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

HRID 573591Notes

Reaction equation

HRID 573591 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:17])=[CH:16][C:3]=12.CC(C)([O-])C.[Na+].[Cl:24][C:25]1[CH:26]=[C:27]([S:31](Cl)(=[O:33])=[O:32])[CH:28]=[CH:29][CH:30]=1>C1COCC1.C(OCC)(=O)C.O>[Br:17][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:31]([C:27]3[CH:28]=[CH:29][CH:30]=[C:25]([Cl:24])[CH:26]=3)(=[O:33])=[O:32])=[C:3]2[CH:16]=1

Participants

7

Reactant 3

HCID 179093-Chlorobenzenesulphonyl chlorideHCID 23676156Sodium t-butoxideHCID 68323734Ethyl 4-amino-2-bromo-6-methylthieno[2,3-b]pyridine-5-carboxylate

Product 1

HCID 68323811Ethyl 2-bromo-4-{[(3-chlorophenyl)sulfonyl]amino}-6-methylthieno[2,3-b]pyridine-5-carboxylateYield 41.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of ethyl 4-amino-2-bromo-6-methylthieno[2,3-b]pyridine-5-carboxylate (Description 66) (390 mg, 1.24 mmol) in THF (12 mL) was added sodium tert-butoxide (297 mg, 3.09 mmol) and 3-chlorobenzenesulfonyl chloride (0.35 mL, 2.47 mmol). The reaction mixture was stirred at RT under nitrogen for ca. 3 h. The reaction mixture was diluted with ethyl acetate (ca. 30 mL) and water (ca. 50 mL). The organic layer was separated and the aqueous layer re-extracted with ethyl acetate (ca. 30 mL×2). The combined organic phase was dried over Na2SO4 and then concentrated in vacuo. Purification by chromatography on silica, eluting with a gradient of 0-20% ethyl acetate in DCM, afforded the title compound (252 mg). LCMS (A) m/z: 490/492 [M+1]+, Rt 1.48 min (acidic).

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous layer re-extracted with ethyl acetate (ca. 30 mL×2)
  3. dry with materialThe combined organic phase was dried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customPurification by chromatography on silica
  6. washeluting with a gradient of 0-20% ethyl acetate in DCM

Sources & evidence

ORD record
ord-f3abf947222f4bfcaf0c7422ee44297e
Source dataset
uspto-grants-2015_05
Patent number
US09029545B2

Reaction notes

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