Claridge, Robert Peter; (1993) The reaction of nitrogen dioxide with conjugated and non conjugated alkenes. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

The reactions between nitrogen dioxide and 2,5-dimethyl-2,4-hexadiene, 2,4-hexadiene and 2,3-dimethyl-1,3-butadiene were investigated in various organic solvents. The major products isolated were where the nitrogen dioxide had added at each end of the conjugated system i.e. 2,5-dimethyl-2,5-dinitro-3-hexene (78%), 2,5-dinitro-3-hexene (56%) and 2,3-dimethyl-1,4-dinitro-3-butene (68%). X-ray crystal structures were obtained for 2,5-dimethyl-2,5-dinitro-3-hexene and 2,3-dimethyl-1,4-dinitro-3-butene. t-2,3-Dimethyl-1,4-dinitro-3-butene was found to isomerise to c-2,3-dimethyl-1,4-dinitro-3-butene when a catalytic excess of nitrogen dioxide was present. c,t,t-1,5,9-Cyclododecatriene reacted with nitrogen dioxide to form the 1,2-dinitro-t,t,-5,9-cyclododecadiene (35%) and 5,6-dinitro-c,t,-1,9- cyclododecadiene (32%) predominantly. Tetranitrocyclododecene (10%) was also isolated. 1,6-Heptadiene reacted with nitrogen dioxide to form the straight chain adducts 1,2-dinitro-6-heptene (51%) and 2-hydroxy-1-nitro-6-heptene (37%) predominantly. Cis and trans 1,2-(nitromethyl)-cyclopentane (19%) were isolated when slow addition times (6h or longer) of nitrogen dioxide were employed. Allyl ether reacted with nitrogen dioxide to form cis and trans 2,3-(nitromethyl)-tetrahydrofuran (59%) and traces of the straight chain adducts 1,2-dinitropropyl-3,3'-oxy-1'-propene and 2-hydroxy-1-nitropropyl-3,3'-oxy-1 propene. This reaction was also investigated using 15N labelled nitrogen dioxide and the reaction studied using 15N.m.r. spectroscopy. Chemically induced dynamic nuclear polarisation (C.I.D.N.P.) effects were observed in the spectra for the formation of both the tetrahydrofuran, and the straight chain adducts. The C.I.D.N.P. effects were consistent with the attack of two separate nitrogen dioxide radicals.

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