Hydrogen Bromide → HCID 11782148, compound

HRID 1857504Notes

Reaction equation

HRID 1857504 reaction equation
N[C:2]1[CH:3]=[CH:4][C:5]([F:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].N([O-])=O.[Na+].[BrH:17]>CO.CC(C)=O.O>[Br:17][CH:6]([CH2:5][C:2]1[CH:3]=[CH:4][C:5]([F:12])=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

7

Reactant 3

HCID 260Hydrogen BromideHCID 15621043Methyl 5-amino-2-fluorobenzoateHCID 23668193Sodium Nitrite

Product 1

HCID 11782148HCID 11782148, compoundYield 45%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a solution of methyl 5-amino-2-fluorobenzoate (4.12 g) in 47% hydrobromic acid (11.4 ml), methanol (20 ml) and acetone (50 ml), a solution of sodium nitrite (1.88 g) in water (3 ml) was slowly added dropwise under cooling with salt-ice and stirring so as to keep an internal temperature of not higher than -5° C. After stirred for 30 minutes as it was, ice bath was removed, methyl acrylate (13.3 ml) was added, and cuprous oxide (225 mg) was added little by little while stirring vigorously. After no nitrogen became to generate, the reaction liquor was concentrated under reduced pressure. The residue was dissolved into ethyl acetate, washed with water, saturated aqueous solution of sodium hydrogencarbonate and water in order, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by means of silica gel column chromatography (developing solvent; n-hexane:ethyl acetate=10:1) to obtain 3.48 g (45%) of aimed compound as an oily material.

Workup

  1. customhigher than -5° C
  2. stirringAfter stirred for 30 minutes as it
  3. customice bath was removed
  4. additionmethyl acrylate (13.3 ml) was added
  5. additioncuprous oxide (225 mg) was added little by little
  6. stirringwhile stirring vigorously
  7. concentrationthe reaction liquor was concentrated under reduced pressure
  8. dissolutionThe residue was dissolved into ethyl acetate
  9. washwashed with water, saturated aqueous solution of sodium hydrogencarbonate and water in order
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationconcentrated under reduced pressure
  12. customThe residue was purified by means of silica gel column chromatography (developing solvent; n-hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-7fa25f474d1348e9913d16650be9b6d0
Source dataset
uspto-grants-2000_11
Patent number
US06147101

Reaction notes

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