Reacción #1973949

Ecuación de reacción

Phosphorus trichloride

diethyl 7-(hydroxymethyl)dipyrido[3,2-f:2′,3′-h]quinoxaline-2,3-dicarboxylate

→

glass

Rendimiento 26.0%

Diethyl 7-(chloromethyl)dipyrido[3,2-f:2′,3′-h]quinoxaline-3,2-dicarboxylate

Rendimiento 26.0%

Disolventes

CHCl3

Condiciones de reacción

Tratamiento posterior

1. 1
   TemperaturaThe reaction mixture was heated
2. 2
   Temperaturaunder reflux for 6 h
3. 3
   OtroThe reaction was quenched by addition of concentrated Na2CO3 solution (150 ml)
4. 4
   OtroThe layers were separated
5. 5
   Extracciónthe water was extracted by CH2Cl2 (3×150 ml) and CHCl3 (1×50 ml)
6. 6
   SecadoThe organic layer was dried over K2CO3
7. 7
   OtroThe solvent was removed under reduced pressure
8. 8
   Otroto give the crude product
9. 9
   OtroPurification

Procedimiento

Phosphorus trichloride (473 mg, 3.44 mmol) was added to a solution diethyl 7-(hydroxymethyl)dipyrido[3,2-f:2′,3′-h]quinoxaline-2,3-dicarboxylate (350 mg, 0.86 mmol) in CHCl3 (150 ml). The reaction mixture was heated under reflux for 6 h and allowed to cool down to room temperature afterwards. The reaction was quenched by addition of concentrated Na2CO3 solution (150 ml). The layers were separated and the water was extracted by CH2Cl2 (3×150 ml) and CHCl3 (1×50 ml). The organic layer was dried over K2CO3. The solvent was removed under reduced pressure to give the crude product. Purification was achieved by chromatography on alumina (gradient elution: CH2Cl2 to 2% CH3OH—CH2Cl2) The product was obtained as a yellow glass (95 mg, 0.22 mmol, 26%). 1H NMR (300 MHz, CDCl3): δ 1.45 (6H, t, J=7.2, OCH2CH3), 4.53 (4H, q, J=7.2, OCH2), 5.07 (2H, s, CH2Cl), 7.78 (1H, dd, J=8.1, 4.5, H11), 8.05 (1H, d, J=8.4, H6), 9.31 (1H, dd, J=4.5, 1.8, H10), 9.50 (1H, dd, J=8.1, 1.8, H12), 9.53 (1H, d, J=8.7, H5). 13C NMR (75 MHz, CDCl3): δ14.4 (CH3), 47.3 (CH2Cl), 63.2 (OCH2), 123.8 (C11), 124.6 (C6), 125.6 (q Ar), 126.6 (q Ar), 134.5 (C12), 135.7 (C5), 140.1 (q Ar), 140.4 (q Ar), 144.3 (q Ar), 144.4 (q Ar), 147.6 (q Ar), 148.1 (q Ar), 153.8 (C10), 161.0 (C7), 165.0 (CO), 165.1 (CO). m/z (ES+) 447 (MNa+).

Fuente