Kinetics of Reactions of α,β-Unsaturated Surfactants with Secondary Amines in a Solution

The kinetics of reactions of acrylamide derivatives (acrylamidotrihydroxymethylmethane (TA), sodium 4-acrylamidobutanoate (AA₃), sodium 6-acrylamidohexanoate (AA₅), and sodium 11-acrylamido-undecanoate (AA10)) with piperidine and morpholine in water (for TA, also in DMF, DMSO, and formamide) is studied at 293 K. These compounds are weak surfactant monomers. The critical concentrations of micelle formation (CCM) for them are determined. The self-association of AA₃, AA₅, and AA₁₀ producing micelles results in a decrease in their reactivity compared to the monomeric forms. The rates of the reactions of surfactant monomers (SM) with morpholine and piperidine are described by the second-order rate law w ₀ = k[SM]₀[Amine]₀. An empirical equation is derived that relates the CCM values to the rate constant for the reaction of a surfactant monomer with a secondary amine with charges on the -carbon and oxygen atoms of the amide group of a surfactant monomer. The rates of the reactions of TA with piperidine and morpholine are determined by the electrophilicity (acidity) of the medium, which is favorable for the Michael reaction.     

Effects of Solvents and the Structure of Amines on the Rates of Reactions of α,β-Unsaturated Nitriles and Amides with Secondary Amines

The kinetics of reactions between ,-unsaturated compounds (UCs) (acrylonitrile (AN), acryl-amide (AA), and methacrylamide (MAA)) and secondary amines (As) (piperidine, morpholine, diethanolamine, diethylamine, and dipropylamine) in water, as well as in DMF, DMSO, formamide, and 1,4-dioxane for acrylonitrile, was studied. It was found that w= k[HC]₀[A]₀for all of the test pairs. Viscosity, permittivity, and solvation characteristics, such as solvent polarity, nucleophilicity, and electrophilicity, were taken into account in considering the solvent effect on the overall reaction rate. The electrophilicity (acidity) of a medium was found to exert the greatest effect on the reaction rate. It is believed that an increase in the electrophilicity is favorable for the rapid protonation of the UC–amine intermediate complex. The effects of amine basicity, ionization potential, and dipole moment and the steric parameters of substituents in amine molecules on the rates of reactions between the unsaturated compounds and secondary amines were considered.     

Michael Condensation in a Two-Phase System: The Application of Inverse Phase-Transfer Catalysis to the Reaction of Butyl Acrylate with Diethylamine in a Water–Heptane System

The kinetics of a heterogeneous reaction of fat-soluble butyl acrylate (BA) with water-soluble diethylamine (DEA) in a two-phase water–heptane system in the presence and absence of small amounts of water-soluble surfactants was studied by the methods of inverse phase-transfer and interfacial catalysis. It was found that the rate of the reaction in either a homogeneous medium or the two-phase system is described by the same equation, w ₀ = k[BA]₀[DEA]₀. The influences of the type and concentration of surfactant, temperature, stirring rate, interfacial surface area, and degree of dispersion on the reaction rate were studied. The rate of the reaction of BA with DEA in the presence of a cationic surfactant (dodecyltrimethylammonium bromide) increased by almost two orders of magnitude in the two-phase system at high stirring rates.     

Synthesis of New Surface-Active β-Amino Amides,Agents for Fixation of Dyes on Cotton Fibers,from N-[Tri(hydroxymethyl)methyl]acrylamide

Amines containing amido and hydroxy groups were prepared. Their surface activity was studied, and the possibility of their use as cotton fiber modifiers was examined.