Ethyl Acetate → 4-(tert-Butoxycarbonyl)-3-methylbenzoic acid

HRID 1522787Notes

Reaction equation

HRID 1522787 reaction equation
[CH:1]([C:3]1[CH:15]=[CH:14][C:6]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])=[C:5]([CH3:16])[CH:4]=1)=[O:2].[OH:17]OS([O-])=O.[K+].C(OCC)(=O)C>CN(C=O)C.O.CCCCCC>[C:10]([O:9][C:7]([C:6]1[CH:14]=[CH:15][C:3]([C:1]([OH:17])=[O:2])=[CH:4][C:5]=1[CH3:16])=[O:8])([CH3:11])([CH3:12])[CH3:13]

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 23707502Potassium hydroxy sulfiteHCID 59563495Tert-butyl 4-formyl-2-methylbenzoate

Product 1

HCID 894448004-(tert-Butoxycarbonyl)-3-methylbenzoic acidYield 27%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8058HexaneSolvent

Procedure

To a solution of tert-butyl 4-formyl-2-methyl-benzoate (390 g, ˜78% purity, 1.8 mol) in DMF (2.0 L) was added oxone (270 g, 1.8 mol) over a period of 15 min at 10° C. After complete addition, the reaction mixture was warmed to room temperature and stirred for 12 h. After complete conversion of starting material, the reaction mixture was diluted with water at 10° C. The aqueous layer was extracted with ethyl acetate (2×5 L), washed with water (3×1 L) dried over sodium sulphate and concentrated to yield a crude residue (217 g). Pure 4-tert-butoxycarbonyl-3-methyl-benzoic acid (115 g) was obtained by column chromatography with ethyl acetate (6%) in hexane.

Workup

  1. additionAfter complete addition
  2. extractionThe aqueous layer was extracted with ethyl acetate (2×5 L)
  3. washwashed with water (3×1 L)
  4. dry with materialdried over sodium sulphate
  5. concentrationconcentrated
  6. customto yield a crude residue (217 g)

Sources & evidence

ORD record
ord-b29408cdfaaa4d95b8836a920919fc1d
Source dataset
uspto-grants-2015_07
Patent number
US09078444B2

Reaction notes

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