反応 #61357

反応方程式

ethyl benzoylacetate

m-anisidine

HCl dioxane

ester c

→

4-hydroxy-2-phenyl-7-methoxyquinoline

溶媒

toluene

反応条件

後処理

1. 1
   洗浄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
   乾燥The toluene phase was dried (MgSO4)
3. 3
   ろ過filtered
4. 4
   濃縮concentrated under reduced pressure
5. 5
   その他to give
6. 6
   workup.DISTILLATIONwhile distilling
7. 7
   その他The cooled dark solid obtained
8. 8
   その他was triturated with CH2Cl2 (200 mL)
9. 9
   ろ過The suspension was filtered
10. 10
    洗浄the resulting solid washed with CH2Cl2
11. 11
    その他to give e (22.6 g, 17% from a) as a beige solid

実験手順

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).

出典