Relation between the structure and extracting power of higher tertiary amines

The effect of the composition and structure of higher tertiary amines on their efficiency in extracting nitric acid has been examined. The ionization constants of the amines in methanol have been determined by potentiometric titration. The extraction constants for nitric acid have been determined at constant ionic strength in the aqueous phase (μ=1). The dependence of these constants upon the concentrations and the degree of association of the amine salts in the organic phase has been examined. For the cases in which the role of steric factors is negligible it has been shown that at low amine salt concentrations in the organic phase there are quantitative regularities between the ionization constants of the amines in methanol, their extraction constants for nitric acid and the inductive effects of the substituents on the nitrogen atom.     

Hydrogen bond formation between aliphatic alcohols and tertiary amines

Hydrogen bond formation between tertiary amines and long chain and branched chain alcohols has been studied in order to understand the influence of chain length and the steric effect on the complex formation between tertiary amines and alcohols. On the addition of the amine to the alcohol the intensity of the monomeric OH band decreases and the new band appears corresponding to the alcohol—amine complex. The equilibrium constants of the complex formation are correlated by a two parameter equation. The three correlation equations obtained for three tertiary amines are: log K = 3.41 + 10.01σ* + 0.02χ (for triethylamine-alcohol) log K = 0.97 + 2.54σ* + 0.21χ (for tributylamine-alcohol) log K = 1.01 + 1.81σ* + 0.26χ (for trioctylamine-alcohol), where σ* is Taft's polar constant and χ the molecular connectivity index of the R skeleton of the alcohol.     

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.     

Efficient synthesis of tertiary amines from secondary amines

Reliable N-alkylations of secondary amines have been developed. By using DIAD and TPP (or PS-TPP) a variety of secondary amines can be converted to the corresponding tertiary amines in good to excellent yields with diverse alkylhalides; no formation of quaternary amine salts are observed. These protocols are amenable to combinatorial chemistry libraries, and are also useful for the syntheses of secondary amines by an acid lysis of the cleavable tertiary amino resins.     

Photoreactions between [60]fullerene and various aromatic tertiary amines

The photoreactions of [60]fullerene with aromatic tertiary amines such as N,N-dimethylaniline and N,N-dimethyl-1-naphthylamine gave two or three types of [60]fullerene adducts. The reaction efficiency in the series of p-substituted N,N-dimethylanilines remarkably increased with increasing electron-donating properties of aromatic tertiary amines employed.     

Cyclopalladation of carborane tertiary amines

Conclusions Starting from, tertiary amines of the carborane series, cyclic complexes with B-Pd bonds have been obtained, which give insertion products with two molecules of diphenylacetylene, at the B-Pd bond.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, 1646–1649, July, 1984.     

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.     

Photostabilizing activity of tertiary hindered amines

The influence of the N-alkyl group of tertiary hindered amines on the photostabilization of polymers was studied. The photostabilizing effects of the tertiary amine derivatives of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine ( 1a ) in polypropylene were compared. All tertiary amine derivatives having α-H to hindered N showed higher effectiveness than 1a . Model liquid phase photoxidations were carried out by irradiating (UV-lamp) the solutions of tertiary hindered amines containing tert-butyl hydroperoxide as a photoinitiator. The tertiary hindered amines were oxidized more easily than corresponding parent hindered amine and converted to the parent amine, which was identified as its salt, resulting from the carboxylic acid produced from the N-alkyl group by oxidation. The thermal reaction of the tertiary hindered amines with tert-butyl hydroperoxide was also studied in the liquid phase. The tertiary hindered amines decomposed tert-butyl hydroperoxide more rapidly than the parent secondary hindered amine, and generated the parent amine. It was also found that the photostabilizing effects of tertiary hindered amines for polyolefins were higher than that of the parent secondary hindered amine.     

Fluorescence decay of tertiary aliphatic amines

The fluorescence decay of the tertiary aliphatic animes trimethylamine (TMA), triethylamine (TEA) and tri-n-propylamine (TPA) in the vapour phase excited between 260 and 215 nm has been shown to consist of a single, wavelength-dependent, component when the first excited state is uniquely excited, but two components when the first and second excited states are simultaneously excited. This dual exponentiality persists at pressures as low as 10 mTorr, and it is argued that the two-component decay does not arise from collisional vibrational relaxation.     

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.     

Oxidation of tertiary amines by hexachloroacetone

Triethylamine and ethyldiisopropylamine are oxidized by hexachloroacetone. The vinyldialkylamines are acylated by hexachloroacetone, a discussion of the mechanism is presented.     

Low-temperature polyesterification in the presence of tertiary amines

Several variations of catalysis (nucleophilic and general basic) responsible for the lowtemperature polyesterification in solution have been investigated. The type of catalysis which predominates depends on the chemical structure of the initial reagents and the reaction conditions. Increasing basicity of the tertiary amine and increasing acidity of the bisphenol promote the general base catalysis.     

A one-pot synthesis of tertiary amines from amines,lactams and urethanes

A one-pot synthesis of unsymmetrical tertiary amines from amides, lactams and urethanes has been developed. The reaction is general for all cases examined with the exception of N-aryl containing examples, which are not accessible by this method.     

Ruthenium catalyzed synthesis of secondary or tertiary amines from amines and alcohols

Unsymmetrical secondary and tertiary amines are prepared by the ruthenium catalyzed reaction of alcohols with amines, which provides highly efficient method for synthesis of cyclic amines.     

杂环芳胺的结构与致突性之间的定量关系研究

基于杂环芳胺在生物体内的代谢特征 ,对 19种杂环芳胺类致突变化合物进行了半经验分子轨道法理论计算 ,求得了该类化合物的结构与致突变活性相关关系 .结果表明 ,杂环上氨基经羟基化后形成亲电活性中心的难易程度以及活性中心的稳定性等因素决定其致突性 ,计算预测值与实验结果相吻合 ,19种杂环芳胺的致突性实验值与PM 3计算结果之间存在非常显著的相关性 ,其相关系数r =0 .919,F =19.0 >F 0 .0 1 .