Diethyl Ether → HCID 22180771, compound

HRID 1796009Notes

Reaction equation

HRID 1796009 reaction equation
Cl.Cl[C:3]1[CH:8]=[C:7]([Cl:9])[CH:6]=[CH:5][N:4]=1.[C:10]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1B(O)O)#[N:11].C(=O)([O-])[O-].[K+].[K+].C(OCC)C>O1CCCC1.O.[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>[Cl:9][C:7]1[CH:6]=[CH:5][N:4]=[C:3]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=2[C:10]#[N:11])[CH:8]=1

Participants

8

Reactant 4

HCID 3283Diethyl EtherHCID 11430Potassium CarbonateHCID 27346102-Cyanophenylboronic acidHCID 22180777HCID 22180777, compound

Product 1

HCID 22180771HCID 22180771, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A suspension of 2,4-dichloropyridine hydrochloride (prepared according to Effenberger et al. in Chem. Ber., 1992, 125, 1131) (1.24 g, 6.75 mmol), 2-cyanophenylboronic acid (0.97 g, 0.98 mmol) and potassium carbonate (2.84 g, 20.5 mmol) in tetrahydrofuran (23 ml) and water (11 ml) was degassed with nitrogen for 15 min. Tetrakis(triphenylphosphine)-palladium(0) (382 mg, 0.3 mmol) was then added and the mixture heated at reflux for 3 h then cooled to ambient temperature. The tetrahydrofuran layer was removed and the aqueous layer extracted with ethyl acetate. The organics were combined, dried over magnesium sulfate, filtered and adsorbed onto silica. Purification by chromatography on silica gel eluting with isohexane on a gradient of ethyl acetate (10-50%) gave an oil. Trituration with diethyl ether afforded 2-(4-chloropyridin-2-yl)benzonitrile (122 mg) as a white solid: δH (400 MHz, CDCl3) 7.39 (1H, dd, J 5.3 and 1.8), 7.53-7.57 (1H, m), 7.69-7.73 (1H, m), 7.76-7.84 (3H, m), 8.68 (1H, d, J 4.7); m/z (ES+) 215, 217 (M++H).

Workup

  1. customwas degassed with nitrogen for 15 min
  2. temperaturethe mixture heated
  3. temperatureat reflux for 3 h
  4. customThe tetrahydrofuran layer was removed
  5. extractionthe aqueous layer extracted with ethyl acetate
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customPurification by chromatography on silica gel eluting with isohexane on a gradient of ethyl acetate (10-50%)
  9. customgave an oil

Sources & evidence

ORD record
ord-e1ef93e2ea7c47a4abc4c258cca278b9
Source dataset
uspto-grants-2006_04
Patent number
US07030128B2

Reaction notes

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