51848-91-0Relevant academic research and scientific papers
Synthesis of novel sulfonyl-stabilized phosphorus ylides, and the kinetics and mechanism of their conventional and flash vacuum pyrolysis reactions
Al-Bashir, Rasha F.,Al-Awadi, Nouria A.,El-Dusouqui, Osman M.E.
, p. 1543 - 1553 (2007/10/03)
Nine substituted sulfonyl-stabilized phosphorus ylides were prepared by treating their intermediate ylide analogues with phenylmethanesulfonyl fluoride. The stoichiometric ratio of the reactants for each preparation needed to be adjusted according to the basicity of each ylide intermediate. The nine ylide compounds were then subjected to conventional (sealed-tube) gas-phase pyrolysis at 470-545 K. The pyrolytic reactions were homogeneous and obeyed a first-order rate equation. The values of the Arrhenius log A (s-1) and E a (kJ mol-1) obtained for these reactions averaged 11.12 ± 2.00 and 131.8 ± 24.4, respectively. Analysis of the pyrolysates from conventional pyrolysis and from flash vacuum pyrolysis at 600 K showed the products to be complex mixtures of triphenylphosphine, triphenylphosphine oxide, triphenylphosphine sulfide, and symmetric and unsymmetric alkenes. Conventional pyrolysis also gave novel mixed sulfones and, for the p-methoxyaryl substituent, p-anisaldehyde. The products of the reactions under study are explained on the basis of a mechanism involving a sulfonyl carbene intermediate, and the reaction mechanism is used to rationalize the kinetic results and molecular reactivities.
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 12. Extrusion of Ph3P from sulfonyl ylides and reactivity of the resulting sulfonyl carbenes
Aitken, R. Alan,Drysdale, Martin J.,Ferguson, George,Lough, Alan J.
, p. 875 - 880 (2007/10/03)
Twelve sulfonyl stabilised phosphorus ylides have been prepared and their behaviour upon flash vacuum pyrolysis at 600°C has been examined. Examples with an arylsulfonyl substituent undergo loss of Ph3PO to give intractable products but those with an arylmethylsulfonyl substituent separately lose Ph3P and SO2 to give products consistent with the intermediacy of sulfonyl carbenes. X-Ray structure determinations of one ylide from each series show a more significant P-O non-bonding interaction in the first case, providing some explanation for the different thermal reactivity.
