134816-76-5Relevant academic research and scientific papers
Vinylidene to alkyne rearrangement to form polyynes: Synthesis and photolysis of dialkynylmethylenebicyclo[4.3.1]deca-1,3,5-triene derivatives
Tobe, Yoshito,Iwasa, Naruhito,Umeda, Rui,Sonoda, Motohiro
, p. 5485 - 5488 (2001)
Dialkynylmethylenebicyclo[4.3.1]deca-1,3,5-triene derivatives were synthesized as precursors to generate dialkynylvinylidenes by extrusion of an aromatic fragment, indane. Photolysis of the trienes gave linear polyynes as the major products produced by rearrangement of the vinylidenes, together with the isomerization products having a methylenecycloheptatriene moiety.
Expanded Radialenes with Bicyclo[4.3.1]decatriene Units: New Precursors to Cyclo[n]carbons
Tobe, Yoshito,Umeda, Rui,Iwasa, Naruhito,Sonoda, Motohiro
, p. 5549 - 5559 (2003)
A new method for the formation of conjugated polyynes has been developed based on both the rearrangement of vinylidenes to alkynes and the [2+1] cheletropic fragmentation of dialkynylmethylenebicyclo-[4.3.1]deca-1,3,5-triene derivatives. A model study of the photolysis of simple dialkynylmethylenebicyclo[4.3.1]deca-1,3,5-trienes resulted in cheletropic fragmentation followed by 1,2-migration to give the corresponding linear polyynes, although undesired isomerization to methylenebicyclo[5.3.0]triene derivatives took place concurrently. Expanded [3]-, [4]-, [5]-, and [6] radialene derivatives with exocyclic bicyclo[4.3.1]decatriene units were prepared by oxidative coupling of the monomeric units as precursors to the corresponding cyclo[n]carbons, monocyclic forms of carbon clusters. The spectroscopic properties of the expanded radialenes were investigated in connection with cross conjugation of the core π system and with its perturbation by the extraannular bicyclic π system. In negative-mode laser-desorption time-of-flight (LD-TOF) mass spectra, the expanded radialenes exhibited peaks due to the corresponding cyclo[n]carbon anions (n = 18, 24, 30, and 36) formed by the stepwise loss of the aromatic indane fragments.
Photochemical Method for Generation of Linear Polyynes: Cycloreversion of Propellatrienes Extruding Indan
Tobe, Yoshito,Fujii, Toshihiko,Naemura, Koichiro
, p. 1236 - 1237 (2007/10/02)
Photolysis of trienediynes 1a and 1b and trienetetrayne 1c having a propellane framework yielded the respective linear polyynes 2a-c in good efficiency through cycloreversion, extruding indan (3).
