Benzofuran-[3,4-f] quinoline derivatives, combination containing the same and application thereof
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Embodiment 1
[0434] 2,5-Dihydro-11-methoxy-5-phenyl-2,2,4-trimethyl-1H-[1]benzopyrano[3,4-f]quinoline
Embodiment 1A
[0436] Methyl 2-hydroxy-3-methoxybenzoate (20.0 g, 110 mmol) in trifluoroacetic acid was treated with sodium nitrate (10.2 g, 121 mmol) in water (70 mL) over 45 minutes at 0°C (150ml) solution, stirred at 0°C for 30 minutes, and poured into ice (450ml). The precipitate was collected by filtration, washed with cold water, and dried in vacuo to give the designated compound.
[0437] MS (DCI / NH 3 )m / z 245(M+NH 4 ) + ;
[0438] 1 H NMR (300MHz, CDCl 3 )δ11.73(s, 1H), 8.45(d, J=7.8Hz, 1H), 7.87(d, J=8.2Hz, 1H), 4.04(s, 3H), 4.01(s, 3H).
Embodiment 1B
[0440] Example 1A (5.74 g, 25.3 mmol) in dichloromethane (100 ml) was treated with diisopropylethylamine (13.2 ml, 75.9 mmol) and freshly distilled trifluoroacetic anhydride ( 10.0g, 35.4mmol) was processed through the addition funnel for 30 minutes, stirred at -40°C for 15 minutes, when the initial phenol had reacted, stopped the reaction with water (30ml), stirred at 23°C until a uniform, two phase solution and treated with dichloromethane (65ml). The organic extract was washed successively with 5% hydrochloric acid, brine and saturated sodium bicarbonate, dried (sodium sulfate), filtered and concentrated. Recrystallization from hot hexanes afforded the desired compound. The residue was purified by flash chromatography using 15% ethyl acetate / hexanes to afford the desired compound, which could be stored indefinitely at -10°C under nitrogen without detectable decomposition.
[0441] mp84-86℃
[0442] MS (DCI / NH 3 )m / z377(M+NH4 ) + ;
[0443] 1 H NMR (300MHz, CDCl 3 )δ...
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