Carbon Dioxide → 4-Cyano-3-methylbenzoic acid

HRID 558942Notes

Reaction equation

HRID 558942 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-a22974cbb8ed447eb6199415a3a178d9
Source dataset
uspto-grants-2011_11
Patent number
US08063038B2

Reaction notes

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