Effect of a Competing n Donor on the Rate of AlCl3-Catalyzed Diels-Alder Reaction of 9,10-Dimethylanthracene with Maleic Anhydride

The catalytic effect of AlCl₃ on the Diels-Alder reaction of 9,10-dimethylanthracene with maleic anhydride is dramatically weakened on addition of a competing n donor, dibutyl ether. The n,v complex of aluminum chloride with dibutyl ether is considerably more stable than the complex with maleic anhydride; therefore, the catalytic effect is suppressed even at comparable concentrations of these n donors.     

Solvent Effect on the Volume of the Diels-Alder Reaction between Tetracyanoethylene and trans,trans-1,4-Diphenyl-1,3-butadiene

From the partial molar volumes of tetracyanoethylene, trans,trans-1,4-diphenyl-1,3-butadiene, and their Diels-Alder adduct, the volumes of the reaction in a series of solvents at 25°C (cm³ mol^{- 1}) were calculated: in dioxane, -26.4; in chloroform, -34.9; in ethyl acetate, -34.5; in acetonitrile, -4.4; in cyclohexanone, -34.0; in 1,2-dichloroethane, -31.8; in benzene, -26.9; in toluene, -24.5; in o-xylene, -21.1; and in mesitylene, -16.9. The solvent effects on the activation and reaction volumes and on the partial molar volumes of the reactants, activated complex, and adduct were discussed.     

Diels-Alder reaction volumes in the solid state and solution

The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm³ mol^–1), and slightly different from the reaction volumes (–8±1 cm³ mol^–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm³ mol^–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004.     

Effect of Elevated External Pressure on the Rate of the Diels-Alder Reaction of 9-Methylanthracene with Acrylonitrile,Catalyzed by Gallium Chloride

External pressure was found to similarly affect the rate of a gallium chloride-catalyzed Diels-Alder reaction between 9-methylanthracene with acrylonitrile and a noncatalyzed reaction of 9,10-dimethylanthracene with acrylonitrile. The observation of equal activation volumes is consistent with the assumption that elevated pressure very weakly affects the bond energy in the n, complex of acrylonitrile with gallium chloride.     

Activation and Reaction Volumes for [4+2] and [3+2] Additions Involving Maleic Anhydride

The partial molar volumes of reactants and products of the [3+2] addition of C-(p-nitrophenyl)-N-phenylnitrone to maleic anhydride and of the [4+2] addition of 9,10-dimethylanthracene to the same dienophile were determined, and the reaction volumes were calculated. A new method was suggested for determining the reaction volume. The activation volumes of both reactions were calculated from the dependences of the reaction rates on the external pressure. The volume parameters of the reactions involving the reagents of close size are close. The ratios of the activation volumes to the reaction volumes are unity, which suggests a common concerted mechanism of the reactions. Factors that could be responsible for significant changes in the absolute values of the reaction volume parameters are discussed.     

Enthalpies of the Diels–Alder reactions of a series of dienes with tetracyanoethylene and 4-phenyl-1,2,4-triazoline-3,5-dione

Russian Chemical Bulletin - The enthalpies of the Diels–Alder reactions of twenty dienes with two active dienophiles, tetracyanoethylene and 4-phenyl-1,2,4-triazoline-3,5-dione, are compared,...     

Hydrophobic acceleration in the Diels—Alder reaction of 9-hydroxymethylanthracene with <Emphasis Type="Italic">N</Emphasis>-phenylmaleimide

The Diels—Alder reaction rates of 9-hydroxymethylanthracene with N-phenylmaleimide and N-ethylmaleimide in water, butan-1-ol, ethylene glycol, acetonitrile, chloroform, and 1,4-dioxane have been compared.     

Energy and volume activation parameters of the retro-Diels—Alder reaction in different solvents

The temperature and pressure effects on the decay rate of an adduct obtained from 9-chloroanthracene and tetracyanoethene by a Diels—Alder reaction were studied. The rate constants (298.2 K) and the enthalpies, entropies, and volumes of activation were determined for the retro-Diels—Alder reaction in different solvents. The data obtained confirm a possible decrease in the molar volume of the solvated adduct upon partial bond cleavage on the way to the transition state. The reversal of the sign in front of the activation volume cannot be indicative of a changed reaction mechanism.     

Solvent Effect on the Enthalpy of Solution and Partial Molar Volume of the Ionic Liquid 1-Butyl-3-methylimidazolium Tetrafluoroborate

Enthalpies of solution and partial molar volumes of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate were determined in 15 solvents of different polarity. Very large differences of the enthalpies of solution (????_sol H _IL=38.9?kJ?mol^?1) and partial molar volumes (??V _IL=43 cm³?mol^?1) are nearly the same as observed for lithium perchlorate solutions. These results clearly indicate that the low values of the macroscopic polarity parameters of [bmim]BF₄ do not correspond with the large differences of the intermolecular interactions in IL solutions. The values of the partial molar volume of the cation, $V_{[\mathrm{bmim}]^{+}}$ , were estimated for the first time. The changes of the partial molar volumes, V _IL, reflect mainly the changes of anion volume, $V_{\mathrm{BF}_{4}^{-}}$ . The rate of the Diels?CAlder reaction of 9,10-dimethylanthracene with maleic anhydride in the [bmim]BF₄ medium was nearly the same as in common molecular solvents.