Ethyl Acetate → 5-(5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)-3,3-diethyl-benzo[c][1,2]oxaborol-1(3H)-ol

HRID 532220Notes

Reaction equation

HRID 532220 reaction equation
[CH2:1]([C:3]1([CH2:16][CH3:17])[O:7][B:6]([OH:8])[C:5]2[CH:9]=[CH:10][C:11]([CH:13]=[N:14][OH:15])=[CH:12][C:4]1=2)[CH3:2].C1C(=O)N(Cl)C(=O)C1.[Cl:26][C:27]1[CH:32]=[C:31]([C:33]([C:35]([F:38])([F:37])[F:36])=[CH2:34])[CH:30]=[C:29]([Cl:39])[CH:28]=1.CC(=O)OCC>CN(C=O)C>[Cl:26][C:27]1[CH:32]=[C:31]([C:33]2([C:35]([F:38])([F:36])[F:37])[O:15][N:14]=[C:13]([C:11]3[CH:10]=[CH:9][C:5]4[B:6]([OH:8])[O:7][C:3]([CH2:1][CH3:2])([CH2:16][CH3:17])[C:4]=4[CH:12]=3)[CH2:34]2)[CH:30]=[C:29]([Cl:39])[CH:28]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 31398ChlorosuccinimideHCID 231598231,3-Dichloro-5-(3,3,3-trifluoroprop-1-en-2-yl)benzeneHCID 866850853,3-Diethyl-1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbaldehyde oxime

Product 1

HCID 715721205-(5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)-3,3-diethyl-benzo[c][1,2]oxaborol-1(3H)-olYield 35.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
45 °C

Procedure

To a solution of 3,3-diethyl-1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbaldehyde oxime (251 mg, 1.07 mmol) in DMF (15 ml) at rt was added NCS (151 mg, 1.13 mmol). The reaction mixture was warmed to 45° C., stirred for 1.5 h and cooled to −10° C. To this mixture was successively added 1,3-dichloro-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene (516 mg, 2.15 mmol) and TEA (326.3 mg, 3.23 mmol) below −10° C. The mixture was stirred at this temperature for 2 h, poured into ice-water and extracted with EA (40 ml×2). The combined organic layers were washed with aqueous NaHCO3 and brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography over silica gel eluted with PE:EA (10:1 to 5:1) to give the desired title compound 5-(5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl)-3,3-diethylbenzo[c][1,2]oxaborol-1(3H)-ol (180 mg, yield 35.5%) as white solid. 1H NMR (300 MHz, DMSO-d6): δ 9.22 (s, 1H), 7.85-7.45 (m, 6H), 4.48-4.22 (m, 2H), 2.00-1.70 (m, 4H), 0.68-0.42 (m, 6H) ppm. MS: m/z=472 [M+1]+.

Workup

  1. temperaturecooled to −10° C
  2. stirringThe mixture was stirred at this temperature for 2 h
  3. extractionextracted with EA (40 ml×2)
  4. washThe combined organic layers were washed with aqueous NaHCO3 and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by column chromatography over silica gel
  9. washeluted with PE

Sources & evidence

ORD record
ord-4417475f09644a38a6e565655d2b549e
Source dataset
uspto-grants-2014_10
Patent number
US08853186B2

Reaction notes

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