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Kitani

oxidation of pyridine derivative to N-oxide

Case Engelen  Follow
DMDO is a useful oxidant - have used it in the past.

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David Bradbury  Follow
Rolnor - they write it as (Tf)2O in the review, so I think that is what they meant - didn't look up the original paper

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Blake Bartmus  Follow
While looking for something else, I did find a paper that oxidises pyridine to the N-oxide in quantitative yield using cyclohexanone dioxirane (compound h). I don't have any experience with the cyclohexanone version, but have worked with DMDO extensively in the past with a lot of success. The only obvious concern is in terms of safety - dioxiranes tend to be vigorously unstable. DMDO you make at such low concentrations that the risk is negligible, or you generate it in situ; I wonder if you couldn't adapt their procedure to use in situ generation of the cyclohexanone dioxirane as well.

https://doi.org/10.1021/ja00030a032

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Bob Mouk  Follow
I know that you can make pertrifluoroacetic acid from trifluoroacetic acid and sodiumpercarbonate, this is a strong reagent. I dont have a reference, sorry. You should find in in Fieser&Fieser Reagents for Organic Synthesis I think.

Here is a reference:

https://www.organic-chemistry.org/chemicals/oxidations/trifluoroacetic-peracid.shtm

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David Charles Leithauser  Follow
Thanks guys, I think I found the review (not sure if its the exact one, Im at home atm) but they mention UHP+TFAA and it seems to work. Might have to fiddle with the equivalents a bit but it works at room temperature 

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David O'Malley  Follow
Great!

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Chaitanya Kulkarni  Follow
Quote from:
Hopper had a review in 2009 in Progress in Heterocyclic chemistry.  The reagents discussed are MCPBA, peracetic acid, peroxy triflic acid, urea - peroxide complex, and triflic anhydride with sodium carbonate and hydrogen peroxide.  The last one is supposed to be good for resistant pyridines.

Do you really mean triflic anhydride? Trifluoromethanesulphonic anhydride?
A question is do you get bad conversion or byproduct formation? If the latter it does not help with stronger oxidizer maybe?

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Darshan Aryal  Follow
Quote from:
While looking for something else, I did find a paper that oxidises pyridine to the N-oxide in quantitative yield using cyclohexanone dioxirane (compound h). I don't have any experience with the cyclohexanone version, but have worked with DMDO extensively in the past with a lot of success. The only obvious concern is in terms of safety - dioxiranes tend to be vigorously unstable. DMDO you make at such low concentrations that the risk is negligible, or you generate it in situ; I wonder if you couldn't adapt their procedure to use in situ generation of the cyclohexanone dioxirane as well.

https://doi.org/10.1021/ja00030a032

Thanks, I tried running the raction in acetone and using oxone to  make it in situ but didnt work. However, I got full conversion using TFA+H2O2 or TFAA+UHP so Im fine now :)
THanks for help guys

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Daniel Hobbs  Follow
Hopper had a review in 2009 in Progress in Heterocyclic chemistry.  The reagents discussed are MCPBA, peracetic acid, peroxy triflic acid, urea - peroxide complex, and triflic anhydride with sodium carbonate and hydrogen peroxide.  The last one is supposed to be good for resistant pyridines.

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