Acetic Acid → Benzoic acid, 4-(acetyloxy)-

HRID 2309128Notes

Reaction equation

HRID 2309128 reaction equation
C[C:2]([C:4]1[CH:9]=[CH:8][C:7]([O:10][C:11]([CH3:13])=[O:12])=[CH:6][CH:5]=1)=[O:3].C(=[O:16])C.C(OC(=O)C)(=O)C.C(O)(=O)C>C(OCC)(=O)C.[Cr].[Co].O.O.O.O.C([O-])(=O)C.[Mn+2].C([O-])(=O)C>[C:11]([O:10][C:7]1[CH:8]=[CH:9][C:4]([C:2]([OH:3])=[O:16])=[CH:5][CH:6]=1)(=[O:12])[CH3:13]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 177AcetaldehydeHCID 7918Acetic AnhydrideHCID 83063p-Acetylphenyl acetate

Product 1

HCID 16865Benzoic acid, 4-(acetyloxy)-

Reagents, catalysts & solvents 3

HCID 93021Manganese acetate tetrahydrateCatalystHCID 11332432Hastelloy CCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A 300 cc Hastelloy C autoclave was charged with 17.8 g (0.1 mol) of 4-acetoxy acetophenone (4-AAP), 0.25 g of manganese (II) acetate tetrahydrate, 1.0 g of acetaldehyde, 25 g of acetic anhydride, and 125 g of acetic acid. An oxygen/nitrogen mixture was sparged into the autoclave at 1000 cc/min such that 5% oxygen was maintained in the vent. A 10% acetaldehyde in acetic acid solution was fed at a rate of 3.0 cc/h. The reaction was run at 150° C. and 100 psig for 3 h. using a stirring speed of 1000 rpm whereupon the acetic acid and acetic anhydride were removed on a rotary evaporator to yield orange crystals. The crystals were dissolved in ca. 150 mL of ethyl acetate and the solution was extracted with 100 mL of water (3×). The organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed on a rotary evaporator to yield 4-acetoxybenzoic acid (4-ABA) at a conversion of 92.7% based on 4-HAP and with 55.1% selectivity to 4-ABA.

Workup

  1. customAn oxygen/nitrogen mixture was sparged into the autoclave at 1000 cc/min such that 5% oxygen
  2. temperaturewas maintained in the vent
  3. customwas run at 150° C.
  4. customa stirring speed of 1000 rpm whereupon the acetic acid and acetic anhydride were removed on a rotary evaporator
  5. customto yield orange crystals
  6. extractionthe solution was extracted with 100 mL of water (3×)
  7. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customthe solvent was removed on a rotary evaporator

Sources & evidence

ORD record
ord-9aae2a9c066947a7b6f6c9f7bb0d42d3
Source dataset
uspto-grants-1987_09
Patent number
US04692546

Reaction notes

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