Polyfluoro-compounds based on the cycloheptane ring system. Part 6. Bicyclic compounds derived from nonafluorocyclohepta-1, 3-dienes and from octafluorocyclohepta-1, 3, 5-triene
作者:David J. Dodsworth、Charles M. Jenkins、Robert Stephens、John Colin Tatlow
DOI:10.1016/s0022-1139(00)83171-1
日期:1984.4
5-dimethoxy-compound. A Diels-Alder reaction between ethylene and 1H-nonafluorocyclohepta-1, 3- diene afforded 1H,8H,8H,9H,9H-nonafluoro-bicyclo(3,2,2)non-6-ene. Cobalt (III) fluoride at 300°C converted this principally to 1H-pentadecafluoro- bicyclo(3,2,2)nonane. The bridgehead hydrogen of this was exchanged for deuterium using deuterium oxide alone or containing potassium hydroxide. However, dehydrofluorination
1H-,2H-和5H-九氟-和1H,4H-八氟-环庚1,3二烯通过形成交叉环键提供了相应的H-取代的多氟双环(3,2,0)-庚6-烯。在位置1和位置4之间。八氟环庚-1、3、5-三烯类似地得到八氟双环-(3,2,0)七-2,6-二烯。通过在100°C下通过氟化钴(III),1H-双环-6-烯生成1H-十一碳双环(3,2,0)庚烷,然后生成相应的碳氟化合物。1H-双环烷的桥头氢足够酸性,可以单独或含有一些氢氧化钾的氘与氧化氘交换氘,但长时间暴露于钾水溶液中则得到十氟双环(3,2,0)庚-1(5)-烯。丙酮中的高锰酸钾将其氧化,得到十氟-1,5-二羟基-8-氧杂双环(3,2,1)辛烷(水合),将其通过重氮甲烷甲基化为相应的1,5-二甲氧基化合物。乙烯与1H-九氟环庚-1-1,3-二烯之间的Diels-Alder反应得到1H,8H,8H,9H,9H-九氟双环(3,2,2)非6-烯。氟化钴(III