Triphenylphosphine → HCID 66655178, compound

HRID 517738Notes

Reaction equation

HRID 517738 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([O:23][CH2:24][C:25]([NH:27][C:28]1[CH:33]=[CH:32][C:31]([C:34]#[N:35])=[C:30]([O:36][C:37]([F:40])([F:39])[F:38])[CH:29]=1)=O)(=[O:22])[CH3:21].C[Si]([N:45]=[N+:46]=[N-:47])(C)C>C1COCC1>[C:20]([O:23][CH2:24][C:25]1[N:27]([C:28]2[CH:33]=[CH:32][C:31]([C:34]#[N:35])=[C:30]([O:36][C:37]([F:40])([F:39])[F:38])[CH:29]=2)[N:47]=[N:46][N:45]=1)(=[O:22])[CH3:21]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 78378AzidotrimethylsilaneHCID 66654500HCID 66654500, compound2×

Product 1

HCID 66655178HCID 66655178, compoundYield 80.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Triphenylphosphine (17.29 g, 65.7 mmol) and diisopropylazodicorboxylate (13.3 g, 65.7 mmol) were added to a solution of 2-({4-cyano-3-[(trifluoromethyl)oxy]phenyl}amino)-2-oxoethyl acetate (Intermediate 52, 8.0 g, 26.5 mmol) in THF (160 mL) at 0° C. and the mixture was stirred for 30 min. Trimethylsilyl azide (7.60 g, 66.0 mmol) was added dropwise at room temperature and the mixture was heated to reflux for 4 hr. THF was removed under reduced pressure and the residue was diluted with EtOAc and washed with ice-cooled water. The extracted organic layer was washed with brine solution, dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford the crude product. This was purified by column chromatography (100-200 mesh silica gel), eluting with 20% EtOAc/pet ether to give the title compound (7.0 g).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 4 hr
  3. customTHF was removed under reduced pressure
  4. additionthe residue was diluted with EtOAc
  5. washwashed with ice-
  6. temperaturecooled water
  7. washThe extracted organic layer was washed with brine solution
  8. dry with materialdried over anhydrous Na2SO4
  9. concentrationconcentrated under reduced pressure
  10. customto afford the crude product
  11. customThis was purified by column chromatography (100-200 mesh silica gel)
  12. washeluting with 20% EtOAc/pet ether

Sources & evidence

ORD record
ord-a9aab2b416af4c3bad8be5213afa3f10
Source dataset
uspto-grants-2015_08
Patent number
US09115132B2

Reaction notes

Loading…