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A Synthetic and Structural Study of 17,18‐Dicyano[3 2 ](1,6)cyclooctatetraen(1,4)cyclophane Generated by Photolysis of [3 2 ](1,4)Barrelenophane
Author(s) -
MatsudaSentou Wakana,
Shinmyozu Teruo
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200009)2000:18<3195::aid-ejoc3195>3.0.co;2-1
Subject(s) - chemistry , cycloaddition , ampoule , toluene , photodissociation , adduct , yield (engineering) , photochemistry , high pressure , irradiation , cyclophane , quantum yield , crystal structure , organic chemistry , catalysis , fluorescence , materials science , physics , engineering physics , quantum mechanics , nuclear physics , engineering , metallurgy
[3 2 ]Cyclooctatetraenophane (6) has been generated by photolysis of [3 2 ](1,4)barrelenophane (5) , which, in turn, has been found to be most conveniently obtained by the uncatalyzed cycloaddition of dicyanoacetylene to [3 2 ](1,4)cyclophane (4) at 150 °C in a sealed ampoule. Under high‐pressure conditions, the reaction furnished 5 in lower yield, along with trace amounts of the naphthalenophane 11 or the novel 1:2 adduct 12 depending on the pressure. Photoirradiation of 5 in CH 3 CN led to the formation of 6 , while irradiation in toluene afforded the semibullvalenophane 13 as the major product along with some 6 . Interestingly, irradiation of 13 with a high‐pressure Hg lamp in toluene led to the formation of an alternative semibullvalenophane 14 . The crystal structures of the new products 5 , 6 , 11 , 12 , and 13 are described.