Tetrahydro-4H-pyran-4-one → HCID 25104046, compound

HRID 238541Notes

Reaction equation

HRID 238541 reaction equation
Cl.[NH2:2]O.C([O-])(=O)C.[Na+].[O:9]1[CH2:14][CH2:13][C:12](=O)[CH2:11][CH2:10]1.[N:16]1[O:17][N:18]=[C:19]2[CH:24]=[C:23]([C:25](Cl)=[O:26])[CH:22]=[CH:21][C:20]=12>C(O)C.ClCCl>[O:9]1[CH2:14][CH2:13][CH:12]([NH:2][C:25]([C:23]2[CH:22]=[CH:21][C:20]3=[N:16][O:17][N:18]=[C:19]3[CH:24]=2)=[O:26])[CH2:11][CH2:10]1

Participants

7

Reactant 4

HCID 121599Tetrahydro-4H-pyran-4-oneHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 27354532,1,3-Benzoxadiazole-5-carbonyl chloride

Product 1

HCID 25104046HCID 25104046, compoundYield 82.9%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of hydroxylamine hydrochloride (5.56 g), sodium acetate (6.56 g) and tetrahydro-4H-pyran-4-one (4 g, 40 mmol) in ethanol (100 ml) was refluxed over night. The solids were filtered off and the solvent evaporated. The remaining material was suspended in 100 ml of dry THF and decanted. LiAlH4 (6.07 g) was slowly added and the mixture was refluxed for 1 hour. The cooled mixture was quenched with 10% sodium hydroxide solution, celite was added, and the solids were filtered off. The solvent was evaporated and the residue re-dissolved in dichloromethane (10 ml) and triethylamine (1 ml). This mixture was slowly added to a solution of [2,1,3]-benzoxadiazole-5-carbonylchloride (365 mg, 2.0 mmol) in dichloromethane (10 ml) and stirred at room temperature for 0.5 h. The mixture was washed with 1N HCl (100 ml) and NaHCO3 (100 ml) solution and the aqueous re-extracted with dichloromethane (100 ml). The combined organics were dried over magnesium sulfate, and concentrated under vacuum to give a white solid (410 mg). Mp=204-205° C., 1H NMR (300 MHz, CDCl3) δ 8.20-8.18 (m, 1H), 7.92 (dd, 1H, J=9.3 and 1.2 Hz); 7.82 (dd, 1H, J=9.3 and 1.2 Hz); 6.25-6.10 (m, NH, 1H); 4.33-4.17 (m, 1H), 4.07-4.00 (m, 2H), 3.59-3.51 (m, 2H), 2.07-2.03 (m, 2H) and 1.69-1.58 ppm (m, 2H).

Workup

  1. temperaturewas refluxed over night
  2. filtrationThe solids were filtered off
  3. customthe solvent evaporated
  4. customdecanted
  5. additionLiAlH4 (6.07 g) was slowly added
  6. temperaturethe mixture was refluxed for 1 hour
  7. customThe cooled mixture was quenched with 10% sodium hydroxide solution, celite
  8. additionwas added
  9. filtrationthe solids were filtered off
  10. customThe solvent was evaporated
  11. dissolutionthe residue re-dissolved in dichloromethane (10 ml)
  12. washThe mixture was washed with 1N HCl (100 ml) and NaHCO3 (100 ml) solution
  13. extractionthe aqueous re-extracted with dichloromethane (100 ml)
  14. dry with materialThe combined organics were dried over magnesium sulfate
  15. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-e6eb661cd781467e92eb08b441518994
Source dataset
uspto-grants-2014_02
Patent number
US08642633B2

Reaction notes

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