Sodium Bicarbonate → 6-[2-(4-Bromo-2-chloro-phenyl)-acetyl]-3-methyl-3H-benzooxazol-2-one

HRID 2096831Notes

Reaction equation

HRID 2096831 reaction equation
[CH3:1][N:2]1[C:6]2[CH:7]=[CH:8][C:9]([C:11](Cl)=[O:12])=[CH:10][C:5]=2[O:4][C:3]1=[O:14].[Br:15][C:16]1[CH:21]=[CH:20][C:19]([CH2:22]Br)=[C:18]([Cl:24])[CH:17]=1.C([O-])(O)=O.[Na+]>COCCOC.[Zn].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:15][C:16]1[CH:21]=[CH:20][C:19]([CH2:22][C:11]([C:9]2[CH:8]=[CH:7][C:6]3[N:2]([CH3:1])[C:3](=[O:14])[O:4][C:5]=3[CH:10]=2)=[O:12])=[C:18]([Cl:24])[CH:17]=1

Participants

7

Reactant 3

HCID 516892Sodium BicarbonateHCID 219144864-Bromo-1-(bromomethyl)-2-chlorobenzeneHCID 866458793-Methyl-2-oxo-2,3-dihydro-benzooxazole-6-carbonyl chloride

Product 1

HCID 666971236-[2-(4-Bromo-2-chloro-phenyl)-acetyl]-3-methyl-3H-benzooxazol-2-one

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

To a suspension of 3-methyl-2-oxo-2,3-dihydro-benzooxazole-6-carboxylic acid (1.0 g, [CAS Reg. No. 140934-94-7]) in CH2Cl2 (14 mL) were added two drops of DMF and oxalylchloride (0.71 mL). The mixture was stirred at room temperature for 1 hour and was then concentrated to dryness. 1,2-Dimethoxyethane (20 mL) was added and the solvent was evaporated again to give the crude acid chloride (3-methyl-2-oxo-2,3-dihydro-benzooxazole-6-carbonyl chloride). To a suspension of zinc powder (677 mg) in 1,2-dimethoxyethane (8 mL) was added tetrakis(triphenylphosphine)palladium(0) (60 mg). A suspension of the acid chloride in 1,2-dimethoxyethane (8 mL) was added. The mixture was cooled in an ice bath and a solution of 4-bromo-1-bromomethyl-2-chloro-benzene (1.47 g, [CAS Reg. No. 89720-77-4]) in 1,2-dimethoxyethane (10 mL) was slowly added over a period of 15 minutes. The mixture was stirred for 10 minutes at 0° C. and then for 2 hours at r.t. The reaction mixture was poured into ice and basified with sat. NaHCO3. The aqueous phase was then extracted two times with ethyl acetate and the organic layers were washed with brine, dried over Na2SO4, filtered and the solvent was evaporated. Ethyl acetate (20 mL) was added to the resulting precipitate and the suspension was stirred for 1 hour at r.t. The solid was filtered off and dried in vacuo. The title compound was obtained as an off-white solid (747 mg, 38%). MS (neg. ion, m/e)=380.2 [(M−H)−].

Workup

  1. additionwas added
  2. temperatureThe mixture was cooled in an ice bath
  3. waitfor 2 hours at r.t
  4. extractionThe aqueous phase was then extracted two times with ethyl acetate
  5. washthe organic layers were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. customthe solvent was evaporated
  9. additionEthyl acetate (20 mL) was added to the resulting precipitate
  10. stirringthe suspension was stirred for 1 hour at r.t
  11. filtrationThe solid was filtered off
  12. customdried in vacuo

Sources & evidence

ORD record
ord-4598c950fc874508822360963162e60f
Source dataset
uspto-grants-2013_05
Patent number
US08450313B2

Reaction notes

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