Some reactions of 1,2,3,4,7,7-hexafluorobicyclo[2,2,1]hepta-2,5-diene: Thermolysis and attack by methoxide ion and by bistrifluoromethyl nitroxide
作者:Ronald Eric Banks、Alan Prodgers
DOI:10.1016/s0022-1139(00)80921-5
日期:1984.10
7-hexafluoro-5-methoxybicyclo [2,2,1]hept-2-ene thought, on the basis of 19F nmr data, to be the 6-endo-F,5-exo-MeO isomer. Radical attack on 1,2,3,- 4,7,7-hexafluorobicyclo[2,2,1]hepta-2,5-diene by bistrifluoromethyl nitroxide took place at both olefinic sites, with a ca. 10:1 preference for the CFCF linkage; all three geometrical isomers of 5,6-bis(bistrifluoromethylamino-oxy)-1,4,5,6,7,7- hexafluorobicyclo[2
1,2,3,4,7,7-六氟双环[2,2,1]庚-2,5-二烯在加热至450°C时以至少73%的收率得到1,2,3,4-四氟苯。密封管;CF 2桥部分以八氟环丁烷的形式出现。甲醇钠-甲醇对二烯的亲核攻击仅发生在CFCF键上,导致形成1,2,4,7,7-五氟-3-甲氧基双环-[2,2,1] hepta-2,在19的基础上,以5-二烯和1,4,5,6,7,7-六氟-5-甲氧基双环[2,2,1]庚-2-烯为基础F nmr数据,为6-endo-F,5-exo-MeO异构体。双三氟甲基硝基氧对1,2,3,4,7,7-六氟双环[2,2,1]庚-2,5-二烯的自由基攻击发生在两个烯烃位点,CF 3的优先级为10:1 CF联动;形成了5,6-双(双三氟甲基氨基-氧基)-1,4,5,6,7,7-六氟双环[2,2,1]庚-2-烯的所有三个几何异构体。