化学学报 ›› 1955, Vol. 21 ›› Issue (3): 303-314. 上一篇    下一篇

论文

稠瑗化合物的研究Ⅱ.甲.γ-(6-甲氧基-2-羧基-1, 2, 3, 4-四氢化萘-1-)丁酸的拆开乙.d及1-1-羟基-2-甲基-2-甲氧羰基-7-甲氧基-1, 2, 3, 4, 9, 10, 11, 12, -八氢化菲-1-乙酸甲酯的合成

张锦   

  1. 北京石油学院
  • 投稿日期:1955-06-15 发布日期:2013-06-04

STUDIES ON FUSED RING SYSTEMS Ⅱ. A. REsOLUTION OF γ-(6-METHOXY-2-CARBOXY-1, 2, 3, 4-TETRAHY-DRO-l-NAPHTHYL)-BUTYRIC ACID INTOd-AND 1-ISOMERS. B. PREPARATION OF METHYL d-AND l-1-HYDROXY-2-METHYL-2. CARBOMETHOXY-7-METHOXYI-l, 2, 3, 4, 9, 10, 11, 12-OCTAHY-DRoPHE

CHANG CHIN   

  1. Peking Petroleum Institute
  • Received:1955-06-15 Published:2013-06-04

1.用Cr2O3精製過的乙酸爲溶劑,5% Pd-C爲催化劑,γ-(6-甲氧基-2-羧基-3,4-二氫化萘-1-)丁酸很容易還原爲γ(6-甲氧基-2-羧基-1,2,3,4-四氫化萘-1-)丁酸.由此反應,祇得到一個非對映體爲主要產品.將此非對映體在純甲醇溶液內與馬錢子鹼化合,得到兩部分溶解度不同的鹽.溶解度較小的鹽結晶析出.此部分爲l-γ-(6-甲氧基-2-羧基-1,2,3,4-四氫化萘-1-)丁酸-馬錢子鹼鹽.由此鹽得到 l-γ(6-甲氧基-2-羧基-1,2,3,4-四氫化萘-1-)丁酸.將溶劑除去後得到的剩餘物爲d-γ-(6-甲氧基-2-羧基-1,2,3,4-四氫化萘-1-)丁酸馬錢子鹼鹽.由此部分得到d-γ-(6-甲氧基-2-羧基-1,2,3,4-四氫化萘-1-)丁酸.2.由1-γ-(6-甲氧基-2-甲氧羰基-1,2,3,4-四氫化萘-1-)丁酸甲酯用Dieck-mann反應及甲基化後,得到d-1-酮-2-甲基-2-甲氧羰基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲的非對映體混合物.由d-γ-(6-甲氧基-2-甲氧羰基-1,2,3,4-四氫化萘-1-)丁酸甲酯用Dieckmann反應及甲基化後,得到1-1-酮-2-甲基-2-甲氧羰基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲的非對映體混合物.由每一組非對映體混合物,我們現在祇分離了在丙酮-石油醚混合溶劑中溶解度最小的那部分結晶體.3.由d-1-酮-2-甲基-2-甲氧羰基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲及溴代乙酸甲酯,用Reformatsky反應,得到d-1-羥基-2-甲基-2-甲氧羰基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲-1-乙酸甲酯.由l-1-酮-2-甲基-2-甲氧羰基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲及溴代乙酸甲酯,用Reformatsky反應,得到l-1-羥基-2-甲基-2-甲氧羰基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲-1-乙酸甲酯.

γ-(6-Methoxy-2-carboxy-3, 4-dihydro-l-naphthyl)-butyric acid was reduced in the presence of 5% Pd-C to the saturated acid, γ-(6-methoxy-2-carboxy-1, 2, 3, 4-tetrahydro-1-naphthyl)-butyric acid, by the method of Bachmann and co-workers.From this reaction only one of the two diastereoisomers was obtained as the principal product.This acid was resolved into its optical antipodes with brucine in anhydrous methanol.