331676-39-2Relevant academic research and scientific papers
Photorearrangement of vinylidenecyclopropanes to 1,2,3-butatriene derivatives
Mizuno, Kazuhiko,Maeda, Hajime,Sugita, Hikaru,Nishioka, Shogo,Hirai, Takayoshi,Sugimoto, Akira
, p. 581 - 584 (2007/10/03)
(Matrix presented) Photoirradiation of benzene solutions containing 1-diarylvinylidene-2,2,3,3-tetramethylcyclopropanes (2a-d) afforded rearranged products 1,2,3-butatrienes (3a-d) in good to high yields. Photorearrangement from 2,2,3-trimethyl and 2,2- and 2,3-dimethyl derivatives 2e-g also proceeded but the rates of the rearrangement were lower than those of 2a-d. A singlet mechanism is proposed for this photorearrangement, where alky migration occurs from 1,3-biradical intermediates generated via the homolysis of the C1-C2 bond. Generate of diarylvinylidene carbenes from 1,3-biradicals might be competitive with the formation of 3.
