Sodium Hydroxide → N-(3-Bromo-4-methylphenyl)-3-methyl-2-butenamide

HRID 915186Notes

Reaction equation

HRID 915186 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[CH3:9])[NH2:5].[OH-].[Na+].[CH3:12][C:13]([CH3:18])=[CH:14][C:15](Cl)=[O:16]>ClCCl.O>[Br:1][C:2]1[CH:3]=[C:4]([NH:5][C:15](=[O:16])[CH:14]=[C:13]([CH3:18])[CH3:12])[CH:6]=[CH:7][C:8]=1[CH3:9]

Participants

6

Reactant 3

HCID 14798Sodium HydroxideHCID 82187Benzenamine, 3-bromo-4-methyl-HCID 1023943-Methyl-2-butenoyl chloride

Product 1

HCID 60729710N-(3-Bromo-4-methylphenyl)-3-methyl-2-butenamideYield 97%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a biphasic mixture of 3-bromo-4-methylaniline (50 g, 0.269 mol, Example e), 10% NaOH (270 mL) and dichloromethane (160 mL) was added dropwise over a period of 2 hours 3,3-dimethylacryloyl chloride (36 mL, 0.322 mol) in dichloromethane (95 mL). The solution was stirred at room temperature for 48 hours then diluted with water (100 mL). The aqueous layer was further extracted with dichloromethane. The organic layers were combined and washed with water and brine, dried (Mg2SO4), filtered and evaporated. The white solid was triturated with hexane and collected to give 70 g (97%) of 3-Methyl-but-2-enoic acid (3-bromo-4-methyl-phenyl)-amide. 1H NMR (300 MHz; CDCl3): 1.89 (s, 3 H), 2.21 (s, 3 H), 2.33 (s, 3 H), 5.68 (s, 1 H), 7.14 (d, J=8.0 Hz, 1 H), 7.17 (br s, 1 H), 7.33 (d, J=8.0 Hz, 1 H), 7.79 (s, 1 H).

Workup

  1. extractionThe aqueous layer was further extracted with dichloromethane
  2. washwashed with water and brine
  3. dry with materialdried (Mg2SO4)
  4. filtrationfiltered
  5. customevaporated
  6. customThe white solid was triturated with hexane
  7. customcollected

Sources & evidence

ORD record
ord-46dec1354d164196a39d6f30a472fb95
Source dataset
uspto-grants-2007_09
Patent number
US07265139B2

Reaction notes

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