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

HRID 2249378Notes

Reaction equation

HRID 2249378 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 then 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 then cooled to room temperature and 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 dried over Na2SO4 (with charcoal). Filtration and concentration gave 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 (bs, 1H) 5.81 (bs, 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. temperaturethen cooled to room temperature
  5. additionpoured over ice
  6. extractionThe mixture was extracted with two portions of ethyl acetate
  7. dry with materialthe combined organic layers dried over Na2SO4 (with charcoal)
  8. filtrationFiltration and concentration

Sources & evidence

ORD record
ord-39aa6e5412b14a648632b1fd63ce67f8
Source dataset
uspto-grants-2008_01
Patent number
US07314849B2

Reaction notes

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