Triphenylphosphine → HCID 178432640, compound

HRID 1371135Notes

Reaction equation

HRID 1371135 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.C([Sn](CCCC)(CCCC)[C:23]1[S:24][CH:25]=[CH:26][N:27]=1)CCC.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:8][C:6]1[NH:5][C:4]2[C:3]([N:11]=[C:10]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[CH:9]=2)=[C:2]([C:23]2[S:24][CH:25]=[CH:26][N:27]=2)[N:7]=1

Participants

6

Reactant 3

HCID 11776Triphenylphosphine2×HCID 27632592-(Tributylstannyl)-1,3-thiazole2×HCID 178432852HCID 178432852, compound

Product 1

HCID 178432640HCID 178432640, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 4-chloro-2-methyl-6-phenylpyrrolo[3,2-d]pyrimidine (Example 1(e)) (200 mg, 0.82 mmol), 2-tributylstannylthiazole (Frontier Scientific) (338 mg, 0.90 mmol), tris(dibenzylideneacetone)dipalladium(0) (Aldrich Chemical Company) (19 mg, 0.021 mmol) and triphenylphosphine (Aldrich Chemical Company.) (43 mg, 0.16 mmol) in anhydrous toluene (2 mL) was refluxed under N2 for 4 d. TLC showed that the reaction was not complete. Therfore, additional portions of 2-tributylstannylthiazole (338 mg, 0.90 mmol), tris(dibenzylideneacetone)dipalladium(0) (19 mg, 0.021 mmol) and triphenylphosphine (43 mg, 0.16 mmol) were added to the reaction mixture, and the mixture was stirred at 120° C. for 3 d. Upon cooling to the room temperature, the reaction was quenched with 5% HCl (50 mL) and the solution was extracted with CHCl3 (3×100 mL). The organic extracts were washed with H2O (2×150 mL), filtered through a pad of Celite, washed with saturated NaCl (150 ml), dried over Na2SO4 and concentrated with a rotary evaporator. Chromatography on silica gel with a gradient eluant of MeOH (1-3%):CH2Cl2 (99-97%) afforded 119 mg (50%) of the title compound as a yellow solid. Mp: 248-250° C. 1H NMR (acetone-d6; 400 MHz): δ 2.69 (s, 3), 7.01(s, 1), 7.57-7.47 (m, 3), 8.06 (di 2, J=7.17), 8.97 (s, 1), 9.18 (s, 1), 10.76 (s, 1). MS m/z: 293 (M+1), 291 (M−1). HRMS: Calcd for M+H: 293.0861. Found: 293.0866.

Workup

  1. temperaturewas refluxed under N2 for 4 d
  2. temperatureUpon cooling to the room temperature
  3. customthe reaction was quenched with 5% HCl (50 mL)
  4. extractionthe solution was extracted with CHCl3 (3×100 mL)
  5. washThe organic extracts were washed with H2O (2×150 mL)
  6. filtrationfiltered through a pad of Celite
  7. washwashed with saturated NaCl (150 ml)
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated with a rotary evaporator

Sources & evidence

ORD record
ord-6e9ad8f6e9dd4fd9bc596177c6cd0fc4
Source dataset
uspto-grants-2003_06
Patent number
US06583154B1

Reaction notes

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