Water → 6-Cyano-4-chromanone

HRID 896242Notes

Reaction equation

HRID 896242 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C-:20]#[N:21].[K+].FC(F)(F)S(O[C:29]1[CH:38]=[C:37]2[C:32]([C:33](=[O:39])[CH2:34][CH2:35][O:36]2)=[CH:31][CH:30]=1)(=O)=O.O>C(#N)C.[Zn].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Ni+2].[Br-].[Br-]>[C:20]([C:29]1[CH:38]=[C:37]2[C:32]([C:33](=[O:39])[CH2:34][CH2:35][O:36]2)=[CH:31][CH:30]=1)#[N:21]

Participants

8

Reactant 4

HCID 962WaterHCID 9032Potassium CyanideHCID 11776TriphenylphosphineHCID 103571863,4-Dihydro-4-oxo-2H-1-benzopyran-7-yl 1,1,1-trifluoromethanesulfonate

Product 1

HCID 223499736-Cyano-4-chromanoneYield 76%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 2733341Bis(triphenylphosphine)nickel (II) bromideCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

A dry, 250 mL round bottom flask was charged with 0.27 g (1.01 mmol) of triphenylphosphine, 0.73 g (11.15 mmol) of potassium cyanide, 0.22 g (3.38 mmol) of zinc dust, and 0.38 g (0.51 mmol) of bis(triphenylphosphine)nickel (II) bromide. The flask was then purged with argon, and an air-free solution of 3 g (10.14 mmol) of 7-(((trifluoromethyl)sulfonyl)oxy)-4-chromanone [Koch et al., J. Org. Chem. 59, 1216 (1994)] in 40 ml of dry acetonitrile was introduced by syringe. The solution was then heated at 60° C. for 3 hours, under argon. After cooling the solution to room temp, the solution was added to an equal volume of water. The organic layer was extracted out, and the aqueous layer was extracted several times with ethyl acetate and ether. The combined organic phase was dried over magnesium sulfate, filtered and evaporated. The crude mixture was chromatographed using a 20% ethyl acetate/hexane solvent system which yielded 1.3 g (76%) of 7-cyano-4-chromanone as a white solid.

Workup

  1. customThe flask was then purged with argon
  2. temperatureAfter cooling the solution to room temp
  3. extractionThe organic layer was extracted out
  4. extractionthe aqueous layer was extracted several times with ethyl acetate and ether
  5. dry with materialThe combined organic phase was dried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude mixture was chromatographed

Sources & evidence

ORD record
ord-4e50693282e2433ab7efee1c119401ca
Source dataset
uspto-grants-2005_07
Patent number
US06919347B2

Reaction notes

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