Dimethylformamide → 4-(5-Bromo-6-chloro-pyridine-3-sulfonyl)-5-nitro-thiophene-2-carboxylic acid methyl ester

HRID 2216033Notes

Reaction equation

HRID 2216033 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([N+:11]([O-:13])=[O:12])=[C:8](Br)[CH:9]=1)=[O:4].[Br:14][C:15]1[CH:16]=[C:17]([S:22][OH:23])[CH:18]=[N:19][C:20]=1[Cl:21].CN(C=[O:28])C>>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([N+:11]([O-:13])=[O:12])=[C:8]([S:22]([C:17]2[CH:18]=[N:19][C:20]([Cl:21])=[C:15]([Br:14])[CH:16]=2)(=[O:28])=[O:23])[CH:9]=1)=[O:4]

Participants

4

Reactant 3

HCID 6228Dimethylformamide2×HCID 13291027Methyl 4-bromo-5-nitrothiophene-2-carboxylateHCID 218865015-Bromo-6-chloro-pyridine-3-sulphenic acid

Product 1

HCID 210571744-(5-Bromo-6-chloro-pyridine-3-sulfonyl)-5-nitro-thiophene-2-carboxylic acid methyl esterYield 48%

Conditions

Temperature
0 °C

Procedure

4-Bromo-5-nitro-thiophene-2-carboxylic acid methyl ester (5.0 g, 19.9 mmol) was dissolved into DMF (20 mL) and cooled to 0° C. To this was added a solution of 5-bromo-6-chloro-pyridine-3-sulphenic acid (Example 118, step a) (1.8 g, 6.6 mmol) in DMF (20 mL) dropwise for 2 hours. The reaction was then warmed to RT and allowed to continue to stir for an additional 2 hours. The reaction was concentrated in vacuo and purified by SiO2 flash column chromatography (Biotage—40 M, 25% EtOAc in hexanes). The product was isolated as a white solid (2.5 g, 48%). ESI-MS (m/z): Calcd. for C11H6BrClN2O6S2: 440.8 (M+H); found: 441.0.

Workup

  1. temperatureThe reaction was then warmed to RT
  2. concentrationThe reaction was concentrated in vacuo
  3. custompurified by SiO2 flash column chromatography (Biotage—40 M, 25% EtOAc in hexanes)

Sources & evidence

ORD record
ord-7b87d363910c4a8db8927c3b16e8f394
Source dataset
uspto-grants-2006_09
Patent number
US07109354B2

Reaction notes

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