作者:Aryeh A. Frimer、Michal Afri、Simeon D. Baumel、Pessia Gilinsky-Sharon、Zilpa Rosenthal、Hugo E. Gottlieb
DOI:10.1021/jo991803b
日期:2000.3.1
enones are the oxygenation products. The oxygenation was slowed by radical inhibitors, but not by (1)O(2) quenchers; nor were any oxidation products observed when these cyclopropenes were reacted with triphenylphosphine ozonide, a chemical (1)O(2) source. The data indicates that a photosensitizer-initiated free radical autoxidative process is involved. Likely intermediates in this oxygenation are epoxide
通过各种合成路线制备双环环丙烯14a,14b和26。聚合物玫瑰孟加拉(p-RB)CDCl(3)中的双环辛烯14a,b的光敏氧合作用缓慢(8小时中可变的O(2)吸收约0.35-0.75当量),并伴有敏化剂漂白作用。14a和14b的复杂产物混合物的制备型气相色谱法同时生成二烯(Z-和E-29、30和31)和烯酮(E-和Z-12、32、34)。相比之下,双环壬烯26在CDCl(3)中的p-RB光敏氧化进行得更快一些(O(2)在2.5小时内吸收约1当量),仅在GC分离时产生烯酮(20,42-45)。在14的情况下观察到的二烯产物是由剩余的未反应的环丙烯热解而产生的,而烯酮是氧化产物。自由基抑制剂可减缓氧合作用,但(1)O(2)淬灭剂则不会减慢;这些环丙烯与三苯基膦恶臭化物(一种化学(1)O(2)来源)反应时,也未观察到任何氧化产物。数据表明涉及光敏剂引发的自由基自氧化过程。对于双环辛烯(14)和双