Hydrogen Bromide → 2-Bromo-3-fluorobenzoic acid

HRID 471607

Reaction equation

HRID 471607 reaction equation
N[C:2]1[C:10]([F:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].C(#N)C.[BrH:15].N([O-])=O.[Na+]>O.[Cu]Br>[Br:15][C:2]1[C:10]([F:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5]

Participants

7

Reactant 4

HCID 260Hydrogen BromideHCID 6342AcetonitrileHCID 5864082-Amino-3-fluorobenzoic acidHCID 23668193Sodium Nitrite

Product 1

HCID 3026222-Bromo-3-fluorobenzoic acidYield 100%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

In a 1 L, three necked flask fitted with a dropping funnel and thermometer, were charged 2-amino-3-fluorobenzoic acid (20.0 g, 0.13 mol) and acetonitrile (160 mL). After cooling to 0° C., HBr (47%, 160 mL) was added drop wise over 10 min. To the resulting solution a solution of NaNO2 (10.0 g, 0.14 mol) in water (20.0 mL) was added drop wise over 1 h. After addition, the reaction mixture was stirred at 0° C. for 5 min, and copper(I) bromide (22.0 g, 0.15 mol) was added portionwise over 30 min. Stirring was continued at 70° C. in a an oil bath for 1 h. After cooling to 0° C., 700 mL of water was added and the precipitate was filtered, washed with cold water and dried under vacuum to give 28.23 g (100%) of the title compound as a white solid. The crude product was used in the next step without purification.

Workup

  1. customIn a 1 L, three necked flask fitted with a dropping funnel
  2. additionAfter addition
  3. stirringStirring
  4. waitwas continued at 70° C. in a an oil bath for 1 h
  5. temperatureAfter cooling to 0° C.
  6. filtrationthe precipitate was filtered
  7. washwashed with cold water
  8. customdried under vacuum

Sources & evidence

ORD record
ord-b7e4cabab20244c384a9c5b988e858d5
Source dataset
uspto-grants-2014_01
Patent number
US08633186B2

Linked notes

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