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

HRID 2180955Notes

Reaction equation

HRID 2180955 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[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.I[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=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:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)(=[O:21])=[O:20])[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

8

Reactant 4

HCID 7912DiisopropylamineHCID 11575IodobenzeneHCID 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 min. The reaction mixture was again cooled to −78° C. and to this mixture added a solution of 1.0 g (3.40 mmol) of the product from Method C in 10 mL of THF over a 10 min period. The reaction mixture was stirred for 1 h 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 h. Iodobenzene (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 h., 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 h
  6. additionwere added
  7. stirringThe resulting mixture was stirred
  8. temperatureat reflux for 3 h.
  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-687b934e1f1b40ac825163290da03f3d
Source dataset
uspto-grants-2005_05
Patent number
US06890929B2

Reaction notes

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