19341-98-1Relevant academic research and scientific papers
Alkynes and Cumulenes, XVII, Photoaddition of Vinylacetylene to other Unsaturated Hydrocarbons
Siegel, Herbert,Eisenhuth, Ludwig,Hopf, Henning
, p. 597 - 612 (2007/10/02)
On irradiation in the presence of triplet sensitizers, vinylacetylene (1) may be added with its double bond to olefins , dienes , allenes , and diynes .The resulting multifunctionalized cyclobutane derivatives are characterized by spectroscopic and chemical methods.Since the ethinyl group of these codimers may be hydrated to the acetyl function, 1 represents a photochemical equivalent of methyl vinyl ketone which itself does not undergo the described photoadditions.When benzene (56) is employed as addition partner the primary product of the codimerisation, 54, isomerizes to vinylcyclooctatetraene (55).
Thermolysis of 1,2,6,7-Octatetraene
Roth, Wolfgang R.,Scholz, Bernhard P.,Breuckmann, Rolf,Jelich, Klaus,Lennartz, Hans-Werner
, p. 1934 - 1946 (2007/10/02)
The energy profile for the rearrangement of 1 to 3 and 4 and their interconversion by way of 5 is established making use of kinetic methods and by the determination of the heat of hydrogenation of the individual products.For the Cope rearrangement 1 -> 4 the competition of concerted and non concerted reaction paths is demonstrated by trapping experiments.
Alkine und Cumulene, XV. Ueber die Photodimerisierung konjugierter Enine
Eisenhuth, Ludwig,Siegel, Herbert,Hopf, Henning
, p. 3772 - 3788 (2007/10/02)
On irradiation in the presence of triplet sensitizers having a triplet energy >250 KJ/mol, vinylacetylene (1a) dimerizes to cis- and trans-1,2-diethynylcyclobutane (cis- and trans-2) as well as minor amounts of 4-ethynyl-1-vinylcyclobutene (3).The effect of substituents on the course of the reaction is investigated: whereas alkyl, vinyl, and phenyl substituents, respectively, in the 4-position of 1a do not influence the photoaddition, 2-substituted enynes yield the corresponding cyclobutanes in poor yields only.Finally, 1-substituted vinylacetylenes (besides the substituents mentioned above the influence of ethynyl, chloro, and methoxy groups has been investigated) do not provide photodimers; they are cis-trans-isomerized instead.The mechanism of the photoaddition is discussed.
