US EPA

2346573 

Journal Article 

Selective Oxidation of Acetophenones Bearing Various Functional Groups to Benzoic Acid Derivatives with Molecular Oxygen 

Nakamura, R; Obora, Y; Ishii, Y 

2009 

1 

Advanced Synthesis & Catalysis
ISSN: 1615-4150
EISSN: 1615-4169 

351 

10 

1677-1684 

10.1002/adsc.200900099 

WOS:000268200500024 

Acetophenones substituted by alkyl, alkoxy, acetoxy, and halogen groups were selectively oxidized with molecular oxygen to the corresponding benzoic acids by using the N,N',N ''-trihydroxyisocyanuric acid (THICA)/cobalt(II) acetate [Co(OAC)(2)] anese(II) acetate and THICA/Co(OAc)(2)/manganese(II) [Mn(OAc)(2)]. For example, 4-methylacetophenone was selectively oxidized with molecular oxygen to 4-acetylbenzoic acid (85%) by THICA/Co(OAc)(2) and to 4-methylbenzoic acid (93%) by Mn(OAc),, while terephthalic acid was obtained in 93% with the THICA/Co(OAc)(2)/Mn(OAc)(2) catalytic system. It is interesting that the acetyl group Oil the aromatic ring is efficiently converted by a very small amount of Mn(OAc)(2) to the corresponding carboxylic acid. and that the present method provides a versatile route to acetylbenzoic acids which are difficult to prepare by conventional methods. 

acetophenones; aerobic oxidation; benzoic acids; N-hydroxyphthalimide; N,N ',N ''-trihydroxyisocyanuric acid