Dimethyl Sulfate → (1-Methoxyphenylethylidene)malononitrile

HRID 487263ノート

反応式

HRID 487263 の反応式
[H-].[Na+].[OH:3][C:4]1([CH2:10][CH:11]=[C:12]([C:15]#[N:16])[C:13]#[N:14])[CH:9]=[CH:8][CH:7]=[CH:6][CH2:5]1.[CH3:17]OS(OC)(=O)=O>C1COCC1>[CH3:17][O:3][C:4]1([CH2:10][CH:11]=[C:12]([C:13]#[N:14])[C:15]#[N:16])[CH:5]=[CH:6][CH:7]=[CH:8][CH2:9]1

参加物

5

反応物 3

HCID 6497Dimethyl Sulfate2 回HCID 24758Sodium hydride2 回HCID 86747658(1-Hydroxyphenylethylidene)malononitrile

生成物 1

HCID 86747657(1-Methoxyphenylethylidene)malononitrile収率 56.2%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

To a suspension of 60% NaH/mineral oil dispersion (2.9 g, 74.7 mmol) in THF (50 ml) was added dropwise (1-hydroxyphenylethylidene)malononitrile (13.8 g, 74.7 mmol) in THF (75 ml) over 25 minutes, followed by dimethylsulfate (7.1 ml, 74.7 mmol) in THF (50 ml) over 20 minutes. The reaction mixture was stirred at room temperature for 30 minutes, then at reflux for 4 hours. 0.5 equivalents of 60% sodium hydride and dimethylsulfate were added and the reaction mixture was stirred at room temperature for 24 hours. The solvent was removed in vacuo, the residue was partitioned between ether and water, the organic layer was separated and the aqueous layer was extracted with ether (3×150 ml). The combined organic layers were dried over anhydrous MgSO4 and solvent was removed in vacuo. The residue was purified by column chromatography on silica eluting with ethyl acetate/hexanes (1/1) to afford 8.4 g (56%) of (1-methoxyphenylethylidene)malononitrile as an amber liquid.

後処理

  1. temperatureat reflux for 4 hours
  2. stirringthe reaction mixture was stirred at room temperature for 24 hours
  3. customThe solvent was removed in vacuo
  4. customthe residue was partitioned between ether and water
  5. customthe organic layer was separated
  6. extractionthe aqueous layer was extracted with ether (3×150 ml)
  7. dry with materialThe combined organic layers were dried over anhydrous MgSO4 and solvent
  8. customwas removed in vacuo
  9. customThe residue was purified by column chromatography on silica eluting with ethyl acetate/hexanes (1/1)

出典と根拠

ORDレコード
ord-b52ef15881874710899709c5461e86cb
出典データセット
uspto-grants-1994_03
特許番号
US05294612

反応ノート

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