Nitrogen → HCID 23374575, compound

HRID 865658Notes

Reaction equation

HRID 865658 reaction equation
N#N.[C:3]1([CH2:9][C:10]#[N:11])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Cl[CH2:13]/[CH:14]=[CH:15]\[CH2:16]Cl.[OH-].[K+]>C(Cl)Cl.CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].O>[C:10]([C:9]1([C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=2)[CH2:16][CH:15]=[CH:14][CH2:13]1)#[N:11]

Participants

8

Reactant 4

HCID 947NitrogenHCID 8794PhenylacetonitrileHCID 14797Potassium HydroxideHCID 64321151,4-Dichloro-cis-2-butene

Product 1

HCID 23374575HCID 23374575, compoundYield 83.2%

Reagents, catalysts & solvents 3

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a N2 covered, mechanically stirred solution of 4.93 ml (42.6 mmol) of phenylacetonitrile in 85 ml of CH2Cl2 was added 4.94 ml (46.9 mmol) of cis-1,4 dichloro-2-butene followed by 0.86 g (2.1 mmol) of Aliquat 336. There was then added 5.3 g (85.3 mmol) of powdered KOH in portions over 2.25 hours. A cold water bath was used to control a slight exotherm and keep the reaction temperature at about 25° C. during the addition. The reaction was stirred at room temperature for 1 hour and then heated in an oil bath at 55°-60° C. (reflux) for 1 hour. After allowing the reaction to cool, there was added 42 ml of H2O dropwise over 6 minutes. The mixture was transferred to a separatory funnel and mixed well. The aqueous fraction was separated and washed with Et2O. The combined organic fractions were dried over MgSO4 and concentrated in vacuo. The residue was distilled under reduced pressure and a single fraction was collected, 5.39 g, b.p. 62°-86° C. (0.05 mm Hg). This fraction was combined with 4.77 g of material from a previous run and heated neat under N2 in an oil bath at 200° C. for 30 minutes and then allowed to cool. The residue was chromatographed in two portions over silica gel (1% EtOAc: hexane) to yield 6.0 g of 4-Cyano-4-phenylcyclopentene.

Workup

  1. customA cold water bath was used
  2. customat about 25° C.
  3. additionduring the addition
  4. temperatureheated in an oil bath at 55°-60° C.
  5. temperature(reflux) for 1 hour
  6. customthe reaction
  7. temperatureto cool
  8. customThe mixture was transferred to a separatory funnel
  9. additionmixed well
  10. customThe aqueous fraction was separated
  11. washwashed with Et2O
  12. dry with materialThe combined organic fractions were dried over MgSO4
  13. concentrationconcentrated in vacuo
  14. distillationThe residue was distilled under reduced pressure
  15. customa single fraction was collected
  16. temperatureheated neat under N2 in an oil bath at 200° C. for 30 minutes
  17. temperatureto cool
  18. customThe residue was chromatographed in two portions over silica gel (1% EtOAc: hexane)

Sources & evidence

ORD record
ord-2cda1b23e17a4df7926123e0038dd4e5
Source dataset
uspto-grants-1996_10
Patent number
US05567722

Reaction notes

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