2-Bromopyridine → alpha-Phenyl-2-pyridineacetonitrile

HRID 1287497Notes

Reaction equation

HRID 1287497 reaction equation
[C:1]1([CH2:7][C:8]#[N:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[NH2-].[Na+].[OH-].[Na+].Br[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][N:16]=1>O.C1(C)C=CC=CC=1>[C:1]1([CH:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][N:16]=2)[C:8]#[N:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 79732-BromopyridineHCID 8794PhenylacetonitrileHCID 14798Sodium HydroxideHCID 24533Sodium amide

Product 1

HCID 95510alpha-Phenyl-2-pyridineacetonitrile

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
25 °C

Procedure

Phenylacetonitrile 46.8 grams (0.40 mole) was added dropwise to a stirred suspension of 31.2 g. (0.80 mole) of powdered sodium amide in 200 ml. of dry toluene in an oven-dried, 2-liter, three-neck round bottom flask, equipped with dropping funnel, thermometer, stirrer and sodium hydroxide-protected condenser. During the addition, the temperature was maintained at 30°-35°C. with ice bath cooling. Afterwards, the mixture was brought slowly to reflux and maintained there for 41/2 hours with continuous stirring. Then 63.6 grams (0.40 mole) of 2-bromopyridine in 100 ml. of toluene was added dropwise at a rate which maintained refluxing of the solution. After complete addition, stirring and refluxing was continued for 3 hours. The mixture was then cooled at 25°C. and ca. 300 ml. of water was added, at first very cautiously and then in a steady stream. The phases were separated and the toluene layer extracted with ca. 150 ml. of water, and then with several portions of cold 6 N hydrochloric acid. The acid extracts were basified with 50% sodium hydroxide with cooling and extracted with ether. The ether extract was washed with water, dried over sodium sulfate and concentrated, and the residue was distilled. Yield, 41.7 g. (54 %); b.p. 134°-136°C./0.07 mm. The distillate crystallized and after recrystallization from isopropyl ether melted at 87°-88.5°C.

Workup

  1. additionDuring the addition
  2. temperaturethe temperature was maintained at 30°-35°C. with ice bath
  3. temperaturecooling
  4. temperatureto reflux
  5. temperaturemaintained there for 41/2 hours with continuous stirring
  6. temperaturemaintained
  7. temperaturerefluxing of the solution
  8. additionAfter complete addition
  9. temperaturerefluxing
  10. customThe phases were separated
  11. extractionthe toluene layer extracted with ca. 150 ml
  12. temperaturewith cooling
  13. extractionextracted with ether
  14. extractionThe ether extract
  15. washwas washed with water
  16. dry with materialdried over sodium sulfate
  17. concentrationconcentrated
  18. distillationthe residue was distilled
  19. customYield
  20. customThe distillate crystallized
  21. customafter recrystallization from isopropyl ether melted at 87°-88.5°C.

Sources & evidence

ORD record
ord-7a413d08c8a741f38fce2ed1a1b250bb
Source dataset
uspto-grants-1976_10
Patent number
US03984557

Reaction notes

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