Diisopropylamine → 7-Benzenesulfonyl-4-chloro6-phenyl-7H-pyrrolo[2,3-d]pyrimidine

HRID 2099157Notes

Reaction equation

HRID 2099157 reaction equation
C(N[CH:5]([CH3:7])[CH3:6])(C)C.[CH2:8]([Li])[CH2:9][CH2:10]C.[C:13]1([S:19]([N:22]2[C:26]3[N:27]=[CH:28][N:29]=[C:30]([Cl:31])[C:25]=3[CH:24]=[CH:23]2)(=[O:21])=[O:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>O1CCCC1.[Cl-].[Zn+2].[Cl-].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:13]1([S:19]([N:22]2[C:26]3[N:27]=[CH:28][N:29]=[C:30]([Cl:31])[C:25]=3[CH:24]=[C:23]2[C:6]2[CH:5]=[CH:7][CH:10]=[CH:9][CH:8]=2)(=[O:21])=[O:20])[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

7

Reactant 3

HCID 7912DiisopropylamineHCID 109463064-Chloro-7-(phenylsulfonyl)-7H-pyrrolo[2,3-D]pyrimidineHCID 178418339Butyllithium

Product 1

HCID 224845527-Benzenesulfonyl-4-chloro6-phenyl-7H-pyrrolo[2,3-d]pyrimidine

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-78 °C

Procedure

In a flame-dried flask under nitrogen, 0.53 mL (3.79 mmol) of diisopropylamine were dissolved in 5 mL of tetrahydrofuran (THF) and the solution cooled to −78° C. n-Butyllithium (3.75 mmol as a 2.5 M solution in hexanes) was added and the resulting mixture brought to 0° C. with continued stirring for 10 minutes. The reaction mixture was again cooled to −78° C. and to this mixture added a solution of 1.0 grams (3.40 mmol) of the product from Method B in 10 mL of THF over a 10 min period. The reaction mixture was stirred for 1 hour at −78° C., at which time, 8.2 mL (4.10 mmol) of a 0.5 M solution of zinc chloride in THF was added, the reaction mixture was brought to room temperature and stirred for 1 hour. lodobenzene (0.46 mL/4.11 mmol) and a suspension of 197 mg of tetrakis(triphenylphosphine) palladium in 2 mL of THF were added. The resulting mixture was stirred at reflux for 3 hours, cooled to room temperature, and partitioned between dichloromethane and water. The aqueous layer was acidified with 1 N HCl and extracted twice with dichloromethane. The dichloromethane layers were combined, washed with 1 N HCl and brine, dried over magnesium sulfate (MgSO4), filtered and concentrated in vacuo to obtain the title compound. LRMS: 370, 372 (M+2).

Workup

  1. additionwas added
  2. custombrought to 0° C.
  3. additionwas added
  4. customwas brought to room temperature
  5. stirringstirred for 1 hour
  6. additionwere added
  7. stirringThe resulting mixture was stirred
  8. temperatureat reflux for 3 hours
  9. temperaturecooled to room temperature
  10. custompartitioned between dichloromethane and water
  11. extractionextracted twice with dichloromethane
  12. washwashed with 1 N HCl and brine
  13. dry with materialdried over magnesium sulfate (MgSO4)
  14. filtrationfiltered
  15. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-97ea6a16399e42d298651a4237b08000
Source dataset
uspto-grants-2009_08
Patent number
US07569569B2

Reaction notes

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