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Kinetics, mechanism, and endo selectivity of Diels–Alder reactions of alkylmonosubstituted ethenes with cyclohexa-1,3-diene in the gas phase

✍ Scribed by G. Huybrechts; H. Poppelsdorf; L. Maesschalck; B. Van Mele

Publisher
John Wiley and Sons
Year
1984
Tongue
English
Weight
420 KB
Volume
16
Category
Article
ISSN
0538-8066

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✦ Synopsis

The reactions k N n m endo-5-Ybicyclo[2.2.2loct-2-ene (NYBO) eno-5-Ybicyclo[2.2.2loct-2-ene (XYBO) O + < , < (YE) KXYBO (CHD) where Y = CH, (MI, C,H, (E), i-C,H, (I), and t-C,H, (TI have been studied between 488 and 606 K. The pressures of CHD ranged from 16 to 124 torr and those of YE from 57 to 625 torr. These reactions are homogeneous and first order with respect to each reagent. The rate constants (in L/mol.s) are given by 1Ogl OkNMBO = -(26530 f 80)/4.576T f (6.05 f 0.03) lOglOkXMBO = ~(28910 2 130)/4.576T + (6.32 2 0.05) loglOkNEBO = -(26150 f 120)/4.576T + (5.85 2 0.05) 1OglokXEBO = -(28560 f 120)/4.576T + (6.07 f 0.05) 1OglOkNiBO = ~(26560 f 80)/4.576T + (5.57 2 0.03) 1OglOkXIBCJ = -(28350 f 100)/4.576T + (5.47 f 0.04) lOglOkNTBO = -(28920 2 50)/4.576T + (5.86 2 0.02) log1okxTBO = ~(32890 f 120)/4.576T + (6.19 2 0.05)

The Arrhenius parameters are used as a test for a biradical mechanism and to discuss the endo selectivity of the reactions.

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