Quaternary ammonium polyelectrolytes. III. Kinetic studies of amination of chloromethylated polystyrene with tertiary amines

The amination kinetics of benzyl chloride and chloromethylated polystyrene with three tertiary amines were studied: N-2-hydroxyethyl-dimethylamine, N,N-bis(2-hydroxyethyl)-methylamine, and triethylamine in N,N-dimethylformamide. The amination of chloromethylated polystyrene takes place with two reaction rate constants K₁ and K₂. K₂ is higher than K₁; hence there is a self-accelerating effect. This phenomenon is due to the influence of the positive electrostatic field of the macroion chain on amines that are nucleophilic reactants. The magnitude of the self-accelerating effect given by the K₂/K₁ ratio depends on the substituent volume of the nitrogen atom of the amine molecule.     

Cationic polyelectrolytes. II. Amination of chloromethylated polystyrene with hydroxyalkylic secondary amines

The reaction of chloromethylated polystyrene with methyl(2- hydroxyethyl)amine and butyle (2-hydroxyethyl)amine was studied kinetically. The reaction of benzyl chloride with these amines was also investigated for comparison. N,N-dimethylformamide and dioxane were used as solvents. The reactions of benzyl chloride with the two amines in these solvents took place according to normal kinetics of the second order. Reaction kinetics depend on the nature of the amine and solvent in Chloromethylated polystyrene reactions. In dioxane the self-accelerating effect of the reaction for β ? 0.5 is apparent. Steric hindrance of the reaction, beginning with a conversion degree of about 75%, wss observed for butyl(2-hydroxyethyl)amine in N,N-dimethylformamide. This self-accelerating effect is observed in dioxane at the same reaction degree. The activation energies and frequency factors were calculated for the amination of benzyl chloride and chloromethylated polystyrene with the two amines in N,N-dimethylformamide and dioxane.     

Ruthenium-catalyzed direct amination of alcohols with tertiary amines

A highly selective phosphine-based ruthenium catalyst system efficiently catalyzes the direct amination of alcohols with aliphatic tertiary amines, yielding unsymmetric tertiary amines in yields up to 87%. Ligand and solvent both affect the reaction yields significantly. The reaction can be performed with a wide variety of functionalities.     

Synthesis of hindered tertiary amines by a mild reductive amination procedure

An efficient metal-free procedure for the synthesis of tertiary amines by the reductive amination of carbonyl compounds is reported, which allows a convergent access to sterically hindered amines of the general formulas NR(R′)₂ and NRR′R″. The mild and operationally simple protocol uses the Hantzsch ester for transfer hydrogenation and catalytic amounts of thiourea for imine activation.     

Tandem catalytic allylic amination and [2,3]-Stevens rearrangement of tertiary amines

We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.     

Catalytic C-H amination with aromatic amines

Aniline joins the club: A β-diketiminato copper(I) catalyst enables C-H amination of anilines employing low catalyst loadings to preclude oxidation to the diazene ArN=NAr. Electron-poor anilines are particularly resistant towards diazene formation and participate in the amination of strong and unactivated C-H bonds. N-alkyl anilines also take part in C-H amination.     

Synthesis of tertiary alkyl amines from terminal alkenes: copper-catalyzed amination of alkyl boranes

A method for highly selective anti-Markovnikov hydroamination of terminal alkenes is reported. The one-pot procedure involves hydroboration of the alkene followed by a novel electrophilic amination of the alkyl borane catalyzed by an NHC-Cu complex. Terminal alkenes are successfully transformed into tertiary alkyl amines in the presence of a variety of functional groups in yields ranging from 80 to 97% with excellent regioselectivity. Results of a preliminary study of the reaction mechanism are also described.     

Palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines with amines

A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This synthetic methodology can produce various di-substituted pyrimidines in high yields with good functional group tolerance, and provide a complementary tool for the syntheses of important intermediates of nucleosides and purines with bioactivities.     

Complexes of trinitratoborane with tertiary amines

Conclusions Some complexes of trinitratoborane with tertiary amines were synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1883–1884, August, 1979.     

Extraction of antimony with tertiary amines

The extractability of antimony(III) and (V) with tridodecylamine from various aqueous solutions is reported. Extraction from nitric and hydrofluoric acid solutions is low, but extraction from sulphuric, hydrochloric and hydrobromic solutions is high. Antimony-(III) can be separated from antimony(V) in 7M nitric acid or 0.64M hydrobromic acid. The extraction of antimony from hydrochloric acid solutions in methanol, ethanol, and acetone-water mixtures is greater than from pure aqueous solutions of the same acidity. The elements from which antimony can be separated with tertiary amines are given.     

Nickel-catalyzed C-H direct amination of benzoxazoles with secondary amines

In this article, a facile, efficient and practical method for Ni-catalyzed direct C-H amination of benzoxazole with secondary amines has been developed. This procedure requires Ni(OAc)(2)·4H(2)O as catalyst, TBHP as oxidant and acid as the additive. A variety of substituted benzoxazol-2-amines were synthesized in moderate to good yields.     

Laser photolysis study of triplet exciplexes of nitronaphthalenes with tertiary aromatic amines

Conclusions Spectrokinetic characteristics were found for the triplet exciplexes of nitronaphthalenes with tertiary aromatic amines. The state with complete charge transfer makes the major contribution to the structure of the triplet exciplexes. Solvation of the triplet exciplexes by methanol molecules is accompanied by a decrease in the rate of reverse charge transfer.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2367–2370, October, 1987.     

Complexes of tertiary amines with hindered quinones

The generation of radical pairs by low-temperature photolysis of solutions of sterically hindered quinones in aliphatic amines has been studied by ESR. The process of stabilization of radical pairs is related to molecular complexes between amines and quinones in solution.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1736–1738, September, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 95-03-09233a).     

Palladium-catalyzed amination of chloromethylnaphthalene and chloromethylanthracene derivatives with various amines

Palladium-catalyzed amination of chloromethylnaphthalene and chloromethylanthracene derivatives to produce naphthylamines and anthrylamines in satisfactory to good yields has been developed. The unprecedented amination reactions proceeded smoothly under mild conditions in the presence of Pd(PPh(3))(4) as a catalyst.     

A practical Buchwald-Hartwig amination of 2-bromopyridines with volatile amines

A practical Buchwald-Hartwig amination of 2-bromopyridines with volatile amines is developed in sealed tubes. The method provides an expedient entry to a variety of secondary and tertiary aminopyridines that are otherwise not readily synthesized.     

Polymers of tertiary amines

Polymers of tertiary amines and their hydrochlorides of molecular weights in the range 300–2000 have been prepared, starting from trans-1,4-dichlorobutene-2, and primary amines. The polymers present interesting solubility properties. Variation of the reaction conditions leads to crosslinked insoluble polymers. Reaction of the soluble tertiary amine polymers with organic acid dichlorides leads to polymers of tertiary amine–amides, a new type of polymer.     

Kinetic study on reactions between polymer chain-ends. Coupling reactions of living polystyrene with chloro-ended polystyrene

The reaction of living polystyrene with chloro-ended polystrene was studied to examine “the kinetic excluded volume effect” on the intermolecular reaction between reactive chain-ends of two monodisperse polymers. The reaction of living polystyrene with 1-chloropentane was also studied as a model reaction (small molecule-polymer reaction). The second-order rate constants, k₂, for the polymer polymer reaction in benzene (with a small amount of tetrahydrofuran to break the association of living-ends) is independent of the degree of polymerization, DP, for the range of DP studied (up to 400). The ratios of the rate constants for the polymer-polymer and the polymer-small molecule reactions, k₂/k₂⁰, are the same in benzene and in cyclohexane (good and poor solvent for polystyrene respectively), showing that the effect of the coil expansion is not large enough to be detected. These results confirm the Flory basic concept that the reactivity of a functional group attached to an inert polymer is not affected by the presence of the polymer chain in activation-controlled reactions.