Toluene → Methyl 4-(pyridin-2-YL)benzoate

HRID 380230Notes

Reaction equation

HRID 380230 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([C:10]#[N:11])=[CH:6][CH:5]=1.C#C.[C:15]1(C)[CH:20]=CC=[CH:17][CH:16]=1>[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Co+2]>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:17]=[CH:16][CH:15]=[CH:20][N:11]=2)=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 1140Toluene2×HCID 6326AcetyleneHCID 70791Methyl 4-cyanobenzoate

Product 1

HCID 3358924Methyl 4-(pyridin-2-YL)benzoate

Reagents, catalysts & solvents 1

HCID 92884CobaltoceneCatalyst

Conditions

Temperature
180 °C

Procedure

24.0 g (150 mmol) of 4-cyanobenzoic acid methyl ester (Fluka, Buchs, Switzerland) in 150 ml of toluene are placed under an acetylene atmosphere in an autoclave and 0.30 g (1.6 mmol) of cobaltocene (=dicyclopentadienylcobalt; Aldrich, Milwaukee, USA) is added. The mixture is then subjected to an acetylene pressure of 15 atm, heated at 180° C. and stirred for 12 hours. After cooling and release of the pressure, 9.5 g of active carbon are added to the black suspension; the mixture is diluted with 250 ml of toluene, stirred for 30 min, filtered and concentrated by evaporation. Crystallisation from warm ether by the addition of hexane yields the title compound: m.p. 96° C.; TLC (hexane/ethyl acetate 4:1): Rf=0.37; FAB MS (M+H)+=214. Further product can be obtained from the mother liquor by column chromatography (SiO2, hexane/ethyl acetate 19:1→4:1).

Workup

  1. additionis added
  2. temperatureAfter cooling
  3. additionrelease of the pressure, 9.5 g of active carbon are added to the black suspension
  4. stirringstirred for 30 min
  5. filtrationfiltered
  6. concentrationconcentrated by evaporation
  7. customCrystallisation
  8. temperaturefrom warm ether
  9. additionby the addition of hexane

Sources & evidence

ORD record
ord-1c71cf6b53ea4ddfbcc547cad53ddc33
Source dataset
uspto-grants-2001_10
Patent number
US06300519B1

Reaction notes

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