3-Chlorobenzenesulphonyl chloride → Ethyl 2-bromo-4-{[(3-chlorophenyl)sulfonyl]amino}-3,6-dimethylthieno[2,3-b]pyridine-5-carboxylate

HRID 573582Notes

Reaction equation

HRID 573582 reaction equation
[NH2:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]2[S:14][C:15]([Br:18])=[C:16]([CH3:17])[C:3]=12.CC(C)([O-])C.[Na+].[Cl:25][C:26]1[CH:27]=[C:28]([S:32](Cl)(=[O:34])=[O:33])[CH:29]=[CH:30][CH:31]=1>CN(C=O)C.C(OCC)(=O)C.O>[Br:18][C:15]1[S:14][C:4]2=[N:5][C:6]([CH3:13])=[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:2]([NH:1][S:32]([C:28]3[CH:29]=[CH:30][CH:31]=[C:26]([Cl:25])[CH:27]=3)(=[O:34])=[O:33])=[C:3]2[C:16]=1[CH3:17]

Participants

7

Reactant 3

HCID 179093-Chlorobenzenesulphonyl chlorideHCID 23676156Sodium t-butoxideHCID 68324019Ethyl 4-amino-2-bromo-3,6-dimethylthieno[2,3-b]pyridine-5-carboxylate

Product 1

HCID 68324133Ethyl 2-bromo-4-{[(3-chlorophenyl)sulfonyl]amino}-3,6-dimethylthieno[2,3-b]pyridine-5-carboxylateYield 45.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of ethyl 4-amino-2-bromo-3,6-dimethylthieno[2,3-b]pyridine-5-carboxylate (Description 31) (500 mg, 1.519 mmol) in DMF (10 mL) was added sodium tert-butoxide (365 mg, 3.80 mmol) and 3-chlorobenzenesulfonyl chloride (0.428 mL, 3.04 mmol). The whole mixture was stirred at RT under nitrogen for ca. 1.5 h. The reaction mixture was then diluted with ethyl acetate (ca. 30 mL) and water (ca. 50 mL). The organic phase was separated and the aqueous phase re-extracted with ethyl acetate (ca. 30 mL×2). The combined organic phase was dried over Na2SO4 and the solvent concentrated in vacuo. The residue was purified by normal phase chromatography, eluting with a gradient of 0-50% ethyl acetate in cyclohexane, to give the title compound (350 mg). LCMS (A) m/z: 504/506 [M+1]+, Rt 1.59 min (acidic).

Workup

  1. customThe organic phase was separated
  2. extractionthe aqueous phase re-extracted with ethyl acetate (ca. 30 mL×2)
  3. dry with materialThe combined organic phase was dried over Na2SO4
  4. concentrationthe solvent concentrated in vacuo
  5. customThe residue was purified by normal phase chromatography
  6. washeluting with a gradient of 0-50% ethyl acetate in cyclohexane

Sources & evidence

ORD record
ord-41e56b671d0d4c54a8c3b9597e3f09d1
Source dataset
uspto-grants-2015_05
Patent number
US09029545B2

Reaction notes

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