Sodium Carbonate → Methyl 4,5-dicyclopropyl-2-ethoxybenzoate

HRID 531053Notes

Reaction equation

HRID 531053 reaction equation
[CH:1]1(B(O)O)[CH2:3][CH2:2]1.C(=O)([O-])[O-].[Na+].[Na+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.Br[C:43]1[C:44]([CH:56]2[CH2:58][CH2:57]2)=[CH:45][C:46]([O:53][CH2:54][CH3:55])=[C:47]([CH:52]=1)[C:48]([O:50][CH3:51])=[O:49]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O.C1(C)C=CC=CC=1>[CH:56]1([C:44]2[C:43]([CH:1]3[CH2:3][CH2:2]3)=[CH:52][C:47]([C:48]([O:50][CH3:51])=[O:49])=[C:46]([O:53][CH2:54][CH3:55])[CH:45]=2)[CH2:58][CH2:57]1

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 2760897Cyclopropylboronic acidHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 90423807Methyl 5-bromo-4-cyclopropyl-2-ethoxybenzoate

Product 1

HCID 90423797Methyl 4,5-dicyclopropyl-2-ethoxybenzoateYield 92.1%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Cyclopropylboronic acid (1.76 g), a 2 M aqueous sodium carbonate solution (20 mL), tris(dibenzylideneacetone)dipalladium(0) (874 mg), and dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (840 mg) were added at room temperature to a toluene (70 mL) solution of methyl 5-bromo-4-cyclopropyl-2-ethoxybenzoate (4.08 g), and the mixture was stirred at 100° C. for 18 hours in an argon atmosphere. Water was added to the reaction mixture at room temperature, and the mixture was filtered through celite. Then, the filtrate was subjected to extraction with ethyl acetate. The obtained organic layer was washed with water and saturated saline in this order and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the title compound (3.27 g).

Workup

  1. filtrationthe mixture was filtered through celite
  2. extractionThen, the filtrate was subjected to extraction with ethyl acetate
  3. washThe obtained organic layer was washed with water and saturated saline in this order
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationthe solvent was distilled off under reduced pressure
  6. customThe obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-6f7752a56b3c4b1e8ab5203c521761ac
Source dataset
uspto-grants-2016_05
Patent number
US09353108B2

Reaction notes

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