Novel cycloadducts from the reactions of 2,5-dichloro-1,1,1,6,6,6-hexafluoro-3,4-diazahexa-2,4-diene, hexafluoroacetone azine and the azomethine imide, 2-hexafluoroisopropylidene-3-methyl-3-phenyl-5,5-bis(trifiuoromethyl)-tetrahydropyrazol-2-ium-1-ide with quadricyclane

Abstract

Reaction of quadricyclane with the azine CF3CClNNCClCF31 in dichloromethane at 70 °C gives a mixture of two 1 : 1 adducts, the [σ2s+σ2s+π2s] cycloadduct 9a, and an unexpected and hitherto unreported product, the 1,3-dipolar cycloadduct 10, in the ratio 70 : 19 (i) an analogous reaction with the azine (CF3)2CNNC(CF3)25 at 70 °C affords the corresponding [2 + 2 + 2] cycloadduct 9b, which reacts further to some extent with quadricyclane to give the 2 : 1 adduct 11 and (ii) with azine 5 to afford the intermediate azomethine imide 17 and hence the 2 : 2 adduct 12.