Carbon Dioxide → 4-Cyano-3-methylbenzoic acid

HRID 347626Notes

Reaction equation

HRID 347626 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([CH3:10])[CH:3]=1.C([Li])CCC.[C:16](=[O:18])=[O:17].O>C1COCC1>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([C:16]([OH:18])=[O:17])=[CH:3][C:4]=1[CH3:10])#[N:7]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 962WaterHCID 1442674-Bromo-2-methylbenzonitrileHCID 178418339Butyllithium

Product 1

HCID 102410994-Cyano-3-methylbenzoic acid

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 4bromo-2-methylbenzonitrile (2.0 g, 10.2 mmol) in THF (100 ml) at −78° C. under a nitrogen atmosphere was added dropwise a 2.5M solution of n-butyl lithium (4.48 ml, 11.2 mmol). The mixture was stirred at −78° C. for 1 h and then poured onto solid carbon dioxide (5 g) in THF (50 ml). The mixture was allowed to warm to room temperature. Water was added (200 ml) and the mixture was extracted with diethyl ether (3 times). The aqueous layer was acidified by addition of concentrated HCl and extracted with chloroform (3 times). The combined chloroform extracts were washed with water, dried over MgSO4, and concentrated in vacuo to give a white solid; yield 1.2 g (73%).

Workup

  1. temperatureto warm to room temperature
  2. extractionthe mixture was extracted with diethyl ether (3 times)
  3. additionThe aqueous layer was acidified by addition of concentrated HCl
  4. extractionextracted with chloroform (3 times)
  5. washThe combined chloroform extracts were washed with water
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customto give a white solid

Sources & evidence

ORD record
ord-70e55b2962de43f9b7f392051710fcc2
Source dataset
uspto-grants-2007_02
Patent number
US07176195B2

Reaction notes

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