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有机化学
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有机化学 ›› 2003, Vol. 23 ›› Issue (10): 1120-1124. 上一篇    下一篇

研究论文

萜品油烯的DeMayo光环加成产物的反应研究

王进军;殷军港;邬旭然;赵岩;森章;初井敏一;竹下齐   

  1. 烟台大学应用化学系;九州大学机能物质研究所
  • 发布日期:2003-10-25

Study on Reaction of the de Mayo Photocycloaddition Products of Terpinolene

Wang Jinjun;Yin Jungang;Wu Xuran;Zhao Yan;Mori Akira;Hatsui Toshihide;Takeshita Hitoshi   

  1. Department of Applied Chemistry, Yantai University;Institute of Advanced Material Study, Kyushu University
  • Published:2003-10-25

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通过萜品油烯和2，6-二氧代戊酸甲酯的de Mayo反应，使[2 + 2]环加成产物 3-6经retro-aldol重排，开环生成取代环己烯7和12。在不同反应介质中对开环产 物进行再环合，并对其反应机理进行研究。在碱性条件下，经分子内Claisen缩合 反应形成螺环化合物；以对甲本碘酸为催化剂的环合，除生成正常的Claisen缩合 产物以外，7和12均发生烯键亲核加成反应，生成具有二环[3.3.1]结构的桥环化合 物9-11和二环[3.2.1]结构的桥环化合物16-18。所得新化合物的化学结构均经IR, ~1H NMR，~(13)C NMR及元素分析予以确定。

关键词: 环加成反应;缩合反应;亲核反应;螺环化合物;红外分光光度法, 质子磁共振谱法;碳13磁共振谱法

The photocyclo-adducts 36, obtained by photocycloaddition of terpinolene with methyl 2, 3-dioxo-pentanoate, was subjected to retro- aldol rearrangement to give the substituted-cyclohexene 7 and 12. In acidic or basic condition the recyclization of the open-ring products was carried out. In different reaction media the spirocyclic compounds were obtained by intramolecular Claisen condensation. Using TsOH as a catalyst for cyclization the nucleophilic ene-addition of 7 and 12 generated bicyclo [3.3.1] nonene 9～11 and bicyclo [3.2.1] octane 16～ 18 besides forming spirocyclic compounds. The reaction mechanisms were discussed and the structures of all compounds were assigned based on the data from IR, ~1H NMR and ~(13)C NMR and elemental analysis.

Key words: CYCLOADDITION REACTION;CONDENSATION REACTION;NUCLEOPHILIC REACTION, SPIRO COMPOUNDS;IR;1HNMR;C13NMR

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