Selenium Dioxide → Methyl 5-[3-,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-1,2-benzisothiazole-3-glyoxylate

HRID 48998Notes

Reaction equation

HRID 48998 reaction equation
[CH3:1][N:2]1[C:7]([C:8]([F:11])([F:10])[F:9])=[CH:6][C:5](=[O:12])[N:4]([C:13]2[CH:14]=[CH:15][C:16]3[S:20][N:19]=[C:18]([CH2:21][C:22]([O:24][CH2:25]C)=[O:23])[C:17]=3[CH:27]=2)[C:3]1=[O:28].[Se](=O)=[O:30]>C(O)(=O)C>[CH3:1][N:2]1[C:7]([C:8]([F:10])([F:11])[F:9])=[CH:6][C:5](=[O:12])[N:4]([C:13]2[CH:14]=[CH:15][C:16]3[S:20][N:19]=[C:18]([C:21](=[O:30])[C:22]([O:24][CH3:25])=[O:23])[C:17]=3[CH:27]=2)[C:3]1=[O:28]

Participants

4

Reactant 2

HCID 24007Selenium DioxideHCID 11729347Ethyl 5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-1,2-benzisothiazole-3-acetate

Product 1

HCID 20634280Methyl 5-[3-,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-1,2-benzisothiazole-3-glyoxylate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A mixture of ethyl 5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-1,2-benzisothiazole-3-acetate(30.0 g, 0.0750 mol), selenium dioxide (15.0 g, 0.135 mol) and glacial acetic acid is stirred two hours at reflux, cooled and filtered through a pad of Celite. The filtrate is concentrated in vacuo and the residue is stirred in methylene chloride. The mixture is filtered and the filtrate filtered through a pad of Celite. The resultant filtrate is treated with saturated sodium bicarbonate and solid sodium bicarbonate with stirring until bubbling ceases. The organic layer is saved. The aqueous layer is extracted with methylene chloride. The combined organic layers are washed with saturated sodium bicarbonate, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue is stirred overnight in diethyl ether-methylene chloride to afford, after filtration, the title compound as a white solid (24.5 g, 79.0%, mp 101-103° C.) which is identified by NMR spectral analysis.

Workup

  1. temperatureat reflux
  2. temperaturecooled
  3. filtrationfiltered through a pad of Celite
  4. concentrationThe filtrate is concentrated in vacuo
  5. stirringthe residue is stirred in methylene chloride
  6. filtrationThe mixture is filtered
  7. filtrationthe filtrate filtered through a pad of Celite
  8. additionThe resultant filtrate is treated with saturated sodium bicarbonate and solid sodium bicarbonate
  9. stirringwith stirring
  10. customuntil bubbling ceases
  11. extractionThe aqueous layer is extracted with methylene chloride
  12. washThe combined organic layers are washed with saturated sodium bicarbonate
  13. dry with materialdried over anhydrous magnesium sulfate
  14. concentrationconcentrated in vacuo
  15. stirringThe residue is stirred overnight in diethyl ether-methylene chloride
  16. customto afford
  17. filtrationafter filtration

Sources & evidence

ORD record
ord-790cd61beac5466e91ea9b2534a004aa
Source dataset
uspto-grants-2004_03
Patent number
US06706663B2

Reaction notes

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