Ab initio and experimental studies on the hetero-Diels-Alder and cheletropic additions of sulfur dioxide to (E)-1-methoxybutadiene: A mechanism involving three molecules of SO2
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Chemical systems with standard reaction enthalpies (ΔH0r) and an activation energies (Ea) of a few tens of kcal/mol are generally well described by the unimolecular reaction rate theory. The goal of this work is to determine the limits of this model by stu ...
Racemic 6-ethenyl-7-oxabicyclo[2.2.l]hept-5-en-2-one (23), 5-ethenyl-7-oxabicyclo[2.2.1]hept-5-en-2-one (25) and their ethylene acetals 24 and 26, respectively, were derived from the Diels-Alder adduct of furan to 1-cyanovinyl acetate (27). The Diels-Alder ...
At -55-degrees-C SO2 adds to 4-[(tert-butyl)dimethylsilyloxy]-1-methoxy-2,3,6,7-tetramethylidenebicyc lo[3.2.1]octane reversibly and selectively onto the s-cis-butadiene moiety at C(2), C(3) giving a single regioisomeric sultine. At -45-degrees-C the chele ...
A gravimetric app. contg. catalyst particles (H2SO4 on silicate) is used to det. the ethylene [74-85-1] absorption rate during the prepn. of vinyl acetate [108-05-4] from ethylene and AcOH. The influence of the absorption process on the overall reaction at ...
At low temperature and in the presence of CF3COOH, SO2 undergoes Diels-Alder additions with (E)-1-acetoxybutadiene (8d) giving a 1:10 mixture of diastereomeric 6-acetoxysultines (9d + 10d). The Van't Hoff plot for equilibria 8d + SO2 reversible arrow 9d + ...
The electrochem. promotion of RuO2 catalyst films, deposed onto yttria stabilized zirconia solid electrolyte (YSZ), was studied for the gas phase combustion of ethylene. Two order of magnitude increase in the reaction rate was obtained during anodic polari ...
When treated with BuLi in the presence of Na or K tert-butoxide, 2-(trimethylsilyl)- and 2-(triethylsilyl)norbornadiene undergo H/metal-exchange mainly at the 5-position. The latter position is slightly activated relative to unsubstituted norbornadiene whi ...
Under conditions of kinetic control (-20-degrees-C), the competition between the cheletropic and homocheletropic addition of SO2 to 5,6,7,8-tetramethylidenebicyclo[2.2.2]oct-2-ene 8 was unaffected by a methyl substituent at C(2). However, the latter induce ...
Methanol dehydrogenation to formaldehyde was conducted in a fixed-bed flow reactor with sodium carbonate catalyst mixed with active carbons or transition metals. The additives promoted the reaction rate at 880-970 K without modifying formaldehyde selectivi ...
Oscillation of the reaction rate, leading to strong, irregular oscillation of the conversion in dependence on the time, and sudden conversion changes occurred in certain temp. and concn. regions in the exptl. study of the catalytic hydrogenation of C2H4 wi ...
