3-Chloro-2-methyl-1-propene → Methyl 3-methoxy-4-(2-methylallyloxy)benzoate

HRID 1643840Notes

Reaction equation

HRID 1643840 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[O:12][CH3:13].C([O-])([O-])=O.[K+].[K+].Cl[CH2:21][C:22]([CH3:24])=[CH2:23]>CN(C=O)C>[CH3:13][O:12][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:2]=1[O:1][CH2:23][C:22]([CH3:24])=[CH2:21])[C:6]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 3

HCID 112413-Chloro-2-methyl-1-propeneHCID 11430Potassium CarbonateHCID 19844Methyl Vanillate

Product 1

HCID 51109732Methyl 3-methoxy-4-(2-methylallyloxy)benzoateYield 100%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To a suspension of methyl 4-hydroxy-3-methoxybenzoate (100 g, 0.55 mol) and K2CO3 (92 g, 0.66 mol) in DMF (800 ml) was added drop wise 3-chloro-2-methyl-propene (55 g, 0.60 mol). The mixture was stirred at 60° C. overnight. TLC (EtOAc/petroleum ether=1/3) showed no starting material was present. The reaction mixture was filtered and the filtrate was added water (400 ml). The mixture was extracted with EtOAc (400 ml×3). The combined organic phase was washed with brine (400 mL), dried (Na2SO4) and concentrated to give the product (130 g, 100%) as yellow oil. The oil was used directly to the next step without further purification. 1H NMR (400 MHz, CDCl3): δ 7.54 (d, 1H), 7.19 (s, 1H), 6.80 (d, 1H), 5.00(d, 2H), 4.50 (s, 2H), 3.83 (d, 6H), 1.76 (s, 3H).

Workup

  1. filtrationThe reaction mixture was filtered
  2. additionthe filtrate was added water (400 ml)
  3. extractionThe mixture was extracted with EtOAc (400 ml×3)
  4. washThe combined organic phase was washed with brine (400 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-3436145206ff4bb8bb0cbca2aa89f8dd
Source dataset
uspto-grants-2012_02
Patent number
US08119624B2

Reaction notes

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