Lithium Hexamethyldisilazide → HCID 58085708, compound

HRID 657991Notes

Reaction equation

HRID 657991 reaction equation
CON(C)[C:4](=[O:24])[C:5]1[CH:10]=[C:9]([NH:11][C:12](=[O:17])[C:13]([F:16])([F:15])[F:14])[CH:8]=[C:7]([S:18]([F:23])([F:22])([F:21])([F:20])[F:19])[CH:6]=1.[CH3:26][Si]([N-][Si](C)(C)C)(C)C.[Li+].C[Mg]Br>C1COCC1>[C:4]([C:5]1[CH:10]=[C:9]([NH:11][C:12](=[O:17])[C:13]([F:15])([F:16])[F:14])[CH:8]=[C:7]([S:18]([F:20])([F:19])([F:22])([F:23])[F:21])[CH:6]=1)(=[O:24])[CH3:26]

Participants

5

Reactant 3

HCID 2733832Lithium HexamethyldisilazideHCID 58085698N-Methoxy-N-methyl-5-pentafluorosulfanyl-3-(2,2,2-trifluoroacetylamino)benzamideHCID 178418573HCID 178418573, compound

Product 1

HCID 58085708HCID 58085708, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

N-Methoxy-N-methyl-3-(pentafluorosulfanyl)-5-(2,2,2-trifluoroacetylamino)benzamide (O4.075; 1.65 g) was dissolved in THF (25 ml). At 0° C., lithium bis(trimethylsilyl)amide (0.9 ml) was added while stirring. After 30 min, methylmagnesium bromide (3.5 ml, 3 M in diethyl ether) was added dropwise. After the addition had ended, the ice bath was removed and the mixture was stirred at RT for 2 h. While cooling, 1 N hydrochloric acid, water and EA were then added. After removing the organic phase, the aqueous phase was extracted twice more with EA. The combined EA phases were dried with magnesium sulfate, filtered and concentrated. The crude product is a mixture of N-(3-acetyl-5-pentafluorosulfanyl-phenyl)-2,2,2-trifluoroacetamide and 1-[3-amino-5-(pentafluorosulfanyl)phenyl]ethanone, and so the crude product (1.3 g) was taken up in methylene chloride (60 ml) and admixed with triethylamine (155 μl). Thereafter, trifluoroacetic anhydride (160 μl) was added while stirring. After stirring at RT for 3 h, water and saturated sodium hydrogencarbonate solution were added, the phases were separated and the DCM phase was washed three times more with water. The DCM phase was dried with magnesium sulfate, filtered and concentrated. 1.3 g of the title compound were obtained.

Workup

  1. additionAfter the addition
  2. customthe ice bath was removed
  3. stirringthe mixture was stirred at RT for 2 h
  4. temperatureWhile cooling
  5. addition1 N hydrochloric acid, water and EA were then added
  6. customAfter removing the organic phase
  7. extractionthe aqueous phase was extracted twice more with EA
  8. dry with materialThe combined EA phases were dried with magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. additiona mixture of N-(3-acetyl-5-pentafluorosulfanyl-phenyl)-2,2,2-trifluoroacetamide and 1-[3-amino-5-(pentafluorosulfanyl)phenyl]ethanone
  12. additionThereafter, trifluoroacetic anhydride (160 μl) was added
  13. stirringwhile stirring
  14. stirringAfter stirring at RT for 3 h
  15. additionwater and saturated sodium hydrogencarbonate solution were added
  16. customthe phases were separated
  17. washthe DCM phase was washed three times more with water
  18. dry with materialThe DCM phase was dried with magnesium sulfate
  19. filtrationfiltered
  20. concentrationconcentrated

Sources & evidence

ORD record
ord-d666d89995534343818b42f5f54101d5
Source dataset
uspto-grants-2011_12
Patent number
US08076336B2

Reaction notes

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