Sodium Carbonate → HCID 11751156, compound

HRID 2216315Notes

Reaction equation

HRID 2216315 reaction equation
[CH3:1][C:2]1[N:7]=[C:6]([NH:8][C:9]2[C:14]([CH3:15])=[CH:13][C:12]([CH3:16])=[CH:11][C:10]=2[CH3:17])[C:5]([S:18]([C:21]2[CH:26]=[CH:25][C:24](OS(C(F)(F)F)(=O)=O)=[CH:23][CH:22]=2)(=[O:20])=[O:19])=[CH:4][N:3]=1.[N:35]1[CH:40]=[CH:39][C:38](B(O)O)=[CH:37][CH:36]=1.C([O-])([O-])=O.[Na+].[Na+].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])(O)=O.[Na+]>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.COCCOC>[CH3:1][C:2]1[N:7]=[C:6]([NH:8][C:9]2[C:14]([CH3:15])=[CH:13][C:12]([CH3:16])=[CH:11][C:10]=2[CH3:17])[C:5]([S:18]([C:21]2[CH:26]=[CH:25][C:24]([C:38]3[CH:39]=[CH:40][N:35]=[CH:36][CH:37]=3)=[CH:23][CH:22]=2)(=[O:20])=[O:19])=[CH:4][N:3]=1

Participants

8

Reactant 5

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 86595018HCID 86595018, compound

Product 1

HCID 11751156HCID 11751156, compoundYield 61.1%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

A mixture trifluoromethanesulfonic acid 4-[2-methyl-4-(2,4,6-trimethylphenylamino)-pyrimidine-5-sulfonyl]-phenyl ester (72 mg, 0.14 mmol), prepared by the method described in Example 22, pyridine-4-boronic acid (34 mg, 0.28 mmol), 2 M Na2CO3 (1.0 mL, 2.0 mmol) and DME (2 mL) was deoxygenated with N2 for 10 min, and then Pd(PPh3)2Cl2 (20 mg, 0.028 mmol) and PPh3 (15 mg, 0.056 mmol) were added. The mixture was heated at reflux under N2 for 2 h and then cooled to room temperature. Saturated aqueous NaHCO3 was added, and the mixture was extracted three times with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by chromatography on silica gel (50:50 hexanes/EtOAc) to provide the desired product (38 mg, 61%) as a white solid: mp 232–234° C.; 1H NMR (500 MHz, CDCl3) δ 8.79 (s, 1H), 8.73 (d, J=4.5 Hz, 2H), 8.28 (br s, 1H), 8.13 (d, J=8.4 Hz, 2H), 7.78 (d, J=8.4 Hz, 2H), 7.48 (d, J=4.5 Hz, 2H), 6.92 (s, 2H), 2.40 (s, 3H), 2.31 (s, 3H), 2.03 (s, 6H); APCI MS m/z 445 [(M+H)+, calcd for C25H25N4O2S, 445.2].

Workup

  1. customwas deoxygenated with N2 for 10 min
  2. temperatureThe mixture was heated
  3. temperatureat reflux under N2 for 2 h
  4. extractionthe mixture was extracted three times with EtOAc
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by chromatography on silica gel (50:50 hexanes/EtOAc)

Sources & evidence

ORD record
ord-6c867fed5aa542d0a37952e451fc17ab
Source dataset
uspto-grants-2006_09
Patent number
US07112585B2

Reaction notes

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