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Acetic Acid → 2-Methoxy-4-(methylsulfonyl)benzoic acid

HRID 452445
Notes
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Reaction equation

HRID 452445 reaction equation
[CH3:1][O:2][C:3]1[CH:11]=[C:10](SC)[CH:9]=[CH:8][C:4]=1[C:5]([OH:7])=[O:6].OO.[S:16]([O-:19])([O-])=[O:17].[Na+].[Na+].Cl.[C:23](O)(=O)C>O>[CH3:1][O:2][C:3]1[CH:11]=[C:10]([S:16]([CH3:23])(=[O:19])=[O:17])[CH:9]=[CH:8][C:4]=1[C:5]([OH:7])=[O:6]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 24437Sodium SulfiteHCID 6433294-(Methylthio)-o-anisic acid

Product 1

HCID 144781692-Methoxy-4-(methylsulfonyl)benzoic acid

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
10 °C

Procedure

2-methoxy-4-(methylthio)benzoic acid (10.8 g, 54 mmol) is dissolved in acetic acid and the solution was cooled to 10° C. Sodium tungstate 2-hydrate (1.2 g, 3.7 mmol) was added until percipitation. After the precipitation had dissolved and the solution was cooled H2O2 (4.1 ml, 135 mmol) was added dropwise. 10 minutes later the reaction mixture was heated to 50° C. for 1 h. Sodium sulphite (3.4 g, 27 mmol) in water (80 ml) was added and the resulting mixture was stirred for 30 min. Water and aqueous HCl (10%) were added. The aqueous phase was extracted with EtOAc and the combined organic layers were dried (Na2SO4) and evaporated under reduced pressure to give a white powder (5.7 g). No further purification was made of this intermediate. 1H-NMR (400 MHz, MeOH): δ 7.92 (1H, d, J 8 Hz), δ 7.61 (1H, s), δ 7.56 (1H, d, J 8 Hz), δ 3.95 (3H, s), δ 3.18 (3H, s).

Workup

  1. customAfter the precipitation
  2. dissolutionhad dissolved
  3. additionwas added dropwise
  4. temperature10 minutes later the reaction mixture was heated to 50° C. for 1 h
  5. extractionThe aqueous phase was extracted with EtOAc
  6. dry with materialthe combined organic layers were dried (Na2SO4)
  7. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-cea50ee5862f457c9bdcf658cfc1a887
Source dataset
uspto-grants-2013_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08492372B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes