Diflunisal → 1-(Ethoxycarbonyloxy)ethyl 5-(2,4-difluorophenyl)salicylate

HRID 1719725ノート

反応式

HRID 1719725 の反応式
[CH:1]1[C:6]([C:7]2[CH:8]=[CH:9][C:10]([F:14])=[CH:11][C:12]=2[F:13])=[CH:5][C:4]([C:15]([OH:17])=[O:16])=[C:3]([OH:18])[CH:2]=1.[H-].[Na+].[C:21](=[O:29])([O:25][CH:26](Cl)[CH3:27])[O:22][CH2:23][CH3:24]>CN(C=O)C>[F:13][C:12]1[CH:11]=[C:10]([F:14])[CH:9]=[CH:8][C:7]=1[C:6]1[CH:5]=[C:4]([C:15]([O:17][CH:23]([O:22][C:21]([O:25][CH2:26][CH3:27])=[O:29])[CH3:24])=[O:16])[C:3]([OH:18])=[CH:2][CH:1]=1

参加物

5

反応物 3

HCID 3059DiflunisalHCID 24758Sodium hydrideHCID 162095Carbonic acid, 1-chloroethyl ethyl ester

生成物 1

HCID 134913951-(Ethoxycarbonyloxy)ethyl 5-(2,4-difluorophenyl)salicylate

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

To a solution of diflunisal (5.0 g) in 40 ml DMF was added 0.8 g of sodium hydride (oil suspension containing 60% of NaH). The resultant mixture was stirred for 1.5 hours at room temperature before 3.0 ml of ethyl 1-chloroethyl carbonate was added dropwise. The reaction mixture was stirred at room temperature overnight and concentrated in vacuo. The concentrate was partitioned between ether/ethyl acetate and acidified water. The organic layer was separated and the aqueous layer was extracted again with ether. The organic layers were combined, washed well with water, dried over anhydrous sodium sulfate and concentrated to 6.6 g of crude product. After further purification by chromatography (eluted through 120 g of silica gel with hexane, and then 5% ethyl acetate in hexane), the product was crystallized from hexane to afford 3.71 g of 1-(ethoxycarbonyloxy)ethyl 5-(2,4-difluorophenyl)salicylate.

後処理

  1. additionwas added dropwise
  2. concentrationconcentrated in vacuo
  3. customThe concentrate was partitioned between ether/ethyl acetate
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted again with ether
  6. washwashed well with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated to 6.6 g of crude product
  9. customAfter further purification by chromatography (
  10. washeluted through 120 g of silica gel with hexane
  11. custom5% ethyl acetate in hexane), the product was crystallized from hexane

出典と根拠

ORDレコード
ord-f86c552ff4b14b5cbed0245ed8dd00c3
出典データセット
uspto-grants-1985_09
特許番号
US04542158

反応ノート

読み込み中…