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本文报导了莲心碱(Ⅰ)全合成的研究。 (1)合成了1-(3′-溴-4′-苄氧基)苄基-2-甲基-6,7-二甲氧基-1,2,3,4-四氢异喹啉(Ⅷ)和1-(4′-苄氧基)苄基-2-甲基-6-甲氧基7-羟基-1,2,3,4-四氢异喹啉(XV).(2)1-(3′-溴-4′-苄氧基)苄基-6,7-二甲氧基-1,2,3,4-四氢异喹啉(Ⅵ)和1-(4′-苄氧基)苄基-6-甲氧基-7-乙酰氧基-1,2,3,4-四氢异喹啉(ⅩⅢ)借d-和1-DPT-酒石酸各自拆分为其对映体。D-(-)-Ⅵ和L-(+)-Ⅵ以甲酸和甲醛甲基化分别生成D-(-)-Ⅷ和L-(+)-Ⅷ。D-(+)-;ⅩⅢ和L-(-)-ⅩⅢ经N-甲基化后再进行水解卽得D-(-)-ⅩⅤ和L-(+)+ⅩⅤ。(3)D-(-)-Ⅷ和D-(-)-ⅩⅤ在吡啶中有铜粉和碳酸钾存在下进行Ullmann反应,反应物经氧化鋁柱层析可分得一油状物,此油状物经盐酸水解得黄色无定形固体,后者与过氯酸生成过氯酸盐结晶,其理化性质均与天然莲心碱过氯酸盐相同。(±)-Ⅷ和(±)-ⅩⅤ在相似的条件下缩合则生成(±)-莲心碱。
This article reports the study on the total synthesis of liensin (I). (1) Synthesis of 1- (3’-bromo-4’-benzyloxy) benzyl-2-methyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (XV) (2) (2) Preparation of (2) (2) Synthesis of 1- (3’-bromo-4’-benzyloxy) benzyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (VI) and 1- -benzyloxy) benzyl-6-methoxy-7-acetoxy-1,2,3,4-tetrahydroisoquinoline (XIII) was separately resolved by d- and 1-DPT-tartaric acid into Enantiomer. D - (-) - Ⅵ and L - (+) - Ⅵ methylated with formic acid and formaldehyde to form D - (-) - Ⅷ and L - (+) - Ⅷ, respectively. D - (+) -; XIII and L - (-) - XIII are hydrolyzed after N-methylation to give D - (-) - XV and L - (+) + XV. (3) D - (-) - Ⅷ and D - (-) - Ⅹ Ⅴ Ullmann reaction was carried out in the presence of copper powder and potassium carbonate in pyridine. The reaction was separated by alumina column chromatography to obtain an oil. The material was hydrolyzed by hydrochloric acid to give a yellow amorphous solid, which formed perchlorate crystals with perchloric acid and had the same physical and chemical properties as the natural perphenacic acid perchlorate. (±) - ndine and (±) - XV are condensed under similar conditions.