Phosphorus oxychloride → 4-(4-chloro-2-pyridyl)-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile

HRID 892542Notes

Reaction equation

HRID 892542 reaction equation
[C:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:11][C:10]([CH3:13])([CH3:12])[CH2:9][CH:8]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][N+:15]=3[O-])[C:7]=2[CH:21]=1)#[N:2].P(Cl)(Cl)([Cl:24])=O>>[Cl:24][C:18]1[CH:17]=[CH:16][N:15]=[C:14]([CH:8]2[C:7]3[CH:21]=[C:3]([C:1]#[N:2])[CH:4]=[CH:5][C:6]=3[O:11][C:10]([CH3:13])([CH3:12])[CH2:9]2)[CH:19]=1

Participants

3

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 63363852,2-Dimethyl-4-(1-oxidopyridin-1-ium-2-yl)-3,4-dihydrochromene-6-carbonitrile

Product 1

HCID 198956254-(4-chloro-2-pyridyl)-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile

Conditions

Temperature
80 °C

Procedure

1 g of 2-(6-cyano-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-4-yl)pyridine N-oxide was dissolved in 15 ml of phosphorus oxychloride, heated at 80° C. for 2 hours and allowed to cool to room temperature overnight. The phosphorus oxychloride was removed in vacuo and the residue was taken up in sodium bicarbonate solution and ethyl acetate. The aqueous phase was extracted several times with ethyl acetate and the combined ethyl acetate solutions were dried over sodium sulphate and evaporated. The residue was chromatographed on silica gel. Elution with ethyl acetate/petroleum ether (1:4) gave 271 mg of 4-(6-chloro-2-pyridyl)-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile and elution with ethyl acetate/petroleum ether (1:2) gave 170 mg of 4-(4-chloro-2-pyridyl)-3,4-dihydro-2,2-dimethyl-2H-1 -benzopyran-6carbonitrile.

Workup

  1. temperatureto cool to room temperature overnight
  2. customThe phosphorus oxychloride was removed in vacuo
  3. extractionThe aqueous phase was extracted several times with ethyl acetate
  4. dry with materialthe combined ethyl acetate solutions were dried over sodium sulphate
  5. customevaporated
  6. customThe residue was chromatographed on silica gel
  7. washElution with ethyl acetate/petroleum ether (1:4)
  8. customgave
  9. wash271 mg of 4-(6-chloro-2-pyridyl)-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile and elution with ethyl acetate/petroleum ether (1:2)

Sources & evidence

ORD record
ord-1de9ff71d42a4fb7aa4b8d2d6be941d0
Source dataset
uspto-grants-1992_06
Patent number
US05118694

Reaction notes

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