N,1-dihydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbimidoyl chloride → 5-(5-(3,5-dichloro-4-(trifluoromethyl)phenyl)-5-(trifluoromethyl)-4,5-dihydro-isoxazol-3-yl)-3,3-dimethyl-benzo[c][1,2]oxaborol-1(3H)-ol

HRID 1750781Notes

Reaction equation

HRID 1750781 reaction equation
[OH:1][N:2]=[C:3](Cl)[C:4]1[CH:15]=[CH:14][C:7]2[B:8]([OH:13])[O:9][C:10]([CH3:12])([CH3:11])[C:6]=2[CH:5]=1.[Cl:17][C:18]1[CH:23]=[C:22]([C:24]([C:26]([F:29])([F:28])[F:27])=[CH2:25])[CH:21]=[C:20]([Cl:30])[C:19]=1[C:31]([F:34])([F:33])[F:32]>CN(C=O)C>[Cl:17][C:18]1[CH:23]=[C:22]([C:24]2([C:26]([F:29])([F:27])[F:28])[O:1][N:2]=[C:3]([C:4]3[CH:15]=[CH:14][C:7]4[B:8]([OH:13])[O:9][C:10]([CH3:12])([CH3:11])[C:6]=4[CH:5]=3)[CH2:25]2)[CH:21]=[C:20]([Cl:30])[C:19]=1[C:31]([F:32])([F:33])[F:34]

Participants

4

Reactant 2

HCID 86685046N,1-dihydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbimidoyl chlorideHCID 866850511,3-Dichloro-2-(trifluoromethyl)-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene

Product 1

HCID 715716725-(5-(3,5-dichloro-4-(trifluoromethyl)phenyl)-5-(trifluoromethyl)-4,5-dihydro-isoxazol-3-yl)-3,3-dimethyl-benzo[c][1,2]oxaborol-1(3H)-olYield 25%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of crude N,1-dihydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbimidoyl chloride (93 mg, 0.39 mmol) and 1,3-dichloro-2-(trifluoromethyl)-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene (133 mg, 0.43 mmol) in DMF (5 mL) at rt was added TEA (60 μL, 0.43 mmol). The reaction mixture was stirred for 12 h, poured into ice-water and extracted with EA. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by prep-TLC eluted with PE-EA (3:2) and then purified by combiflash to give the title compound 5-(5-(3,5-dichloro-4-(trifluoromethyl)phenyl)-5-(trifluoromethyl)-4,5-dihydro-isoxazol-3-yl)-3,3-dimethyl-benzo[c][1,2]oxaborol-1(3H)-ol (50 mg; yield 25% over 3 steps) as a white solid. 1H NMR (500 MHz, DMSO-d6): δ 9.220 (s, 1 H), 7.837 (s, 2 H), 7.716-7.731 (m, 2 H), 7.650-7.666 (m, 1H), 4.423 (d, J=18.0 Hz, 1 H), 4.311 (d, J=18.0 Hz, 1 H), 1.432 (s,6 H) ppm; HPLC purity: 99.3% at 220 nm and 99.4% at 254 nm.

Workup

  1. extractionextracted with EA
  2. washThe organic layer was washed with brine
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified
  7. washby prep-TLC eluted with PE-EA (3:2)
  8. custompurified by combiflash

Sources & evidence

ORD record
ord-db170fb14cc94da59b006cb2cfde4011
Source dataset
uspto-grants-2015_10
Patent number
US09156860B2

Reaction notes

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