Dimethylformamide → 6-[5-(4-Cyano-phenyl)-furan-2-yl]-nicotinonitrile

HRID 853803Notes

Reaction equation

HRID 853803 reaction equation
Br[C:2]1[O:6][C:5]([C:7]2[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][N:8]=2)=[CH:4][CH:3]=1.C([O-])([O-])=O.[Na+].[Na+].[C:21]([C:23]1[CH:28]=[CH:27][C:26](B(O)O)=[CH:25][CH:24]=1)#[N:22].CN(C=O)C>C1(C)C=CC=CC=1.CO.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:21]([C:23]1[CH:28]=[CH:27][C:26]([C:2]2[O:6][C:5]([C:7]3[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][N:8]=3)=[CH:4][CH:3]=2)=[CH:25][CH:24]=1)#[N:22]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 27343264-Cyanophenylboronic acidHCID 109119016-(5-Bromo-furan-2-yl)-nicotinonitrile

Product 1

HCID 111191846-[5-(4-Cyano-phenyl)-furan-2-yl]-nicotinonitrileYield 76%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 887MethanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

Procedure: J. Org. Chem. 49(26), 5237 (1984). Continuing with Scheme 1, a stirred solution of 2 (1.245 g, 5 mmol), and tetrakis(triphenylphosphine) palladium (288 mg) in toluene (10 mL) under a nitrogen atmosphere was added 5 mL of a 2 M aqueous solution of Na2CO3 followed by 4-cyanophenyl boronic acid (821 mg, 4.6 mmol) in 5 mL of methanol. The vigorously stirred mixture was warmed to 80° C. for 24 h, and then cooled, and the precipitate was filtered. The precipitate was partitioned between methylene chloride (300 mL) and 2 M aqueous Na2CO3 (25 mL) containing 3 mL of concentrated ammonia. The organic layer was dried (Na2SO4), and then concentrated to dryness under reduced pressure to afford 3 in 76% yield; mp 301–302° C. (DMF). 1H nmr (DMSO-d6); δ 7.44 (d, J=3.6 Hz, 1H), 7.49 (d, J=3.6 Hz, 1H), 7.92 (d, J=8.4 Hz, 2H), 8.07 (d, J=8.4 Hz, 2H). 8.12 (d, J=8.4 Hz 1H), 8.36 (dd, J=8.4, 1.5 Hz, 1H), 9.0 (d, J=1.5 Hz, 1H). 13C nmr; δ 153.4, 152.6, 152.3, 150.1, 140.7, 133.1, 132.7, 124.4, 118.3, 116.9, 114.6, 111.8, 110.2, 106.7. MS (m/z, rel.int.); 271 (M+, 100), 243 (10), 140 (20), 103 (20). High resolution mass calcd. for C17H9N3O: 271.07456. Observed 271.07392. Calcd. for C17H9N3O: C, 75.26; H, 3.34; N. 15.49. Found. C, 74.95; H, 3.43; N, 15.23.

Workup

  1. temperaturecooled
  2. filtrationthe precipitate was filtered
  3. customThe precipitate was partitioned between methylene chloride (300 mL) and 2 M aqueous Na2CO3 (25 mL)
  4. additioncontaining 3 mL of concentrated ammonia
  5. dry with materialThe organic layer was dried (Na2SO4)
  6. concentrationconcentrated to dryness under reduced pressure
  7. customto afford 3 in 76% yield

Sources & evidence

ORD record
ord-36aba65b216147748c069659e55586e7
Source dataset
uspto-grants-2007_08
Patent number
US07256203B2

Reaction notes

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