Dichloroacetyl chloride → HCID 54567802, compound

HRID 1415897Notes

Reaction equation

HRID 1415897 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N:13]2[CH2:17][C@H:16]([CH2:18][N:19]=[N+]=[N-])[O:15][C:14]2=[O:22])[CH:5]=[CH:6][C:7]=1[N:8]1[CH:12]=[CH:11][N:10]=[N:9]1.C(N(CC)CC)C.[Cl:30][CH:31]([Cl:35])[C:32](Cl)=[O:33]>C1COCC1.[Ni].C(Cl)Cl>[F:1][C:2]1[CH:3]=[C:4]([N:13]2[CH2:17][C@H:16]([CH2:18][NH:19][C:32](=[O:33])[CH:31]([Cl:35])[Cl:30])[O:15][C:14]2=[O:22])[CH:5]=[CH:6][C:7]=1[N:8]1[CH:12]=[CH:11][N:10]=[N:9]1

Participants

7

Reactant 3

HCID 6593Dichloroacetyl chlorideHCID 8471TriethylamineHCID 53812503HCID 53812503, compound

Product 1

HCID 54567802HCID 54567802, compoundYield 52%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 275 mg (0.91 mmol) of (R)-[3-[3-Fluoro-4-(1H-1,2,3-triazol-1-yl)phenyl]-2-oxo-5-oxazolidinyl]methylazide (from Example 6) in 15 mL THF was treated with 1.5 g of W-2 Raney nickel, and hydrogenated at atmospheric pressure. After 18 h, the mixture was filtered through celite, washing the filter cake with methanol. The filtrate was concentrated in vacuo and the resulting oil was slurried in 15 mL methylene chloride, cooled to 0° C. and treated with 138 mg (0.19 mL, 1.36 mmol) triethylamine, and 161 mg (0.11 mL, 1.09 mmol) dichloroacetyl chloride. After stirring at ambient temperature for 24 h, the mixture was diluted with methylene chloride and extracted with water (3×20 mL) and saturated aqueous sodium chloride (1×20 mL). Drying (Na2SO4) and concentration in vacuo afforded an off-white solid. The crude material was subjected to radial chromatography on a 4 mm chromatotron plate eluting with dichloromethane and 2% (v/v) methanol-dichloromethane. These procedures afforded 182 mg (52%) of the title compound as a white solid, mp 195-198° C. dec.

Workup

  1. filtrationthe mixture was filtered through celite
  2. washwashing the filter cake with methanol
  3. concentrationThe filtrate was concentrated in vacuo
  4. extractionextracted with water (3×20 mL) and saturated aqueous sodium chloride (1×20 mL)
  5. customDrying
  6. concentration(Na2SO4) and concentration in vacuo
  7. customafforded an off-white solid
  8. washeluting with dichloromethane and 2% (v/v) methanol-dichloromethane

Sources & evidence

ORD record
ord-8340e08c73c2475eb06b9a67fc1ddee8
Source dataset
uspto-grants-1999_06
Patent number
US05910504

Reaction notes

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