Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1) → 6-Bromo-7-fluoro-2-(2-hydroxy-1,1-dimethylethyl)-5-methyl-1,3-benzoxazole-4-carbonitrile

HRID 17365Notes

Reaction equation

HRID 17365 reaction equation
[Br:1][C:2]1[C:7]([F:8])=[C:6](O)[C:5]([NH:10][C:11](=[O:17])[C:12]([CH3:16])([CH3:15])[CH2:13][OH:14])=[C:4]([C:18]#[N:19])[C:3]=1[CH3:20].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1>C1(C)C=CC=CC=1.C(OCC)(=O)C>[Br:1][C:2]1[C:7]([F:8])=[C:6]2[O:17][C:11]([C:12]([CH3:16])([CH3:15])[CH2:13][OH:14])=[N:10][C:5]2=[C:4]([C:18]#[N:19])[C:3]=1[CH3:20]

Participants

5

Reactant 2

HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 86630842N-(4-Bromo-2-cyano-5-fluoro-6-hydroxy-3-methylphenyl)-3-hydroxy-2,2-dimethyl-1-propanamide

Product 1

HCID 685850036-Bromo-7-fluoro-2-(2-hydroxy-1,1-dimethylethyl)-5-methyl-1,3-benzoxazole-4-carbonitrileYield 54%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

N-(4-Bromo-2-cyano-5-fluoro-6-hydroxy-3-methylphenyl)-3-hydroxy-2,2-dimethyl-1-propanamide (I-107) (1.80 g, 5.21 mmol) was dissolved in toluene (36 ml), pyridinium p-toluenesulfonate (262 mg, 1.04 mmol) was added, followed by heating under reflux for 28 hours. After cooling to room temperature, this was diluted with ethyl acetate, and washed with aqueous sodium hydrogencarbonate solution and saturated brine. The obtained organic layer was dried over anhydrous sodium sulfate, the solvent was evaporated away under reduced pressure. The resulting residue was recrystallized and purified with n-hexane/ethyl acetate to obtain the entitled compound (912.6 mg, 54%) as a white solid. The filtrate was concentrated under reduced pressure to obtain a crude form (514.3 mg, 30%) as a pale yellow oily substance.

Workup

  1. temperatureby heating
  2. temperatureunder reflux for 28 hours
  3. washwashed with aqueous sodium hydrogencarbonate solution and saturated brine
  4. dry with materialThe obtained organic layer was dried over anhydrous sodium sulfate
  5. customthe solvent was evaporated away under reduced pressure
  6. customThe resulting residue was recrystallized
  7. custompurified with n-hexane/ethyl acetate

Sources & evidence

ORD record
ord-42157eb6382648df99d975387e42a2c2
Source dataset
uspto-grants-2010_06
Patent number
US07737166B2

Reaction notes

Loading…