Triethylamine → 2,2-Dioxo-6-(1,1-dimethylethyl)-8-iodo-1,2,3-benzoxathiazine

HRID 261605Notes

Reaction equation

HRID 261605 reaction equation
[S:1](Cl)(=[O:4])(=[O:3])[NH2:2].[I:6][C:7]1[CH:14]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:12]=[C:9]([CH:10]=O)[C:8]=1[OH:19].C(N(CC)CC)C>C(Cl)Cl>[O:3]=[S:1]1(=[O:4])[N:2]=[CH:10][C:9]2[CH:12]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:14]=[C:7]([I:6])[C:8]=2[O:19]1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 24499Chlorosulfamic acidHCID 127618365-tert-Butyl-2-hydroxy-3-iodobenzaldehyde

Product 1

HCID 127618412,2-Dioxo-6-(1,1-dimethylethyl)-8-iodo-1,2,3-benzoxathiazineYield 14%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

To a solution of sulfamoyl chloride (13.8 g, 0.12 mole) in anhydrous methylene chloride (75 ml) is added a solution of 3-iodo-5-(1,1-dimethylethyl)salicylaldehyde (6 g., 0.02 mole) and triethylamine (12.1 g, 0.12 mole) in anhydrous methylene chloride (100 ml.) dropwise with stirring at 20° C. Upon completing the addition, the resulting reaction mixture is stirred at 20° C. for 3 days. Removal of the solvent in vacuo leaves a tacky residue which is partitioned between ether and 2 N hydrochloric acid. After separating the phases, the organic phase is washed with water and saturated bromine, dried over sodium sulfate and filtered. Evaporation of the filtrate leaves an oily residue (6 g.) which is chromatographed on silica gel (300 g.) with benzene. Elution with benzene (840 ml.) gives recovered 3-iodo-5-(1,1-dimethylethyl)salicylaldehyde (2.2 g., 37% recovery), m.p. 76°-78° C. Continued elution with benzene (500 ml.) provides an impure solid (2.4 g.) which is triturated with hexane (20 ml.) and filtered to afford the title compound as a pale yellow solid (1.0 g, 14%), m.p. 130°-134° C. Crystallization from hexane-benzene (9.1; viv) gives an analytical sample of 2,2-dioxo-6-(1,1-dimethylethyl)-8-iodo-1,2,3-benzoxathiazine, m.p. 135°-136° C.

Workup

  1. additionthe addition
  2. customthe resulting reaction mixture
  3. stirringis stirred at 20° C. for 3 days
  4. customRemoval of the solvent in vacuo
  5. customleaves a tacky residue which
  6. customis partitioned between ether and 2 N hydrochloric acid
  7. customAfter separating the phases
  8. washthe organic phase is washed with water and saturated bromine
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. customEvaporation of the filtrate
  12. customleaves an oily residue (6 g.) which
  13. customis chromatographed on silica gel (300 g.) with benzene
  14. washElution with benzene (840 ml.)
  15. customgives
  16. customrecovered 3-iodo-5-(1,1-dimethylethyl)salicylaldehyde (2.2 g., 37% recovery), m.p. 76°-78° C
  17. washContinued elution with benzene (500 ml.)
  18. customprovides an impure solid (2.4 g.) which
  19. customis triturated with hexane (20 ml.)
  20. filtrationfiltered

Sources & evidence

ORD record
ord-307ec17f73114e24b7045ec207673d1e
Source dataset
uspto-grants-1979_08
Patent number
US04166177

Reaction notes

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