Cesium carbonate → N-(2,4-dimethylphenyl)-N-isobutyl-4-vinylbenzenesulfonamide

HRID 1746413Notes

Reaction equation

HRID 1746413 reaction equation
[B-](F)(F)(F)[CH:2]=[CH2:3].[K+].Br[C:9]1[CH:14]=[CH:13][C:12]([S:15]([N:18]([C:23]2[CH:28]=[CH:27][C:26]([CH3:29])=[CH:25][C:24]=2[CH3:30])[CH2:19][CH:20]([CH3:22])[CH3:21])(=[O:17])=[O:16])=[CH:11][CH:10]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.O.ClCCl.[Pd](Cl)Cl>[CH3:30][C:24]1[CH:25]=[C:26]([CH3:29])[CH:27]=[CH:28][C:23]=1[N:18]([CH2:19][CH:20]([CH3:22])[CH3:21])[S:15]([C:12]1[CH:13]=[CH:14][C:9]([CH:2]=[CH2:3])=[CH:10][CH:11]=1)(=[O:17])=[O:16]

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 11776TriphenylphosphineHCID 23679353Potassium vinyltrifluoroborate2×HCID 867315904-bromo-N-(2,4-dimethylphenyl)-N-isobutylbenzenesulfonamide

Product 1

HCID 86731589N-(2,4-dimethylphenyl)-N-isobutyl-4-vinylbenzenesulfonamide

Reagents, catalysts & solvents 4

HCID 24290Palladium ChlorideCatalystHCID 962WaterSolvent3×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
140 °C

Procedure

A suspension of potassium trifluoro(vinyl)borate (241 mg, 1.800 mmol), 4-bromo-N-(2,4-dimethylphenyl)-N-isobutylbenzenesulfonamide (595 mg, 1.5 mmol), cesium carbonate (1466 mg, 4.50 mmol), palladium(II) chloride (5.32 mg, 0.030 mmol) and triphenylphosphine (23.61 mg, 0.090 mmol) was prepared in tetrahydrofuran (THF) (2 mL) and Water (0.2 mL). The mixture was heated to 140° C. by microwaves for 30 min, to yield a black suspension. Additional ½ eq of potassium trifluoro(vinyl)borate (121 mg, 0.9 mmol) was added, along with extra water (0.2 mL) and THF (2 mL) and reaction heated for a further 1 hour at 140° C. The reaction mixture was diluted with dichloromethane (15 mL) and water (5 mL), then filtered through a plug of celite to remove palladium catalyst. The resulting yellow solution was dried using a hydrophobic frit, concentrated, then purified by flash (Si) using 0-25% ethyl acetate/cyclohexane over 40 minutes. Fractions were combined to give a clear oil, 385.3 mg, and the product taken directly to the next step, without further purification. LCMS (M+1) 344, RT 1.48 mins.

Workup

  1. customto yield a black suspension
  2. temperatureheated for a further 1 hour at 140° C
  3. filtrationfiltered through a plug of celite
  4. customto remove palladium catalyst
  5. customThe resulting yellow solution was dried
  6. concentrationconcentrated
  7. custompurified by flash (Si)
  8. customover 40 minutes
  9. customto give a clear oil, 385.3 mg
  10. customthe product taken directly to the next step, without further purification
  11. customLCMS (M+1) 344, RT 1.48 mins

Sources & evidence

ORD record
ord-bf01cbe4e52f431d89d6dc9380d88c07
Source dataset
uspto-grants-2015_10
Patent number
US09150508B2

Reaction notes

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