Magnesium → 6-Fluoro-3,4-dihydro-2H-1-benzopyran-4-carbonitrile

HRID 487203Notes

Reaction equation

HRID 487203 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][CH:8]=[C:7]([C:11]#[N:12])[C:6]=2[CH:13]=1.[Mg]>CO>[F:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][CH2:8][CH:7]([C:11]#[N:12])[C:6]=2[CH:13]=1

Participants

4

Reactant 2

HCID 5462224MagnesiumHCID 149865356-fluoro-4-cyano-2H-benzopyran

Product 1

HCID 143394306-Fluoro-3,4-dihydro-2H-1-benzopyran-4-carbonitrileYield 55.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 16.1 g (0.092 moles) of 6-fluoro-4-cyano-2H-benzopyran in 270 mL of absolute methanol was added 5.52 g (0.23 mole) of magnesium turnings. The resulting exothermic reaction was allowed to reflux then stirred at room temperature for 2 hours. The volatiles were evaporated and the residue dissolved in water which was acidified to pH 2.0 with concentrated HCl. The aqueous was extracted with EtOAc and the EtOAc layer was dried over Na2SO4, filtered and evaporated to give 16 g of crude product. The crude aproduct was purified by chromatography and 450 g of silica gel eluting with CH2Cl2 /ether to give 9 g of product m.p. 67°-68° C. NMR CDCl3 ppm (delta): 2.25 (dt, 2H, J=5 Hz), 4.95 (s, 1H, J=5 Hz), 4.00-4.30 (m, 2H), 6.70-7.05 (m, 3H).

Workup

  1. customThe resulting exothermic reaction
  2. temperatureto reflux
  3. customThe volatiles were evaporated
  4. dissolutionthe residue dissolved in water which
  5. extractionThe aqueous was extracted with EtOAc
  6. dry with materialthe EtOAc layer was dried over Na2SO4
  7. filtrationfiltered
  8. customevaporated
  9. customto give 16 g of crude product
  10. customThe crude aproduct was purified by chromatography and 450 g of silica gel eluting with CH2Cl2 /ether

Sources & evidence

ORD record
ord-2fa8febb921d437d8553f1a8d5e9addd
Source dataset
uspto-grants-1994_03
Patent number
US05294635

Reaction notes

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