Water → 3-Benzoyloxy-4-fluorobenzyl bromide

HRID 19936

Reaction equation

HRID 19936 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[O:9][C:10](=[O:17])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[Br:18]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.O>C(Cl)(Cl)(Cl)Cl.C(OCC)C>[Br:18][CH2:8][C:5]1[CH:6]=[CH:7][C:2]([F:1])=[C:3]([O:9][C:10](=[O:17])[C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:4]=1

Participants

7

Reactant 4

HCID 962WaterHCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 167492203-Benzoyloxy-4-fluorotoluene

Product 1

HCID 167478383-Benzoyloxy-4-fluorobenzyl bromide

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of benzoic acid 2-fluoro-5-methyl-phenyl ester (CAB02145, 2.47 g, 10.0 mmol), N-bromo-succinimide (1.96 g, 11.0 mmol) and dibenzoylperoxide (10 mg) in carbon tetrachloride (25 mL) was heated to reflux for 2 h (TLC monitored). After cooling to room temperature, water (50 mL) and diethyl ether (100 mL) were added. The organic layer was separated, washed with brine (20 mL), dried over sodium sulphate and concentrated under reduced pressure. The residue was purified by column chromatography (EtOAc:hexane, 1:25, Rf: 0.28). Yield: 1.80 g (58%), white solid. 1H-NMR (400 MHz, CDCl3) δ=4.48 (s, 2H, —CH2Br), 7.18 (dd, J=9.8, 8.6 Hz, 1H), 7.28 (ddd, J=8.6, 4.3, 2.3 Hz, 1H), 7.34 (dd, J=7.0, 2.3 Hz, 1H), 7.50-7.55 (m, 2H), 7.64-7.69 (m, 1H), 8.18-8.23 (m, 2H). LRMS (FAB+): 229.1 (95), 309.0 (100, [M+]+). Found: C, 54.1, H, 3.22%; C14H10BrFO2 (309.13) requires C, 54.39, H, 3.26%.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 2 h (TLC monitored)
  3. customThe organic layer was separated
  4. washwashed with brine (20 mL)
  5. dry with materialdried over sodium sulphate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography (EtOAc:hexane, 1:25, Rf: 0.28)

Sources & evidence

ORD record
ord-fcb20ac347e042dcb5f0de838d995e0f
Source dataset
uspto-grants-2010_06
Patent number
US07745472B2

Linked notes

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