Reacción #2460288

Ecuación de reacción

1-ethynylnaphthalene

1,2,2,6,6-pentamethylpiperidine

ethyl chloroformate

→

ethyl 1-naphthylpropiolate

Rendimiento 36.0%

Disolventes

acetonitrile

—

ligroin

Condiciones de reacción

Tratamiento posterior

1. 1
   OtroFirst, ethyl 1-naphthylpropiolate was prepared
2. 2
   Otrowas sparged with nitrogen for 10 min
3. 3
   OtroThe mixture was sparged with nitrogen for 10 min
4. 4
   Temperaturaheated
5. 5
   Temperaturato reflux
6. 6
   Temperaturaat reflux for 2 h
7. 7
   TemperaturaThe reaction mixture was cooled to ambient and
8. 8
   LavadoThe solution was washed three times with water
9. 9
   Secadowith brine, dried (Na2SO4)
10. 10
    Concentraciónconcentrated
11. 11
    OtroThe crude product was purified by column chromatography

Procedimiento

First, ethyl 1-naphthylpropiolate was prepared. A mixture of 1-ethynylnaphthalene (7.7 g, 50.6 mmol), 4-(dimethylamino)pyridine (0.06 g, 0.5 mmol), 1,2,2,6,6-pentamethylpiperidine (8.8 g, 55.7 mmol), and acetonitrile (120 mL) was sparged with nitrogen for 10 min, and then tetrakis(triphenylphosphine)palladium(0) (1.3 g, 1.1 mmol) was added. The mixture was sparged with nitrogen for 10 min, heated to reflux, treated dropwise with ethyl chloroformate (12.1 g, 111.3 mmol), and held at reflux for 2 h. The reaction mixture was cooled to ambient and diluted with ligroin. The solution was washed three times with water and then with brine, dried (Na2SO4), and concentrated to deposit a brown oil. The crude product was purified by column chromatography to provide 4.0 g (36% of theory) of ethyl 1-naphthylpropiolate. 1H NMR (CDCl3): δ 1.40 (t, 3H), 4.33 (q, 2H), 7.50 (m, 3H), 7.90 (m, 3H), 8.30 (d, 1H).

Fuente