Benzonitrile → HCID 15179550, compound

HRID 1464633Notes

Reaction equation

HRID 1464633 reaction equation
O.O.O.O.O.O.O.[Cl-].[Ce+3].[Cl-].[Cl-].[CH2:12]([Li])[CH2:13][CH2:14][CH3:15].[C:17](#[N:24])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>O1CCCC1>[CH2:12]([C:17]([NH2:24])([CH2:12][CH2:13][CH2:14][CH3:15])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[CH2:13][CH2:14][CH3:15]

Participants

5

Reactant 3

HCID 7505BenzonitrileHCID 21585214Cerium trichloride heptahydrateHCID 178418339Butyllithium

Product 1

HCID 15179550HCID 15179550, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Cerium chloride heptahydrate (15.0 g 40.2 mmol) was dried with magnetic stirring at 140°-150° under 0.1 mm vacuum for two hours. Nitrogen was admitted and the flask containing the solid was cooled with an ice bath. Anhydrous tetrahydrofuran (80 mL) was added and the suspension was stirred at room temperature for 2 hours. n-Butyllithium (24 mL of a 1.6M solution in hexanes, 40 mmol) was added below -55° by syringe, and the mixture was stirred in a dry ice acetone bath for 30 minutes. Benzonitrile (1.34 g, 13 mmol) in 2 mL of anhydrous tetrahydrofuran was added, and the cooling bath was removed. Aqueous ammonium hydroxide (25 mL) was added after 2 hours, keeping the temperature below 0°, and the mixture was filtered with the aid of celite™. The solids were washed three times with methylene chloride, and the aqueous layer of the filtrate was extracted twice with methylene chloride. The combined organic phases were dried and concentrated and the residue was short-path distilled to give 2.53 g (90%) of the title compound distilling at a bath temperature of 80°-130° (0.003 mm). 1H-NMR (in CDCl3) ∂0.8 (t, J=6 Hz, 6H), 1.0 (m, 2H), 1.2 (m, 6H), 1.4 (br, 2H), 1.6 (m, 2H), 1.8 (m, 2H), 7.2-7.4 (m, 5H).

Workup

  1. additionthe flask containing the solid
  2. temperaturewas cooled with an ice bath
  3. stirringthe suspension was stirred at room temperature for 2 hours
  4. stirringthe mixture was stirred in a dry ice acetone bath for 30 minutes
  5. customthe cooling bath was removed
  6. additionAqueous ammonium hydroxide (25 mL) was added after 2 hours
  7. customthe temperature below 0°
  8. filtrationthe mixture was filtered with the aid of celite™
  9. washThe solids were washed three times with methylene chloride
  10. extractionthe aqueous layer of the filtrate was extracted twice with methylene chloride
  11. customThe combined organic phases were dried
  12. concentrationconcentrated
  13. distillationthe residue was short-path distilled

Sources & evidence

ORD record
ord-fffd1139847e4854bcdec412356e6a6b
Source dataset
uspto-grants-1994_04
Patent number
US05306821

Reaction notes

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