Methanol → 5-(Bromomethyl)-1,3-difluoro-2-nitrobenzene

HRID 420301Notes

Reaction equation

HRID 420301 reaction equation
P(Br)(Br)[Br:2].[F:5][C:6]1[CH:7]=[C:8]([CH2:16]O)[CH:9]=[C:10]([F:15])[C:11]=1[N+:12]([O-:14])=[O:13].CO.C([O-])(O)=O.[Na+]>CCOCC>[Br:2][CH2:16][C:8]1[CH:9]=[C:10]([F:15])[C:11]([N+:12]([O-:14])=[O:13])=[C:6]([F:5])[CH:7]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 24614Phosphorus tribromideHCID 516892Sodium BicarbonateHCID 55271003(3,5-Difluoro-4-nitrophenyl)methanol

Product 1

HCID 573863065-(Bromomethyl)-1,3-difluoro-2-nitrobenzene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
25 °C

Procedure

To a solution of PBr3 (7.04 mL, 73 mmol) in Et2O (200 mL) is added under argon at 0° C. a solution of (3,5-difluoro-4-nitro-phenyl)-methanol (9.3 g, 48.7 mmol) in Et2O (200 mL). The reaction mixture was allowed to warm to 25° C. and stirred for 24 h at 25° C. After the addition of MeOH (5 mL) at 0° C., the reaction mixture was poured onto cold aq. NaHCO3 solution and the product was extracted with EtOAc. Combined organic extracts were washed with saturated NaHCO3 solution and brine, dried over MgSO4, filtered and concentrated to provide the title compound after filtration through a plug of silicagel with hexane-EtOAc 3:1 as a yellow solid: TLC (hexane-EtOAc 3:1) Rf=0.40; HPLC RtA=2.01 min; 1H NMR (400 MHz, CDCl3): δ 7.14 (d, 2H), 4.40 (s, 2H).

Workup

  1. extractionthe product was extracted with EtOAc
  2. washCombined organic extracts were washed with saturated NaHCO3 solution and brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-38dbef6ab78942f8aa885838e8db11bb
Source dataset
uspto-grants-2012_01
Patent number
US08093406B2

Reaction notes

Loading…