Dimethyl Sulfoxide → Methyl 5-formyl-2-methylbenzoate

HRID 2071103Notes

Reaction equation

HRID 2071103 reaction equation
[OH:1][CH2:2][C:3]1[CH:4]=[CH:5][C:6]([CH3:13])=[C:7]([CH:12]=1)[C:8]([O:10][CH3:11])=[O:9].C(Cl)(=O)C(Cl)=O.CS(C)=O.CCN(CC)CC>C(Cl)Cl>[CH:2]([C:3]1[CH:4]=[CH:5][C:6]([CH3:13])=[C:7]([CH:12]=1)[C:8]([O:10][CH3:11])=[O:9])=[O:1]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 6850259472985-24-1

Product 1

HCID 19700886Methyl 5-formyl-2-methylbenzoateYield 71.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 377 mg of methyl 5-(hydroxymethyl)-2-methylbenzoate and 0.8 mL (9.17 mmol) of oxalyl chloride in 20 mL of CH2Cl2 was cooled to −78° C. To this solution was added 1.1 mL (15.5 mmol) of DMSO dropwise, and after stirring for 10 min., 3.2 mL of Et3N was added and stirring was continued at −78° C. for 10 min. The dry ice-acetone bath was removed, and the mixture was allowed to warm to r.t. and after 2 h, 30 mL of sat. NH4Cl solution was added. The organic layer was washed with 25 mL of brine, dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (10% EtOAc/hexanes) provided 268 mg of methyl 5-formyl-2-methylbenzoate as a red liquid in 71% yield with some impurity.

Workup

  1. stirringstirring
  2. waitwas continued at −78° C. for 10 min
  3. customThe dry ice-acetone bath was removed
  4. addition30 mL of sat. NH4Cl solution was added
  5. washThe organic layer was washed with 25 mL of brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by flash silica gel chromatography (10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-600c6552b92541e0ab767b1a4b612992
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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