Allyl bromide → alpha-(2-Propenyl)-[2-(2-nitro-5-trifluoromethylphenyl)-1-(4-methoxyphenyl)ethyl]propanedioic acid, dimethyl ester

HRID 580401Notes

Reaction equation

HRID 580401 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]([F:13])([F:12])[F:11])=[CH:6][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[CH:6]=[C:7]([C:10]([F:11])([F:12])[F:13])[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 14156190[2-(2-Nitro-5-trifluoromethylphenyl)-1-(4-methoxyphenyl)ethyl]propanedioic acid, dimethyl ester

Product 1

HCID 15128661alpha-(2-Propenyl)-[2-(2-nitro-5-trifluoromethylphenyl)-1-(4-methoxyphenyl)ethyl]propanedioic acid, dimethyl ester

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

[2-(2-Nitro-5-trifluoromethylphenyl)-1-(4-methoxyphenyl)ethyl]propanedioic acid, dimethyl ester (46.54 g; 0.102 mole; see Example 4A) was dissolved in dry dimethylformamide (290 ml) under argon. Fifty percent sodium hydride (5.89 g; 0.123 mole; prewashed-hexane) was added with stirring which was continued for 20 minutes before allyl bromide (44 ml; 61.7 g; 0.510 mmole; d=1.398; 5 eq.) was added dropwise. After six hours, 40 minutes, the reaction was quenched with 1N hydrochloric acid. The solution was extracted with ethyl acetate (two times) and the extract was washed with 1N hydrochloric acid (two times), saturated potassium carbonate (two times), saturated sodium chloride, and dried (magnesium sulfate). The concentrated solution (viscous oil) was flash chromatographed (silica gel/9:1-hexane: ethyl acetate, followed by 8:2-hexane:ethyl acetate) in two portions. After drying in vacuo overnight, the yellow viscous oil product weighed 54.77 g. The product was used "as is" in the next step.

Workup

  1. additionwas added dropwise
  2. custom40 minutes, the reaction was quenched with 1N hydrochloric acid
  3. extractionThe solution was extracted with ethyl acetate (two times)
  4. washthe extract was washed with 1N hydrochloric acid (two times), saturated potassium carbonate (two times), saturated sodium chloride
  5. dry with materialdried (magnesium sulfate)
  6. customchromatographed (silica gel/9:1-hexane: ethyl acetate, followed by 8:2-hexane:ethyl acetate) in two portions
  7. customAfter drying in vacuo overnight

Sources & evidence

ORD record
ord-de83a6d2977d470caa8cd4eba76e9d02
Source dataset
uspto-grants-1988_06
Patent number
US04752645

Reaction notes

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