HCID 9925718、化合物 → HCID 19895589、化合物

HRID 892581

反応式

HRID 892581 の反応式
[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[N:19]=[CH:18][CH:17]=[CH:16][N+:15]=3[O-])[C:7]=2[CH:21]=1)#[N:2].CC1(C)CC(C2C=CC=CN=2)C2C=C(C(O)=O)C=CC=2O1.IC1N=CC=CN=1>C(N(CC)CC)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:21][CH:7]=1)[C:9]#[C:8][C:14]1[N:15]=[CH:16][CH:17]=[CH:18][N:19]=1

参加物

8

反応物 3

HCID 9925718HCID 9925718、化合物HCID 113562002-IodopyrimidineHCID 150389033,4-dihydro-2,2-dimethyl-4-(2-pyridyl)-2H-1-benzopyran-6-carboxylic acid

生成物 1

HCID 19895589HCID 19895589、化合物

試薬・触媒・溶媒 4

HCID 11776Triphenylphosphine触媒HCID 24290Palladium Chloride触媒HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8471Triethylamine溶媒

実験手順

The 3,4-dihydro-2,2-dimethyl-4-(2-pyrimidinyl)-2H-1-benzopyran-6-carbonitrile used as the starting material was prepared as follows: (A) 0.63 g of 4-(1,1-dimethyl-2-propynyloxy)benzonitrile, 0.75 g of 2-iodopyrimidine, 18 mg of triphenylphosphine, 12 mg of palladium(II) chloride and 3.5 mg of copper(I) iodide were stirred overnight in 20 ml of triethylamine under nitrogen. The mixture was evaporated to dryness and then ethyl acetate and water were added. The organic phase was dried over sodium sulphate and evaporated. The residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:3) and subsequently ethyl acetate/petroleum ether (1:1) for the elution. There were obtained 580 mg of 4-[1,1-dimethyl-3-(2-pyrimidinyl)-2-propynyloxy]benzonitrile as an oil. (B) 580 mg of 4-[1,1-dimethyl-3-(2-pyrimidinyl)-2-propynyloxy]benzonitrile were heated at reflux for 3 hours in 20 ml of dichlorobenzene. The solution was allowed to cool and was then evaporated to dryness. The residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:2) and subsequently ethyl acetate/petroleum ether (1:1) for the elution. There was obtained 361 mg of 2,2-dimethyl-4-(2-pyrimidinyl)-2H-1-benzopyran-6-carbonitrile which melted at 108°-109.5° C. after recrystallization from tert-butyl methyl ether. (C) 1.0 g of 2,2-dimethyl-4-(2-pyrimidinyl)-2H-1-benzopyran-6-carbonitrile was dissolved in 100 ml of ethanol, added to 10% palladium-on-charcoal and shaken under an atmosphere of hydrogen at room temperature. After 2 hours the catalyst was filtered off and the filtrate was evaporated. The residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:1) for the elution. The product was recrystallized from cyclohexane to give 0.5 g of 3,4-dihydro-2,2-dimethyl-4-(2-pyrimidinyl)-2H-1-benzopyran-6-carbonitrile of melting point 109°-111° C.

後処理

  1. customwas prepared
  2. customThe mixture was evaporated to dryness
  3. additionethyl acetate and water were added
  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

出典と根拠

ORDレコード
ord-d351e111c46042aba4d3aee485891ffe
出典データセット
uspto-grants-1992_06
特許番号
US05118694

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