反应 #61357

反应方程式

ethyl benzoylacetate

m-anisidine

HCl dioxane

ester c

→

4-hydroxy-2-phenyl-7-methoxyquinoline

溶剂

toluene

反应条件

后处理

1. 1
   洗涤The cooled toluene solution was successively washed with aqueous 10% HCl (2×300 mL), 1 N NaOH (2×300 mL), H2O (300 mL) and brine (150 mL)
2. 2
   干燥The toluene phase was dried (MgSO4)
3. 3
   过滤filtered
4. 4
   浓缩concentrated under reduced pressure
5. 5
   其他to give
6. 6
   workup.DISTILLATIONwhile distilling
7. 7
   其他The cooled dark solid obtained
8. 8
   其他was triturated with CH2Cl2 (200 mL)
9. 9
   过滤The suspension was filtered
10. 10
    洗涤the resulting solid washed with CH2Cl2
11. 11
    其他to give e (22.6 g, 17% from a) as a beige solid

实验过程

A solution of ethyl benzoylacetate (b) (100.0 g, 0.52 mol), m-anisidine (a) (128.1 g, 1.04 mol) and 4 N HCl/dioxane (5.2 mL) in toluene (1.0 L) was refluxed for 6.25 h in a Dean-Stark apparatus. The cooled toluene solution was successively washed with aqueous 10% HCl (2×300 mL), 1 N NaOH (2×300 mL), H2O (300 mL) and brine (150 mL). The toluene phase was dried (MgSO4), filtered and concentrated under reduced pressure to give a 1.2:1.0 mixture of ester c and amide d (144.6 g, 45%/38% crude yield) as a dark brown oil. The crude oil was heated to 280° C. for 80 min while distilling generated EtOH. The cooled dark solid obtained was triturated with CH2Cl2 (200 mL). The suspension was filtered and the resulting solid washed with CH2Cl2 to give e (22.6 g, 17% from a) as a beige solid: 1H NMR (DMSO-d6) δ 8.00 (d, J=9.0 Hz, 1H), 7.81-7.82 (m, 2H), 7.57-7.59 (m, 3H), 7.20 (d, J=2.2 Hz, 1H), 6.94 (dd, J=9.0, 2.2 Hz, 1H), 6.26 (s, 1H), 3.87 (s, 3H).

来源