Carbon Dioxide → 4-Cyano-2-methylbenzoic acid

HRID 906079Notes

Reaction equation

HRID 906079 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[CH3:10].[Li]CCCC.[C:16](=[O:18])=[O:17].O>C1(C)C=CC=CC=1>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([C:16]([OH:18])=[O:17])=[C:3]([CH3:10])[CH:4]=1)#[N:7]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 962WaterHCID 27374944-Bromo-3-methylbenzonitrileHCID 178418339Butyllithium

Product 1

HCID 118193394-Cyano-2-methylbenzoic acidYield 20.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a solution of 4-bromo-3-methylbenzonitrile (0.48 g, 2.43 mmol) in 1 ml of toluene at −78° C. was added 1 ml of 2.6M n-BuLi in toluene followed by quenching with dry ice (0.5 g, 12.5 mmol). The reaction mixture was warmed to room temperature, then taken into water and extracted with ethyl acetate (2×15 ml). The water layer was acidified to pH 1-2 by addition of concentrated aqueous hydrochloric acid and extracted with ethyl acetate (3×15 ml). The organic layer was dried over anhydrous sodium sulfate, then filtered and concentrated to give 4-cyano-2-methylbenzoic acid (0.08 g, 20% yield). 1H-NMR (400 MHz, DMSO-d6): 13.10 (br s, 1H), 7.92 (d, 1H), 7.84 (m, 1H), 7.76 (d, 1H), 2.53 (s, 3H).

Workup

  1. extractionextracted with ethyl acetate (2×15 ml)
  2. additionThe water layer was acidified to pH 1-2 by addition of concentrated aqueous hydrochloric acid
  3. extractionextracted with ethyl acetate (3×15 ml)
  4. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-f0bef1e3c2f143bc8dccb3bca5a6d242
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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