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Boron Trichloride → 2-(2-Fluorophenyl)-5-hydroxy-6-methoxyquinolin-4-one

HRID 38632
Notes
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Reaction equation

HRID 38632 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH2:17][C:16](=[O:18])[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([O:21][CH3:22])[C:14]=2[O:19]C)[N:9]=1.B(Cl)(Cl)Cl>C(Cl)Cl>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH2:17][C:16](=[O:18])[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([O:21][CH3:22])[C:14]=2[OH:19])[N:9]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

4

Reactant 2

HCID 25135Boron TrichlorideHCID 666596222-(2-Fluorophenyl)-5,6-dimethoxyquinolin-4-one

Product 1

HCID 666594142-(2-Fluorophenyl)-5-hydroxy-6-methoxyquinolin-4-oneYield 24.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of 16 (0.2 g, 0.67 mmol) in CH2Cl2 (3 mL) was added 5 mL of BCl3 solution (1 M in CH2Cl2) dropwise at 0°±1° C. The mixture was stirred at 25±1° C. for 2 h and then poured into crushed ice, extracted with EtOAc. The organic layer was washed with H2O, dried over MgSO4 and evaporated. The crude was purified by column chromatography (SiO2, CHCl3: MeOH=15:1) and recrystallized from MeOH to give 37. Yellow solid; yield: 24.1%; mp 268-270° C.; MS (EI, 70 eV): m/z 285 (M+); IR (KBr): 1604.77 (C═O) cm−1; 1H-NMR (DMSO-d6. 200 MHz): δ 3.78 (s, 3H), 6.11 (s, 1H), 7.01 (d, J=7.4 Hz, 1H), 7.36-7.48 (m, 3H), 7.54-7.72 (m, 2H), 12.25 (s, 1H), 14.54 (s, 1H); 13C-NMR (DMSO-d6, 50 MHz): δ 55.80, 106.22, 106.43, 112.88, 116.36 (d, J=23 Hz), 120.81, 121.96 (d, J=13.5 Hz), 125.04, 130.85, 132.67 (d, J=8.6 Hz), 135.09, 141.02, 146.27, 149.29, 158.92 (d, J=247.7 Hz), 181.97; Anal. calcd for C16H12FNO3: C, 67.36; H, 4.24; N, 4.91. Found: C, 67.32; H, 4.26; N, 4.89.

Workup

  1. additionpoured
  2. custominto crushed ice
  3. extractionextracted with EtOAc
  4. washThe organic layer was washed with H2O
  5. dry with materialdried over MgSO4
  6. customevaporated
  7. customThe crude was purified by column chromatography (SiO2, CHCl3: MeOH=15:1)
  8. customrecrystallized from MeOH

Sources & evidence

ORD record
ord-080f8d77e39243f3b660a58d9e2c0690
Source dataset
uspto-grants-2013_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08524740B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes