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1984 (1)
1977 (1)
1Author    S.Requires cookie*
 Title    Strahlenchemische Cycloadditionen mit Äthylen und Acetylen (Produktbildung und Lösungsmittelwahl)  
 Abstract    R a d ia tio n Chemical C ycloaddition Reactions w ith Ethylene and Acetylene M a n f r e d J . M i r e a c h 1, M a r l i s F. M i r b a c h 1 u n d A l f o n s S a u The (2 + 2) cycloadditions of maleic acid anhydride (MSA) and 1,3-cyclohexadiene (CHD) to ethylene and acetylene were initiated with gamma-rays in different solvents. The four-membered ring products were formed with high selectivity and surprisingly high energy yields in solvents with triplett energies smaller than ethylene and acetylene but higher than MSA and CH D resp. In benzonitrile as a solvent MSA reacts with ethylene to give cyclobutane-l,2-dicarboxylic acid anhydride (1) (G = 0.04) and with acetylene to give cyclobut-3-ene-l,2-dicarboxylic acid anhydride (2) (G = 3.7). The cyclobutene derivative (2) is formed in >80% yield and the bicyclopropyl derivative (3), which is the main product in the photochemical reaction, with a yield of <20%. 1,3-Cyclohexadiene was also added to ethylene to give bicyclo(4,2,0)oct-2-ene (G = 0.4) and bicyclo(2,2,2)oct-2-ene (G = 0.1) under gamma irradiation in methylnaphthalene as a solvent. Under similar conditions addition to acetylene gave bicyclo(4,2,0)octa-2,7-diene (G = 0.04) and bicyclo(2,2,2)octa-2,5-diene (G = 0.3), respectively. 
  Reference    (Z. Naturforsch. 32b, 281—284 [1977]; eingegangen am 6. Oktober 1976) 
  Published    1977 
  Keywords    Cycloaddition, Ethylene, Acetylene, Maleic Acid Anhydride, 1, 3-Cyclohexadiene 
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 TEI-XML for    default:Reihe_B/32/ZNB-1977-32b-0281.pdf 
 Identifier    ZNB-1977-32b-0281 
 Volume    32 
2Author    Alicja Piesiak, M. An, Nien Schuchmann, Henryk Zegota, Clemens Von SonntagRequires cookie*
 Title    ß-Hydroxyethylperoxyl Radicals: A Study of the y-Radiolysis and Pulse Radiolysis of Ethylene in Oxygenated Aqueous Solutions  
 Abstract    Hydroxyl radicals (and H atom s) generated in the radiolysis of N20-co n tain in g w ater add to ethylene forming /3-hydroxyethyl radicals (and ethyl radicals). In the presence of oxygen these are converted into the corresponding peroxyl radicals which decay bim olecularly (2 k — 2 x 108 M ~'s-1) as m easured by pulse radiolysis. The m ajor products (G values in brackets) are glycolaldehyde (3.3), form aldehyde (1.6), ethylene glycol (0.8), acetaldehyde (0.5), organic peroxidic m aterial (0.5), and hydrogen peroxide (2.4) (dose rate 0.26 Gy s-1, pH 5.6). A m aterial balance has been obtained with respect to the primary w ater radicals (6.0) and oxygen uptake (4.8). The products and their yields can be accounted for if in the rate determ ining step atetro x id e is form ed which decomposes via three m ajor pathways leading to; (i) H 20 2 and two m olecules of glycolaldehyde (ca. 45%), (ii) 0 2, glycolaldehyde and ethylene glycol (ca. 30%), and (iii) 0 2, two molecules of form aldehyde and two C H 2OH radicals (ca. 15%). A 1,2-H shift of interm ediate oxyl radicals is unim portant in this system. 
  Reference    Z. Naturforsch. 39b, 1262—1267 (1984); received March 5 1984 
  Published    1984 
  Keywords    Peroxyl Radicals, Oxyl Radicals, Pulse Radiolysis, Ethylene, Reaction Kinetics 
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 TEI-XML for    default:Reihe_B/39/ZNB-1984-39b-1262.pdf 
 Identifier    ZNB-1984-39b-1262 
 Volume    39