Reacción #2175485

Ecuación de reacción

water

methyl pyruvate

sodium 2,2-bis(hexyloxy)propyl sulfate

1-hexanol

sodium 2,2-bis(hexyloxy)propyl sulfate

→

hexyl 2,2-bis(hexyloxy)propanoate

Rendimiento 84.0%

Disolventes

toluene

Condiciones de reacción

Tratamiento posterior

1. 1
   TemperaturaThe mixture is heated
2. 2
   OtroThe reaction is quenched with saturated NaHCO3 (100 mL)
3. 3
   Extracciónthe reaction mixture is extracted with ethyl acetate (2×100 mL)
4. 4
   LavadoThe combined organic layers are washed with brine (100 mL)
5. 5
   Secadodried over anhydrous sodium sulfate
6. 6
   OtroThe solvent is removed
7. 7
   Otrothe residue is purified by silica gel chromatography (1→10% ethyl acetate/hexane)

Procedimiento

To a solution of methyl pyruvate 1 (10.0 g, 98.0 mmol) in toluene (100 mL) is added 1-hexanol 2 (40.1 g, 392 mmol) and p-Ts0H (186 mg, 0.98 mmol). The mixture is heated to reflux for 10 hours with azeotropic removal of water from the reaction mixture. The reaction is quenched with saturated NaHCO3 (100 mL), and the reaction mixture is extracted with ethyl acetate (2×100 mL). The combined organic layers are washed with brine (100 mL) and dried over anhydrous sodium sulfate. The solvent is removed and the residue is purified by silica gel chromatography (1→10% ethyl acetate/hexane) to give hexyl 2,2-bis(hexyloxy)propanoate 3 (29.5 g, 84%) as a colorless oil: Rf (15% EtOAc/hexane)=0.53; IR (thin film, cm−1) 2956, 2930, 2860, 1746 (C═O), 1467, 1280, 1137, 1062. 1H NMR (600 MHz, CDCl3) δ 4.14 (t, J=7.2 Hz, 2H), 3.48 (ddd, J=9.0, 7.2, 6.6 Hz, 2H), 3.35 (ddd, J=9.0, 7.2, 6.6 Hz, 2H), 1.65-1.63 (m, 2H), 1.59-1.54 (m, 4H), 1.49 (s, 3H), 1.35-1.24 (m, 18H), 0.86 (t, J=7.2 Hz, 9H); 13C NMR (150 MHz, CDCl3) δ 170.2, 99.5, 65.4, 62.6, 31.7, 31.3, 29.7, 28.5, 25.8, 25.5, 22.6, 22.5, 21.9, 14.0, 13.9.

Fuente