Unsaturated nitrogen compounds containing fluorine. Part 20. Reactions of 2,5-dichloro-1,1,1,6,6,6-hexafluoro-3,4-diazahexa-2,4-diene and hexafluoroacetone azine with cycloheptatriene

Abstract

Thermal reaction (70 °C) of the dichloroazine CF 3CCl=NN=CClCF 3, 1, with cycloheptatriene ( 7) gave a complex mixture from which the major products were separated and identified as the dehydrochlorinated rearranged [32] cycloadducts 9 (28%) and 10 (23%) containing a CF 3CHClN= group, a rearranged 1:1 adduct ( 12 or 13) (4%) and the amide 14 (18%) formed by hydrolysis on silica gel of the rearranged [36] cycloadduct 31 containing a CF 3CCl 2N= group. At 100 °C in solvent CH 2Cl 2, the isolated products were the isomers 9 (4%), 10 (4%) and 11 (5.5%), amide 14 (1%) and the reduced compounds 15 (6%) and 16 (19%) containing a CF 3CH 2N group. Reaction between hexafluoroacetone azine (CF 3) 2C=NN=C(CF 3) 2 ( 5) and 7 at 70 °C was much cleaner and gave the bis[32] criss-cross cycloadduct 18 (15%), the bis-ene adduct 20 (17%) and the azo compound 19 (21%) together with the imine 17 (20%) formed from the oxidation of 20 by azine 5 and the [36] cycloadduct, the diaziridine 21 (7%).