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Thermische, nichtkatalysierte Cycloadditionen der Acrylverbindungen an Cycloheptatrien
Author(s) -
Belluš D.,
Helferich G.,
Weis C. D.
Publication year - 1971
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19710540205
Subject(s) - cycloheptatriene , chemistry , acrylonitrile , cycloaddition , methyl acrylate , intramolecular force , adduct , yield (engineering) , bicyclic molecule , medicinal chemistry , diene , stereochemistry , organic chemistry , copolymer , catalysis , polymer , materials science , natural rubber , metallurgy
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 bicyclo[4,2,1]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.