Cesium carbonate → 4-(3-Bromo-5-triisopropylsilanyloxy-phenylamino)-benzonitrile

HRID 1784850Notes

Reaction equation

HRID 1784850 reaction equation
Br[C:2]1[CH:3]=[C:4]([O:9][Si:10]([CH:17]([CH3:19])[CH3:18])([CH:14]([CH3:16])[CH3:15])[CH:11]([CH3:13])[CH3:12])[CH:5]=[C:6]([Br:8])[CH:7]=1.[C:20]([O-])([O-])=O.[Cs+].[Cs+].[NH2:26][C:27]1[CH:28]=[CH:29][C:30]([C:33]#[N:34])=N[CH:32]=1>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[Br:8][C:6]1[CH:7]=[C:2]([NH:26][C:27]2[CH:32]=[CH:20][C:30]([C:33]#[N:34])=[CH:29][CH:28]=2)[CH:3]=[C:4]([O:9][Si:10]([CH:17]([CH3:19])[CH3:18])([CH:14]([CH3:16])[CH3:15])[CH:11]([CH3:13])[CH3:12])[CH:5]=1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 38713955-Aminopyridine-2-carbonitrileHCID 50994104(3,5-Dibromo-phenoxy)-triisopropyl-silane

Product 1

HCID 688441304-(3-Bromo-5-triisopropylsilanyloxy-phenylamino)-benzonitrileYield 46.4%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To 1.0 g (2.45 mmol) of 3,5-dibromotriisopropylsiloxybenzene in 20.0 mL of anhydrous 1,4-dioxane was added 1.12 g (3.43 mmol) of Cs2CO3, 0.32 g (2.7 mmol) of 5-amino-pyridine-2-carbonitrile and 43 mg (0.074 mmol) Xantphos. The reaction mixture was deoxygenated by bubbling argon for 30 mins and then treated with 57 mg (0.049 mmol) of Pd(PPh3)4. The reaction vial was capped and heated at 100° C. for 4 hours. The reaction mixture was cooled to room temperature, filtered through Celite®, and the filter cake was washed with ethyl acetate. The ethyl acetate layer was washed with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was chromatographed on silica gel using 5:1 hexane:ethyl acetate to give 506 mg of 4-(3-bromo-5-triisopropylsilanyloxy-phenylamino)-benzonitrile.

Workup

  1. customThe reaction mixture was deoxygenated
  2. customby bubbling argon for 30 mins
  3. customThe reaction vial was capped
  4. temperatureThe reaction mixture was cooled to room temperature
  5. filtrationfiltered through Celite®
  6. washthe filter cake was washed with ethyl acetate
  7. washThe ethyl acetate layer was washed with water and brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude product was chromatographed on silica gel using 5:1 hexane

Sources & evidence

ORD record
ord-cd02b07b92ea4fdab52c52bb2c8b01b1
Source dataset
uspto-grants-2009_03
Patent number
US07504401B2

Reaction notes

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