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High‐Pressure Influence on the Rate of Diels–Alder Cycloaddition Reactions of Maleic Anhydride with Some Dienes
Author(s) -
Kiselev Vladimir D.
Publication year - 2013
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20800
Subject(s) - chemistry , maleic anhydride , cycloaddition , diene , enthalpy , toluene , diels–alder reaction , adduct , reaction rate , reaction rate constant , cyclopentadiene , organic chemistry , photochemistry , catalysis , thermodynamics , kinetics , polymer , natural rubber , physics , quantum mechanics , copolymer
The rate constants for temperature and pressure range, enthalpy, entropy, and volume of activation and reaction were measured in toluene solution for the Diels–Alder cycloaddition reaction of maleic anhydride ( 1 ) with a very active diene, 9,10‐dimethylanthracene ( 4 ), and with a very inactive diene, 9‐phenylanthracene ( 6 ), which is less reactive in the reaction with 1 by five orders of magnitude. Reaction rates under pressure up to 2600 bar were measured by using a high‐pressure optical cell, adjusted to a UV‐spectrophotometer. The volume of reaction was determined by two independent methods: by the difference of the partial molar volumes of the reactants and by the dependence of a specific volume of solution on the adduct concentration during the reaction. All parameters of activation and reaction were discussed.