During the irradiation of 1-acetylnaphthaline in the presence of c,d-substituted olefines with a cyclic amine as a donor different products were generated. The reaction pathways were monitored by NMR-spectroscopy and it was proved that the main products were generated by a Photo-Diels-Alder-reaction. The c,d-olefines are added head-to-tail with the donor substituent in endo-position to the remaining aromatic system. Their structures could unambiguously be proven by single crystal x-ray structure analysis. Furthermore their thermal and photochemical properties were investigated: the activation enthalpies and activation entropies for their thermal decompositions were investigated and during their irradiation in solution with light of 254 nm a Di-p-methane-rearrangement could be observed.