Potassium Carbonate → HCID 178493147, compound

HRID 2233504Notes

Reaction equation

HRID 2233504 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]2[CH2:17][CH2:16][CH2:15][N:14]([CH3:18])[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.[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>[CH3:24][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]([C:2]4[CH:7]=[CH:6][C:5]([S:8]([N:11]5[CH2:17][CH2:16][CH2:15][N:14]([CH3:18])[CH2:13][CH2:12]5)(=[O:10])=[O:9])=[CH:4][CH:3]=4)[CH:41]=[C:36]3[N:35]=2)[CH:27]=1

Participants

9

Reactant 5

HCID 11430Potassium CarbonateHCID 433294Lithium ChlorideHCID 517044Potassium AcetateHCID 549176541-(4-Bromobenzene-1-sulfonyl)-4-methyl-1,4-diazepaneHCID 178493175HCID 178493175, compound2×

Product 1

HCID 178493147HCID 178493147, compoundYield 55.6%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
85 °C

Procedure

A mixture of 0.5 g of 1-(4-bromo-benzene-sulfonyl)-4-methyl-[1,4]diazepane, 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 85° 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 120° 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 22-15:1+1% NH4OH). Concentration of the chromatographically pure fractions, crystallization of the residue from ethyl acetate and recrystallization from ethylacetate/acetonitril (4:1) gives 0.275 g of the title compound as a solid of m.p. 160-162° 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 120° 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 22-15:1+1% NH4OH)
  8. customConcentration of the chromatographically pure fractions, crystallization of the residue
  9. customfrom ethyl acetate and recrystallization from ethylacetate/acetonitril (4:1)

Sources & evidence

ORD record
ord-70de6648ffe045588c6a295a16f878f0
Source dataset
uspto-grants-2010_05
Patent number
US07709488B2

Reaction notes

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