1,3-Dibromobenzene → 3-Bromo-3'-vinylbiphenyl

HRID 1043429Notes

Reaction equation

HRID 1043429 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[CH:15]([C:17]1[CH:18]=[C:19](B(O)O)[CH:20]=[CH:21][CH:22]=1)=[CH2:16]>COCCOC.O>[Br:8][C:4]1[CH:3]=[C:2]([C:21]2[CH:20]=[CH:19][CH:18]=[C:17]([CH:15]=[CH2:16])[CH:22]=2)[CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 79271,3-DibromobenzeneHCID 11430Potassium CarbonateHCID 43668863-Vinylphenylboronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 592665703-Bromo-3'-vinylbiphenylYield 60%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 1,3-dibromobenzene (5.3 mL, 43.9 mmol), potassium carbonate (14.0 g, 101 mmol) and 3-vinylphenylboronic acid (5 g, 33.8 mmol) in DME (100 mL) and water (20 mL) (in a pressure vessel) was sparged with nitrogen for 15 min. Pd(PPh3)3 (1.17 g, 1.014 mmol) was added and then the reaction was 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 (0-5% EtOAc:Hex) to give 3-bromo-3′-vinylbiphenyl (5.21 g, 20.10 mmol, 60% yield) as a clear liquid. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 5.33 (d, J=10.79 Hz, 1H) 5.84 (dd, J=17.57, 0.75 Hz, 1H) 6.80 (dd, J=17.57, 10.79 Hz, 1H) 7.32 (t, J=7.78 Hz, 1H) 7.38-7.48 (m, 3H) 7.51 (dddd, J=13.24, 7.84, 1.76, 1.00 Hz, 2H) 7.56-7.61 (m, 1H) 7.76 (t, J=1.88 Hz, 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 (0-5% EtOAc:Hex)

Sources & evidence

ORD record
ord-ccae06a7d45b488fb54190fb3a1e0423
Source dataset
uspto-grants-2013_10
Patent number
US08563505B2

Reaction notes

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