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

HRID 1790197Notes

Reaction equation

HRID 1790197 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), 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-e4616a7bf65640f491ce4b54c4225ed0
Source dataset
uspto-grants-2006_07
Patent number
US07071218B2

Reaction notes

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