Toluene → HCID 44554257, compound

HRID 1254045Notes

Reaction equation

HRID 1254045 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[C:10]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=3)[N:11]([CH3:21])[C:12]=2[S:13][C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=2)=[CH:4][CH:3]=1.C1(C)C=CC=CC=1.[CH3:35][CH2:36][O:37]C(C)=O>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:20][C:17]1[CH:18]=[CH:19][C:14]([S:13][C:12]2[N:11]([CH3:21])[C:10]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=3)=[N:9][C:8]=2[C:5]2[CH:6]=[CH:7][C:2]([C:36](=[O:37])[CH3:35])=[CH:3][CH:4]=2)=[CH:15][CH:16]=1

Participants

5

Reactant 3

HCID 1140TolueneHCID 8857Ethyl AcetateHCID 44555246HCID 44555246, compound

Product 1

HCID 44554257HCID 44554257, compound

Reagents, catalysts & solvents 1

HCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
100 °C

Procedure

A mixture of 2-{4-(4-bromophenyl)-5-[(4-chlorophenyl)thio]-1-methyl-1H-imidazol-2-yl}pyridine (Example 15, 2 g, 4.38 mmol), (1-ethoxyvinyul)tributyltin (1.7 g, 4.82 mmol), PdCl2(PPh3)2 (67 mg, 0.2 mmol), and 15 mL of toluene under nitrogen was heated at 100° C. overnight. The reaction mixture was diluted with EtOAc, washed with H2O, brine, dried over MgSO4, filtered. To the filtrate was added KF/Celite (50% wt from Aldrich) which was stirred for 1.5 h. Upon filtration and concentration, the residue was taken up in 20 mL of EtOH and 10 mL of 2 N HCl, stirred at rt for 1 h. The precipitate was collected by filtration, washed with water and a small amount of EtOAc. The solid was further purified by silica gel column chromatography (10-50% EtOAc in hexanes) to give the title compound. 1H NMR (500 MHz, (CDCl3): 8.62 (d, 1H), 8.38 (d, 1H), 8.26 (d, 2H), 8.19 (d, 2H), 7.83 (t, 1H), 7.31 (t, 1H), 7.23 (d, 2H), 7.04 (d, 2H), 4.13 (s, 3H), 2.61 (s, 3H). LCMS: m/z 420 (M+H)+.

Workup

  1. washwashed with H2O, brine
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. additionTo the filtrate was added KF/Celite (50% wt from Aldrich) which
  5. filtrationUpon filtration and concentration
  6. stirring10 mL of 2 N HCl, stirred at rt for 1 h
  7. filtrationThe precipitate was collected by filtration
  8. washwashed with water
  9. customThe solid was further purified by silica gel column chromatography (10-50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-b3367326dd6b49169479c46b4814a908
Source dataset
uspto-grants-2013_06
Patent number
US08455528B2

Reaction notes

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