Triphenylphosphine → 4-[1,1-Dimethyl-3-(2-methoxyphenyl)-2-propynyloxy]benzonitrile

HRID 892596Notes

Reaction equation

HRID 892596 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:9]1[C:14]2[CH:15]=[C:16]([C:19]#[N:20])[CH:17]=[CH:18][C:13]=2[O:12][C:11]([CH3:22])([CH3:21])[CH:10]=1.CC1(C)CC(C2C=CC=CN=2)C2C=C(C(O)=O)C=CC=2O1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)(OC1C=CC(C#N)=CC=1)C#C>C(NCC)C.[Pd](Cl)Cl.[Cu]I>[CH3:21][C:11]([CH3:22])([O:12][C:13]1[CH:14]=[CH:15][C:16]([C:19]#[N:20])=[CH:17][CH:18]=1)[C:10]#[C:9][C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[O:2][CH3:1]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 27790724-[(2-Methylbut-3-yn-2-yl)oxy]benzonitrileHCID 150389033,4-dihydro-2,2-dimethyl-4-(2-pyridyl)-2H-1-benzopyran-6-carboxylic acidHCID 19895586HCID 19895586, compound

Product 1

HCID 198956454-[1,1-Dimethyl-3-(2-methoxyphenyl)-2-propynyloxy]benzonitrile

Reagents, catalysts & solvents 3

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

Procedure

The 4-(2-methoxyphenyl)-2.2-dimethyl-2H-1-benzopyran-6-carbonitrile used as the starting material was prepared as follows: (A) 2.34 g of 2-iodoanisole were added at room temperature to a solution of 9 mg of palladium(II) chloride, 26 mg of o triphenylphosphine and 19 mg of copper(I) iodide in 25 ml of diethylamine. This mixture was treated with 1.85 g of 4-(1,1-dimethyl-2-propynyloxy)benzonitrile and the resulting mixture was stirred for 48 hours. The mixture was evaporated and the residue was dissolved in a mixture of ethyl acetate and water. The organic phase was separated, dried over sodium sulphate and evaporated. The residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:4) for the elution to give 0.99 g of 4-[1,1-dimethyl-3-(2-methoxyphenyl)-2-propynyloxy]benzonitrile in the form of an oil. (B) 0.99 g of 4-[1,1-dimethyl-3-(2-methoxyphenyl)-2-propynyloxy]benzonitrile was dissolved in 10 ml of 1,2-dichlorobenzene and heated at reflux for 1.5 hours. After cooling the solution was evaporated and the residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:4) for the elution. After recrystallization from petroleum ether (boiling point 60°-80° C.) there were obtained 480 mg of 4-(2-methoxyphenyl)-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile of melting point 109°-111° C.

Workup

  1. customwas prepared
  2. customThe mixture was evaporated
  3. dissolutionthe residue was dissolved in a mixture of ethyl acetate and water
  4. customThe organic phase was separated
  5. dry with materialdried over sodium sulphate
  6. customevaporated
  7. customThe residue was chromatographed on silica gel
  8. washfor the elution

Sources & evidence

ORD record
ord-64ff50fdc180487789feb20f36a87a16
Source dataset
uspto-grants-1992_06
Patent number
US05118694

Reaction notes

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