I put a tiny bit of 70% IPA in there and it started slowly turning yellow until I shook it some and the solution turned a very brownish yellow color and bubbled violently, releasing a puff of brown gas I'm certain was NO2. The solution went back to clear (maybe slightly yellowish) after that.
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entropy51 - 20-9-2009 at 16:55

Quote: Originally posted by ketel-one  
I think those equations I put were correct.


I don't think any of your equations have been correct.

ketel-one - 20-9-2009 at 19:29

Quote: Originally posted by entropy51  
I don't think (cut)

That's exactly the problem. You DON'T think. :P

Picric-A - 20-9-2009 at 22:58

NH4NO3 + HCl forms nitric acid which is corrosive to copper forming blue Cu(NO3)2 and nitrogen dioxide gas.

NOCl is in equilibrium in water;
HNO3 + HCl  NOCl + H2O

Anhydrous NOCl can be formed by passing NO/Cl2 over acitivated carbon and condensing the vapour formed, separating out the NOCl from the unreacted gasses. Purified by distillation under pressure.

Picric-A - 20-9-2009 at 23:00

Quote: Originally posted by ketel-one  
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I think those equations I put were correct. I mixed some NH4NO3 pellets with concentrated HCl. Stirred them, nothing happened as expected. I put a tiny bit of 70% IPA in there and it started slowly turning yellow until I shook it some and the solution turned a very brownish yellow color and bubbled violently, releasing a puff of brown gas I'm certain was NO2. The solution went back to clear (maybe slightly yellowish) after that.
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The reaction you describe is a nitration runaway. nothing to do with NOCl.

ketel-one - 21-9-2009 at 10:32

Nitration runaway? Not exactly sure how that would work, could you tell me the results then of the reaction I described?
Quote: Originally posted by Picric-A  
NH4NO3 + HCl forms nitric acid which is corrosive to copper forming blue Cu(NO3)2 and nitrogen dioxide gas.

I would have to disagree, by personal experience. NH4NO3 forms a tiny bit of nitric acid by equilibrium NH4NO3  NH3 + HNO3, which with HCl makes what's called a "poor man's aqua regia", instead of the nitric acid itself reacting. I've tried this experiment a while back, the results were copper(II) chloride (which crystallizes very nicely btw) and small amount of chlorine bubbles, not NO/NO2. Feel free to confirm or disprove these results.

entropy51 - 21-9-2009 at 16:28

Quote: Originally posted by ketel-one  
Quote: Originally posted by entropy51  
I don't think (cut)

That's exactly the problem. You DON'T think. :P


You seem to think that any equation that is balanced means the reaction can actually occur. But consider:

AcOH + NaCl -> AcCl + NaOH

The equation is balanced, but that's not the reaction that occurs. Most of the equations you have written here are just as stupid. It's dumb to balance an equation unless you know the products. A guess doesn't get you to a solution.

Amateur chemistry doesn't mean ignorant chemistry.

ketel-one - 21-9-2009 at 21:10

I did think a lot before proposing this idea- and seeing the violent reaction with IPA, I think that there is some potential to using aqua regia to react somehow with alcohols, but not a lot since I couldn't get it to react with a primary alcohol (ethanol). Dry NOCl hydrolyzes in water to HCl + HNO2, as such when dry it might have more potential for ethers, primary alcohols, and a 1:2 mix of Cl2 and NOCl could very possibly cleave ethers in the way I originally described. It is a guess, but an educated guess based on what I know.

I don't want to keep bumping this thread, so I'll stop responding.

Picric-A - 22-9-2009 at 01:50

I think the result of a nitration runaway is the oxidation of the alcohol to CO2 and water, i am not sure though.

If an exess of HCl is used then yes this would react with the Nitric produced to form NOCl but the nitric would oxidise alcohols before the NOCl had a chance to react.
If you wanted to try that you would have to make anhydrous NOCl via the method i showed earlier then try that.

Good idea.