Bromine → HCID 59316609, compound

HRID 1183768Notes

Reaction equation

HRID 1183768 reaction equation
[O:1]=[C:2]1[CH2:11][CH2:10][C:9]2[C:4](=[CH:5][C:6]([O:12][CH2:13][C:14]3[CH:26]=[CH:25][C:17]([C:18]([O:20]C(C)(C)C)=[O:19])=[CH:16][CH:15]=3)=[CH:7][CH:8]=2)[NH:3]1.[Br:27]Br.[Br-].[K+]>C(O)(=O)C>[Br:27][C:7]1[CH:8]=[C:9]2[C:4](=[CH:5][C:6]=1[O:12][CH2:13][C:14]1[CH:26]=[CH:25][C:17]([C:18]([OH:20])=[O:19])=[CH:16][CH:15]=1)[NH:3][C:2](=[O:1])[CH2:11][CH2:10]2

Participants

5

Reactant 3

HCID 24408BromineHCID 253877Potassium BromideHCID 68588682HCID 68588682, compound

Product 1

HCID 59316609HCID 59316609, compoundYield 57.1%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

To a suspension of tert-butyl 4-((2-oxo-1,2,3,4-tetrahydroquinolin-7-yloxy)methyl)benzoate (550 mg, 1.56 mmol) in glacial acetic acid (5 mL) was added dropwise a solution of bromine (800 mg, 5.00 mmol) and potassium bromide (595 mg, 5.0 mmol) in acetic acid (10 mL) under an atmosphere of dry N2, and the mixture stirred at room temperature for 1 hour. The reaction mixture was warmed to 60° C. for 18 hours, then cooled, and the solvent evaporated under reduced pressure. The residue was poured slowly into water (40 mL) with stirring, diethyl ether (3 mL) was added, and the mixture sonicated, filtered, the solid thus obtained was washed with saturated sodium carbonate (30 mL), water (50 mL), diethyl ether (10 mL), and dried under reduced pressure to afford 4-((6-bromo-2-oxo-1,2,3,4-tetrahydroquinolin-7-yloxy)methyl)benzoic acid (334 mg, 0.89 mmol, 57%). LCMS mz 375.9 (M−H) and 377.9 (M+H), anal HPLC>91% in purity, 1H NMR (400 MHz; CD3CN) δ8.25 (bs, 1H); 8.09 (d, J=8.6 Hz, 2H); 7.65 (d, J=8.6 Hz, 2H); 7.42 (s, 1H); 6.62 (s, 1H); 5.26 (s, 2H); 2.91 (m, 2H); 2.53 (m, 2H).

Workup

  1. temperatureThe reaction mixture was warmed to 60° C. for 18 hours
  2. temperaturecooled
  3. customthe solvent evaporated under reduced pressure
  4. additionThe residue was poured slowly into water (40 mL)
  5. stirringwith stirring
  6. additiondiethyl ether (3 mL) was added
  7. customthe mixture sonicated
  8. filtrationfiltered
  9. customthe solid thus obtained
  10. washwas washed with saturated sodium carbonate (30 mL), water (50 mL), diethyl ether (10 mL)
  11. customdried under reduced pressure

Sources & evidence

ORD record
ord-52b0bd205c4d4d7caaea053ed3ff23ef
Source dataset
uspto-grants-2014_03
Patent number
US08664379B2

Reaction notes

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