Potassium Carbonate → Methyl 4-cyclopropyl-2-methylbenzoate

HRID 1488177Notes

Reaction equation

HRID 1488177 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 under reduced pressure. 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 under reduced pressure
  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-8a8cc4f47e274615b2b392d2b5b875c2
Source dataset
uspto-grants-2016_08
Patent number
US09428502B2

Reaction notes

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