Methane → 5-(4-Methylphenyl)-4,6-dichloro-2-(2-thienyl)pyrimidine

HRID 1082314ノート

反応式

HRID 1082314 の反応式
[S:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.C([Li])CCC.CCCCCC.[CH3:17][C:18]1[CH:23]=[CH:22][C:21]([C:24]2[C:25]([Cl:31])=[N:26][CH:27]=[N:28][C:29]=2[Cl:30])=[CH:20][CH:19]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C>O1CCCC1.O.C(O)(=O)C>[CH3:17][C:18]1[CH:19]=[CH:20][C:21]([C:24]2[C:29]([Cl:30])=[N:28][C:27]([C:2]3[S:1][CH:5]=[CH:4][CH:3]=3)=[N:26][C:25]=2[Cl:31])=[CH:22][CH:23]=1

参加物

9

反応物 5

HCID 297MethaneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8030ThiopheneHCID 219795544,6-Dichloro-5-(4-methylphenyl)pyrimidineHCID 178418244HCID 178418244、化合物

生成物 1

HCID 196895045-(4-Methylphenyl)-4,6-dichloro-2-(2-thienyl)pyrimidine収率 49.1%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

To a solution of thiophene (1.69 g) in anhydrous tetrahydrofuran (20 ml) is added dropwise a 1.6 M n-butyl lithium/n-hexane solution (11.4 ml) at 0° C. under argon atmosphere over a period of 30 minutes. To the mixture is added dropwise and gradually a solution of 5-(4-methylphenyl)-4,6-dichloropyrimidine (4.0 g) in anhydrous tetrahydrofuran (5 ml) at -60° C. The mixture is warmed to 0° C., and stirred for 1.5 hour. After the reaction is complete, to the mixture are added acetic acid (1.5 g) and water (0.25 g), and further added thereto a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.70 g) in tetrahydrofuran (5 ml), and the mixture is stirred at 0° C. for one hour. The mixture is treated with an active charcoal, and extracted with a mixture of ethyl acetate and aqueous citric acid solution. The extract is washed, dried and evaporated to remove the solvent. The residue is purified by silica gel column chromatography (solvent; n-hexane/ethyl acetate=50:1) to give 5-(4-methylphenyl)-4,6-dichloro-2-(2-thienyl)pyrimidine (2.64 g) as powder.

後処理

  1. additionTo the mixture is added dropwise
  2. customat -60° C
  3. additionfurther added
  4. extractionextracted with a mixture of ethyl acetate and aqueous citric acid solution
  5. washThe extract is washed
  6. customdried
  7. customevaporated
  8. customto remove the solvent
  9. customThe residue is purified by silica gel column chromatography (solvent; n-hexane/ethyl acetate=50:1)

出典と根拠

ORDレコード
ord-50e981dd1abe471fbf1b0a5edf5e85fd
出典データセット
uspto-grants-1996_12
特許番号
US05589478

反応ノート

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