Potassium Carbonate → HCID 178493155, compound

HRID 2233507Notes

Reaction equation

HRID 2233507 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]2[CH2:17][CH2:16][C:15](=[O:18])[NH:14][CH2:13][CH2:12]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.C([O-])(=O)C.[K+].[CH3:24][O:25][C:26]1[CH:31]=[CH:30][N:29]=[C:28]([CH2:32][CH2:33][C:34]2[NH:43][C:37]3=[N:38][CH:39]=[C:40](I)[CH:41]=[C:36]3[N:35]=2)[CH:27]=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].[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>[N:11]1([S:8]([C:5]2[CH:6]=[CH:7][C:2]([C:40]3[CH:41]=[C:36]4[N:35]=[C:34]([CH2:33][CH2:32][C:28]5[CH:27]=[C:26]([O:25][CH3:24])[CH:31]=[CH:30][N:29]=5)[NH:43][C:37]4=[N:38][CH:39]=3)=[CH:3][CH:4]=2)(=[O:10])=[O:9])[CH2:17][CH2:16][C:15](=[O:18])[NH:14][CH2:13][CH2:12]1

Participants

10

Reactant 5

HCID 11430Potassium CarbonateHCID 433294Lithium ChlorideHCID 517044Potassium AcetateHCID 15353701-(4-Bromophenyl)sulfonyl-1,4-diazepan-5-oneHCID 178493175HCID 178493175, compound2×

Product 1

HCID 178493155HCID 178493155, compoundYield 25.3%

Reagents, catalysts & solvents 4

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
90 °C

Procedure

A mixture of 0.50 g of 1-(4-bromo-benzene-sulfonyl)-1,4-diazepan-5-one, 0.42 g of bis-(pinacolato)-diboron, 0.025 g of 1,1′-bis-(diphenylphosphino)-ferrocene, 0.033 g of [1,1′-bis(diphenyl-phosphino)ferrocene]palladium-dichloride (complex with CH2Cl2), 0.442 g of potassium acetate in 6 ml of degassed dioxane are heated to 90° C. in a sealed tube under N2 for 17 hours. To the resulting mixture 5 ml of degassed dioxane, 0.371 g of 2-[2-(4-methoxypyridin-2-yl)ethyl]-6-iodo-3H-imidazo[4,5-b]pyridine (starting material A1), 0.113 g of tetrakis(triphenylphosphine)-palladium(0) and a solution of 027 g of potassium carbonate and 0.083 g of lithium chloride in 5 ml of degassed water are added under N2. The tube is sealed again, the mixture is heated to 115° under N2 for 7 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 20-12:1+1% NH4OH). Concentration of the chromatographically pure fractions and crystallization of the residue from acetonitril gives 0.125 g of the title compound as a solid of m.p. 230-232° C. The mass spectrum shows the molecular peak MH+ at 507.3 Da.

Workup

  1. customThe tube is sealed again
  2. temperaturethe mixture is heated to 115° under N2 for 7 hours
  3. temperatureafter cooling
  4. extractionis extracted three times with dichloromethane
  5. dry with materialThe combined organic phases are dried over sodium sulfate
  6. concentrationconcentrated
  7. customthe residue is chromatographed on a silica gel column (dichloromethane/methanol 20-12:1+1% NH4OH)
  8. customConcentration of the chromatographically pure fractions and crystallization of the residue from acetonitril

Sources & evidence

ORD record
ord-1e26b3b27fa34e069fed8ad0042f50d2
Source dataset
uspto-grants-2010_05
Patent number
US07709488B2

Reaction notes

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