alpha,alpha,alpha-Trifluoro-3-nitro-o-xylene → [1-(4-Methoxyphenyl)-2-[2-nitro-6-(trifluoromethyl)phenyl]ethyl]propanedioic acid, dimethyl ester

HRID 344787Notes

Reaction equation

HRID 344787 reaction equation
[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[CH3:19][C:20]1[C:25]([C:26]([F:29])([F:28])[F:27])=[CH:24][CH:23]=[CH:22][C:21]=1[N+:30]([O-:32])=[O:31].[CH3:33][O:34][C:35]1[CH:40]=[CH:39][C:38]([CH:41]=[C:42]([C:47]([O:49][CH3:50])=[O:48])[C:43]([O:45][CH3:46])=[O:44])=[CH:37][CH:36]=1>O1CCCC1>[CH3:33][O:34][C:35]1[CH:36]=[CH:37][C:38]([CH:41]([CH:42]([C:47]([O:49][CH3:50])=[O:48])[C:43]([O:45][CH3:46])=[O:44])[CH2:19][C:20]2[C:25]([C:26]([F:29])([F:28])[F:27])=[CH:24][CH:23]=[CH:22][C:21]=2[N+:30]([O-:32])=[O:31])=[CH:39][CH:40]=1

Participants

5

Reactant 3

HCID 81171alpha,alpha,alpha-Trifluoro-3-nitro-o-xyleneHCID 100478Dimethyl (p-methoxybenzylidene)malonateHCID 2724141Tetrabutylammonium Fluoride

Product 1

HCID 14156192[1-(4-Methoxyphenyl)-2-[2-nitro-6-(trifluoromethyl)phenyl]ethyl]propanedioic acid, dimethyl esterYield 90.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a vigorously stirring mixture of molecular sieves (5.25 g) and tetra-n-butylammonium fluoride (0.882 g) was added dry tetrahydrofuran (10 ml) at 0° C. 2-Methyl-1-nitro-3-(trifluoromethyl)benzene (0.425 ml; 2.8 mmol) was added to the suspension followed by the addition of a solution of 2-[(4-methoxyphenyl)methylene]propanedioic acid, dimethyl ester (0.44 g; 1.75 mmol) in 5 ml of tetrahydrofuran. After 30 minutes of 0° C. the reaction was brought to room temperature and stirred for another 20 minutes. The reaction was quenched with 30% acetic acid until a light yellow color was observed and thereafter was diluted with 45 ml of ethyl ether, filtered and washed twice with 30 ml of ethyl ether. The combined organic solution was washed with sodium hydrogen carbonate and dried over magnesium sulfate. Concentration and chromatography provided 0.72 g of the title compound as a foam.

Workup

  1. stirringstirred for another 20 minutes
  2. customThe reaction was quenched with 30% acetic acid until a light yellow color
  3. additionwas diluted with 45 ml of ethyl ether
  4. filtrationfiltered
  5. washwashed twice with 30 ml of ethyl ether
  6. washThe combined organic solution was washed with sodium hydrogen carbonate
  7. dry with materialdried over magnesium sulfate
  8. concentrationConcentration and chromatography

Sources & evidence

ORD record
ord-45659c1bed634b0f93a3e63c11ffa472
Source dataset
uspto-grants-1991_10
Patent number
US05053504

Reaction notes

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