The preparation of 7,8-epoxy-2,3,5,6-tetrakis(methylene)bicyclo[2,2,2] octane (5) is described. Evidence for transannular interaction between the homoconjugated s-cis-butadiene functions in 5 is found in the UV absorption spectrum. The Diels-Alder addition of 5 to tetracyanoethylene (TCE) is syn-regioselective and leads to the monoaducts 16:17 (85:15). The dienes 16,17 are less reactive than 5 toward TCE. anti-regioselectivity (leading to exo-2, endo-3-bis(chloromethyl)-5,6-bis(methylene)-syn-7,8-epoxybicyclo[2.2.2]octaves (25) is observed in the double elimination of HCl from the syn-7,8-epoxy-exo-2,endo-3,exo-5,endo-6-tetrakis(chloromethyl)bicyclo[2.2.2]octane (11), precursor of 5. The structures of the regioisomers 16,17 were confirmed spectroscopically and chemically. Elimination of HCl from the chloromethyl groups in 26 (TCE adduct of 25) and HCN from the TCE adducts 16, 17 and 26 can be induced by CsF in DMF.

中文翻译：

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7,8-环氧-2,3,5,6-四（亚甲基）双环[2.2.2]辛烷；合成与狄尔斯-阿尔德反应性

描述了7,8-环氧-2,3,5,6-四（亚甲基）双环[2,2,2]辛烷（5）的制备。在紫外线吸收光谱中发现了5中的同构共轭s-顺式-丁二烯官能团之间的跨环相互作用的证据。在四氰基乙烯（TCE）中，狄尔斯-阿尔德（Diels-Alder）加成5是顺-区域选择性的，并导致单加合物16:17（85:15）。二烯16，17对TCE的反应性小于5。抗-regioselectivity（导致外-2，内-3-二（氯甲基）-5,6-双（亚甲基） -顺式-7,8- epoxybicyclo [2.2.2]八度（25）在HCl的双重消除观察从顺-7,8-环氧外型-2，内切-3，外-5，内切-6-四（氯甲基）二环[2.2.2]辛烷（11） ，5的前身。区域异构体16，17的结构在光谱和化学上得到确认。在DMF中，CsF可以诱导从26个氯甲基中的HCl （25的TCE加合物）和TCE加合物16、17和26中的HCN消除。