Boron trifluoride → HCID 71269853, compound

HRID 540778Notes

Reaction equation

HRID 540778 reaction equation
[CH2:1]([N:3]1[C:7]([C:9]2[CH:10]=[C:11]([CH:14]=[CH:15][CH:16]=2)[C:12]#[N:13])(O)[C:6](F)([F:17])[C:5]([O:19][C:20]2[CH:25]=[CH:24][C:23]([C:26]([F:29])([F:28])[F:27])=[CH:22][CH:21]=2)=[N:4]1)[CH3:2].C([SiH](CC)CC)C.B(F)(F)F.C1CCN2C(=NCCC2)CC1>CCOC(C)=O.C(Cl)Cl>[CH2:1]([N:3]1[C:7]([C:9]2[CH:10]=[C:11]([CH:14]=[CH:15][CH:16]=2)[C:12]#[N:13])=[C:6]([F:17])[C:5]([O:19][C:20]2[CH:25]=[CH:24][C:23]([C:26]([F:29])([F:27])[F:28])=[CH:22][CH:21]=2)=[N:4]1)[CH3:2]

Participants

7

Reactant 4

HCID 6356Boron trifluorideHCID 12052TriethylsilaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 67111069HCID 67111069, compound

Product 1

HCID 71269853HCID 71269853, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3-{1-ethyl-4,4-difluoro-5-hydroxy-3-[4-(trifluoromethyl)phenoxy]-4,5-dihydro-1H-pyrazol-5-yl}benzonitrile (crude, 2.1 g, 5.11 mmol), DCM (25.5 mL) and triethylsilane (2.45 mL, 15.3 mmol) was cooled to −78° C. and treated with BF3 etherate (1.94 mL, 15.3 mmol) in a single portion. The reaction was allowed to warm to rt overnight and checked via LCMS at 16 h. The reaction was treated with DBU (3.85 mL, 25.6 mmol) dropwise and checked via LCMS after 30 minutes, requisite product dominates. The reaction was diluted with EtOAc and washed with sat aq. NaHCO3 2×, brine, dried (MgSO4) and concentrated to afford an opaque brown residue purified via MPLC, 100 g silica, 5-35% EtOAc in heptanes to afford 3-{1-ethyl-4-fluoro-3-[4-(trifluoromethyl)phenoxy]-1H-pyrazol-5-yl}benzonitrile as a clear, colorless oil. MS: cal'd 376 (MH+), exp 376 (MH+).

Workup

  1. waitchecked via LCMS after 30 minutes
  2. washwashed
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customto afford an opaque brown residue
  6. custompurified via MPLC, 100 g silica, 5-35% EtOAc in heptanes

Sources & evidence

ORD record
ord-bc7447aa81694e4584e113691c325c04
Source dataset
uspto-grants-2014_10
Patent number
US08871796B2

Reaction notes

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