Reaktion #929214

Reaktionsgleichung

methyl 2-chloronicotinate

phenyltributyltin

lithium chloride

→

Methyl 2-phenylnicotinate

Lösungsmittel

toluene

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigewas degassed
2. 2
   Temperaturat reflux for 5 hours
3. 3
   SonstigeThe cooled reaction mixture
4. 4
   Filtrationwas filtered
5. 5
   Sonstigethe filtrate evaporated
6. 6
   Sonstigethe residue partitioned between acetonitrile (50 ml) and hexane (5×20 ml)
7. 7
   ExtraktionThe combined hexane layers were extracted with hydrochloric acid (lM, 4×10 ml)
8. 8
   Waschenthe extracts washed with ethyl acetate (15 ml), and basified (4M NaOH)
9. 9
   ExtraktionThe resulting suspension was extracted with dichloromethane (4×10 ml)
10. 10
    Trocknenthe combined extracts dried over MgSO4
11. 11
    Sonstigeevaporated
12. 12
    Sonstigeto leave a colourless oil
13. 13
    SonstigeMeanwhile, the acetonitrile layer from above was evaporated
14. 14
    workup.DISSOLUTIONthe residual oil dissolved in diethyl ether (50 ml)
15. 15
    Extraktionethyl acetate (25 ml) and the solution extracted with hydrochloric acid (1M, 4×10 ml)
16. 16
    ExtraktionBasification of the acid extracts (4M NaOH) and extraction of the resulting suspension with dichloromethane (4×10 ml)
17. 17
    Trocknenby drying of the combined extracts with MgSO4 and evaporation
18. 18
    Sonstigegave an oil which
19. 19
    Sonstigethat obtained

Vorschrift

A mixture of methyl 2-chloronicotinate (3.10 g, 18.1 mmol), phenyltributyltin (6.30 g, 17 mmol), lithium chloride (5.04 g, 120 mmol), and tetrakis(triphenylphosphine)palladium (1.12 g, 1 mmol) in toluene (65 ml) was degassed and then stirred under a nitrogen atmosphere overnight at 90° C. and at reflux for 5 hours. The cooled reaction mixture was filtered, the filtrate evaporated, and the residue partitioned between acetonitrile (50 ml) and hexane (5×20 ml). The combined hexane layers were extracted with hydrochloric acid (lM, 4×10 ml), the extracts washed with ethyl acetate (15 ml), and basified (4M NaOH). The resulting suspension was extracted with dichloromethane (4×10 ml), the combined extracts dried over MgSO4 and evaporated to leave a colourless oil. Meanwhile, the acetonitrile layer from above was evaporated and the residual oil dissolved in diethyl ether (50 ml) and ethyl acetate (25 ml) and the solution extracted with hydrochloric acid (1M, 4×10 ml). Basification of the acid extracts (4M NaOH) and extraction of the resulting suspension with dichloromethane (4×10 ml) followed by drying of the combined extracts with MgSO4 and evaporation gave an oil which was combined with that obtained as described above (2.62 g).

Quelle