- Reaktion von trans-1-Arylbutadienen und 1,1-Diarylbutadienen mit Tetracyanethylen (TCNE) und 2,2-Bis(trifluormethyl)ethylen-1,1-dicarbonitril (BTF): Kinetische Studie
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Kinetic data (substituent effects, solvent effects, activation parameter) are reported for the reactions of trans-1-arylbutadienes 1 and 1,1-diarylbutadienes 3 with TCNE 4 and BTF 5. (2+2)- and (4+2)-cycloadducts 7 respectively 9 can rearrange or undergo cycloreversions with quite different reaction rates depending on the substituent in the aryl-ring.
- Drexler, J.,Lindermayer, R.,Hassan, M. A.,Sauer, J.
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p. 2559 - 2562
(2007/10/02)
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- Production of Acrylonitrile and Other Unsaturated Nitriles from Alkenes and Alkynes
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Passage of unsaturated organic molecules trough a 13.56-MHz radio-frequency discharge, in the presence of cyanogen, results in the formation of unsaturated nitriles.Acrylonitrile was the major product from ethylene, propylene, acrolein, methyl vinyl ketone, or 1,1,1-trifluoropropylene. 1-Butene, 2-butene, and isobutylene gave mixtures of nitrile products with the CN situated at vinylic or allylic positions. 2-Butyne gave 1-cyanopropyne.Other compounds gave only low yields of nitriles and considerable polymer.The effects of power, pressure, flow rate, and ratios of reactants on the yields of acrylonitrile from propylene and cyanogen were studied.A typical power yield of acrylonitrile was 30 g kW-1 h-1.Maximum material yields of nitrile products were obtained at intermediate powers and pressures.The products are consistent with a reaction scheme involving attack of initially formed cyano radicals on the organic substrate.This step forms activated radical intermediates, which decay through elimination of an atom or group.The atom or group which is most weakly bound is preferentially lost.
- Henis, Neil B.,Miller, Larry L.
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p. 2526 - 2529
(2007/10/02)
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