Thionyl Chloride → 9H-Fluorene-9-carbonitrile

HRID 1456676Notes

Reaction equation

HRID 1456676 reaction equation
S(Cl)(Cl)=O.C1C2C(C(O)=O)C3C(=CC=CC=3)C=2C=CC=1.[CH:21]1[C:33]2[CH:32]([C:34]([NH2:36])=O)[C:31]3[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=3)[C:25]=2[CH:24]=[CH:23][CH:22]=1.P(Cl)(Cl)(Cl)=O>>[C:34]([CH:32]1[C:33]2[CH:21]=[CH:22][CH:23]=[CH:24][C:25]=2[C:26]2[C:31]1=[CH:30][CH:29]=[CH:28][CH:27]=2)#[N:36]

Participants

5

Reactant 4

HCID 24386Thionyl ChlorideHCID 24813Phosphorus oxychlorideHCID 748099-CarboxyfluoreneHCID 3450289H-fluorene-9-carboxamide

Product 1

HCID 737219H-Fluorene-9-carbonitrileYield 65%

Procedure

100 ml (1.37 mol) of thionyl chloride are added to 21.0 g (0.10 mol) of fluorene-9-carboxylic acid and the mixture is refluxed for about 90 minutes. The excess thionyl chloride is evaporated off on a vacuum rotary evaporator. The residue is taken up three times with about 50 ml of toluene each time and the mixture evaporated on a vacuum rotary evaporator. The oily residue is added in portions to a mixture of about 1 kg of ice and 240 ml of concentrated ammonia solution. The fluorene-9-carboxylic acid amide which has precipitated is filtered off, washed with water and dried under a high vacuum. The dried fluorene-9-carboxylic acid amide is then added to 160 ml (1.75 mol) of phosphorus oxychloride and the mixture is refluxed for about 2 hours. The reaction mixture is cooled and concentrated on a vacuum rotary evaporator. The residue is taken up in toluene and the mixture is washed with water. The organic phases are combined, dried over sodium sulfate and concentrated on a vacuum rotary evaporator. Crystallization of the residue from cyclohexane gives 12.4 g (65%) of 9-cyano-fluorene, melting point 152°-154° C. (compound (101), Table 1).

Workup

  1. temperaturethe mixture is refluxed for about 90 minutes
  2. customThe excess thionyl chloride is evaporated off on a vacuum rotary evaporator
  3. customthe mixture evaporated on a vacuum rotary evaporator
  4. additionThe oily residue is added in portions to a mixture of about 1 kg of ice and 240 ml of concentrated ammonia solution
  5. customThe fluorene-9-carboxylic acid amide which has precipitated
  6. filtrationis filtered off
  7. washwashed with water
  8. customdried under a high vacuum
  9. temperaturethe mixture is refluxed for about 2 hours
  10. temperatureThe reaction mixture is cooled
  11. concentrationconcentrated on a vacuum rotary evaporator
  12. washthe mixture is washed with water
  13. dry with materialdried over sodium sulfate
  14. concentrationconcentrated on a vacuum rotary evaporator
  15. customCrystallization of the residue from cyclohexane

Sources & evidence

ORD record
ord-5720341f9741413c85953343c2c0fe10
Source dataset
uspto-grants-1998_12
Patent number
US05844024

Reaction notes

Loading…