Hydrochloric Acid → 4-cyano-2,2-bisfluoromethyl-6-nitro-2H-1-benzopyran

HRID 1067645Notes

Reaction equation

HRID 1067645 reaction equation
[F:1][CH2:2][C:3]1([CH2:17][F:18])[CH2:8][C:7](=O)[C:6]2[CH:10]=[C:11]([N+:14]([O-:16])=[O:15])[CH:12]=[CH:13][C:5]=2[O:4]1.C[Si]([C:23]#[N:24])(C)C.P(Cl)(Cl)(Cl)=O.Cl>[I-].[Zn+2].[I-].N1C=CC=CC=1.C1C=CC=CC=1>[F:1][CH2:2][C:3]1([CH2:17][F:18])[CH:8]=[C:7]([C:23]#[N:24])[C:6]2[CH:10]=[C:11]([N+:14]([O-:16])=[O:15])[CH:12]=[CH:13][C:5]=2[O:4]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 24813Phosphorus oxychlorideHCID 82115Trimethylsilyl cyanideHCID 155458532,2-bisfluoromethyl-3,4-dihydro-6-nitro-2H-1-benzopyran-4-one

Product 1

HCID 211949804-cyano-2,2-bisfluoromethyl-6-nitro-2H-1-benzopyran

Reagents, catalysts & solvents 3

HCID 9883512zinc(II)iodideCatalystHCID 241BenzeneSolventHCID 1049PyridineSolvent

Procedure

To a mixture of 4.05 g of 2,2-bisfluoromethyl-3,4-dihydro-6-nitro-2H-1-benzopyran-4-one and 10 ml of dry benzene were added 2.52 ml of trimethylsilyl cyanide and 0.82 g of zinc iodide with stirring under ice-cooling, and the mixture was stirred at room temperature for 12 hours. The mixture was further combined with 8 ml of pyridine and 4.41 ml of phosphorus oxychloride and heated to reflux for 6 hours. The reaction mixture was acidified with ice water and aqueous hydrochloric acid and extracted with methylene chloride. The organic layer was washed with water and dried, then concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (eluent; methylene chloride:hexane=7:3) to give 0.99 g of 2,2-bisfluoromethyl-6-nitro-2H-1-benzopyran-4-carbonitrile; m.p. 136-137° C.;

Workup

  1. temperaturecooling
  2. stirringthe mixture was stirred at room temperature for 12 hours
  3. temperatureheated
  4. temperatureto reflux for 6 hours
  5. extractionextracted with methylene chloride
  6. washThe organic layer was washed with water
  7. customdried
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-03f6b0217dc9415cb693a47ed6e36d0f
Source dataset
uspto-grants-2001_06
Patent number
US06248777B1

Reaction notes

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