1,2,3,4-Tetrahydroisoquinoline derivatives, preparation methods and applications thereof
A technology of tetrahydroisoquinoline and its derivatives, applied in its preparation, 1, can solve problems such as cognitive changes, drug resistance, dependence, and side effects
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[0116] Preparation of intermediates
[0117] 1. Intermediate 1: Preparation of ethyl 3-(2-(benzyloxy)-3-methoxyphenyl)-2-((diphenylmethylene)amino)propionate
[0118]
[0119] At room temperature, to 2-(benzyloxy)-1-(chloromethyl)-3-methoxybenzene (6.8g, 25.88mmol) in acetonitrile (60mL) was added potassium iodide (5.59g, 33.65mmol) , Cesium carbonate (16.87g, 51.76mmol), ethyl 2-((diphenylmethylene)amino) acetate (6.92g, 25.88mmol), then under nitrogen protection, stir overnight in an oil bath at 50°C . After cooling, the organic solvent was removed by rotary evaporation under reduced pressure, ethyl acetate and water layer were added, the ethyl acetate phase was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated by column chromatography (eluent: petroleum ether / Ethyl acetate=10:1) to obtain ethyl 3-(2-(benzyloxy)-3-methoxyphenyl)-2-((benzylidene)amino)propionate (8.9g, 70%).
[0120] MS m / z(ESI): 494.6[M+H] + .
[0121] 2. Intermediate 2: Prepar...
Embodiment 1
[0130] Example 1: 5-(Benzyloxy)-6-methoxy-2-(1-phenylcyclohexane-1-carbonyl)-1,2,3,4-tetrahydroisoquinoline-3- Preparation of carboxylic acid
[0131]
[0132] Step 1: Preparation of 1-phenylcyclohexane-1-carbonyl chloride
[0133]
[0134] At room temperature, oxalyl chloride (248 mg, 1.96 mmol) and DMF (0.2 mL) were added to a solution of 1-phenylcyclohexane-1-carboxylic acid (200 mg, 0.98 mmol) in dichloromethane (5 mL), and the reaction was at room temperature After stirring for 2 hours, the solvent was removed under reduced pressure to obtain crude 1-phenylcyclohexane-1-carbonyl chloride (230 mg), which was directly used in the next reaction.
[0135] The second step: Ethyl 5-(benzyloxy)-6-methoxy-2-(1-phenylcyclohexane-1-carbonyl)-1,2,3,4-tetrahydroisoquinoline- Preparation of 3-carboxylate
[0136]
[0137] At room temperature, add ethyl 5-(benzyloxy)-6-methoxy-1 to a solution of 1-phenylcyclohexane-1-carbonyl chloride (100mg, 0.45mmol) in dichloromethane (5mL) , 2,3,4-Tetra...
Embodiment 2
[0143] Example 2: 5-(Benzyloxy)-6-methoxy-2-(1-phenylcyclopropane-1-carbonyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxy Acid preparation
[0144]
[0145] Preparation method of 5-(benzyloxy)-6-methoxy-2-(1-phenylcyclopropane-1-carbonyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid Refer to Example 1. MS m / z(ESI): 458.2[M+H] + ;
[0146] 1 H NMR(400MHz, CDCl 3 )δ7.41-7.28(m,6H), 7.23-7.13(m,4H), 6.88-6.69(m,1H), 6.68-6.44(m,1H), 5.11-4.82(m,3H), 4.66 4.13 (m, 2H), 3.84 (s, 3H), 3.40-2.75 (m, 2H), 1.54-1.19 (m, 4H).
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