Falvin
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Registered: 8-3-2021
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Analogs of haloform reaction?
Chloropicrin can be made by reaction of bleach with nitromethane. This seems a bit analogous to the haloform reaction, except that, in the case of
chloropicrin, the C-N bond does not get cleaved after the halogenaion is complete. On a related note, I recently read that esters of acetic acid can
also be susceptible to the haloform reaction. This gave me an idea:
For instance, could methyl trichloromethanesulfonate be prepared through the reaction of bleach with methyl methanesulfonate? If yes, would this also
work for preparing any other organic acid derivatives?
Source for the claim of acetates being susceptible to haloform reaction: https://link.springer.com/article/10.1007/s42452-021-04777-0
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Boffis
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@Falvin, if you want to get useful responses to a post you need to put a bit more effort into your posts. Firstly, what is it you want to know? The
chlorination of nitromethane by hypochlorite is not a haloform reaction, as you pointed out yourself there is no splitting off of chloroform. Then
your question about methyl methanesulphonate, what are you trying to achieve and what from? Are you talking about the widely sold nutraceutical which
is actual dimethylsulphone and not a sulphonate ester?
If the latter; then there are papers and patents on the oxidation of alkyl sulphone with carbon tetrachloride and KOH in t-butanol but it isn't a
haloform reaction. The product with C2 or longer alkyl groups are a alpha-beta di-substituted ethylene sulphonic acids with no elimination of
chlorinated carbon. In theory dimethylsulphone should therefore give K ethylenesulphonate but this simplest example doesn't seem to be mentioned in
the paper I saw. Maybe in the referenced paper though. If you are interested try Tetrahedron Letters, 1973 p1843 and references therein. The reaction
is of interest since it results in a C-C bond being formed from the two alpha carbons and the movement of the sulphur group to a side position. There
is also a US patent to this effect too but I don't have the reference to hand. It might be worth trying this out with hypochlorite to see if you can
produce methylsulphonic acid as the paper does report that the alpha chlorinated carbon is more readily chlorinated a second time than the other. So
with dimethylsulphone it may be possible to get 1,1,1-trichloromethyl methylsulphone and split this like a haloform reaction, check out the refs and
let us know!
While trichloroacetic acid does split into chloroform and carbonate when heated with excess alkali it is much harder to chlorinate acetic acid than a
methyl ketone so the reaction is less useful. It has been reported on SM, try the search engine.
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