Potassium Carbonate → HCID 84769512, compound

HRID 1748732Notes

Reaction equation

HRID 1748732 reaction equation
Br[C:2]1[CH:9]=[C:8]([Cl:10])[C:7]([O:11][CH3:12])=[CH:6][C:3]=1[CH:4]=[O:5].[CH3:13]B1OB(C)OB(C)O1.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:10][C:8]1[C:7]([O:11][CH3:12])=[CH:6][C:3]([CH:4]=[O:5])=[C:2]([CH3:13])[CH:9]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 574072Trimethylboroxine2×HCID 848037721616359-84-2

Product 1

HCID 84769512HCID 84769512, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 312751,4-DioxaneSolvent

Procedure

To a degassed solution of 2-bromo-4-chloro-5-methoxybenzaldehyde (1.46 g, 5.9 mmol) and trimethylboroxine (0.82 mL, 5.9 mmol) in 1,4-dioxane (80 mL) was added potassium carbonate (2.43 g, 17.6 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.68 g, 0.6 mmol). The mixture was heated under reflux for about 23 h, then more tetrakis(triphenylphosphine)palladium(0) (0.17 g, 0.15 mmol) and trimethylboroxine (0.2 mL, 1.4 mmol) were added and the mixture was heated under reflux for about another 8 h. After cooling to rt the mixture was filtered over diatomaceous earth and concentrated in vacuo. The residue was purified by column chromatography (SiO2, diethyl ether/hexanes 1:6) to give 4-chloro-5-methoxy-2-methylbenzaldehyde (0.87 g, 4.7 mmol, 81%) as a pale yellow solid: 1H-NMR (CDCl3, Bruker 400 MHz) δ 2.60 (3 H, s); 3.95 (3 H, s); 7.29 (1 H, s); 7.37 (1 H, s); 10.3 (1 H, s).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for about 23 h
  3. temperaturethe mixture was heated
  4. temperatureunder reflux for about another 8 h
  5. filtrationwas filtered over diatomaceous earth
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography (SiO2, diethyl ether/hexanes 1:6)

Sources & evidence

ORD record
ord-fda3b95226a148ebbf5d846d4b671adf
Source dataset
uspto-grants-2015_10
Patent number
US09150592B2

Reaction notes

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