Allyl bromide → alpha-(2-Propenyl)-[2-(2-nitro-6-trifluoromethylphenyl)-1-(4-methoxyphenyl)ethyl]propanedioic acid, dimethyl ester

HRID 580405Notes

Reaction equation

HRID 580405 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]([F:13])([F:12])[F:11])[C:5]=1[CH2:14][CH:15]([CH:24]([C:29]([O:31][CH3:32])=[O:30])[C:25]([O:27][CH3:28])=[O:26])[C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)([O-:3])=[O:2].[H-].[Na+].[CH2:35](Br)[CH:36]=[CH2:37]>CN(C)C=O>[CH2:37]([C:24]([CH:15]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)[CH2:14][C:5]1[C:6]([C:10]([F:11])([F:12])[F:13])=[CH:7][CH:8]=[CH:9][C:4]=1[N+:1]([O-:3])=[O:2])([C:29]([O:31][CH3:32])=[O:30])[C:25]([O:27][CH3:28])=[O:26])[CH:36]=[CH2:35]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 14156192[1-(4-Methoxyphenyl)-2-[2-nitro-6-(trifluoromethyl)phenyl]ethyl]propanedioic acid, dimethyl ester

Product 1

HCID 15128658alpha-(2-Propenyl)-[2-(2-nitro-6-trifluoromethylphenyl)-1-(4-methoxyphenyl)ethyl]propanedioic acid, dimethyl esterYield 97.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

[2-(2-Nitro-6-trifluoromethylphenyl)-1-(4-methoxyphenyl)ethyl]propanedioic acid, dimethyl ester (14.55 g; 31.96 mmole) was dissolved in dry dimethylformamide (90 ml) under argon. Prewashed 50% sodium hydride (1.85 g; 38.5 mmole) was added with stirring and stirring was continued for 20 minutes before allyl bromide (19.33 g; 159.8 mmole; 13.8 ml; d=1.398; 5 eq.) was added dropwise. The mixture was quenched (1N hydrochloric acid) after a few minutes of reaction time, and extracted with ethyl acetate (two times). The organic extract was washed with saturated potassium carbonate (two times), saturated sodium chloride, and dried (magnesium sulfate). The solution was concentrated on a high vacuum pump leaving 23.0 g. This material was flash chromatographed (silica gel/9:1-hexane:ethyl acetate) and the appropriate fractions were combined and concentrated giving 15.45 g of the title compound as an oil.

Workup

  1. stirringstirring
  2. additionwas added dropwise
  3. customThe mixture was quenched (1N hydrochloric acid) after a few minutes
  4. customof reaction time
  5. extractionextracted with ethyl acetate (two times)
  6. extractionThe organic extract
  7. washwas washed with saturated potassium carbonate (two times), saturated sodium chloride
  8. dry with materialdried (magnesium sulfate)
  9. concentrationThe solution was concentrated on a high vacuum pump
  10. customleaving 23.0 g
  11. customchromatographed (silica gel/9:1-hexane:ethyl acetate)
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-86832b3174454d7b859a4a3bbe2e950d
Source dataset
uspto-grants-1988_06
Patent number
US04752645

Reaction notes

Loading…