Thermische,nichtkatalysierte Cycloadditionen der Acrylverbindungen an Cycloheptatrien

The cycloaddition reactions of cycloheptatriene with acrylonitrile and methyl acrylate have been investigated in some detail. The exo ( 1 ) and endo ( 2 ) adducts resulting from the 2+2+2]-cycloaddition of acrylic components to the 2,5-positions of cycloheptatriene have been separated and the structures have been elucidated by NMR. The by-products are 7-endo-substitued derivatives of bicyclo4,2,1]nona-2,4-diene ( 3 ), resulting from the formal 6+2]-cycloaddition to the 1,6-positions of cycloheptatriene. The mechanism of their formation is discussed. Irradiation (λ = 253,7 nm) of 3 in various solvents gave an almost quantitativ yield of 2+2]-cyclodimers of the 14 type. No intramolecular photocyclization of 3 to cyclobutenes 13a and/or 13b was observed.