1,4-Dibromobenzene → 4'-Bromo-5-chlorobiphenyl-2-carbaldehyde

HRID 1043424Notes

Reaction equation

HRID 1043424 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[Cl:15][C:16]1[CH:17]=[CH:18][C:19]([CH:25]=[O:26])=[C:20](B(O)O)[CH:21]=1>COCCOC.O.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>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([C:18]2[C:19]([CH:25]=[O:26])=[CH:20][CH:21]=[C:16]([Cl:15])[CH:17]=2)=[CH:3][CH:4]=1

Participants

7

Reactant 3

HCID 78041,4-DibromobenzeneHCID 11430Potassium CarbonateHCID 38069525-Chloro-2-formylphenylboronic acid

Product 1

HCID 592665424'-Bromo-5-chlorobiphenyl-2-carbaldehydeYield 52.1%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 1,4-dibromobenzene (8.3 g, 35.3 mmol), potassium carbonate (11.3 g, 81 mmol) and 5-chloro-2-formylphenylboronic acid (5 g, 27.1 mmol) in DME (150 mL) and water (30 mL) (in a pressure vessel) was sparged with nitrogen for 15 min. Pd(PPh3)4 (0.94 g, 0.814 mmol) was added and the reaction heated to 80° C. overnight. The reaction was cooled to r.t. and evaporated on the rotovap. The residue was diluted in EtOAc and washed with water then brine, dried over MgSO4, filtered and evaporated to give the crude material. The crude material was purified by flash chromatography on the Biotage (0-15% EtOAc:Hex) to give 4′-bromo-5-chlorobiphenyl-2-carbaldehyde (4.17 g, 14.11 mmol, 52% yield) as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.18-7.28 (m, 2H) 7.42 (d, J=2.01 Hz, 1H) 7.50 (ddd, J=8.41, 2.01, 0.88 Hz, 1H) 7.59-7.69 (m, 2H) 7.98 (d, J=8.53 Hz, 1H) 9.92 (s, 1H).

Workup

  1. temperatureThe reaction was cooled to r.t.
  2. customevaporated on the rotovap
  3. additionThe residue was diluted in EtOAc
  4. washwashed with water
  5. dry with materialbrine, dried over MgSO4
  6. filtrationfiltered
  7. customevaporated
  8. customto give the crude material
  9. customThe crude material was purified by flash chromatography on the Biotage (0-15% EtOAc:Hex)

Sources & evidence

ORD record
ord-bd583aecd4dd47ef89be12dc839fe60d
Source dataset
uspto-grants-2013_10
Patent number
US08563505B2

Reaction notes

Loading…