【摘要】 通过萜品油烯和 2 ,6 二氧代戊酸甲酯的deMayo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 ;以对甲苯磺酸为催化剂的环合 ,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 ,1HNMR ,13 CNMR及元素分析予以确定 .更多还原

【Abstract】 The photocyclo-adducts 3～6, 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 13C NMR and elemental analysis.更多还原