Ethyl Acetate → HCID 59750383, compound

HRID 499438

Reaction equation

HRID 499438 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([OH:12])[C:5](=[CH:10][CH:11]=1)[C:6]([O:8][CH3:9])=[O:7].[CH3:13][N:14]([CH3:18])[C:15](Cl)=[S:16].N12CCN(CC1)CC2.C(OCC)(=O)C>CN(C=O)C.O>[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([O:12][C:15]([N:14]([CH3:18])[CH3:13])=[S:16])[CH:3]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 9237DabcoHCID 27871Dimethylthiocarbamoyl chlorideHCID 13983552Methyl 4-bromo-2-hydroxybenzoate

Product 1

HCID 59750383HCID 59750383, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

4-Bromosalicylic acid (15.5 g, 71 mmol) was dissolved in methanol (500 ml), and concentrated sulfuric acid (9.7 g, 99 mmol) was added thereto. The reaction mixture was refluxed for 24 hrs, and the solvent was evaporated. The residue was neutralized with 2 N aqueous sodium hydroxide solution and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated. The residue was subjected to a silica gel column chromatography. The fractions eluted with ethyl acetate-hexane (1:20, v/v) were collected and concentrated to give methyl 4-bromosalicylate (8.7 g, 52%). Methyl 4-bromosalicylate (8.7 g, 37 mmol) and N,N-dimethylthiocarbamoyl chloride (6.0 g, 48 mmol) were dissolved in DMF (80 ml), and 1,4-diazabicyclo[2.2.2]octane (5.5 g, 49 mmol) was added thereto. The reaction mixture was stirred at room temperature for 24 hrs. The reaction mixture was combined with ethyl acetate and water. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was subjected to a silica gel column chromatography. The fractions eluted with ethyl acetate-hexane (1:4, v/v) were collected, concentrated and recrystallized from ethyl acetate-hexane to give the titled compound (10.6 g, 88%) as white crystals.

Workup

  1. washThe organic layer was washed with saturated brine
  2. dry with materialdried over anhydrous magnesium sulfate
  3. customThe solvent was evaporated
  4. washThe fractions eluted with ethyl acetate-hexane (1:4, v/v)
  5. customwere collected
  6. concentrationconcentrated
  7. customrecrystallized from ethyl acetate-hexane

Sources & evidence

ORD record
ord-0cf4a7edbe914f51aabbadbf9cb35fcd
Source dataset
uspto-grants-2010_08
Patent number
US07767665B2

Linked notes

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