4-Bromo-[1,1'-biphenyl]-2-carboxylic acid → (4-Bromobiphenyl-2-yl)methanol

HRID 1043415Notes

Reaction equation

HRID 1043415 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:14](O)=[O:15])[C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:6][CH:7]=1>C1COCC1.CCOC(C)=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[C:4]([CH2:14][OH:15])[CH:3]=1

Participants

4

Reactant 1

HCID 199224694-Bromo-[1,1'-biphenyl]-2-carboxylic acid

Product 1

HCID 59266499(4-Bromobiphenyl-2-yl)methanolYield 65%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

4-bromobiphenyl-2-carboxylic acid (5.71 g, 20.61 mmol) was dissolved in THF (50 mL) and cooled to 0° C. 1.0M borane tetrahydrofuran complex (41.2 mL, 41.2 mmol) was added dropwise over 15 min. and allowed to warm up to r.t. overnight. The reaction was diluted with EtOAc and washed with water, sat. ammonium chloride, and then brine. The organic layer was collected, dried over MgSO4, filtered and evaporated to give the crude product. The crude product was purified by flash chromatography on the Biotage (5-35% EtOAc:Hex) to give (4-bromobiphenyl-2-yl)methanol (3.5 g, 13.30 mmol, 65% yield) as a light orange oil. LCMS: rt=1.43 min.; Phenomenex-Luna C-18 (5μ) (3.0×50 mm); Solvent A=10% acetonitrile—90% water—0.1% TFA, Solvent B=90% acetonitrile—10% water—0.1% TFA; gradient 0% to 100% solvent B over 2 min. and then hold for 1 min.; 4 mL/min; inj. vol.=5 uL; wavelength=220. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 4.60 (d, J=5.77 Hz, 2H) 7.15 (d, J=8.28 Hz, 1H) 7.29-7.35 (m, 2H) 7.36-7.46 (m, 3H) 7.48 (dd, J=8.28, 2.01 Hz, 1H) 7.75 (d, J=2.01 Hz, 1H).

Workup

  1. addition1.0M borane tetrahydrofuran complex (41.2 mL, 41.2 mmol) was added dropwise over 15 min.
  2. temperatureto warm up to r.t. overnight
  3. washwashed with water, sat. ammonium chloride
  4. customThe organic layer was collected
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated
  8. customto give the crude product
  9. customThe crude product was purified by flash chromatography on the Biotage (5-35% EtOAc:Hex)

Sources & evidence

ORD record
ord-df511e8a91ba445ab5f327f731d9d076
Source dataset
uspto-grants-2013_10
Patent number
US08563505B2

Reaction notes

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