Реакция #1973949

Уравнение реакции

Phosphorus trichloride

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

→

glass

Выход 26.0%

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

Выход 26.0%

Растворители

CHCl3

Условия реакции

Обработка

1. 1
   ТемператураThe reaction mixture was heated
2. 2
   Температураunder reflux for 6 h
3. 3
   ДругоеThe reaction was quenched by addition of concentrated Na2CO3 solution (150 ml)
4. 4
   ДругоеThe layers were separated
5. 5
   Экстракцияthe water was extracted by CH2Cl2 (3×150 ml) and CHCl3 (1×50 ml)
6. 6
   СушкаThe organic layer was dried over K2CO3
7. 7
   ДругоеThe solvent was removed under reduced pressure
8. 8
   Другоеto give the crude product
9. 9
   ДругоеPurification

Методика

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+).

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