N-bromobutanimide → 3-Benzoyloxy-4-fluorobenzyl bromide

HRID 1685647Notes

Reaction equation

HRID 1685647 reaction equation
[C:1]([O:9][C:10]1[CH:11]=[C:12]([CH3:17])[CH:13]=[CH:14][C:15]=1[F:16])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Br:18]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.CCOCC.O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[C:1]([O:9][C:10]1[CH:11]=[C:12]([CH:13]=[CH:14][C:15]=1[F:16])[CH2:17][Br:18])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 2

HCID 67184N-bromobutanimideHCID 167492203-Benzoyloxy-4-fluorotoluene

Product 1

HCID 167478383-Benzoyloxy-4-fluorobenzyl bromideYield 58.2%

Reagents, catalysts & solvents 4

HCID 7187Benzoyl PeroxideCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

Commercial N-bromosuccinimide (NBS) was recrystallised from water and thoroughly dried in vacuo (24 h) prior to use (mp. 180-182° C., lit. 180-183° C.). To a solution of 3-benzoyloxy-4-fluorotoluene (2.47 g, 10 mmol) in anhydrous carbon tetrachloride (25 mL) was added finely powdered NBS (1.96 g, 11 mmol) and benzoylperoxide (0.01 g). The mixture heated at reflux for 2 h, cooled and diluted with Et2O (100 mL) and water (50 mL). The ethereal layer was washed with brine (20 mL) and dried (Na2SO4). Concetration in vacuo and subsequent purification by flash column chromatography [SiO2, EtOAc/n-hexane (1:25)] gave 3-benzoyloxy-4-fluorobenzyl bromide as a white solid (1.80 g, 58%); δH (400 MHz, CDCl3) 4.48 (s, 2H), 7.18 (dd, J=9.8, 8.6, 1H), 7.28 (ddd, J=8.6, 4.3, 2.3, 1H), 7.34 (dd, J=7.0, 2.3, 1H), 7.50-7.55 (m, 2H), 7.64-7.69 (m, 1H), 8.18-8.23 (m, 2H); LRMS (FAB+) m/z (rel. intensity) 229.1 (95), 309.0 (100, [M+H]+). Found: C, 54.1, H, 3.22; C14H10BrFO2 requires C, 54.39, H, 3.26%.

Workup

  1. customCommercial N-bromosuccinimide (NBS) was recrystallised from water
  2. customthoroughly dried in vacuo (24 h)
  3. custom(mp. 180-182° C., lit. 180-183° C.)
  4. temperatureThe mixture heated
  5. temperatureat reflux for 2 h
  6. temperaturecooled
  7. washThe ethereal layer was washed with brine (20 mL)
  8. dry with materialdried (Na2SO4)
  9. customConcetration in vacuo and subsequent purification by flash column chromatography [SiO2, EtOAc/n-hexane (1:25)]

Sources & evidence

ORD record
ord-54d0fc5ada3c4e77930bb4c69e88d1f7
Source dataset
uspto-grants-2012_04
Patent number
US08148415B2

Reaction notes

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