Nitrogen → (E)-Ethyl 3-(4-((E)-2-phenyl-1-(1-(tetrahydro-2H-pyran-2-yl)-1H-benzo[d][1,2,3]triazol-5-yl)but-1-en-1-yl)phenyl)acrylate

HRID 1057172Notes

Reaction equation

HRID 1057172 reaction equation
N#N.[C:3]([C:7]1[CH:21]=[CH:20][C:10]2[N:11]([CH:14]3[CH2:19][CH2:18][CH2:17][CH2:16][O:15]3)[N:12]=[N:13][C:9]=2[CH:8]=1)#[C:4][CH2:5][CH3:6].I[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.[CH2:29]([O:31][C:32](=[O:44])/[CH:33]=[CH:34]/[C:35]1[CH:40]=[CH:39][C:38](B(O)O)=[CH:37][CH:36]=1)[CH3:30].C([O-])([O-])=O.[K+].[K+]>CN(C)C=O.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.CN(C)C=O.O>[C:23]1(/[C:4](/[CH2:5][CH3:6])=[C:3](\[C:38]2[CH:39]=[CH:40][C:35](/[CH:34]=[CH:33]/[C:32]([O:31][CH2:29][CH3:30])=[O:44])=[CH:36][CH:37]=2)/[C:7]2[CH:21]=[CH:20][C:10]3[N:11]([CH:14]4[CH2:19][CH2:18][CH2:17][CH2:16][O:15]4)[N:12]=[N:13][C:9]=3[CH:8]=2)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

9

Reactant 5

HCID 947NitrogenHCID 11430Potassium CarbonateHCID 11575IodobenzeneHCID 59425074-(E-3-Ethoxy-3-oxo-1-propen-1-yl)benzeneboronic acidHCID 668020395-(But-1-yn-1-yl)-1-(tetrahydro-2H-pyran-2-yl)-1H-benzo[d][1,2,3]triazole

Product 1

HCID 86695284(E)-Ethyl 3-(4-((E)-2-phenyl-1-(1-(tetrahydro-2H-pyran-2-yl)-1H-benzo[d][1,2,3]triazol-5-yl)but-1-en-1-yl)phenyl)acrylate

Reagents, catalysts & solvents 3

HCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 6228DimethylformamideSolventHCID 21962138N,N-Dimethylformamide--water (1/1)Solvent

Conditions

Temperature
45 °C

Procedure

A 100-mL round-bottom flask equipped with a magnetic stir bar, a rubber septum and N2 inlet was charged with 5-(but-1-yn-1-yl)-1-(tetrahydro-2H-pyran-2-yl)-1H-benzo[d][1,2,3]triazole (0.2 g, 0.78 mmol), iodobenzene (0.48 g, 2.35 mmol), (E)-(4-(3-ethoxy-3-oxoprop-1-en-1-yl)phenyl)boronic acid (0.51 g, 2.35 mmol), K2CO3 (0.32 g, 2.35 mmol), and N,N-dimethylformamide/water (2:1, 39 mL). This mixture was degassed with three vacuum/N2 cycles and then heated at 45° C. for 10 minutes. With continued heating, a solution of Pd(PhCN)2Cl2 (0.003 g, 0.008 mmol) in N,N-dimethylformamide (0.2 mL) was added dropwise. The resulting mixture was stirred at 45° C. overnight. The reaction was monitored by TLC. Upon completion, the reaction mixture was cooled down to room temperature, quenched with water (100 mL), and extracted with ethyl acetate (2×200 mL). The combined organics were washed with water (100 mL), washed with brine (50 mL), dried over sodium sulfate, filtered, and concentrated to give the crude product. This crude material was purified on a silica gel column eluted with 0-25% ethyl acetate in hexanes affording the title compound as an off-white solid (0.28 g). LCMS: 424 [(M-THP+H)+H]+.

Workup

  1. customA 100-mL round-bottom flask equipped with a magnetic stir bar
  2. customThis mixture was degassed with three vacuum/N2 cycles
  3. temperatureWith continued heating
  4. temperatureUpon completion, the reaction mixture was cooled down to room temperature
  5. customquenched with water (100 mL)
  6. extractionextracted with ethyl acetate (2×200 mL)
  7. washThe combined organics were washed with water (100 mL)
  8. washwashed with brine (50 mL)
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-acef847cd556494194a113ee1b90e73c
Source dataset
uspto-grants-2016_07
Patent number
US09399646B2

Reaction notes

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