Potassium Carbonate → 5-Fluoro-3-[5-fluoro-4-(methylsulfinyl)-2-pyrimidinyl]-1-[(4-methylphenyl)sulfonyl]-1H-pyrrolo[2,3-b]pyridine

HRID 1055045Notes

Reaction equation

HRID 1055045 reaction equation
[F:1][C:2]1[CH:3]=[C:4]2[C:10]([C:11]3[N:16]=[C:15]([S:17][CH3:18])[C:14]([F:19])=[CH:13][N:12]=3)=[CH:9][N:8]([S:20]([C:23]3[CH:28]=[CH:27][C:26]([CH3:29])=[CH:25][CH:24]=3)(=[O:22])=[O:21])[C:5]2=[N:6][CH:7]=1.ClC1C=CC=C(C(OO)=[O:38])C=1.C([O-])([O-])=O.[K+].[K+]>ClCCl.ClC1C=CC=C(C(OO)=O)C=1>[F:1][C:2]1[CH:3]=[C:4]2[C:10]([C:11]3[N:16]=[C:15]([S:17]([CH3:18])=[O:38])[C:14]([F:19])=[CH:13][N:12]=3)=[CH:9][N:8]([S:20]([C:23]3[CH:28]=[CH:27][C:26]([CH3:29])=[CH:25][CH:24]=3)(=[O:22])=[O:21])[C:5]2=[N:6][CH:7]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 70297m-Chloroperbenzoic acid2×HCID 672859485-Fluoro-3-(5-fluoro-4-methylsulfanyl-pyrimidin-2-yl)-1-(p-tolylsulfonyl)pyrrolo[2,3-b]pyridine2×

Product 1

HCID 672853275-Fluoro-3-[5-fluoro-4-(methylsulfinyl)-2-pyrimidinyl]-1-[(4-methylphenyl)sulfonyl]-1H-pyrrolo[2,3-b]pyridineYield 96%

Reagents, catalysts & solvents 2

HCID 70297m-Chloroperbenzoic acidCatalystHCID 6344DichloromethaneSolvent

Procedure

5-fluoro-3-(5-fluoro-4-methylsulfanyl-pyrimidin-2-yl)-1-(p-tolylsulfonyl)pyrrolo[2,3-b]pyridine, 24a, (2.30 g, 5.32 mmol) was dissolved in dichloromethane (107 mL) and treated portionwise with 3-chloroperbenzoic acid (1.19 g, 5.30 mmol), keeping the temperature below 20° C. After stirring for 2 hours, another portion of 3-chloroperbenzoic acid (0.18 g, 0.80 mmol) was added, and stirring was continued for another hour. A third portion of 3-chloroperbenzoic acid (0.07 g, 0.05 mmol) was added and stirring was continued for 30 minutes. The reaction mixture was treated with an aqueous 15% K2CO3 solution (30 mL) and the layers were separated. The organic layer was washed with 15% K2CO3 and brine, dried (Na2SO4), filtered and concentrated in vacuo to afford 2.3 g (96%) of the desired product as a yellow solid, which was used without further purification: 1H NMR (300 MHz, DMSO-d6) δ 9.12 (d, J=1.5 Hz, 1H), 8.70 (s, 1H), 8.67 (dd, J=9.1, 2.8 Hz, 1H), 8.53 (d, J=1.5 Hz, 1H), 8.11 (d, J=8.4 Hz, 2H), 7.46 (d, J=8.2 Hz, 2H), 3.05 (s, 3H), 2.36 (s, 3H).

Workup

  1. customthe temperature below 20° C
  2. stirringstirring
  3. waitwas continued for another hour
  4. stirringstirring
  5. waitwas continued for 30 minutes
  6. customthe layers were separated
  7. washThe organic layer was washed with 15% K2CO3 and brine
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e4ac29704fda4d14a0286ea03db43a8b
Source dataset
uspto-grants-2016_07
Patent number
US09394302B2

Reaction notes

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