Ayub Khurshid, Mitchell Reginald H
Department of Chemistry, University of Victoria , P.O. Box 3065, Victoria, BC, Canada V8W 3V6.
J Org Chem. 2014 Jan 17;79(2):664-78. doi: 10.1021/jo4024446. Epub 2014 Jan 6.
Synthesis of a variety of 8,16-disubstituted-anti-[2.2]metacyclophanedienes (CPD) with alkenyl and alkynyl internal (8,16) groups is described together with their analogous dihydropyrenes (DHP). Eyring and Arrhenius parameters were determined for the thermal closing reaction, CPD to DHP, and half-lives at 20 °C were found to range from 11 days (X = CHO) to 36 years (X = CN), with alkenyl functions being from 56 days to 10 years. The visible light opening reaction, DHP to CPD, showed relative rates of 1 (X = CN) to 240 (X = CH═CMe2).
描述了多种带有烯基和炔基内（8,16）基团的8,16-二取代-反式-[2.2]间环芳二烯（CPD）及其类似的二氢芘（DHP）的合成。测定了CPD到DHP热闭环反应的艾林和阿累尼乌斯参数，发现20℃下的半衰期范围为11天（X = CHO）至36年（X = CN），烯基官能团的半衰期为56天至10年。DHP到CPD的可见光开环反应显示相对速率为1（X = CN）至240（X = CH═CMe2）。
