On page 11 of Organic Chemistry of Explosives (J. P. Agrawal & R. D. Hodgson, 2007), there appears to be an error. They show NaOH and
Cl2 converting nitromethane to chloronitromethane. One of the references they give (attached below) describes this process with nitroethane
to form 1-chloro-1-nitroethane, but I was under the impression that nitromethane in strong aqueous base immediately condenses to the 2-nitroacetate
salt.
If it is possible to produce chloronitromethane from aqueous base, would sodium hypochlorite serve as a workable chlorinating agent?
Attachment: jo01055a513.pdf (223kB) This file has been downloaded 369 times AndersHoveland - 7-9-2013 at 15:41
No, it is not an error. In fact, chlorination of nitromethane with hypochlorite results in chloropicrin (trichloro-nitromethane).
The ratio of reactants may be important here. Chlorine is known to react with hydroxide to form hypochlorite. And I would suspect that
monochloro-nitromethane is not stable for long in the presence of excess base.
In case you did not know, there is always some hydroxide ions and free chlorine in equilibrium in aqueous hypochlorite solutions
That's why I suggested it. Reading the paper made me wonder why they went to the trouble of constructing special apparatus to pump chlorine into
alkaline media.
I still wonder to what extent condensation would compete with chlorination.
