Dimethyl Sulfoxide → HCID 136118862, compound

HRID 1609004Notes

Reaction equation

HRID 1609004 reaction equation
CS(C)=O.[C:5]([C:9]1[C:10](=[O:34])[CH2:11][CH:12]([C:16]2[CH:17]=[CH:18][C:19]3[O:24][CH2:23][C:22](=[O:25])[N:21]([CH2:26][C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[C:20]=3[CH:33]=2)[CH2:13][C:14]=1[OH:15])(=O)[CH2:6][CH3:7].Cl.[CH2:36]([O:38][NH2:39])[CH3:37].C([O-])(=O)C.[Na+]>Cl.CCOCC>[CH2:36]([O:38][N:39]=[C:5]([C:9]1[C:10](=[O:34])[CH2:11][CH:12]([C:16]2[CH:17]=[CH:18][C:19]3[O:24][CH2:23][C:22](=[O:25])[N:21]([CH2:26][C:27]4[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=4)[C:20]=3[CH:33]=2)[CH2:13][C:14]=1[OH:15])[CH2:6][CH3:7])[CH3:37]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 76850O-ethylhydroxylamine hydrochlorideHCID 517045Sodium AcetateHCID 178458819HCID 178458819, compound

Product 1

HCID 136118862HCID 136118862, compound

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 3283Diethyl EtherSolvent

Procedure

To 10 mL of methyl sulfoxide were added in sequence 1.4 g (3.5 mmol) of 2-propionyl-3-hydroxy-5-(N-benzyl-3-oxo-(2H)-1,4-benzoxazin-6-yl)cyclohex-2-en-1-one, 0.42 g (4.4 mmol) of ethoxyamine hydrochloride and 0.37 g (4.5 mmol) of anhydrous sodium acetate. The resulting mixture was stirred at ambient temperature for 3 hours. The reaction mixture was diluted with 50 mL of 0.5N HCl and extracted twice with 30 mL portions of ethyl acetate. The extracts were combined, dried over MgSO4 and filtered. Evaporation off of the solvent gave an oily residue. The residue was dissolved in 50 mL of ether, washed with water, then an aqueous NaCl solution, dried over MgSO4 and filtered. Evaporation off of the solvent gave a light amber glass which crystallized upon standing. The crude solid product was triturated in ether and the above-named product was isolated by filtration as a tan solid in a yield of 0.90 g (58 percent of theoretical). The product melted at 108°-110° C.; 1H NMR (CDCl3): d1.05-1.41 (m, 6H, both --CH2CH3 's), 2.42-3.45 (m, 7H), 4.12 (q, J=7 Hz, 2H, --OCH2CH3), 4.72 (2, 2H, --OCH2C=O), 5.20 (s, 2H, --CH2Ph), 6.75-7.08 (m, 3H, aromatic H's), 7.30 (s, 5H, --CH2Ph) ca. 14.7 (broad s, 1H, enol H); (Compound 7).

Workup

  1. extractionextracted twice with 30 mL portions of ethyl acetate
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. customEvaporation off of the solvent
  5. customgave an oily residue
  6. washwashed with water
  7. dry with materialan aqueous NaCl solution, dried over MgSO4
  8. filtrationfiltered
  9. customEvaporation off of the solvent
  10. customgave a light amber glass which
  11. customcrystallized
  12. customThe crude solid product was triturated in ether
  13. customthe above-named product was isolated by filtration as a tan solid in a yield of 0.90 g (58 percent of theoretical)

Sources & evidence

ORD record
ord-18a7921e36ec496aa647ca030f14bc70
Source dataset
uspto-grants-1995_03
Patent number
US05399542

Reaction notes

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