rudy090992
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2-methyl-3-nitrophenol
I was doing a little bit of lurking and I found this thread:
http://www.sciencemadness.org/talk/viewthread.php?tid=17735
It interests me because I have a compound I'm interested in ('2-methyl-3-nitrophenol') and the synthesis I came up with involved a lot of nitros and
nitro reductions and sandmeyers. It was a big mess. However, this thread reignited my interest in the compound.
The new synthesis I came up with is
2'-methylacetophenone--->2'-methyl-3'-nitroacetophenone--->6-acetoxy-2-nitrotoluene--->2-methyl-3-nitrophenol
The problem is synthesizing 2-methylacetophenone. I'm thinking I should preform a friedel-crafts acetylation with acetyl chloride/AlCl3 on
p-toluenesulfonic acid and then hydrolyze the sulfonyl by refluxing with phosphoric acid. Is there a better way to do this? If there is, I'm unaware
of it.
[Edited on 17-5-2013 by rudy090992]
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rudy090992
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Maybe there is some way I could utilize a formylation reaction instead of the acetylation. I should still be able to perform a baeyer-villiger on an
aromatic aldehyde and subsequently hydrolyze it to a phenol.
A formylation reaction with HMTA is so much more attractive than an acetylation with acetyl chloride/lewis acid.
The duff doesn't quite seem possible. It tends to be formylate para to the methyl when I need it ortho (reported ratio is 84% para and the rest
ortho.) Sulfonating the para position deactivates the ring so much I don't know if the duff would be possible.
The sommelet reaction could work but I would need to have another methyl group meaning I would have to start with o-xylene and halogenate just one of
the methyl groups which I have no idea how to do effectively.
I could use Cu(I) and methylmagnesium bromide to make the methyl group but starting with toluene just seems to be FAR more practical.
I could also create the phenol through a diazonium salt but that seems like it would be inefficient compared to the baeyer-villiger/hydrolysis
approach. (I also have more access to peracids than I do NaNO2/Cu(I).
Idea's anyone?
If I were to go the route of producing the phenol via peracid oxidation, then my starting compound would be o-tolualdehyde. I could sulfonate the
aldehyde, then nitrate, then cleave sulfonyl, then peracid followed by reflux in aqueous acid. Still seems like a lot of work. Especially considering
the high cost of o-tolualdehyde.
[Edited on 17-5-2013 by rudy090992]
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