Effect of high pressure on the rate constant of the Diels-Alder reaction between furan and maleic anhydride

Zhulin, V. M.; Kel'tseva, M. V.; Bogdanov, V. S.; Koreshkov, Yu. D.; Kabotyanskaya, E. B.

doi:10.1007/bf00959558

Cited by 6 publications

(9 citation statements)

References 1 publication

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“…The former reaction ( 1 + 2 ) was studied both experimentally − and theoretically. ,, Nevertheless, recent NMR measurements, , supported by correlated quantum chemical calculations, sharply disagree with the earlier results of Lee and Herndon . The new results suggest that the predominant formation of 5 is caused by its higher thermodynamic stability, and only a very small kinetic preference for isomer 4 (the activation barrier is about 0.8 kJ mol -1 higher 22 for isomer 5 ) was determined.…”

Section: Introductionmentioning

confidence: 83%

An Experimental and Theoretical Study of Stereoselectivity of Furan−Maleic Anhydride and Furan−Maleimide Diels−Alder Reactions

et al. 2005

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The stereoselectivity of the reaction of furan (1) with maleic anhydride (2) and maleimide (3) was studied experimentally and theoretically. Although the two reactions are highly similar with regard to their preference for endo and exo steroisomers, notable differences were experimentally observed and explained on the basis of calculated reaction-free energies and transition-state barriers. The experimental values of rate constants (k(1+2endo) = (1.75 +/- 0.48) x 10(-5); mol(-1) l s(-1); k(1+2exo) = (3.10 +/- 0.55) x 10(-5); mol(-1) l s(-1); k(1+3endo) = (1.93 +/- 0.082) x 10(-5); mol(-1) l s(-1), k(1+3exo) = (1.38 +/- 0.055) x 10(-5); mol(-1) l s(-1) all at 300 K) and the observed reaction course clearly confirm that neither of these reactions are prototypical examples of Diels-Alder [4 + 2] cycloadditions, whose dominant preference is for endo isomers. However, only by comparing their energetics-calculated at the CCSD(T) level of theory-with the analogous reactions involving cyclopentadiene (8) as a diene can these observations be understood. The low thermodynamic stability of furan [4 + 2] adducts opens retro-Diels-Alder reaction channels and overrules the very small kinetic preference (calculated and measured here) of initial formation for endo stereoisomers. On a macroscopic scale "an irregular"-thermodynamically more stable-exo stereoisomer was consequently observed as a dominant species.

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Section: Introductionmentioning

confidence: 83%

An Experimental and Theoretical Study of Stereoselectivity of Furan−Maleic Anhydride and Furan−Maleimide Diels−Alder Reactions

et al. 2005

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“…Zhulin et al showed from NMR studies at 20°C (293 K) that the rate of formation of the exo‐isomer was very close to that of the endo‐isomer. [ 10 ] Calvo‐Losada and Suarez [ 11 ] computationally studied the solvent effect [ 12 ] of CH 3 CN using the polarizable continuum model [ 13 ] and demonstrated that it stabilized the exo transition state (TS) structure more than the endo one by 0.25 kcal/mol at MP2/6‐31G(d) level of theory. However, because the exo‐stabilization contrasted the endo‐stabilization observed in other theoretical studies of DA reactions in solution, [ 14 ] the authors chose to ignore the noted solvent effect and assigned the kinetic preference to the effects of dispersion interactions favoring endo‐orientation through π − π contacts instead.…”

Section: Introductionmentioning

confidence: 99%

“…However, as we will show below, the differential activation energies in our calculations are of the order of less than 1.0 kcal/mol. Zhulin et al 10 showed from NMR studies at 20 o C (293 K) that the rate of formation of the exo-isomer was very close to that of the endo-isomer. Calvo-Losada and Suarez 11 computationally studied the solvent effect 12 of CH3CN using the polarizable continuum model 13 and demonstrated that it stabilized the exo transition state (TS) structure more than the endo one by 0.25 kcal/mol at the MP2/6-31G(d) level of theory.…”

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confidence: 99%

On the solvent‐ and temperature‐driven stereoselectivity of the Diels–Alder cycloaddition reactions of furan with maleic anhydride and maleimide

Yadav

Prasad

Yadav

et al. 2020

J of Physical Organic Chem

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In quantum chemical calculations, the Diels-Alder cycloaddition reaction of maleic anhydride with furan favors the endo-isomer kinetically in the gas phase. This preference, however, changes in favor of the exo-isomer on inclusion of solvent effects. For example, in acetonitrile, the exo-isomer was calculated to form twice as fast as the endo-isomer at room temperature, an observation that corroborates well with the experiments. The free energy change of the reaction is such that it allows faster reversal of the endo-isomer to the reactants in an equilibrium process and, thus, the predominance of the more stable exo-isomer eventually. The reaction of maleimide with furan is similar to that of maleic anhydride. However, it favors predominantly endo selectivity at temperatures below 320 K which is in excellent agreement with the experimental studies of temperature dependence of this DA reaction. Further, a gedanken calculation of the DA reaction of cyclopropene with furan has been investigated to delineate the effect of the retro-pathway on the stereoselectivity.

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“…In fact, there are very few experimental , and theoretical studies of DA adducts of furan aside from 1 . Compound 1 is the most extensively characterized derivative of 7-oxabicyclo[2.2.1]hept-2-ene, with X-ray structural data and theoretical as well as kinetic and thermodynamic studies at atmospheric , and elevated , pressures reported.…”

Section: Introductionmentioning

confidence: 99%

Retro Diels−Alder Reactions of 5,6-Disubstituted-7-oxabicyclo[2.2.1]hept-2-enes: Experimental and Density Functional Theory Studies

et al. 2000

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Several 5,6-disubstituted-7-oxabicyclo[2.2.1]hept-2-enes (1-4) were synthesized on > or = 0.1 mol scale. The heat-induced retro Diels-Alder (rDA) decomposition of these derivatives was studied by thermal analysis, and the kinetics of the rDA were measured for 4. First-order rate constants (k = 1.91-14.2 x 10(-5) s(-1)), measured at four temperatures between 124 and 150 degrees C, were used to calculate Arrhenius activation parameters Ea (34.5 +/- 0.5 kcal/mol) and ln A (1.77 +/- 0.03 x 10(4)). The observed activation energy was significantly larger (by 9.5 kcal/mol) than that previously measured for the maleic anhydride adduct 1, and this was attributed to the difference in LUMO energies for the two dienophiles. Modeling of the activation parameters found for 4 with density functional theory (DFT) calculations for similar compounds 5 and 6 gave close quantitative correlations for deltaH double dagger, deltaG double dagger, deltaS double dagger. The rDA reactions studied were found to be entropy-driven.

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Effect of high pressure on the rate constant of the Diels-Alder reaction between furan and maleic anhydride

Cited by 6 publications

References 1 publication

An Experimental and Theoretical Study of Stereoselectivity of Furan−Maleic Anhydride and Furan−Maleimide Diels−Alder Reactions

An Experimental and Theoretical Study of Stereoselectivity of Furan−Maleic Anhydride and Furan−Maleimide Diels−Alder Reactions

On the solvent‐ and temperature‐driven stereoselectivity of the Diels–Alder cycloaddition reactions of furan with maleic anhydride and maleimide

Retro Diels−Alder Reactions of 5,6-Disubstituted-7-oxabicyclo[2.2.1]hept-2-enes: Experimental and Density Functional Theory Studies

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