ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The Diels-Alder addition of acrolein to cyclohexa-1,3-diene has been studied between 486 and 571°K at pressures ranging from 55 to 240 torr. The products are endo- and exo-5-formylbicyclo[2.2.2]oct-2-ene (endo- and exo-FBO), and their formations are second order. The rate constants (in l./mole · sec) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm endo}} = -(19,470 \pm 50)/4.576T + (5.65 \pm 0.02)$$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm exo}} = - (20,630 \pm 50)/4.576T + (5.51 \pm 0.02)$$\end{document}The retro-Diels-Alder pyrolysis of endo-FBO has also been studied. In the ranges of 565-638°K and 6-38 torr, the reaction is first order, and its rate constant (in sec-1) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm p}} = - (46,390 \pm 110)/4.576T + (12.98 \pm 0.04)$$\end{document}The reaction mechanism is discussed. The heat of formation and the entropy of endo-FBO are estimated.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550080502
