Hydrogen Peroxide → N-(4-bromo-3-chlorophenyl)-7-chlorobenzo[d]oxazol-2-amine

HRID 885105Notes

Reaction equation

HRID 885105 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[OH:9].[Cl:10][C:11]1[CH:12]=[C:13]([N:18]=[C:19]=S)[CH:14]=[CH:15][C:16]=1[Br:17].O[Li].O.OO>O1CCCC1>[Br:17][C:16]1[CH:15]=[CH:14][C:13]([NH:18][C:19]2[O:9][C:3]3[C:4]([Cl:8])=[CH:5][CH:6]=[CH:7][C:2]=3[N:1]=2)=[CH:12][C:11]=1[Cl:10]

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 360674-Bromo-3-chlorophenyl isothiocyanateHCID 168937Lithium hydroxide, monohydrateHCID 64860252-Amino-6-chlorophenol

Product 1

HCID 68749729N-(4-bromo-3-chlorophenyl)-7-chlorobenzo[d]oxazol-2-amine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

An ambient solution of 2-amino-6-chlorophenol (0.86 g, 6.0 mmol) and 3-chloro-4-bromophenyl isothiocyanate (1.49 g, 6.0 mmol) in tetrahydrofuran (20 mL) was stirred for 16 h. The reaction was cooled (0° C.), and LiOH.H2O (0.521 g, 12.41 mmol) was added, followed by the drop wise addition of 30% H2O2 (3.41 mL, 31.0 mmol) over 15 minutes. The reaction was warmed to room temperature and stirred for 16 h. The reaction was then quenched by the addition of 20% aqueous sodium sulfite solution (50 mL) and ethyl acetate (75 mL). The layers were separated, and the aqueous was extracted with additional ethyl acetate (2×75 mL). The combined organics were dried with anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by chromatography on SiO2 gel, eluting with 25% ethyl acetate in hexane, to give the title compound. MS (ESI) m/z 359[M+H]+.

Workup

  1. additionwas added
  2. customThe reaction was then quenched by the addition of 20% aqueous sodium sulfite solution (50 mL) and ethyl acetate (75 mL)
  3. customThe layers were separated
  4. extractionthe aqueous was extracted with additional ethyl acetate (2×75 mL)
  5. dry with materialThe combined organics were dried with anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by chromatography on SiO2 gel
  9. washeluting with 25% ethyl acetate in hexane

Sources & evidence

ORD record
ord-1730b88e3fd44af39526e71052bc05da
Source dataset
uspto-grants-2012_08
Patent number
US08242139B2

Reaction notes

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