4-[(2-Methylbut-3-yn-2-yl)oxy]benzonitrile → HCID 19895699, compound

HRID 892598Notes

Reaction equation

HRID 892598 reaction equation
C(C1C=CC([C:9]2[C:14]3[CH:15]=[C:16]([C:19]#[N:20])[CH:17]=[CH:18][C:13]=3[O:12][C:11]([CH3:22])([CH3:21])[CH:10]=2)=C(OC)C=1)#N.CC1(C)CC(C2C=CC=CN=2)C2C=C(C(O)=O)C=CC=2[O:27]1.C[C:47](C)([O:50][C:51]1[CH:58]=[CH:57][C:54]([C:55]#[N:56])=[CH:53][CH:52]=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>[C:19]([C:16]1[CH:15]=[CH:14][C:13]([O:12][C:11]([CH3:21])([CH3:22])[C:10]#[C:9][O:27][C:52]2[CH:53]=[C:54]([CH:57]=[CH:58][C:51]=2[O:50][CH3:47])[C:55]#[N:56])=[CH:18][CH:17]=1)#[N:20]

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 19895617HCID 19895617, compound

Product 1

HCID 19895699HCID 19895699, compound

Reagents, catalysts & solvents 4

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

Procedure

The 4-(4-cyano-2-methoxyphenyl)-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile used as the starting material was prepared as follows: (A) 5.18 g of 3-iodo-4-methoxybenzonitrile 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 and the mixture was stirred under a nitrogen atmosphere for 2 days. 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 4.8 g of 3-[3-(4-cyanophenoxy)-3-methyl-1-butyn-1-yloxy]-4-methoxybenzonitrile as a solid which was used without further purification. (B) 4.8 g of 3-[3-(4-cyanophenoxy)-3-methyl-1-butyn-1-yloxy]-4-methoxybenzonitrile was heated at reflux for 2.5 hours in 50 ml of 1,2-dichlorobenzene and then allowed to cool to room temperature. The mixture was evaporated and the residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:2) for the elution. The product was recrystallized from isopropanol to give 3.8 g of 4-(4-cyano-2-methoxyphenyl)-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile of melting point 137°-139° C.

Workup

  1. customwas prepared
  2. customThe mixture was 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-3d567802021843dc901d1a22b37fe731
Source dataset
uspto-grants-1992_06
Patent number
US05118694

Reaction notes

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