Lithium Hexamethyldisilazide → HCID 10362093, compound

HRID 1830928Notes

Reaction equation

HRID 1830928 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][CH:17]=2)[S:9]([CH2:12][C:13](=[O:15])[CH3:14])(=[O:11])=[O:10])=[CH:4][CH:3]=1.[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[F:33]NS(C1C=CC=CC=1)(=O)=O>C1COCC1.O>[Cl:22][C:19]1[CH:18]=[CH:17][C:16]([CH:8]([C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=2)[S:9]([CH:12]([F:33])[C:13](=[O:15])[CH3:14])(=[O:10])=[O:11])=[CH:21][CH:20]=1

Participants

6

Reactant 3

HCID 2733832Lithium HexamethyldisilazideHCID 15373214N-FluorobenzenesulfonamideHCID 22049841HCID 22049841, compound

Product 1

HCID 10362093HCID 10362093, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirring solution of the methyl ketone (Example 1, 0.6 g, 1.7 mmol) in dry THF (11 mL) at 0° C., under dry nitrogen was added LiHMDS (1.0 M/THF, 2.2 mL, 1.2 mmol) and the mixture stirred for 30 minutes without warming. After this time, the resulting enolate was lowered to −78° C., whereupon a solution of N-fluorobenzenesulfonamide (0.85 g, 2.7 mmol) in dry THF (5.0 mL) was added via canula. The reaction was then stirred for 30 minutes and then at room temperature for 1 hour, and was then diluted with water and extracted with ethyl acetate. The organic layers were combined, dried on Na2SO4, and filtered to give a mixture that was purified on SiO2 with 15%–20% EtOAcHexane to give (0.075 g, the fluorinated species as a colorless oil. Anal. Calcd for C16H13Cl2F1O3S1: 0.15H2O: Calcd C, 50.85; H, 3.55; Cl, 18.76; F, 5.03; O, 13.33; S, 8.48. Found: C, 50.45; H, 3.51; S, 8.15. 1H NMR (CDCl3, 400 MHz): δ 2.1 (s, 3H), 5.2 (d, 1H, J=49.0 Hz), 5.65 (s, 1H), 7.28–7.5 (m, 4H), 7.5–7.7 (m, 4H).

Workup

  1. temperaturewithout warming
  2. additionwas added via canula
  3. stirringThe reaction was then stirred for 30 minutes
  4. waitat room temperature for 1 hour
  5. extractionextracted with ethyl acetate
  6. customdried on Na2SO4
  7. filtrationfiltered
  8. customto give a mixture that
  9. customwas purified on SiO2 with 15%–20% EtOAcHexane
  10. customto give (0.075 g

Sources & evidence

ORD record
ord-bdeb76d3ea7c4ed79714c6a81f8a3d8d
Source dataset
uspto-grants-2006_06
Patent number
US07067538B2

Reaction notes

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