Hydrogen Bromide → 1(3H)-Isobenzofuranone, 6-bromo-3-methyl-

HRID 1061448Notes

Reaction equation

HRID 1061448 reaction equation
N[C:2]1[CH:11]=[C:10]2[C:5]([CH:6]([CH3:12])[O:7][C:8]2=[O:9])=[CH:4][CH:3]=1.N([O-])=O.[Na+].[BrH:17]>[Cu](Br)Br>[Br:17][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]([CH3:12])[O:7][C:8]2=[O:9])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 260Hydrogen BromideHCID 4877771(3H)-Isobenzofuranone, 6-amino-3-methyl-HCID 23668193Sodium Nitrite

Product 1

HCID 4877791(3H)-Isobenzofuranone, 6-bromo-3-methyl-

Reagents, catalysts & solvents 1

HCID 24611Copper bromide (CuBr2)Catalyst

Procedure

58.25 g of 6-amino-3-methylphtalide (3-4) was dissolved in 1.5 l of 4.7% hydrobromic acid and 405.60 g of copper (II) bromide was added thereto, and under cooling with ice, 400 ml of aqueous solution of 41.92 g of sodium nitrite was dropped thereto. The resulting mixture was stirred at the same temperature for 2 hours and then stirred at a room temperature for 15 hours, and thereafter, extracted with chloroform. The resulting organic layer was washed with saturated sodium bicarbonate solution and saturated salt water in order, and dried over anhydrous magnesium sulfate, and thereafter, the solvent was distilled off under reduced pressure, the resulting residue was purified by silica gel column chromatography (eluent; hexane:ethyl acetate=3:1) to obtain 71.56 g of 6-bromo-3-methylphtalide (3-5).

Workup

  1. additionwas dropped
  2. stirringstirred at a room temperature for 15 hours
  3. extractionextracted with chloroform
  4. washThe resulting organic layer was washed with saturated sodium bicarbonate solution and saturated salt water in order
  5. dry with materialdried over anhydrous magnesium sulfate
  6. distillationthe solvent was distilled off under reduced pressure
  7. customthe resulting residue was purified by silica gel column chromatography (eluent; hexane:ethyl acetate=3:1)

Sources & evidence

ORD record
ord-2856f3d782654f86ac649f586d09d890
Source dataset
uspto-grants-2003_02
Patent number
US06525066B2

Reaction notes

Loading…