The 1st rxn does look weird - even more so since, if you notice, they don't mention any solvent and still say 'reflux for 1h' - whilst DMS (if that should bee the only solvt employed) not only boils at ~190 C, but also decomposes on boiling.
So i'd suggest they missed some essential detail there.
Now tell me this. How come there is never a single mention of someone trying to reduce a sulfonate to a thiol? Is that too hard to do?
I mean, the same result that is achieved here in that example can bee easily had by simply sulfonating , say, p-diMeO-benzene w/sulfuric acid. No?
THAT could well bee a very interesting area for the bees to research. Sulfuric acid itself gets reduced to H2S w/, e.g. aluminium - unfortunately, can't say anything on sulfonates. So, you, the ones who can - please do!
Antoncho
P.S. Yes, the 2nd rxn is a simple Duff formylation, only HMTA which is conventionally used is made in situ (or rather HMTA itself is decomposed in situ in the 'usual' Duff formylations - is that right?) from HCHO and NH4OH.
BTW, this aqueous acetic Duff formylation gives a great yield on 2,6-ditertbutyl-phenol, see Patent US4009210 (http://l2.espacenet.com/dips/viewer?PN=US4009210&CY=gb&LG=en&DB=EPD)
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