Potassium Carbonate → Methyl 4-cyclopropyl-2-methylbenzoate

HRID 541264Notes

Reaction equation

HRID 541264 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[CH:19]1(B(O)O)[CH2:21][CH2:20]1>C1(C)C=CC=CC=1.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CC([O-])=O.CC([O-])=O.[Pd+2]>[CH:19]1([C:2]2[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[CH:3]=2)[CH2:21][CH2:20]1

Participants

8

Reactant 3

HCID 11430Potassium CarbonateHCID 2760897Cyclopropylboronic acidHCID 22031226Methyl 4-bromo-2-methylbenzoate

Product 1

HCID 59020660Methyl 4-cyclopropyl-2-methylbenzoateYield 68.1%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of methyl 4-bromo-2-methylbenzoate (5.00 g, 20.7 mmol, 1.00 equiv, 95%) in a mixture of toluene and H2O (20 mL/1 mL) were added potassium carbonate (6.10 g, 44.1 mmol, 2.00 equiv), cyclopropylboronic acid (2.30 g, 26.8 mmol, 1.20 equiv), Pd(dppf)Cl2 (900 mg, 1.23 mmol, 0.05 equiv), and Pd(OAc)2 (250 mg, 1.12 mmol, 0.05 equiv). The reaction mixture was purged with nitrogen and stirred at 80° C. overnight. After cooling to room temperature, the mixture was then concentrated in vacuo. The resulting residue was purified via silica gel column chromatography with ethyl acetate/petroleum ether (1:50) as eluent to yield 2.68 g (61%) of methyl 4-cyclopropyl-2-methylbenzoate as a colorless oil.

Workup

  1. customThe reaction mixture was purged with nitrogen
  2. temperatureAfter cooling to room temperature
  3. concentrationthe mixture was then concentrated in vacuo
  4. customThe resulting residue was purified via silica gel column chromatography with ethyl acetate/petroleum ether (1:50) as eluent

Sources & evidence

ORD record
ord-e3a638e8eaa24071bef6c325f81e95ff
Source dataset
uspto-grants-2014_10
Patent number
US08871790B2

Reaction notes

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