ketel-one
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NOCl as chlorinating/nitrating agent?
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]
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Picric-A
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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.
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ketel-one
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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
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I don't think any of your equations have been correct.
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ketel-one
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That's exactly the problem. You DON'T think. 
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Picric-A
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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.
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Picric-A
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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.
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ketel-one
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Nitration runaway? Not exactly sure how that would work, could you tell me the results then of the reaction I described?
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.
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entropy51
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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.
Better to remain silent and appear a fool than to open your mouth and remove all doubt.
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ketel-one
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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.
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Picric-A
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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.
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