Cesium carbonate → Methyl 3-((3-Bromo-2-methylphenylamino)methyl)-5-tert-butylthiophene-2-carboxylate

HRID 872136Notes

Reaction equation

HRID 872136 reaction equation
Br[CH2:2][C:3]1[CH:7]=[C:6]([C:8]([CH3:11])([CH3:10])[CH3:9])[S:5][C:4]=1[C:12]([O:14][CH3:15])=[O:13].[Br:16][C:17]1[C:18]([CH3:24])=[C:19]([CH:21]=[CH:22][CH:23]=1)[NH2:20].C(=O)([O-])[O-].[Cs+].[Cs+]>C(#N)C>[Br:16][C:17]1[C:18]([CH3:24])=[C:19]([NH:20][CH2:2][C:3]2[CH:7]=[C:6]([C:8]([CH3:11])([CH3:10])[CH3:9])[S:5][C:4]=2[C:12]([O:14][CH3:15])=[O:13])[CH:21]=[CH:22][CH:23]=1

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 1235383-Bromo-o-toluidineHCID 66610052Methyl 3-(bromomethyl)-5-tert-butylthiophene-2-carboxylate

Product 1

HCID 86697931Methyl 3-((3-Bromo-2-methylphenylamino)methyl)-5-tert-butylthiophene-2-carboxylateYield 70.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A 250-mL single-necked round-bottomed flask equipped with a magnetic stirrer was purged with nitrogen and charged with 101c (1.09 g, 4.68 mmol), 3-bromo-2-methyl-aniline (2.61 g, 14.0 mmol) and acetonitrile (25 mL). Cesium carbonate (1.67 g, 5.15 mmol) was added and the mixture was stirred at room temperature for 16 h. The reaction mixture was then concentrated under reduced pressure. Purification of the resulting residue by column chromatography afforded a 70% yield (1.30 g) of 101d as a yellow oil: 1H NMR (300 MHz, CDCl3) δ 6.92 (m, 2H), 6.85 (s, 1H), 6.57 (dd, 1H, J=4.8, 2.1 Hz), 4.60 (s, 2H), 3.86 (s, 3H), 2.29 (s, 3H), 1.37 (s, 9H); MS (ESI+) m/z 396.2 (M+H).

Workup

  1. customA 250-mL single-necked round-bottomed flask equipped with a magnetic stirrer
  2. customwas purged with nitrogen
  3. concentrationThe reaction mixture was then concentrated under reduced pressure
  4. customPurification of the resulting residue by column chromatography

Sources & evidence

ORD record
ord-d39e3700d3504875afeb576673118ae7
Source dataset
uspto-grants-2015_03
Patent number
US08975260B2

Reaction notes

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