Bromide ion → HCID 22625972, compound

HRID 277762Notes

Reaction equation

HRID 277762 reaction equation
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([F:9])=[C:5]([F:10])[CH:4]=1.[Br-].[C:12](#[N:20])[C:13]1[C:14](=[CH:16][CH:17]=[CH:18][CH:19]=1)[NH2:15].[C:21](=O)(OCC)[O:22]CC.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1COCC1>[F:10][C:5]1[CH:4]=[C:3]([C:12]2[C:13]3[C:14](=[CH:16][CH:17]=[CH:18][CH:19]=3)[NH:15][C:21](=[O:22])[N:20]=2)[CH:8]=[CH:7][C:6]=1[F:9]

Participants

8

Reactant 6

HCID 259Bromide ionHCID 311Citric AcidHCID 7766Diethyl CarbonateHCID 676754-Bromo-1,2-difluorobenzeneHCID 729132-AminobenzonitrileHCID 5462224Magnesium

Product 1

HCID 22625972HCID 22625972, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
40 °C

Procedure

An oven dried round-bottom flask was charged with magnesium turnings (3.55 g, 146 mmol) in THF (100 mL) under argon. 1-Bromo-3,4-difluorobenzene (4.0 mL, 35.3 mmol) was added to the suspension in one portion. The solution was heated to 40° C. Once the temperature had stabilized at 50° C., the remainder of the bromide (13.52 mL, 155 mmol total) was added dropwise. After complete addition, the solution was stirred for 1 hour at 65° C. A solution of anthranilonitrile (4.95 g, 41.9 mmol) in THF (25 mL) was added dropwise while keeping the internal temperature constant. After stirring or two hours at 65° C., diethyl carbonate (16.3 mL, 135 mmol) was added dropwise to the brownish-red solution . This solution was stirred for an additional 30 minutes at 65° C. and then cooled to room temperature. The solution was poured into a mixture of 250 mL of 1 M citric acid and ice. The mixture was extracted three times with CHCl3 (50 mL) and the combined extracts were washed with a 10% Na2CO3 solution. The organics were dried over Na2SO4, concentrated, and triturated with Et2O to afford the title compound.

Workup

  1. customhad stabilized at 50° C.
  2. additionAfter complete addition
  3. stirringAfter stirring or two hours at 65° C.
  4. stirringThis solution was stirred for an additional 30 minutes at 65° C.
  5. temperaturecooled to room temperature
  6. extractionThe mixture was extracted three times with CHCl3 (50 mL)
  7. washthe combined extracts were washed with a 10% Na2CO3 solution
  8. dry with materialThe organics were dried over Na2SO4
  9. concentrationconcentrated
  10. customtriturated with Et2O

Sources & evidence

ORD record
ord-d125b61294be44e19df75cd33740d0a5
Source dataset
uspto-grants-2002_03
Patent number
US06358959B1

Reaction notes

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