Lithium Chloride → 4-Chloro-2,6-dimethyl-5-(1-ethoxyvinyl)pyrimidine

HRID 129017ノート

反応式

HRID 129017 の反応式
[Cl:1][C:2]1[C:7](I)=[C:6]([CH3:9])[N:5]=[C:4]([CH3:10])[N:3]=1.[CH2:11]([O:13][C:14]([Sn](CCCC)(CCCC)CCCC)=[CH2:15])[CH3:12].[Cl-].[Li+].[F-].[K+]>CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O1CCOCC1>[Cl:1][C:2]1[C:7]([C:11]([O:13][CH2:14][CH3:15])=[CH2:12])=[C:6]([CH3:9])[N:5]=[C:4]([CH3:10])[N:3]=1

参加物

8

反応物 4

HCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 14911174-Chloro-5-iodo-2,6-dimethylpyrimidine

生成物 1

HCID 107272924-Chloro-2,6-dimethyl-5-(1-ethoxyvinyl)pyrimidine収率 61%

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒2 回HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

実験手順

A mixture of 4-chloro-2,6-dimethyl-5-iodopyrimidine (13.5 g, 0.050 mol), (1ethoxyvinyl)tributyltin (20.0 g, 0.055 mol), lithium chloride (6.4 g, 0.150 mol), tetrakis(triphenylphosphine)palladium(0) (1.7 g, 0.0015 mol), and dioxane (100 mL) was heated under reflux for 23 h. Additional tetrakis(triphenylphosphine)palladium(0) (1.1 g, 0.0010 mol) was added and heating was continued for 25 h. The mixture was cooled, diluted with EtOAc, and ! N KF (100 mL) was added. The solids were removed by filtration through Celite and the layers were separated. The organic phase was washed with pH 7 phosphate buffer (100 mL), brine (100 mL), dried MgSO4), and concentrated. Purification by flash chromatography (twice; 5-10% EtOAc/hexane) gave 6.44 g (61%) of product as a colorless oil.

後処理

  1. temperaturewas heated
  2. temperatureunder reflux for 23 h
  3. temperatureheating
  4. temperatureThe mixture was cooled
  5. customThe solids were removed by filtration through Celite
  6. customthe layers were separated
  7. washThe organic phase was washed with pH 7 phosphate buffer (100 mL), brine (100 mL), dried MgSO4), and
  8. concentrationconcentrated
  9. customPurification by flash chromatography (twice

出典と根拠

ORDレコード
ord-cca7c6f3a4b4453d984fecd152333a56
出典データセット
uspto-grants-1995_11
特許番号
US05466692

反応ノート

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