2-Bromobenzonitrile → 3'-Amino-biphenyl-2-carbonitrile

HRID 586216Notes

Reaction equation

HRID 586216 reaction equation
Br[C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].O.[NH2:11][C:12]1[CH:13]=[C:14](B(O)O)[CH:15]=[CH:16][CH:17]=1>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>[NH2:11][C:12]1[CH:17]=[C:16]([C:2]2[C:3]([C:4]#[N:5])=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 2

HCID 162722-BromobenzonitrileHCID 143894233-Aminophenylboronic acid monohydrate

Product 1

HCID 13931123'-Amino-biphenyl-2-carbonitrileYield 98%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
80 °C

Procedure

A mixture of 2-bromobenzonitrile (9.1 g, 50 mmol), 3-aminobenzeneboronic acid monohydrate (11.6 g, 75 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.73 g, 1.5 mmol) in ethylene glycol dimethyl ether (50 ml) and 2 M aqueous sodium carbonate (25 ml) was heated at 80° C. for 20 h. After cooling to ambient temperature the reaction was partitioned between ethyl acetate (400 ml) and water (400 ml). The organic layer was washed with brine (400 ml), dried (Na2SO4), and evaporated in vacuo. Purification of the residue by flash chromatography (silica gel, 0-25% EtOAc/isohexane) gave 9.5 g (98%) of 3′-aminobiphenyl-2-carbonitrile as a colourless oil that solidified on standing to afford a white solid: 1H NMR (400 MHz, CDCl3) δ 3.79 (2H, br), 6.75 (1H, ddd, J 8, 3, 1 Hz), 6.84 (1H, dd, J 3, 3 Hz), 6.92 (1H, dd, J 8, 3 Hz), 7.25 (1H, dd, J 8, 8 Hz), 7.40 (1H, ddd, J 8, 8, 1 Hz), 7.50 (1H, dd, J 8, 1 Hz), 7.62 (1H, ddd, J 8, 8, 1 Hz), 7.73 (1H, dd, J 8, 1 Hz).

Workup

  1. temperatureAfter cooling to ambient temperature the reaction
  2. customwas partitioned between ethyl acetate (400 ml) and water (400 ml)
  3. washThe organic layer was washed with brine (400 ml)
  4. dry with materialdried (Na2SO4)
  5. customevaporated in vacuo
  6. customPurification of the residue by flash chromatography (silica gel, 0-25% EtOAc/isohexane)

Sources & evidence

ORD record
ord-edea2eb4bdb44b0eabad70465b4f41ab
Source dataset
uspto-grants-2005_08
Patent number
US06936608B2

Reaction notes

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