Allyl bromide → Methyl 3-(allyloxy)-4-formylbenzoate

HRID 965838Notes

Reaction equation

HRID 965838 reaction equation
[CH:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][C:4]=1[OH:13])=[O:2].C([O-])([O-])=O.[K+].[K+].[CH2:20](Br)[CH:21]=[CH2:22]>CC(C)=O>[CH2:22]([O:13][C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][C:3]=1[CH:1]=[O:2])[C:7]([O:9][CH3:10])=[O:8])[CH:21]=[CH2:20]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 14395860Methyl 4-formyl-3-hydroxybenzoate

Product 1

HCID 22313312Methyl 3-(allyloxy)-4-formylbenzoateYield 94.1%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Conditions

Temperature
48 °C

Procedure

To a stirred solution of methyl 4-formyl-3-hydroxybenzoate [see: Harayama, Chem. Pharm. Bull. 1994, 2170] (0.8 g, 4.1 mmol) and anhydrous K2CO3 (1.1 g, 8.0 mmol) in acetone (12 mL) is added allyl bromide (0.70 mL, 8.1 mmol). The mixture is heated in a 48° C. oil bath for 2 h. The reaction mixture is cooled to rt and filtered. The mother liquor is concentrated in vacuo to a brown oil. The crude product is purified by flash chromatography on SiO2. Elution with hexanes-EtOAc (85:15) gives 0.85 g (49%) of methyl 3-(allyloxy)-4-formylbenzoate as a clear solid: 1H NMR (400 MHz, CDCl3) δ 10.6, 7.9, 7.7, 6.1, 5.5, 5.4, 4.8, 4.0.

Workup

  1. temperatureThe reaction mixture is cooled to rt
  2. filtrationfiltered
  3. concentrationThe mother liquor is concentrated in vacuo to a brown oil
  4. customThe crude product is purified by flash chromatography on SiO2
  5. washElution with hexanes-EtOAc (85:15)

Sources & evidence

ORD record
ord-40f8c9dbbc5f4e83980478700b6d6db0
Source dataset
uspto-grants-2005_10
Patent number
US06951868B2

Reaction notes

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