Sodium Carbonate → HCID 70654785, compound

HRID 2091555Notes

Reaction equation

HRID 2091555 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5](Br)=[CH:4][N:3]=1.[CH2:9]([S:11]([C:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1)(=[O:13])=[O:12])[CH3:10].C([O-])([O-])=O.[Na+].[Na+]>CCCCO.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:9]([S:11]([C:14]1[CH:19]=[CH:18][C:17]([C:5]2[CH:6]=[CH:7][C:2]([NH2:1])=[N:3][CH:4]=2)=[CH:16][CH:15]=1)(=[O:12])=[O:13])[CH3:10]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 706222-Amino-5-bromopyridineHCID 27734204-(Ethylsulphonyl)benzeneboronic acid

Product 1

HCID 70654785HCID 70654785, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 2631-ButanolSolvent

Conditions

Temperature
100 °C

Procedure

In particular, a slurry of 2-amino-5-bromopridine (1.24 g, 4.67 mmol), 4-(ethylsulfonyl)phenylboronic acid (1.10 g, 5.14 mmol), and Pd(PPh3)4 (0.16 g, 0.13 mmol) in n-BuOH (20 mL) was treated with 2.0 M aq. Na2CO3 (4.5 mL). The reaction was sparged with dry N2 under sonication for 10 min to degas, and then refluxed for 16 h at 100° C. At completion, the reaction was cooled to room temperature and concentrated to dryness. The residue was partitioned between EtOAc (50 mL) and water (30 mL). The layers were separated and the aqueous layer was extracted with EtOAc (2×50 mL). The combined organics were washed with brine (20 mL), dried over Na2SO4 and concentrated. The crude material was purified by flash chromatography over silica gel (30-100% EtOAc:hexane eluent) to provide 5-(4-(ethylsulfonyl)phenyl)pyridin-2-amine as a white solid (0.57 g, 47% yield). 1H NMR (300 MHz, MeOH) δ ppm 8.27-8.31 (m, 1H), 7.91-7.98 (m, 2H), 7.79-7.89 (m, 3 H), 6.71 (dd, J=8.7, 0.7 Hz, 1H), 3.30-3.35 (m, 2H), 3.24 (q, J=7.4 Hz, 2H), 1.25 (t, J=7.4 Hz, 3H); MS (EI) m/z: 263 [M+H]+.

Workup

  1. customThe reaction was sparged with dry N2 under sonication for 10 min
  2. customto degas
  3. temperatureAt completion, the reaction was cooled to room temperature
  4. concentrationconcentrated to dryness
  5. customThe residue was partitioned between EtOAc (50 mL) and water (30 mL)
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with EtOAc (2×50 mL)
  8. washThe combined organics were washed with brine (20 mL)
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated
  11. customThe crude material was purified by flash chromatography over silica gel (30-100% EtOAc:hexane eluent)

Sources & evidence

ORD record
ord-54736a6cfb8f4378b0a8324d57fe1d78
Source dataset
uspto-grants-2013_05
Patent number
US08440652B2

Reaction notes

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