Sulfuric Acid → 2-Chloro-5-bromo-6-fluorobenzamide

HRID 1363937Notes

Reaction equation

HRID 1363937 reaction equation
S(=O)(=O)(O)O.[Br:6][C:7]1[C:8]([F:16])=[C:9]([C:12]([Cl:15])=[CH:13][CH:14]=1)[C:10]#[N:11].[OH-:17].[NH4+]>>[Br:6][C:7]1[C:8]([F:16])=[C:9]([C:12]([Cl:15])=[CH:13][CH:14]=1)[C:10]([NH2:11])=[O:17]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 14923Ammonium HydroxideHCID 509979493-Bromo-6-chloro-2-fluorobenzonitrile

Product 1

HCID 184515062-Chloro-5-bromo-6-fluorobenzamide

Conditions

Temperature
55 °C

Procedure

Concentrated sulfuric acid (15 mL) was placed in a 100 mL 3-neck flask equipped with an internal thermometer and heated to 55° C. 3-Bromo-2-fluoro-6-chlorobenzonitrile (11.0 g, 47 mmol) was added portion-wise to the acid with stirring maintaining the temperature above 50° C. The dark solution was heated at 65° C. for 24 hours, allowed to cool to room temperature, poured over ice, and cautiously neutralized with concentrated ammonium hydroxide. The mixture was extracted with two portions of ethyl acetate and the combined organic layers were dried and concentrated to give 3-bromo-2-fluoro-6-chlorobenzamide (11.5 g, 45.5 mmol) as a light orange solid: mp 157-158° C., 1H NMR (CDCl3): δ 7.54 (t, 1H), 7.14 (dd, 1H), 6.03 (br s, 1H) 5.81 (br s, 1H).

Workup

  1. customequipped with an internal thermometer
  2. temperaturemaintaining the temperature above 50° C
  3. temperatureThe dark solution was heated at 65° C. for 24 hours
  4. temperatureto cool to room temperature
  5. additionpoured over ice
  6. extractionThe mixture was extracted with two portions of ethyl acetate
  7. customthe combined organic layers were dried
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-5dcad29ac0df416dbb00d9462fa7707b
Source dataset
uspto-grants-2011_02
Patent number
US07888287B2

Reaction notes

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