2-(2,2-diaryl vinyl) cyclamine derivative and preparation method thereof
A technology of diarylethene and its derivatives, which is applied in the fields of active ingredients of heterocyclic compounds, drug combinations, and pharmaceutical formulations, etc.
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Embodiment 1
[0123] Synthesis of 2-[(E)-2-(2-hydroxy-phenyl)-2-phenylethenyl]-N-methylpiperidine (I-1)
[0124]
[0125] 1.1 Synthesis of (2-methoxymethoxy-phenyl)(phenyl)-methanone
[0126] Dissolve (2-hydroxy-phenyl)(phenyl)-methanone (1.98g, 10mmol) in dichloromethane (50ml), add diisopropylethylamine (30mmol), stir at room temperature, add methyl chloride methyl ether (20 mmol). Heated to reflux for 12 hours, monitored by TLC, after the reaction was completed. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and purified by silica column chromatography to obtain 2.2 g of a brown oily product of (2-methoxymethoxy-phenyl) (phenyl)-methanone (yield 91 %). 1 H NMR (400MHz, CDCl 3 ), δ: 7.84-7.82(m, 2H), 7.58-7.54(m, 1H), 7.47-7.42(m, 3H), 7.37(q, J=12.0Hz, 1H), 7.21(d, J=8.0 Hz, 1H), 7.12-7.09(m, 1H), 5.05(s, 2H), 3.29(s, 3H).
[0127] 1.2 Synthesis of 3-(2-methoxymethoxy-phenyl)-3-(phenyl)-methyl acrylate
[0128] At room tempera...
Embodiment 2
[0140] Synthesis of 2-[2,2-bis(2-hydroxy-phenyl)-vinyl]-N-methylpiperidine (I-2)
[0141]
[0142] 2.1 Synthesis of bis(2-methoxymethoxy-phenyl)-methanone
[0143] According to the steps described in 1.1 in Example 1, using bis(2-hydroxyl-phenyl)-methanone as raw material, and the consumption of DIEA and chloromethyl methyl ether is doubled, bis(2-methoxymethoxy A brown oily product of phenyl-phenyl)-methanone in 92% yield. 1 H NMR (400MHz, CDCl 3 ), δ: 7.54-7.52 (m, 2H), 7.43-7.39 (m, 2H), 7.12-7.04 (m, 4H), 4.98 (s, 4H), 3.26 (s, 6H).
[0144] 2.2 Synthesis of 3,3-bis(2-methoxymethoxy-phenyl)-methyl acrylate
[0145] According to the steps described in 1.2 in Example 1, using bis(2-methoxymethoxy-phenyl)-methanone as raw material, 3,3-bis(2-methoxymethoxy-phenyl)- Brown oily product of methyl acrylate, 81% yield. 1 H NMR (400MHz, CDCl 3 ), δ: 7.29-7.22(m,2H),7.15(d,J=8.0Hz,1H),7.11-7.04(m,3H),6.98-6.92(m,2H),6.36(s,1H), 5.05(s,2H), 4.99(s,2H), 3.60(s,3H), 3.28(s,3H...
Embodiment 3
[0157] 2-[(E)-2-(2-Hydroxy-5-methyl-phenyl)-2-phenylvinyl]-N-methylpiperidine (I-3, and its chiral monomer I- 3-1 and I-3-2) synthesis:
[0158]
[0159] 3.1 Synthesis of (2-hydroxy-5-methyl-phenyl)(phenyl)-methanone
[0160] Weigh p-cresol (2.16g, 20mmol) and anhydrous AlCl 3 (3.2g, 24mmol), put into a 250ml round bottom flask and heat to 120°C. After 20 minutes, add benzoyl chloride (3.37g, 24mmol) in batches as a raw material, control the temperature at 100-140°C and stir the reaction, monitor by TLC. After the reaction is completed, pour 50ml of ice water into the bottle, and then add 10ml of concentrated hydrochloric acid . The suspension was stirred for 10 minutes, extracted with dichloromethane (3x50ml), the organic phases were combined, dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and purified by silica column chromatography to obtain a yellow solid product (2-hydroxyl-5 -Methyl-phenyl)(phenyl)-methanone 3.4 g (80% yield). (Reference...
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