Morphinan derivatives the quaternary ammonium salts thereof substituted in position 14, method for production and use thereof
A compound, C1-C6 technology, applied in the field of morphinan derivatives and their 14-substituted quaternary ammonium salts, preparation and their use, can solve the problems of weak effects
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Embodiment 1
[0170] Synthesis of 17-allyl-4,5α-epoxy-3-methoxy-14β-(3-phenylpropyloxy)morphinan-6-one hydrochloride (compound 1·HCl)
[0171]
[0172] Under stirring, N 2 Protection, 0°C (bath temperature), NaH (0.97g, 40.4mmol) (obtained from 1.62g of 60% NaH oil dispersion washed with petroleum ether) was added to 14-hydroxycodeinone (Iijima et al.J .Med.Chem.1978,21,pg.398) (3.00g, 9.6mmol) in 100ml of anhydrous N,N-dimethylformamide solution, after 20 minutes, add cinnamyl bromide (2.28g, 11.6mmol ), the mixture was stirred at 0° C. (bath temperature) for an additional 30 minutes and for a further 4.5 hours with cooling removed. Ice cubes were added to terminate the reaction until no more hydrogen gas was evolved, finally bringing the water volume to 100 ml. The precipitated product was extracted with dichloromethane (3×100ml), the organic phases were combined, washed with 250ml of saturated sodium chloride, and dried over anhydrous sodium sulfate. The solvent was removed under r...
Embodiment 2
[0177] Synthesis of 17-cyclobutylmethyl-4,5α-epoxy-3-methoxy-14β-(3-phenylpropoxy)morphinan-6-one hydrochloride (compound 2·HCl)
[0178]
[0179] Compound 2
[0180] 4,5α-epoxy-3-methoxy-14β-(3-phenylpropoxy)morphinan-6-one hydrochloride (500mg, 1.19mmol), potassium carbonate (1.00g, 7.24mmol) and Cyclobutylmethyl bromide (0.6ml, 5.43mmol) was dissolved in anhydrous N,N-dimethylformamide (7ml), and stirred at 80°C (bath temperature) for 24 hours under the protection of nitrogen in the absence of moisture, and the inorganic residue, and washed three times with dichloromethane, each 20ml. The filtrate was evaporated under reduced pressure, the oily residue was dissolved in 100ml of dichloromethane, washed with water (3×100ml) and saturated sodium chloride (4×100ml), dried over anhydrous sodium sulfate, the solvent was evaporated, and the residue (520mg brown oil) was purified by column chromatography (silica gel: CH 2 Cl 2 / MeOH / conc.NH 4 OH=250:2:0.5), the oily distill...
Embodiment 3
[0182] Synthesis of 17-cyclopropylmethyl-4,5α-epoxy-3-methoxy-14β-(3-phenylpropoxy)morphinan-6-one hydrochloride (compound 3·HCl)
[0183]
[0184] Compound 3
[0185] 4,5α-epoxy-3-methoxy-14β-(3-phenylpropoxy)morphinan-6-one hydrochloride (1.5g, 3.57mmol), potassium carbonate (3.00g, 21.7mmol) and cyclopropylmethyl bromide (1.0ml, 6.62mmol) in anhydrous N,N-dimethylformamide (10ml), in the absence of moisture, under the protection of nitrogen, stirred at 80°C (bath temperature) for 4 hours, The inorganic residue was filtered off and washed three times with 10 mL of dichloromethane. The filtrate was evaporated under reduced pressure, the oily residue was dissolved in 50ml of dichloromethane, washed with water (3×50ml) and saturated sodium chloride (4×50ml), dried over anhydrous sodium sulfate, the solvent was evaporated, and the residue (1.42g yellow oil) was purified by column chromatography (silica gel: CH 2 Cl 2 / MeOH / conc.NH 4 OH=250:2:0.5), the oily distillation r...
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