Oxymetallation. Part 13. Synthesis of bicyclic peroxides via peroxymercuriation of cyclic dienes
作者:A. J. Bloodworth、Jamil A. Khan、M. E. Loveitt
DOI:10.1039/p19810000621
日期:——
2]decane has been prepared by peroxymercuriation of cis,cis-cyclo-octa-1,5-diene, but substantial amounts of bicyclic ethers are also formed in the reaction. The bicyclic peroxides (4) and (5) have been obtained from (12) by reduction and brominolysis respectively. 8,9-Dioxabicyclo[5.2.1]decane (6) and the dibromo-derivative (7) have similarly been prepared by peroxymercuriation and demercuriation of cyclo-octa-1
9,10-二氧杂双环[3.3.2]癸烷的双巯基衍生物(12)是通过顺式,顺式的过氧汞化反应制得的。-环-八--1,5-二烯,但在反应中也形成了大量的双环醚。双环过氧化物(4)和(5)分别通过还原和溴分解作用从(12)获得。类似地,通过环辛-1,4-二烯的过氧汞化和脱汞制备了8,9-二氧杂双环[5.2.1]癸烷(6)和二溴衍生物(7)。建议过氧化物的异构体纯度和同时形成的双环醚均来自平衡控制可逆(全)氧化汞-脱(全)氧化汞。通过环己-1,4-二烯的过氧汞化和溴解反应,已获得[3.2.1]-过氧化物(8)的低收率,但尝试由5,5-二取代的环戊二烯制备[2.2.1]-化合物的方法有失败了。