1-substituted phenanthrenyl-n-alkyl (acyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline derivatives and their preparation methods and uses
A tetrahydroisoquinoline and dimethoxy technology, which can be used in drug combinations, pharmaceutical formulations, and medical preparations containing active ingredients, etc., can solve the problems of high price, high toxicity of compounds, and low bioavailability.
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Embodiment 1
[0090] Example 1: 1-(3,6,7-trimethoxy-9-phenanthrenyl)-N-methyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (Compound 1) Preparation
[0091] 1) Preparation of (E)-2-(3,4-dimethoxyphenyl)-3-(4-methoxyphenyl)ethanoic acid
[0092] Add 3,4-dimethoxyphenylacetic acid (19.6 g, 0.1 mol), p-methoxybenzaldehyde (16.3 g, 0.12 mol) acetic anhydride (38 mL) and triethylamine (19 mL) into a 100 mL eggplant-shaped flask , heated to reflux for 9h under the protection of argon. Stop the reaction, pour the reaction solution into hot 150mL 10% sodium hydroxide aqueous solution, heat to reflux for 0.5h, and cool down to room temperature. The solution was extracted with ether (3×100mL), the organic layer was discarded, and concentrated hydrochloric acid solution was added to the water layer in an ice bath to adjust the pH to 3. A large amount of khaki solid was precipitated, stirred for 0.5h, filtered with suction, and the filter cake was dried. 16.62 g of a khaki solid was obtained, with a...
Embodiment 2
[0107] Example 2: 1-(2,3,6,7-tetramethoxy-9-phenanthrenyl)-N-methyl-6,7-dimethoxy-1,2,3,4-tetrahydro Preparation of isoquinoline (compound 2)
[0108] The preparation process of compound 2 is the same as that of compound 1. 3,4-dimethoxybenzaldehyde and 3,4-dimethoxyphenylacetic acid are used as starting materials. After condensation, esterification, coupling, hydrolysis, acylation, cyclization, reduction, and alkylation, 1-(2,3,6,7-tetramethoxy-9-phenanthrenyl)-N-methyl- 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (compound 2), the total yield is 17.2%. 1 H-NMR (300MHz, CDCl 3 , ppm) δ: 2.25(s, 3H), 2.70(s, 1H), 2.85-2.88(d, 1H), 3.25-3.26(d, 1H), 3.40(s, 3H), 3.50(s, 1H) , 3.87(s, 3H), 3.95(s, 3H), 4.05(s, 3H), 4.07(s, 3H), 4.08(s, 3H), 4.59(s, 1H), 6.15(s, 1H), 6.63(s, 1H), 6.92(s, 1H), 7.48(s, 1H), 7.63(s, 1H), 8.31(s, 1H), 9.01(s, 1H); ESI-MS: m / z 504. 2[M+H] + .
Embodiment 3
[0109] Example 3: 1-(2-Hydroxy-3,6,7-trimethoxy-9-phenanthrenyl)-N-methyl-6,7-dimethoxy-1,2,3,4-tetra Preparation of Hydroisoquinoline (Compound 3)
[0110] The preparation process of compound 3 is similar to that of compound 2. Using 3-hydroxy-4-methoxybenzaldehyde and 3,4-dimethoxyphenylacetic acid as starting materials, after alkylation, condensation, esterification, coupling, hydrolysis, acylation, cyclization, reduction , Alkylation to get 1-(2-hydroxy-3,6,7-trimethoxy-9-phenanthrenyl)-N-methyl-6,7-dimethoxy-1,2,3,4- Tetrahydroisoquinoline.
[0111] 1-(2-Hydroxy-3,6,7-trimethoxy-9-phenanthryl)-N-methyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (0.25g, 0.46mmol) was dissolved in 100mL of anhydrous methanol, 30mg of 10% anhydrous Pd / C was added, 1,4 cyclohexadiene (0.26mL, 2.75mmol), ultrasonically reacted at 25°C for 1.5 hours, and Pd was filtered off / C, the filtrate was evaporated, and purified by column chromatography to obtain the target product with a total yie...
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