2-(n-arylmethylpiperidine-4-amino)-4-(substituted phenol)benzene ring derivatives and their preparation methods and applications
An arylmethylpiperidine and derivative technology, applied in the fields of organic synthesis and pharmaceutical applications, can solve the problems of low oral bioavailability, and achieve the effects of low cytotoxicity and strong HIV-1 inhibitory activity
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Embodiment 1
[0068] Embodiment 1: Preparation of intermediate tert-butyl 4-(5-chloro-2-nitroanilino)piperidine-1-carboxylate (2)
[0069] Dissolve 0.09g (0.5mmol) 4-chloro-2-fluoro-1-nitrobenzene (1), 0.1g (0.5mmol) N-Boc piperidinamine, 0.15g (1.4mmol) sodium carbonate in 5mlN,N -Dimethylformamide (N,N-dimethylformamide), stirred and reacted at 80°C for 1 hour. Distill N,N-dimethylformamide under reduced pressure, dissolve the obtained solid in 10ml of dichloromethane (dichloromethane), wash with saturated brine, collect the organic phase, dry over anhydrous sodium sulfate, filter, concentrate, dry 0.18 g of tert-butyl 4-(5-chloro-2-nitroanilino)piperidine-1-carboxylate (2) was obtained by separation and purification on a column using the method. Yellow solid, yield: 100%, melting point: 93-95°C.
[0070] Product spectral analysis data:
[0071] ESI-MS: m / z373.3(M+18),375.4(M+2+18),378.4(M+23).C 16 h 22 ClN 3 o 4 [355.13].;
Embodiment 2
[0072] Example 2: Intermediate tert-butyl 4-(5-(4-cyano-2,6-dimethylphenoxy)-2-nitroanilino)piperidine-1-carboxylate (3a) preparation of
[0073]0.1g (0.28mmol) tert-butyl 4-(5-chloro-2-nitroanilino)piperidine-1-carboxylate (2), 0.04g (0.27mmol) 4-cyano-3,5 -Dimethylphenol, 0.08g (0.58mmol) potassium carbonate, 0.02g (0.062mmol) tetrabutylammonium bromide, 0.01g (0.060mmol) potassium iodide dissolved in 5ml N,N-dimethylformamide, heated to 120 React at -130°C for 12 hours. Evaporate N,N-dimethylformamide under reduced pressure, dissolve the residue in 10ml of dichloromethane, wash with saturated brine, collect the organic phase, dry over anhydrous sodium sulfate, filter, concentrate, and apply to the column by dry method Separation and purification gave 0.11 g of tert-butyl 4-(5-(4-cyano-2,6-dimethylphenol)-2-nitroanilino)piperidine-1-carboxylate (3a). Yellow solid, yield: 84.62%, melting point: 125-127°C.
[0074] Product spectral analysis data:
[0075] ESI-MS: m / z467.5...
Embodiment 3
[0076] Example 3: Preparation of intermediate tert-butyl 4-(5-(2,4,6-trimethylphenoxy)-2-nitroanilino)piperidine-1-carboxylate (3b)
[0077] 0.05g (0.14mmol) tert-butyl 4-(5-chloro-2-nitroanilino) piperidine-1-carboxylate (2), 0.04g (0.29mmol) 2,4,6-trimethyl Base phenol, 0.08g (0.58mmol) potassium carbonate, 0.01g (0.03mmol) tetrabutylammonium bromide and 0.005g (0.03mmol) potassium iodide were dissolved in N,N-dimethylformamide and heated to 120-130 The reaction was stirred at ℃ for 6h. The reactant was poured into water, the aqueous solution was extracted with ethyl acetate, the organic phase was collected, dried over anhydrous sodium sulfate, filtered, concentrated, separated and purified by dry loading column to obtain 63.5 mg tert-butyl 4-(5-(2,4 ,6-trimethylphenoxy)-2-nitroanilino)piperidine-1-carboxylate (3b). Yellow solid, yield: 99.22%.
[0078] Product spectral analysis data:
[0079] ESI-MS: m / z 456.5(M+1), 473.3(M+18), 478.4(M+23).C25H33N3O5[455.24].
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