Molecular control over vitrimer-like mechanics – tuneable dynamic motifs based on the Hammett equation in polyimine materials

Controlling macroscopic material properties of dynamic covalent polyimines via the electronic effect of dianiline monomers based on the Hammett equation.

INFLUENCE OF SUBSTITUTES ON THE RATE OF REACTION OF SUBSTITUTED ANILINES WITH A BENZOIC ACID, CATALYZED BY POLYBUTOXYTITANATES

The catalytic production of benzanilide by the interaction of benzoic acid with aniline is an important model process recently intensively developed in the field of the concept of «green chemistry», direct catalytic amidation, and its study is an urgent scientific and practical task. To solve this problem, the effect of substituents in the aniline core on the catalysis by polybut-oxytitanates on acylation of substituted anilines by benzoic acid was studied. The rate constants of this the second-order reaction (the first with respect to substituted aniline and benzoic acid; boiling ortho-xylene, 145 °С, nitrogen flow) are well correlated according to the Hammett equation with three straight lines for individual groups of substituents with ρ = –0.86 (electron donors), 1.12 (weak electron acceptors), –2.83 (strong electron acceptors). To explain this dependence, a variant of the catalytic amidation mechanism is proposed, which takes into account the formation of titanium butoxybenzoates in the first minutes of the reaction — a true amidation catalyst; coordination (polarization of the carbonyl bond in the interaction with the catalyst titanium atom) and acid (polarization of the carbonyl bond in the interaction with the complex of the formed substitu- ted benzanilide with the titanium butoxyben-zoates) catalysis routes. Inhibition of the catalytic reaction is associated with the presence in the mass of water, relative excess of benzoic acid and a possible amide–imide tautomerism of substituted benzanilides, accompanied by the interaction of the imide form of the latter with titanium butoxybenzoates, which does not lead to the route of acid catalysis. The rate constants for catalytic acylation of substituted anilines, containing electron-donating substituents, with benzoic acid in the air are correlated according to the Hammett equation by a straight line segment with ρ = 0.99, which is associated with the predominant influence of the oxidation processes of the corresponding amines. Catalytic acylation under comparable conditions of substituted anilines, containing electron-withdrawing substituents, oxidation processes due to atmospheric oxygen have little effect on.

Resonance-assisted/impaired anion–π interaction: towards the design of novel anion receptors

Substituents alter the electron density distribution in benzene in various ways, depending on their electron withdrawing and donating capabilities, as summarized by the empirical Hammett equation.

Data enhanced Hammett-equation: reaction barriers in chemical space

We generalize Hammett's original approach to predict potential energies of activation in non aromatic molecular scaffolds with multiple substituents.