Triethylborane → HCID 22911835, compound

HRID 1378593Notes

Reaction equation

HRID 1378593 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:29]=[C:30]([Cl:32])[CH:31]=1)[O:5][CH2:6][C:7]1[S:8][C:9]([C:19]2[CH:24]=[CH:23][C:22]([S:25](C)(=[O:27])=[O:26])=[CH:21][CH:20]=2)=[C:10]([C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=2)[N:11]=1.C([Mg]Cl)CCC.C(B(CC)CC)C.C([O-])(=O)C.[Na+].[NH2:51]OS(O)(=O)=O>C1COCC1.C(OCC)(=O)C.O>[F:18][C:15]1[CH:16]=[CH:17][C:12]([C:10]2[N:11]=[C:7]([CH2:6][O:5][C:4]3[CH:3]=[C:2]([Cl:1])[CH:31]=[C:30]([Cl:32])[CH:29]=3)[S:8][C:9]=2[C:19]2[CH:24]=[CH:23][C:22]([S:25]([NH2:51])(=[O:27])=[O:26])=[CH:21][CH:20]=2)=[CH:13][CH:14]=1

Participants

9

Reactant 5

HCID 7357TriethylboraneHCID 76284hydroxylamine-O-sulfonic acidHCID 517045Sodium AcetateHCID 10229202HCID 10229202, compoundHCID 178418265HCID 178418265, compound

Product 1

HCID 22911835HCID 22911835, compoundYield 28.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 2-((3,5-dichlorophenoxy)methyl)-4-(4-fluorophenyl)-5-(4-methylsulfonylphenyl)thiazole (Example 33) (0.508 g, 1.0 mmol) in THF (5 mL) at 0° C. under nitrogen was added 2.0M n-butyl magnesium chloride in THF (1.6 mL, 3.2 mmol) slowly, via syringe, and the mixture stirred at 0° C. for 30 minutes and then at room temperature (25° C.) for 2 hours. After cooling to 0° C., a 1.0M solution of triethyl borane in THF (5 mL, 5 mmol) was added and the mixture was warmed to room temperature and stirred for 2 hours, and then heated to reflux for 36 hours. After cooling to room temperature and stirring for 3 hours, water (3 mL) was added followed by sodium acetate (1.2 g) and hydroxylamine-O-sulfonic acid (0.82 g). After stirring at room temperature overnight, the mixture was poured into 3 volumes of ethyl acetate, and the organic layer washed with water and brine and dried over MgSO4. After solvent removal, the white solids (a mixture of product and starting material) were purified by flash chromatography on silica gel using 30% ethyl acetate/70% hexane to provide 4-[4-(4-fluorophenyl)-2-((3,5-dichlorophenoxy)methyl)-5-thiazolyl]benzenesulfonamide as a white solid (0.147 g): Anal. Calc'd for C22H15N2O3S2FCl2 : C, 51.87; H, 2.97; N, 5.50. Found: C, 52.19; H, 2.84; N, 5.40

Workup

  1. waitat room temperature (25° C.) for 2 hours
  2. temperatureAfter cooling to 0° C.
  3. temperaturethe mixture was warmed to room temperature
  4. stirringstirred for 2 hours
  5. temperatureheated
  6. temperatureto reflux for 36 hours
  7. temperatureAfter cooling to room temperature
  8. stirringstirring for 3 hours
  9. stirringAfter stirring at room temperature overnight
  10. washthe organic layer washed with water and brine
  11. dry with materialdried over MgSO4
  12. customAfter solvent removal
  13. additionthe white solids (a mixture of product and starting material)
  14. customwere purified by flash chromatography on silica gel using 30% ethyl acetate/70% hexane

Sources & evidence

ORD record
ord-ed5467e1ad7542d7a82e00840353b3d1
Source dataset
uspto-grants-1997_09
Patent number
US05668161

Reaction notes

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