4-[(2-Methylbut-3-yn-2-yl)oxy]benzonitrile → 4-[1,1-Dimethyl-3-(2-quinolyl)-2-propynyloxy]benzonitrile

HRID 892592Notes

Reaction equation

HRID 892592 reaction equation
[C:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:11][C:10]([CH3:13])([CH3:12])[CH:9]=[C:8]([C:14]3[CH:23]=[CH:22][C:21]4[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=4)[N+:15]=3[O-])[C:7]=2[CH:25]=1)#[N:2].CC1(C)CC(C2C=CC=CN=2)C2C=C(C(O)=O)C=CC=2O1.CC(C)(OC1C=CC(C#N)=CC=1)C#C>C(NCC)C.[Pd](Cl)Cl.[Cu]I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:12][C:10]([CH3:13])([O:11][C:6]1[CH:5]=[CH:4][C:3]([C:1]#[N:2])=[CH:25][CH:7]=1)[C:9]#[C:8][C:14]1[CH:23]=[CH:22][C:21]2[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=2)[N:15]=1

Participants

8

Reactant 3

HCID 27790724-[(2-Methylbut-3-yn-2-yl)oxy]benzonitrileHCID 150389033,4-dihydro-2,2-dimethyl-4-(2-pyridyl)-2H-1-benzopyran-6-carboxylic acidHCID 198956762-(6-cyano-2,2-dimethyl-2H-1-benzopyran-4-yl)quinoline 1-oxide

Product 1

HCID 198956464-[1,1-Dimethyl-3-(2-quinolyl)-2-propynyloxy]benzonitrile

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 24290Palladium ChlorideCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8021DiethylamineSolvent

Procedure

The 2,2-dimethyl-4-(2-quinolyl)-2H-1-benzopyran-6-carbonitrile used as the starting material was prepared as follows: (A) 5.1 g of 2-iodoquinoline were added at room temperature to a solution of 18 mg of palladium(II) chloride, 52 mg of triphenylphosphine and 38 mg of copper(I) iodide in 100 ml of diethylamine. 3.7 g of 4-(1,1-dimethyl-2-propynyloxy)benzonitrile were added. After stirring at room temperature for 18 hours the mixture was evaporated and the residue was dissolved in ethyl acetate and water. The organic phase was dried over sodium sulphate and evaporated. The residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:2) for the elution to give 5.8 g of 4-[1,1-dimethyl-3-(2-quinolyl)-2-propynyloxy]benzonitrile as a yellow gum. (B) 5.8 g of 4-[1,1-dimethyl-3-(2-quinolyl)-2-propynyloxy]benzonitrile were heated at reflux for 2 hours in 50 ml of dichlorobenzene. The mixture was allowed to cool to room temperature and was then evaporated to dryness. The residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:3) for the elution. The product was recrystallized from isopropanol to give 2.1 g of 2,2-dimethyl-4-(2-quinolyl)-2H-1-benzopyran-6-carbonitrile of melting point 102°-104° C.

Workup

  1. customwas prepared
  2. customwas evaporated
  3. dissolutionthe residue was dissolved in ethyl acetate
  4. dry with materialThe organic phase was dried over sodium sulphate
  5. customevaporated
  6. customThe residue was chromatographed on silica gel
  7. washfor the elution

Sources & evidence

ORD record
ord-01cb704468804f05a73a93b465c38751
Source dataset
uspto-grants-1992_06
Patent number
US05118694

Reaction notes

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