2-Iodotoluene → HCID 49763464, compound

HRID 2067126Notes

Reaction equation

HRID 2067126 reaction equation
[N:1]1([C:6]2[CH:11]=[CH:10][C:9]([CH2:12][N:13]3[C:18]4[CH:19]=[CH:20][S:21][C:17]=4[C:16]4=[N:22][NH:23][C:24](=[O:25])[C:15]4=[N:14]3)=[CH:8][CH:7]=2)[CH:5]=[CH:4][CH:3]=[N:2]1.I[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=1[CH3:33].CN[C@@H]1CCCC[C@H]1NC.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(=O)(O)[O-].[Na+]>CN(C)C=O.[Cu]I>[CH3:33][C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][C:27]=1[N:23]1[C:24](=[O:25])[C:15]2=[N:14][N:13]([CH2:12][C:9]3[CH:8]=[CH:7][C:6]([N:1]4[CH:5]=[CH:4][CH:3]=[N:2]4)=[CH:11][CH:10]=3)[C:18]3[CH:19]=[CH:20][S:21][C:17]=3[C:16]2=[N:22]1

Participants

8

Reactant 5

HCID 51282-IodotolueneHCID 62657Potassium Phosphate, TribasicHCID 516892Sodium BicarbonateHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 66745424HCID 66745424, compound

Product 1

HCID 49763464HCID 49763464, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Procedure

5-{[4-(1H-Pyrazol-1-yl)phenyl]methyl}-2,5-dihydro-3H-pyrazol[4,3-c]thieno[2,3-e]pyridazin-3-one (20 mg, 0.058 mmol), 2-iodotoluene (38 mg, 0.17 mmol, 3 equiv), copper(I) iodide (11 mg, 0.058 mmol, 1 equiv), (±)-trans-N,N′-dimethylcyclohexane-1,2-diamine (24 mg, 0.17 mmol, 3 equiv) and potassium phosphate (86 mg, 0.41 mmol, 7 equiv) were combined in degassed N,N-dimethylformamide (3 mL) and placed into an oil bath preheated to 110° C. for 2 hours. The mixture was cooled to ambient temperature, poured into sodium bicarbonate (25 mL, aqueous saturated) and extracted with ethyl acetate (2×75 mL). The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel gradient chromatography (100:0 to 0:100; hexanes:ethyl acetate containing 5% methanol), providing the titled compound as a deep red solid: 1H-NMR (400 MHz, CDCl3) δ 7.91 (1H, d, J=2.5 Hz), 7.73-7.71 (3H, m), 7.66 (1H, d, J=5.6 Hz), 7.46-7.43 (3H, m), 7.36-7.27 (4H, m), 6.47 (1H, dd, J=2.4, 1.9 Hz), 5.83 (2H, s), 2.35 (3H, s) ppm; high resolution mass spectrometry (ES+) m/z 439.1336 [(M+H)+; calculated for C24H19N6OS: 439.1336].

Workup

  1. customplaced into an oil bath
  2. extractionextracted with ethyl acetate (2×75 mL)
  3. dry with materialThe combined organic extracts were dried with sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel gradient chromatography (100:0 to 0:100; hexanes:ethyl acetate containing 5% methanol)

Sources & evidence

ORD record
ord-659d5bb70b054680a512f65bd056d3e7
Source dataset
uspto-grants-2012_10
Patent number
US08293744B2

Reaction notes

Loading…