NOVEL CYCLOADDITION PRODUCTS FROM THE REACTION OF ORO-1,1,1,6,6,6-HEXAFLUORO-3,4-DIAZAHEXA-2,4-DIENE WITH CYCLOALKENES, CYCLODIENES AND CYCLOHEPTATRIENE, AND OF HEXAFLUOROACETONE AZINE WITH CYCLOHEPTATRIENE

Thermal reaction (20-70-degrees-C) of the dichloroazine CF3CCl = N-N = CClCF3 (2) with cyclopentene (in CH2Cl2 Solvent), cycloheptene, inden e, acenaphthylene, 2,3-dihydrofuran, 2,3-dihydropyran, norbornadiene, cyclopentadiene and dicyclopentadiene gives as the major product in ea ch case the rearranged [3 + 2] cycloadduct (3) containing a CF3CCl2 gr oup; hydrolysis (CF3CCl2 --> CF3CO) to give the amide (4) takes place on attempted chromatographic purification on silica gel. With cyclopen tene the rearranged cyclopentadiene [3 + 2] cycloadduct (3b) is also f ormed, while other products obtained by chromatographic separation fro m the 2,3-dihydropyran reaction are the 5,6-dihydropyran-3-yl azine (5 ), the hydrazone CH2(CH2)2OCH = C-C(CF3) = NNH2 (8) and equimolar quan tities of 5,6-dihydropyran-3-yl trifluoromethyl ketone (6) and the chl orohydrazone O(CH2)4CHNHN = CClCF3 (7) possibly arising via hydrolysis of the 1:2 adduct (16). The reaction of azine 2 with cycloheptatriene at 70-degrees-C gives a complex mixture, in which the major products are the rearranged [3 + 6] cycloadduct (31) and the dehydrochlorinated [3 + 2] cycloadducts (10) and (11) containing a CF3CHCl group. The co rresponding reaction with hexafluoroacetone azine (1) at 70-degrees-C affords the criss-cross [3 + 2] cycloadduct (22), the bis-ene adduct ( 23) and its oxidation product, the azo compound (24), and the [3 + 6] cycloadduct diaziridine (25).