Sulfuric Acid → 2-Nitrotoluene
Reaction equation
S(=O)(=O)(O)O.[N+:6]([O-:9])([O-])=[O:7].[K+].[C:11]1([CH3:17])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>>[N+:6]([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=1[CH3:17])([O-:9])=[O:7]Participants
Procedure
The toluene derivative (1) is charged with concentrated sulfuric acid and potassium nitrate (reaction 11) to obtain the 2-nitro toluene (m), which subsequently is reduced (reaction 12) with hydrogen on palladium/charcoal to the amine (n). The methyl group of the amine (n) is brominated with bromine under illumination (reaction 13). The brominated aniline (o) is charged (reaction 14) with triphenylphosphine in dimethylformamide to give the phosphonium salt (p), which undergoes a Wittig reaction (reaction 15) with n-butyl-lithium and the aldehyde R7 --C(O)H. The ethylene-substituted aniline (q) is reduced with hydrogen over palladiurn-charcoal to the ethyl-substituted aniline (r) (reaction 16), which is further allowed to react with NaNO2 and H2SO4, followed by copper cyanide, and is then heated with formic acid over Raney-nickel to obtain the aldehyde (a) (reaction 18). The ethylene-substituted aniline (q) can also be charged with NaNO2 and H2SO4, followed by copper cyanide (reaction 17), which is then heated with formic acid over Raney-nickel (reaction 19) to give the ethylene-substituted aldehyde (a).
Sources & evidence
- ORD record
- ord-b986886ecd7d406a90332c3aa858007b
- Source dataset
- uspto-grants-2000_02
- Patent number
- US06020379
Reaction notes
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