Expanded radialenes with bicyclo[4.3.1]decatriene units:: New precursors to cyclo[n]carbons

被引:56
作者
Tobe, Y [1 ]
Umeda, R
Iwasa, N
Sonoda, M
机构
[1] Osaka Univ, Fac Engn Sci, Dept Chem, Osaka 5608531, Japan
[2] Japan Sci & Technol Corp, CREST, Osaka, Japan
关键词
alkynes; carbenes; cyclo[n]carbons cycloreversion; radialenes;
D O I
10.1002/chem.200305051
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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, mono-cyclic forms of carbon clusters. The spectroscopic properties of the expanded radialenes were investigated in connection with cross conjugation of the core pi system and with its perturbation by the extraannular bicyclic pi 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.
引用
收藏
页码:5549 / 5559
页数:11
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