Decomposition of perfluoro-(2,4,4,7,7,9-hexamethyl-3,8-dioxa-2,5,6,9-tetraazadec-5-ene) in the presence of fluoroalkenes, ethyne, benzene and nitroso compounds

Article abstract of DOI:10.1016/S0022-1139(00)80120-7

Thermolysis of the azo compound (CF3)2NOC(CF3)2N=NC(CF3)2ON(CF3)2 (1) alone at 140 deg C gives nitrogen, hexafluoroacetone and the hydrazine (CF3)2NN(CF3)2 via (CF3)2N<*> radical coupling in quantitative yield, while from decomposition in the presence of the alkenes CF2=CF2, CF2=CFCl and CF2=CHF (ca. 1:1 molar ratio) the major products are the dimer <(CF3)2NCF2CCl2>2, trimer (CF3)2N(CF2CFCl)2CFClCF2N(CF3)2 and a mixture of tetramers (CF3)2N(C2HF3)4N(CF3)2, respectively.The (CF3)2N<*> radicals generated from 1 can also be trapped with bromine < -> (CF3)2NBr> and nitroso compounds < -> (CF3)2NNRO<*> (R=CF3 and Ph)>, but with ethyne or benzene near-quantitative yields of the amine (CF3)2NH are obtained.