4-Bromophenol → 4'-(Methylsulfonyl)-[1,1'-biphenyl]-4-ol

HRID 423452

Reaction equation

HRID 423452 reaction equation
[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8](B(O)O)=[CH:7][CH:6]=1)(=[O:4])=[O:3].Br[C:15]1[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=1.C([O-])([O-])=O.[Na+].[Na+]>COCCOC.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>[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([C:15]2[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=2)=[CH:7][CH:6]=1)(=[O:4])=[O:3]

Participants

6

Reactant 3

HCID 78084-BromophenolHCID 10340Sodium CarbonateHCID 27343644-(Methanesulfonyl)phenylboronic acid

Product 1

HCID 149826764'-(Methylsulfonyl)-[1,1'-biphenyl]-4-olYield 64%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

[4-(Methylsulfonyl)phenyl]boronic acid (0.69 g, 3.40 mmol) was added to a solution of 4-bromophenol (0.5 g, 2.83 mmol) in DME (25 mL), followed by addition of 2M Na2CO3 (25 mL) and Pd(PPh3)4 (0.17 g, 0.14 mmol). The reaction mixture was heated at 90° C. for 3 h, then cooled to ambient temperature, and extracted with ether. The combined organic extract was washed with brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as an off-white solid. The crude product was purified by chromatography on a silica gel column eluted with 50% EtOAc/hexane to give 0.45 g (64%) of 4′-(methylsulfonyl)-4-biphenylol as a white solid. Alternatively, 4′-(methylsulfonyl)-4-biphenylol was prepared from 4-bromophenyl methyl sulfone (2 g, 8.5 mmol), (4-hydroxyphenyl)boronic acid (1.76 g, 12.75 mmol), 2M Na2CO3 (100 mL) and Pd(PPh3)4 (0.1 g, 0.08 mmol) in DME (100 mL) in a manner similar to the conditions above. 1H NMR (400 MHz, CDCl3): δ 7.97 (d, 2H, J=8.6 Hz), 7.71 (d, 2H, J=8.3 Hz), 7.51 (d, 2H, J=8.6 Hz), 6.94 (d, 2H, J=8.5 Hz), 4.92 (s, 1H), 3.08 (s, 3H); LRMS (ESI), m/z 249 (M+H).

Workup

  1. temperaturecooled to ambient temperature
  2. extractionextracted with ether
  3. extractionThe combined organic extract
  4. washwas washed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated
  8. customto give the crude product as an off-white solid
  9. customThe crude product was purified by chromatography on a silica gel column
  10. washeluted with 50% EtOAc/hexane

Sources & evidence

ORD record
ord-cc1c6b97e4c744338c51e2fe36413402
Source dataset
uspto-grants-2012_01
Patent number
US08101634B2

Linked notes

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