Kinetic study of amination of chloromethylated polystyrene with hydroxyalkylic tertiary amines

The kinetics of the amination of chloromethylated polystyrene with two hydroxyalkylic tertiary amines (1-dimethyl-amino-3-propanol and 1-dimethylamino-2-propanol) in dimethylacetamide and dioxane was studied. The amination of benzyl chloride with the two amines in dimethylacetamide was followed. It was found that the amination of chloromethylated polystyrene is a two-step reaction taking place with different rates. The rate constants k₁ and k₂ were calculated for the two stages, and a self-accelerating effect of the reaction was noticed. Also, the influence of the position of the hydroxyl group versus the tertiary nitrogen was investigated. The increase of the dielectric constant of the solvent favorably influences the reaction rate.     

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. I. Soluble polymers prepared from reaction of chloromethylated polystyrene with tris(2-hydroxythyl)amine

The reaction of chloromethylated polystyrene with tris(2-hydroxyethyl)amine in N,N-dimethylformamide is described for the conditions to prepare soluble reaction products. The groups of the quaternary ammonium salt, which appear in the first stage of the reaction, transpose to the amino-ether groups. The reaction was followed by elementary analysis, IR and ¹H-NMR spectra, and viscosimetric measurements for nondialyzed and dialyzed samples. The presence of the tertiary amine groups on obtained polymers was also shown by titration. The polymers from the reaction of chloromethylated polystyrene with tris(2-hydroxyethyl)amine reacted easily with benzyl chloride.     

Amination of 5-azacinnoline with aromatic amines

The 5-azacinnoline molecule was subjected to quantum-mechanical calculation by the Hückel method. The formation of 4-amino derivatives in the case of the reaction of 5-azacinnoline with aliphatic amines in the presence of an oxidizing agent and of 4,4-bis(5-azacinnolinyl) in the case of dimerization in an oxygenfree medium was substantiated theoretically. The possibility of reactions with anions of aromatic amines was predicted by means of the Klopman method. It is shown that, in practice, the reaction is actually accelerated and that, in conformity with theory, the reaction center is the nitrogen atom of the aromatic amine. Possible products involving reaction with the participation of the pcarbon atom of the arylamine were not recorded. As in the case of aliphatic amines, the formation of a dimer was observed in an oxygen-free medium. The structures of the compounds obtained were proved by means of a combination of physicochemical methods.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 809–812, June, 1978.     

Amination of chloro-substituted heteroarenes with adamantane-containing amines

Russian Chemical Bulletin - Amination of 3,6-dichloropyridazine, chloropyrazine, 2,3and 2,6-dichloropyrazines, 2-chloroquinoxaline, 1-chloroand 1,3-dichloroisoquinolines with various...     

Amination of Bis(trimethylsilyl)-1,2-bisketene with secondary amines: formation of aminodihydrofuranones

The bisketene (Me(3)SiC=C=O)(2) (3) reacts rapidly with 1 equiv of secondary amines to form aminodihydrofuranones 11 as the only observable products. This is in contrast to previous studies (J. Org. Chem. 1999, 64, 4690) of the reactions of 3 with primary amines in which 3 with 1 equiv of amine gives ketenyl amides 4, which slowly cyclize to succinimides 7. The kinetics of the reaction of 3 with morpholine obeyed a rate law with the term [morpholine](2), consistent with rate-limiting formation of the enol amide 14 with catalysis by a second amine molecule. The subsequent formation of 11 is attributed to hindrance of ketonization of intermediate enol amides 14. The furanones 11 react with Me(3)SiOTf to form silyloxyfurans 16, and these react with diethyl diazodicarboxylate, forming maleamide derivatives 17.     

Trichloroethylene in organic synthesis: II. reaction of trichloroethylene with secondary amines

In a novel reaction, trichloroethylene reacts with secondary aliphatic amines in the presence of aqueous solution of NaOH and catalytic quantity of benzyltriethylammonium chloride to give the corresponding N,N,N,'N'-tetraalkylsubstituted glycinamides. The following glycinamides were obtained with high yield: /N-morpholine/acetic acid morpholide, N-/piperidineacetyl/piperidine, N,N,N,'N'-tetra-n-butylglycinamide and N,N,N,'N'-tetraethlyglycinamide. Mechanism of the reaction is discussed.     

Cationic polyelectrolytes. III. Nitrile-group reaction of macromolecular compounds with N,N-dialkylaminoalkylamines

The chemical reaction in aqueous medium of polyacrylonitrile and acrylonitrile–vinyl acetate co-polymer using asymmetrical diamines of H₂N? (CH₂)_m? NR₂ (m = 2,3) structure was studied. It was found that the nitrile group is modified to an dialkylaminoalkylacrylamide group; also determined were the reaction conditions required to obtain the highest degree of chemical transformation of the nitrile groups. All modified compounds were characterized by analytical spectroscopy (IR and ¹H NMR) and by rheological methods. It was also established that glutaronitrile can be used as a low-molecular-weight model to study the chemical transformation of nitrile groups in polyacrylonitrile and related polymers.     

Chloromethylated polystyrene reaction with tris(2-hydroxyethyl)amine. I. Crosslinked polymers prepared by chloromethylated polystyrene with tris(2-hydroxyethyl)amine

A multifunctional crosslinked polymer resulted from a chloromethylated polystyrene reaction with tris(2-hydroxyethyl)amine. A benzyl chloride reaction (chosen as a structural unit model) with tris(2-hydroxyethyl)amine was investigated to explain the reasons for the crosslinking. Amino-ethers and tris(2-hydroxyethyl)amine hydrochloride in addition to ammonium quaternary salt were isolated from this reaction. The formation of amino-ethers proved that an ammonium quaternary salt rearrangement also takes place during the quaternization reaction. This rearrangement leads to chloromethylated polystyrene during its reaction with tris(2-hydroxyethyl)amine.     

Selenium dioxide catalyzed oxidation of secondary amines with hydrogen peroxide. Simple synthesis of nitrones from secondary amines

Oxidation of secondary amines with hydrogen peroxide in the presence of selenium dioxide catalyst at room temperature gives nitrones, which are versatile synthetic intermediates, highly efficiently.     

Preparation of anion-exchange membrane based on block copolymers: Part 1. Amination of the chloromethylated copolymers

The anion-exchange membrane was prepared by a two-step synthesis: chloromethylation of the homemade block copolymers of polysulfone (PSf) and polyphenylenesulfidesulfone (PPSS) in the first step with subsequent amination by means of trimethylamine in the second step. The lowest measured area resistivities, equilibrated in 2 mol/dm³ KCl aqueous solution, were 4.5–3.30 Ω cm². The anion-exchange capacity reached up to 0.92 meq/(g-dry-resin), and the transport number of chlorine anion was in the 0.6–0.7 range.     

Reaction of silylphosphites with secondary amines

The reaction of dialkylsilylphosphites with linear and cyclic secondary amines leads to the formation of acid alkoxydialkylamidophosphites and dialkyl phosphites. Aminolysis of pyrocatecholsilylphosphite was accomplished with retention of the phosphorus atom and formation of the corresponding amidophosphites.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 235–237, January, 1991.     

Reactions of sulfites with secondary amines

The interaction of diethylamine and morpholine with diphenyl, methyl phenyl, ethyl phenyl, and isopropyl phenyl sulfites was studied. It was established that two reactions, substitution and alkylation, can occur in parallel. Diphenyl sulfites react with amines to give only substitution products, while other sulfites react with substitution at the sulfur atom and with alkylation of the amines. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1395–1397, July, 1998.     

Reaction of biacetylene with secondary amines

Conclusions The reaction of biacetylene with secondary saturated diamines proceeds predominantly with the formation of monoaddition products of both linear and cyclic structure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1163–1164, May, 1973.