Sodium Chloride → 7,8-dihydro-6,6-dimethyl-7-hydroxy-8-(4,4-dimethyl-2-oxo-1-piperidinyl)-6H-pyrano[2,3-f]benzo-2,1,3-oxadiazole

HRID 327329ノート

反応式

HRID 327329 の反応式
[CH3:1][C:2]1([CH3:17])[O:14][C:6]2=[CH:7][C:8]3[C:9]([CH:13]=[C:5]2[CH:4]([NH2:15])[CH:3]1[OH:16])=[N:10][O:11][N:12]=3.C(N(CC)CC)C.Br[CH2:26][CH2:27][C:28]([CH3:34])([CH3:33])[CH2:29][C:30](Cl)=[O:31].[Na+].[Cl-]>C(OCC)(=O)C>[CH3:1][C:2]1([CH3:17])[O:14][C:6]2=[CH:7][C:8]3[C:9]([CH:13]=[C:5]2[CH:4]([N:15]2[CH2:26][CH2:27][C:28]([CH3:34])([CH3:33])[CH2:29][C:30]2=[O:31])[CH:3]1[OH:16])=[N:10][O:11][N:12]=3

参加物

6

反応物 4

HCID 5234Sodium ChlorideHCID 8471TriethylamineHCID 11107308(+)-7,8-dihydro-6,6-dimethyl-7-hydroxy-8-amino-6H-pyrano[2,3-f]benz-2,1,3-oxadiazoleHCID 190434955-Bromo-3,3-dimethylpentanoyl chloride

生成物 1

HCID 197348477,8-dihydro-6,6-dimethyl-7-hydroxy-8-(4,4-dimethyl-2-oxo-1-piperidinyl)-6H-pyrano[2,3-f]benzo-2,1,3-oxadiazole収率 62.3%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

実験手順

To 654 mg of (+)-7,8-dihydro-6,6-dimethyl-7-hydroxy-8-amino-6H-pyrano[2,3-f]benzo-2,1,3-oxadiazole dissolved in 10 mL of ethyl acetate were added 337 mg of triethylamine and dropwise added 696 mg of 5-bromo-3,3-dimethylvaleryl chloride at the room temperature over a 10-minute period, followed by stirring at the room temperature for one hour. The reaction mixture was added with 20 ml of saturated aqueous NaCl solution, and extracted twice with ethyl acetate (each 20 mL). After the extract was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was dissolved in 66 g of dimethylformamide and was dropwise added with 2.7 g of 20% tetraethylammonium hydroxide solution over 20 minutes under ice-cooling. Under ice-cooling, the mixture was reacted for 30 min. and then, the solvent was distilled off under reduced pressure and was added with 20 mL of saturated aqueous NaCl solution and extracted thrice with methylchloride (each 20 mL). After the extract was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure The residue was subjected to a silica gel column chromatography (ethyl acetate:n-hexane=1:1, Rf=0.5) to obtain 598 mg of the intended compound as colorless crystals.

後処理

  1. extractionextracted twice with ethyl acetate (each 20 mL)
  2. dry with materialAfter the extract was dried over anhydrous sodium sulfate
  3. distillationthe solvent was distilled off under reduced pressure
  4. dissolutionThe residue was dissolved in 66 g of dimethylformamide
  5. additionwas dropwise added with 2.7 g of 20% tetraethylammonium hydroxide solution over 20 minutes under ice-
  6. temperaturecooling
  7. temperatureUnder ice-cooling
  8. customthe mixture was reacted for 30 min.
  9. distillationthe solvent was distilled off under reduced pressure
  10. additionwas added with 20 mL of saturated aqueous NaCl solution
  11. extractionextracted thrice with methylchloride (each 20 mL)
  12. dry with materialAfter the extract was dried over anhydrous sodium sulfate
  13. distillationthe solvent was distilled off under reduced pressure The residue

出典と根拠

ORDレコード
ord-7dbbe68494714240af3b56484e4814ef
出典データセット
uspto-grants-1993_12
特許番号
US05272271

反応ノート

読み込み中…