Trimethylsilyldiazomethane → 4-Phenyl-5-(trimethylsilyl)-1H-pyrazole-3-carbonitrile

HRID 20317

反応式

HRID 20317 の反応式
C([Li])CCC.[CH3:6][Si:7]([CH:10]=[N+:11]=[N-:12])([CH3:9])[CH3:8].[CH:13](=[C:20](C#C)[C:21]#[N:22])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>C1COCC1.C(OCC)(=O)C>[C:14]1([C:13]2[C:20]([C:21]#[N:22])=[N:12][NH:11][C:10]=2[Si:7]([CH3:9])([CH3:8])[CH3:6])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

参加物

6

反応物 3

HCID 167693TrimethylsilyldiazomethaneHCID 860306562-Benzylidene-but-3-ynenitrileHCID 178418339Butyllithium

生成物 1

HCID 131447894-Phenyl-5-(trimethylsilyl)-1H-pyrazole-3-carbonitrile収率 69.1%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

n-Butyl lithium (2.7 M solution in heptane) (3.3 ml, 9 mmol) was added drop wise to a stirred solution of trimethylsilyl diazomethane (2 M solution in diethyl ether) (4.5 ml, 9 mmol) in anhydrous THF (10 ml) at −78° C. under a nitrogen atmosphere, then stirred for a further 30 minutes. To this was added drop wise a solution of 2-benzylidene-but-3-yne nitrile (920 mg; 6 mmol) in anhydrous THF (5 ml), the mixture stirred for 30 minutes at −78° C. then gradually allowed to warm to room temperature overnight. The reaction mixture was diluted with ethyl acetate (30 ml) then washed with saturated ammonium chloride solution followed by brine. The ethyl acetate layer was separated, dried (MgSO4), filtered and evaporated. The crude product was purified by flash column chromatography eluting with 1:8 then 1:4 ethyl acetate/hexane and the product containing fractions combined and evaporated to give 1.0 g of 4-phenyl-5-trimethylsilanyl-1H-pyrazole-3-carbonitrile.

後処理

  1. stirringthe mixture stirred for 30 minutes at −78° C.
  2. washthen washed with saturated ammonium chloride solution
  3. customThe ethyl acetate layer was separated
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude product was purified by flash column chromatography
  8. washeluting with 1:8
  9. addition1:4 ethyl acetate/hexane and the product containing fractions
  10. customevaporated

出典と根拠

ORDレコード
ord-a49698ccbffb4d44942ba27cc9541a11
出典データセット
uspto-grants-2010_06
特許番号
US07745638B2

関連ノート

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