2-Bromobenzonitrile → HCID 22285268, compound

HRID 2183913Notes

Reaction equation

HRID 2183913 reaction equation
[F:1][C:2]1[CH:3]=[C:4](B2OCC(C)(C)CO2)[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.Br[C:20]1[CH:27]=[CH:26][CH:25]=[CH:24][C:21]=1[C:22]#[N:23]>COCCOC.C(=O)([O-])[O-].[Na+].[Na+].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>[F:1][C:2]1[CH:3]=[C:4]([C:20]2[C:21]([C:22]#[N:23])=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1

Participants

6

Reactant 2

HCID 162722-BromobenzonitrileHCID 22285295HCID 22285295, compound

Product 1

HCID 22285268HCID 22285268, compoundYield 72.1%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 2-(3-fluoro-5-nitrophenyl)-5,5-dimethyl-[1,3,2]dioxaborinane (15 g, 59 mmol) and 2-bromobenzonitrile (12.4 g, 68.2 mmol) in 1,2-dimethoxyethane (125 ml) and 2M aqueous sodium carbonate (50 ml) was degassed with nitrogen for 30 min then treated with tetrakis(triphenylphosphine)palladium(0) (2.06 g, 1.8 mmol). The reaction was then heated at 90° C. for 16 h, cooled to ambient temperature and partitioned between ethyl acetate and water. The organics were washed with brine, dried over anhydrous magnesium sulfate, filtered and pre-adsorbed onto silica. Purification by dry flash chromatography on silica, eluting with isohexane (containing 1% methanol) on a gradient of ethyl acetate (10-40%) afforded 3′-fluoro-5′-nitrobiphenyl-2-carbonitrile as a cream-coloured solid (10.3 g, 72%): δH (400 MHz, CDCl3) 7.54-7.61 (2H, m), 7.65 (1H, ddd, J 8, 2 and 2), 7.74 (1H, ddd, J 8, 8 and 2), 7.84 (1H, dd, J 8 and 2), 8.03 (1H, ddd, J 8, 8 and 2), 8.22-8.24 (1H, m).

Workup

  1. customwas degassed with nitrogen for 30 min
  2. temperaturecooled to ambient temperature
  3. custompartitioned between ethyl acetate and water
  4. washThe organics were washed with brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered and pre-adsorbed onto silica
  7. customPurification
  8. customby dry flash chromatography on silica
  9. washeluting with isohexane (containing 1% methanol) on a gradient of ethyl acetate (10-40%)

Sources & evidence

ORD record
ord-12b394ef98d84a0a9382fa1cfce90d57
Source dataset
uspto-grants-2005_05
Patent number
US06900215B2

Reaction notes

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