Carbon Dioxide → 4-Cyano-3-methylbenzoic acid

HRID 432584Notes

Reaction equation

HRID 432584 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 4-bromo-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-2468c88f658a48078fa876e679464741
Source dataset
uspto-grants-2003_12
Patent number
US06664249B1

Reaction notes

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