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

HRID 327330Notes

Reaction equation

HRID 327330 reaction equation
[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][CH2:28][C:29]([CH3:34])([CH3:33])[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][CH2:28][C:29]([CH3:34])([CH3:33])[C:30]2=[O:31])[CH:3]1[OH:16])=[N:10][O:11][N:12]=3

Participants

6

Reactant 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 197348565-Bromo-2,2-dimethylvaleryl chloride

Product 1

HCID 197348437,8-dihydro-6,6-dimethyl-7-hydroxy-8-(2-oxo-3,3-dimethyl-1-piperidinyl)-6H-pyrano[2,3-f]benzo-2,1,3-oxadiazoleYield 41%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To 289 mg of (+)-7,8-dihydro-6,6-dimethyl-7-hydroxy-8-amino-6H-pyrano[2,3-f]benzo-2,1,3-oxadiazole dissolved in 5 mL of ethyl acetate were added 149 mg of triethylamine. The mixture was dropwise added with 308 mg of 5-bromo-2,2-dimethylvaleryl chloride, followed by stirring at the room temperature for one and half hours. The mixture was added with 10 mL of saturated aqueous NaCl solution and twice extracted with ethyl acetate (each 20 mL). After the extract was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was dissolved in 33 mL of dimethylformamide and was dropped with 1.24 g of 10% tetramethylammonium hydroxide solution under ice-cooling over 15-minute period. After the mixture was reacted under ice-cooling for one hour, the solvent was distilled off under reduced pressure and added with 10 mL of saturated aqueous NaCl solution and extracted twice with chloroform (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 174 mg of the intended compound as fine yellow crystals.

Workup

  1. extractiontwice extracted 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 33 mL of dimethylformamide
  5. additionwas dropped with 1.24 g of 10% tetramethylammonium hydroxide solution under ice-
  6. temperaturecooling over 15-minute period
  7. customAfter the mixture was reacted under ice-
  8. temperaturecooling for one hour
  9. distillationthe solvent was distilled off under reduced pressure
  10. additionadded with 10 mL of saturated aqueous NaCl solution
  11. extractionextracted twice with chloroform (each 20 mL)
  12. dry with materialAfter the extract was dried over anhydrous sodium sulfate
  13. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-9fc11224ff9943f5b46c686445168cfd
Source dataset
uspto-grants-1993_12
Patent number
US05272271

Reaction notes

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