Sodium hydride → 2,2-Dioxo-1-(2-trimethylsilanyl-ethoxymethyl)-2,3-dihydro-1H-2lambda6-2,1-benzothiazin-4-one

HRID 1985507Notes

Reaction equation

HRID 1985507 reaction equation
[CH3:1][S:2]([NH:5][C:6]1[CH:15]=[CH:14][CH:13]=[CH:12][C:7]=1[C:8]([O:10]C)=O)(=[O:4])=[O:3].[CH3:16][Si:17]([CH3:24])([CH3:23])[CH2:18][CH2:19][O:20][CH2:21]Cl.[H-].[Na+]>CN(C)C=O>[O:4]=[S:2]1(=[O:3])[CH2:1][C:8](=[O:10])[C:7]2[CH:12]=[CH:13][CH:14]=[CH:15][C:6]=2[N:5]1[CH2:21][O:20][CH2:19][CH2:18][Si:17]([CH3:24])([CH3:23])[CH3:16]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 669032Methyl 2-[(methylsulfonyl)amino]benzoateHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl ether

Product 1

HCID 597320382,2-Dioxo-1-(2-trimethylsilanyl-ethoxymethyl)-2,3-dihydro-1H-2lambda6-2,1-benzothiazin-4-oneYield 72%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

In a dry round bottom flask under a blanket of nitrogen 60% sodium hydride in mineral oil (1.05 g, 26 mmol) was washed with hexanes and then suspended in N,N-dimethylformamide (50 mL). Mixture was cooled to 0° C. A solution of methyl 2-(methylsulfonamido)benzoate (5.0 g, 22 mmol) in 10 mL N,N-dimethylformamide was added to the mixture drop-wise. Reaction was held at 0° C. with stirring for 25 minutes. 2-(Trimethylsilyl)ethoxymethyl chloride was added to the mixture drop-wise. Reaction stirred for 2 hours slowly warming to ambient temperature. Reaction was quenched with 1N hydrochloric acid. Material was extracted twice with ethyl acetate. Material was washed successively with water and brine. Organic phase was dried (magnesium sulfate), filtered and concentrated to dryness. Residue was dissolved in N,N-dimethylformamide (5 mL) and added drop-wise to a mixture of 60% sodium hydride in mineral oil (1.02 g, 26 mmol) that had been washed with hexanes, suspended in N,N-dimethylformamide (50 mL) and cooled to 0° C. Ice bath was removed and the mixture was allowed to warm to room temperature. Reaction was held at room temperature overnight with stirring. Reaction was quenched with 1N hydrochloric acid. Material was extracted twice with ethyl acetate. Organic phase was washed successively with water and brine. Organic phase was dried (magnesium sulfate), filtered and concentrated to dryness. Silica gel chromatography (ethyl acetate-hexanes) afforded the title compound as a white solid in 72% yield. MS m/e (M−H)−=326.0.

Workup

  1. customReaction
  2. customwas held at 0° C.
  3. customReaction
  4. stirringstirred for 2 hours
  5. temperatureslowly warming to ambient temperature
  6. customReaction
  7. customwas quenched with 1N hydrochloric acid
  8. extractionMaterial was extracted twice with ethyl acetate
  9. washMaterial was washed successively with water and brine
  10. dry with materialOrganic phase was dried (magnesium sulfate)
  11. filtrationfiltered
  12. concentrationconcentrated to dryness
  13. dissolutionResidue was dissolved in N,N-dimethylformamide (5 mL)
  14. additionadded drop-wise
  15. washhad been washed with hexanes
  16. temperaturecooled to 0° C
  17. customIce bath was removed
  18. temperatureto warm to room temperature
  19. customReaction
  20. waitwas held at room temperature overnight
  21. stirringwith stirring
  22. customReaction
  23. customwas quenched with 1N hydrochloric acid
  24. extractionMaterial was extracted twice with ethyl acetate
  25. washOrganic phase was washed successively with water and brine
  26. dry with materialOrganic phase was dried (magnesium sulfate)
  27. filtrationfiltered
  28. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-fdc276bf97be4b489d96d35c26f03993
Source dataset
uspto-grants-2009_06
Patent number
US07544680B2

Reaction notes

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