Sodium Carbonate → HCID 178432507, compound

HRID 1371128Notes

Reaction equation

HRID 1371128 reaction equation
Cl[C:2]1[N:7]=[C:6]([CH3:8])[NH:5][C:4]2=[CH:9][C:10]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)=[N:11][C:3]=12.[Cl:18][C:19]1[CH:24]=[CH:23][C:22](B(O)O)=[CH:21][CH:20]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])([O-])=O.[Na+].[Na+]>O.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(O)C.C1(C)C=CC=CC=1>[Cl:18][C:19]1[CH:24]=[CH:23][C:22]([C:2]2[N:7]=[C:6]([CH3:8])[NH:5][C:4]3=[CH:9][C:10]([C:12]4[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=4)=[N:11][C:3]=23)=[CH:21][CH:20]=1

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 742994-Chlorophenylboronic acidHCID 178432852HCID 178432852, compound

Product 1

HCID 178432507HCID 178432507, compoundYield 49%

Reagents, catalysts & solvents 4

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A mixture of 4-chloro-2-methyl-6-phenylpyrrolo[3,2-d]pyrimidine (Example 1(e)) (50 mg, 0.21 mmol), 4-chlorophenylboronic acid (Aldrich Chemical Company) (39 mg, 0.25 mmol), tris(dibenzylide-neacetone) dipalladium(0) (Aldrich Chemical Company) (4.7 mg, 0.0051 mmol) and triphenylphosphine (Aldrich Chemical Company) (5.4 mg, 0.021 mmol) in a mixed solvent (600 μL of toluene, 300 μL of 1.0 M Na2CO3, and 150 μL of ethanol) was heated at reflux under N2 for 20 h. Upon cooling to the room temperature, the reaction mixture was diluted with H2O (20 mL) and extracted with CHCl3 (3×15 mL), dried over Na2SO4 and concentrated with a rotary evaporator. The crude material was purified by flash chromatography on silica gel with a gradient eluant of EtOAc(0-25%):hexanes(100-75%) to afford 32 mg (49%) of the title compound as a yellow solid. Mp: 281-283° C. 1H NMR (Acetone-d6; 400 MHz): δ 10.89 (s, 1), 8.18 (d, 2, J=8.5), 8.02 (d, 2, J=7.4), 7.60 (d, 2, J=8.5), 7.53 (t, 2, J=7.4) 7.46 (t, 1, J=7.4), 7.01 (s, 1), 2.72 (s, 3). MS m/z: 320 (M+1), 318 (M−1). HRMS (NBA-NaI) m/z Calcd for M+H, C19H14ClN3: 320.0955. Found: 320.0961.

Workup

  1. temperaturewas heated
  2. temperatureat reflux under N2 for 20 h
  3. extractionextracted with CHCl3 (3×15 mL)
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated with a rotary evaporator
  6. customThe crude material was purified by flash chromatography on silica gel with a gradient eluant of EtOAc(0-25%)

Sources & evidence

ORD record
ord-8850cefd2bdb40a192bdade6c5a412f7
Source dataset
uspto-grants-2003_06
Patent number
US06583154B1

Reaction notes

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