Methyl 2-Benzoylnicotinate → 2-Benzylnicotinic acid

HRID 128935Notes

Reaction equation

HRID 128935 reaction equation
[C:1]([C:9]1[N:18]=[CH:17][CH:16]=[CH:15][C:10]=1[C:11]([O:13]C)=[O:12])(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>[OH-].[NH4+].S([O-])([O-])(=O)=O.[Cu+2].[Zn]>[CH2:1]([C:9]1[N:18]=[CH:17][CH:16]=[CH:15][C:10]=1[C:11]([OH:13])=[O:12])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 1

HCID 19700681Methyl 2-Benzoylnicotinate

Product 1

HCID 124287332-Benzylnicotinic acidYield 33%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24462Copper SulfateCatalystHCID 14923Ammonium HydroxideSolvent

Procedure

Methyl 2-Benzoylnicotinate (2.41 g., 10 mmoles) was dissolved in 250 ml ammonium hydroxide. To this solution was carefully added a catalytic amount of copper (II) sulfate (approx. 100 mg) and zinc powder (7.0 g., 100 mmoles). The mixture was refluxed for 6 days and allowed to cool. The mixture was filtered (pad of celite), acidified to pH 5 with 1N HCl, exhaustively extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, concentrated under vacuum, and purified by column chromatography to give 0.70 grams (33% yield) of 2-benzylnicotinic acid as a white solid. Characteristic analytical data are as follows: mp 180°-182.5° C.; TLC in 20:1.8:0.2 (EtOAc/MeOH/HOAc); 1H NMR (DMSO-d6, 300 MHz) δ4.50 (s, 2H), 7.12-7.48 (m, 5H), 8.18 (dd, 1H, J=8.0, 1.6 Hz), 8.63 (dd, 1H, J=4.8, 1.5 Hz); 13C NMR (75 MHz, DMSO-d6) δ167.84, 160.17, 151.55, 139.85, 138.38, 128.75, 128.04, 126.37, 125.79, 121.57, 41.35, 39.76; mass spectrum (EI) , m/e 213.

Workup

  1. temperatureThe mixture was refluxed for 6 days
  2. temperatureto cool
  3. filtrationThe mixture was filtered (pad of celite)
  4. extractionexhaustively extracted with ethyl acetate
  5. washwashed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. custompurified by column chromatography

Sources & evidence

ORD record
ord-6b50fbd1237640d7822c62280e45391c
Source dataset
uspto-grants-1995_11
Patent number
US05466697

Reaction notes

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