Benzoic Acid → P-Toluic Acid

HRID 593247Notes

Reaction equation

HRID 593247 reaction equation
ON1[C:6](=O)[CH2:5][CH2:4][C:3]1=[O:8].[OH2:9].[C:10]([OH:18])(=[O:17])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>C([O-])(=O)C.[Co+2].C([O-])(=O)C.C([O-])(=O)C.[Mn+2].C([O-])(=O)C.CC1C=CC(C)=CC=1>[CH3:3][C:14]1[CH:13]=[CH:12][C:11]([C:10]([OH:18])=[O:17])=[CH:16][CH:15]=1.[C:10]([OH:18])(=[O:17])[C:11]1[CH:12]=[CH:13][C:4]([C:3]([OH:8])=[O:9])=[CH:5][CH:6]=1

Participants

8

Reactant 3

HCID 243Benzoic AcidHCID 962Water2×HCID 80170N-Hydroxysuccinimide

Product 2

HCID 7470P-Toluic AcidYield 28.9%HCID 7489Terephthalic AcidYield 6.68%

Reagents, catalysts & solvents 3

HCID 6277Cobalt diacetateCatalystHCID 12525Manganous AcetateCatalystHCID 7809P-XyleneSolvent2×

Conditions

Temperature
150 °C

Procedure

Into an air-flow pressure reactor (or air-flow pressurizable reactor) equipped with a dehydrator similar to Dean-Stark apparatus, 300 g (2.8 mol) of p-xylene, 0.20 g (1.1 mmol) of cobalt acetate (bivalent), and 0.20 g (1.2 mmol) of manganese acetate (bivalent) were charged. Nitrogen was introduced into the reactor to raise the reactor pressure to 0.5 MPa. The mixture was heated to 150° C., and the reactor was ventilated with a mixed gas of air and nitrogen to adjust the oxygen concentration contained in off-gas to 5%. A separately prepared mixture of 0.25 g (2.2 mmol) of N-hydroxysuccinimide and 2 g of water was continuously fed in the reactor over 5 hours. Incidentally, it was assumed that the reaction was started at the time the addition of the catalyst was started, and that the reaction was completed at the time the addition of the catalyst was completed. Moreover, the reaction was carried out with trapping the produced water. After the reaction was completed, the reactor was cooled and the pressure was released. The reaction mixture was analyzed by a high-performance liquid chromatography (HPLC) to determine the conversion of the substrate and the amount and yield of the product. The conversion of p-xylene was 35.7%, and 110 g of p-toluic acid (yield 28.9%), 31 g of terephthalic acid (yield 6.68%), and 0.32 g of benzoic acid as a by-product (yield 0.094%) were obtained.

Workup

  1. additionwere charged
  2. additionNitrogen was introduced into the reactor
  3. temperatureto raise the reactor pressure to 0.5 MPa
  4. concentrationthe oxygen concentration
  5. additionthe addition of the catalyst
  6. additionthe addition of the catalyst
  7. temperaturethe reactor was cooled

Sources & evidence

ORD record
ord-3f9260f304d248a78860d1e67e4aa0a8
Source dataset
uspto-grants-2016_01
Patent number
US09242921B2

Reaction notes

Loading…