Sodium Carbonate → 4'-Nitro[1,1'-biphenyl]-3-carbaldehyde

HRID 1889699Notes

Reaction equation

HRID 1889699 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6].C([O-])([O-])=O.[Na+].[Na+].[N+:16]([C:19]1[CH:24]=[CH:23][C:22](B(O)O)=[CH:21][CH:20]=1)([O-:18])=[O:17]>CN(C=O)C.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N+:16]([C:19]1[CH:24]=[CH:23][C:22]([C:2]2[CH:9]=[CH:8][CH:7]=[C:4]([CH:5]=[O:6])[CH:3]=2)=[CH:21][CH:20]=1)([O-:18])=[O:17]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 765833-BromobenzaldehydeHCID 27735524-Nitrophenylboronic acid

Product 1

HCID 461934594'-Nitro[1,1'-biphenyl]-3-carbaldehydeYield 49.9%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a sealable flask containing a mixture of 3-bromobenzaldehyde (1.8 mL, 15 mmol) and Na2CO3 (1.6 g, 15 mmol) in anhydrous DMF (20 mL) and water (10 mL), were added 4-nitrophenylboronic acid (2.5 g, 15 mmol) then palladium(II) acetate (0.17 g, 0.75 mmol). Argon was bubbled through the mixture before the flask was sealed and the mixture stirred at room temperature. After 4 days, the reaction mixture was partitioned between ethyl acetate and brine before the entire mixture was filtered through a pad of Celite®. The aqueous and organic layers, of the filtrate, were separated and the aqueous layer was extracted twice more with EtOAc. All of the organic layers were combined, washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. Purification by silica gel flash chromatography (ISCO CombiFlash Companion system, 120 g, RediSep normal phase silica flash column, eluting with 10-50% EtOAc in hexane) afforded the desired compound (1.7 g, 47%) as an off-white solid. 1H NMR (CDCl3) δ 10.05 (s, 1H), 8.31-8.25 (m, 2H), 8.10-8.06 (m, 1H), 7.93-7.81 (m, 2H), 7.77-7.70 (m, 2H), 7.63 (t, J=7.7 Hz, 1H). MS (ESI): 228.1 (M+H)+.

Workup

  1. additionTo a sealable flask containing
  2. customArgon was bubbled through the mixture before the flask
  3. customwas sealed
  4. customthe reaction mixture was partitioned between ethyl acetate and brine before the entire mixture
  5. filtrationwas filtered through a pad of Celite®
  6. customThe aqueous and organic layers, of the filtrate, were separated
  7. extractionthe aqueous layer was extracted twice more with EtOAc
  8. washwashed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customPurification
  13. washby silica gel flash chromatography (ISCO CombiFlash Companion system, 120 g, RediSep normal phase silica flash column, eluting with 10-50% EtOAc in hexane)

Sources & evidence

ORD record
ord-2d09e14e268049448408bc1dcceee523
Source dataset
uspto-grants-2013_08
Patent number
US08501992B2

Reaction notes

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