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

HRID 1416423Notes

Reaction equation

HRID 1416423 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

In an autoclave, 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, and 0.30 g (1.6 mmol) of cobaltocene (=dicyclopentadienylcobalt; Aldrich, Milwaukee/USA) is added. Then an acetylene pressure of 15 atm is applied, and the mixture is heated to 180° C. and stirred for 12 h. 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 by column chromatography (SiO2, hexane/ethyl acetate 19:1→4:1) of the mother liquor.

Workup

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

Sources & evidence

ORD record
ord-a328bdec712342d89e2fe215d2b32c52
Source dataset
uspto-grants-1999_06
Patent number
US05912352

Reaction notes

Loading…