Potassium Carbonate → Methyl 2,2'-dimethyl-1,1'-biphenyl-4-carboxylate

HRID 2246843Notes

Reaction equation

HRID 2246843 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12].[C:13]1([CH3:22])[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1B(O)O.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.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]>[CH3:12][C:3]1[CH:4]=[C:5]([C:6]([O:8][CH3:9])=[O:7])[CH:10]=[CH:11][C:2]=1[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=1[CH3:22]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 27332672-Methylphenyl boronic acidHCID 3294148Methyl 4-bromo-3-methylbenzoate

Product 1

HCID 59606553Methyl 2,2'-dimethyl-1,1'-biphenyl-4-carboxylateYield 108.2%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of methyl 4-bromo-3-methylbenzoate (25.0 g, 110 mmol), o-tolylboronic acid (16.5 g, 120 mmol) and potassium carbonate (50 g, 360 mmol) in dioxane:water (300 mL:200 mL) was purged with nitrogen for 1 hour. [1,1′-bis(Diphenylphosphino)ferrocene]dichloropalladium [II] (4.5 g, 5.5 mmol) was added and the reaction mixture heated to 100° C. with vigorous stirring for 3.5 hours. The cooled reaction mixture was filtered through Celite and the cake washed with ethyl acetate (500 mL). The combined organic phases were washed with 1 M aqueous sodium hydroxide (500 mL) and brine (500 mL), dried over anhydrous potassium carbonate, filtered and concentrated in vacuo to afford a dark oil (28.6 g). Purification by flash chromatography using 2% ethyl acetate in hexanes as solvent provided the title compound (24.7 g) as a pale yellow oil.

Workup

  1. customwater (300 mL:200 mL) was purged with nitrogen for 1 hour
  2. customThe cooled reaction mixture
  3. filtrationwas filtered through Celite
  4. washthe cake washed with ethyl acetate (500 mL)
  5. washThe combined organic phases were washed with 1 M aqueous sodium hydroxide (500 mL) and brine (500 mL)
  6. dry with materialdried over anhydrous potassium carbonate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-073c9f6ddbca4632bc1a51aa87bff69e
Source dataset
uspto-grants-2010_03
Patent number
US07687623B2

Reaction notes

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