mycotheologist
Hazard to Others
Posts: 154
Registered: 16-3-2012
Member Is Offline
Mood: No Mood
|
|
Are amino groups oxidised in the same way hydroxy groups are?
I was pondering things to do with the hydrolysis product of acetaminophen (4-aminophenol) and thought about oxidising it with KMnO4. Would that yield
4-aminobenzoic acid or 4-nitrobenzoic acid?
[Edited on 18-5-2012 by mycotheologist]
|
|
|
sargent1015
Hazard to Others
Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline
Mood: Relaxed
|
|
So which of these do you have?
Attachment: noname01.tif (13kB)
This file has been downloaded 846 times
The one on the right is acetaminophen
|
|
|
UKnowNotWatUDo
Hazard to Self
Posts: 96
Registered: 30-6-2010
Member Is Offline
Mood: No Mood
|
|
He's saying that he has 4-aminophenol, which is the product you get when acetaminophen is hydrolyzed. However this will not yield any benzoic acid
derivatives when oxidized as you are missing a carbon atom.
|
|
|
sargent1015
Hazard to Others
Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline
Mood: Relaxed
|
|
Quote: Originally posted by UKnowNotWatUDo  | | He's saying that he has 4-aminophenol, which is the product you get when acetaminophen is hydrolyzed. However this will not yield any benzoic acid
derivatives when oxidized as you are missing a carbon atom. |
Gotcha, thanks for that. 
|
|
|
mycotheologist
Hazard to Others
Posts: 154
Registered: 16-3-2012
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by UKnowNotWatUDo | | He's saying that he has 4-aminophenol, which is the product you get when acetaminophen is hydrolyzed. However this will not yield any benzoic acid
derivatives when oxidized as you are missing a carbon atom. |
Oh yeah, I didn't think of that. It can't yield a ketone without breaking the aromaticity either. Any idea what an oxidiation would yield? I know that
reducing agents like NaBH4 indiscriminately reduce both nitro and carboxyl groups but I don't know if the same applies for the reverse reaction. I'm
guessing not, otherwise there would be plenty of info on oxidising amino groups to nitro groups.
|
|
|
barley81
Hazard to Others
Posts: 481
Registered: 9-5-2011
Member Is Offline
Mood: No Mood
|
|
Sodium borohydride is actually selective. It will not reduce carboxylic acids, but it will react with aromatic compounds containing nitro groups under
special conditions.
http://pubs.rsc.org/en/content/articlelanding/1980/p2/p29800...
(NaBH<sub>4</sub> reduces 2,4-dinitrobenzene by displacing a nitro group with hydrogen. Nucleophilic aromatic substitution.)
http://pubs.acs.org/doi/abs/10.1021/jo00805a015
(Sodium borohydride can reduce aromatic nitro compounds to azoxy compounds)
Thread on oxidizing amine to nitro:
http://www.sciencemadness.org/talk/viewthread.php?tid=9091
[Edited on 22-5-2012 by barley81]
|
|
|
fledarmus
Hazard to Others
Posts: 187
Registered: 23-6-2011
Member Is Offline
Mood: No Mood
|
|
Amino groups can be oxidized to nitro compounds, but it is usually done with ozone or with peroxides. I don't believe I've ever seen a permanganate
oxidation of an aromatic amine.
If there is a hydrogen available on the alpha carbon, the amines can be oxidized to the imine or enamine with subsequent reactions possible... http://pubs.acs.org/doi/abs/10.1021/jo01285a042
|
|
|
solo
International Hazard
Posts: 3975
Registered: 9-12-2002
Location: Estados Unidos de La Republica Mexicana
Member Is Offline
Mood: ....getting old and drowning in a sea of knowledge
|
|
Reference Information
Oxidation of primary, secondary, and tertiary amines with neutral permanganate. Simple method for degrading amines to aldehydes and
ketones
Surjan S. Rawalay, Harold Shechter
J. Org. Chem.
1967, 32 (10), pp 3129–3131
DOI: 10.1021/jo01285a042
Attachment: Oxidation of primary , secondary, and tertiary amines with neutral permanganate. Simple method for degrading aminet to a (438kB)
This file has been downloaded 682 times
It's better to die on your feet, than live on your knees....Emiliano Zapata.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
