caa a22 4500 465808182 CHVBK 20180323112108.0 cr unu---uuuuu 170327e19900501xx s 000 0 eng 10.1007/BF00641334 doi (NATIONALLICENCE)springer-10.1007/BF00641334 Mass-spectrometric and quantum-chemical study of fragmentation of diallyl esters of dicarboxylic acids [Elektronische Daten] [I. Krainikova, V. Pen'kovskii] In a mechanistic study of thermal breakdown of diallyl polymers, six diallyl esters of dicarboxylic acids have been investigated by means of mass spectrometry. A characteristic feature of the fragmentation of these compounds is the low stability of the molecular ions and detachment of the allyl cation, the peak of which is usually the highest in the mass spectrum. In interpreting such an unusual path of fragmentation of esters, quantum-chemical calculations have been carried out in the MINDO/3 approximation; the preferred conformation of the diallyl maleate molecule and the distribution of electron density in this conformation have been determined, and the most stable cyclic structure of the intermediate cation [CH=CH(CO)2OH]+ has been established. The nature of the "bridge” between the carboxyl groups in diallyl esters of dicarboxylic acids has practically no influence on the direction of fragmentation. The decisive factor in the fragmentation is the electrostatic interaction of charges on the atoms of carbonyl carbon and ester oxygen of the second carboxyl group. A fragmentation scheme with the formation of intermediate cyclic cations is proposed. Plenum Publishing Corporation, 1990 Krainikova I. Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev aut Pen'kovskii V. Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev aut Theoretical and Experimental Chemistry Kluwer Academic Publishers 26/3(1990-05-01), 280-286 0040-5760 26:3<280 1990 26 11237 https://doi.org/10.1007/BF00641334 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF00641334 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Krainikova I. Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev aut NATIONALLICENCE 700 1- Pen'kovskii V. Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev aut NATIONALLICENCE 773 0- Theoretical and Experimental Chemistry Kluwer Academic Publishers 26/3(1990-05-01), 280-286 0040-5760 26:3<280 1990 26 11237 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer