Atkinson 1 Acetylenes

Titanium dioxide suspended in an aqueous solution and irradiated with UV light X = 365 nm) converted benzene to carbon dioxide at a significant rate (Matthews, 1986). Irradiation of benzene in an aqueous solution yields mucondialdehyde. Photolysis of benzene vapor at 1849-2000 A yields ethylene, hydrogen, methane, ethane, toluene, and a polymer resembling cuprene. Other photolysis products reported under different conditions include fulvene, acetylene, substituted trienes (Howard, 1990), phenol, 2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dinitro-phenol, nitrobenzene, formic acid, and peroxyacetyl nitrate (Calvert and Pitts, 1966). Under atmospheric conditions, the gas-phase reaction with OH radicals and nitrogen oxides resulted in the formation of phenol and nitrobenzene (Atkinson, 1990). Schwarz and Wasik (1976) reported a fluorescence quantum yield of 5.3 x 10" for benzene in water. 

The bridge effect was scrutinized in the range of diferrocenyl derivatives, especially of those that are applicable in catalysis and material science (Atkinson et al. 2004). One-electron oxidation of these derivatives also proceeds easily, reversibly, and gives rise to cation-radicals (ferrocenium ions). In contrast to the cation-radical of ferrocenylacrylonitrile, the hole transfers through conjugated systems were proven for the bis(ferrocenyl)acetylene cation-radical (Masuda and Shimizu 2006), the bis(ferrocenyl) ethylene cation-radical (Delgado-Pena et al. 1983), and the cation-radical of bis(fulvaleneiron) (LeVanda et al. 1976). These structures are presented in Scheme 1.30. 

Atkinson, J. G., D. E. Ayer, G. Btichi, and E. W. Robb Photochemical reactions XII. Addition reactions of olefins and acetylenes with benzo-nitrile. J. Amer. chem. Soc. 85, 2257 (1963). 

The observation by Perry, Atkinson, and Pitts (89) of a pressure dependence for the reaction of OH radicals with acetylene Is analogous to that for the reaction of OH radicals with ethene (76, 108, 183, 184), and for the reaction of H atoms with... 

Arsindoles are prepared by cyclization of aryl vinyl arsinous chlorides and aryl vinyl chlorides. Atkinson s review details the generality of these approaches <84CHEC-i(i)539>. In a method of limited scope, the arsindole (33) is prepared by reaction of ASCI3 with the acetylene salt (Equation (33)) <80JHC1341>. 

The AOP (1990) program calculates transformation rate constants for the gas-phase reactions between hydroxyl radicals and organic chemicals in the atmosphere using the fragment method of Atkinson and rate constants for the reaction between ozone and olefins/acetylenes. 

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