Potassium Carbonate → HCID 178493137, compound

HRID 722045Notes

Reaction equation

HRID 722045 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.C([O-])(=O)C.[K+].[CH3:15][O:16][C:17]1[CH:22]=[CH:21][N:20]=[C:19]([CH2:23][CH2:24][C:25]2[NH:34][C:28]3=[N:29][CH:30]=[C:31](I)[CH:32]=[C:27]3[N:26]=2)[CH:18]=1.C(=O)([O-])[O-].[K+].[K+].[Cl-].[Li+]>O1CCOCC1.O.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:15][O:16][C:17]1[CH:22]=[CH:21][N:20]=[C:19]([CH2:23][CH2:24][C:25]2[NH:34][C:28]3=[N:29][CH:30]=[C:31]([C:2]4[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=4)[CH:32]=[C:27]3[N:26]=2)[CH:18]=1

Participants

11

Reactant 5

HCID 11430Potassium CarbonateHCID 12162Benzonitrile, 4-bromo-HCID 433294Lithium ChlorideHCID 517044Potassium AcetateHCID 178493175HCID 178493175, compound

Product 1

HCID 178493137HCID 178493137, compoundYield 46.9%

Reagents, catalysts & solvents 5

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Procedure

A mixture of 0.364 g of 4-bromobenzonitrile, 0.56 g of bis-(pinacolato)-diboron, 0.034 g of 1,1′-bis-(diphenylphosphino)-ferrocene, 0.044 g of [1,1′-bis(diphenylphosphino)ferrocene]palladium-di-chloride 0.588 g of potassium acetate in 20 ml of degassed dioxane are heated to reflux under N2 for 16 hours. To the resulting mixture 13 ml of degassed dioxane, 0.456 g of 2-[2-(4-methoxypyridin-2-yl)ethyl]-6-iodo-3H-imidazo[4,5-b]pyridine (example 7), 0.139 g of tetrakis(triphenylphosphine)-palladium(0) and a solution of 0.332 g of potassium carbonate and 0.102 g of lithium chloride in 10 ml of degassed water are added under N2. The mixture is heated to reflux under N2 for 30 hours and, after cooling, addition of water and adjusting the pH to 7, it is extracted three times with dichloromethane. The combined organic phases are dried over sodium sulfate, concentrated and the residue is chromatographed on a silica gel column (dichloromethane/methanol 25–20:1). Concentration of the chromatographically pure fractions and crystallisation from ethyl acetate gives 0.2 g of the title compound as a solid of m.p. 241–242° C. The mass spectrum shows the molecular peak MH+ at 356.4 Da.

Workup

  1. temperatureare heated
  2. temperatureto reflux under N2 for 16 hours
  3. temperatureThe mixture is heated
  4. temperatureto reflux under N2 for 30 hours
  5. temperatureafter cooling
  6. extractionis extracted three times with dichloromethane
  7. dry with materialThe combined organic phases are dried over sodium sulfate
  8. concentrationconcentrated
  9. customthe residue is chromatographed on a silica gel column (dichloromethane/methanol 25–20:1)
  10. customConcentration of the chromatographically pure fractions and crystallisation from ethyl acetate

Sources & evidence

ORD record
ord-376ebbba1d9a4386ac950e84df82b8ae
Source dataset
uspto-grants-2006_11
Patent number
US07138399B2

Reaction notes

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