Novel Petasis boronic acid-Mannich reactions with tertiary aromatic amines

Tertiary aromatic amines can serve as amine substrates for the Petasis boronic acid-Mannich reaction, providing a practical synthetic route for the CC bond formation of α-(4-N,N-dialkylamino-2-alkyloxyphenyl)carboxylic acids. The scope and limitations of this method have been examined.     

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.     

Synthesis and chirooptical properties of some tertiary amines containing a pyridine ring

Tertiary amines of the pyridine series containing an -phenylethylamine residue have been synthesized. The IR spectra and circular dichroisms of these amines have been measured in the 400–200 nm interval, and an assignment of the bands has been made. It is suggested that the long-wave absorption band in the 315 nm region for N-methyl-N-[2-(pyridin-2-yl) ethyl]--phenylethylamine and the Cotton effect corresponding to it are due to an intramolecular CTC.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 92–96, January, 1984.     

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.     

Complexes of cobalt(II) aryl carboxylates with quinoline and isoquinoline

Summary Several new complexes of cobalt(II) aryl carboxylates Co(O₂CC₆H₄R)₂ (R =o-Me;o,m-Cl:o,m-NO₂ andm-MeO) have been prepared by refluxing an ethanolic solution of the respective cobalt(II) aryl carboxylate with quinoline (Q) and isoquinoline (IQ). The quinoline complexes are green or purple while isoquinoline complexes are pink to reddish pink. All are neutral and soluble in common organic solvents. Analytical data indicate that quinoline complexes are of 1:1 stoichiometry. Magnetic and spectral studies show them to possess the usual copper(II) acetate monohydrate type dimeric carboxylate bridged structures. formulated as Co₂(O₂CC₆H₄R)₄Q₂, in which cobalt(II) is in a square pyramidal geometry. By contrast, isoquinoline yields monomeric bisamine complexes oftrans-octahedral configuration containing bidentate chelating carboxylate groups.     

Novel multicomponent reactions of primary amines and alkyl propiolates with alloxan derivatives in water

A water-accelerated multicomponent synthesis of organic target molecules has been used as a key method for the preparation of novel barbiturate derivatives. The three-component condensation reactions of primary amines with alkyl propiolates in the presence of alloxan derivatives in water are developed as efficient and clean green synthetic procedures for the high-yielding preparation of alkyl 2-(5-hydroxy-2,4,6-trioxohexahydro-5-pyrimidinyl)-3-(alkyl or arylamino)-2-propenoates. The above synthetic protocol provides rapid access to novel and diversely substituted barbiturate derivatives.     

Size-controlled synthesis of monodispersed silver nanoparticles capped by long-chain alkyl carboxylates from silver carboxylate and tertiary amine

Monodispersed silver nanoparticles capped by long-chain alkyl carboxylates were prepared by the reaction of silver carboxylate with tertiary amine at 80 degrees C for 2 h. This approach is a unique, size-controlled synthetic method for the large-scale preparation of silver nanoparticles. Long-chain alkyl carboxylate derived from a precursor acts as a stabilizer to avoid the aggregation of silver nanoparticles and to control particle size. In addition, amine plays an important role both as a reagent to form a thermally unstable, amine-coordinated intermediate, bis(amine)silver(I) carboxylate, and as a mild reducing agent for the intermediate to produce nanoparticles at a low temperature. The silver core and carboxylate-capping ligand of silver nanoparticles were characterized by various techniques such as transmission electron microscopy, optical absorption spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, gas chromatograph mass spectroscopy, and thermogravimetric and differential thermal analysis. The diameter of the nanoparticles can be strongly influenced by the alkyl chain length and the structure of the carboxylate. The average diameters of the silver nanoparticles were controlled to less than 5 nm in the case of silver carboxylate with a single alkyl chain length of 13 or 17 carbon atoms. On the contrary, the average diameters of silver nanoparticles became large and polydisperse in the case of silver carboxylate with a chain length of 7 carbon atoms or a branched chain. In comparing triethylamine with trioctylamine, there was no obvious effect to regulate the size distribution of the nanoparticles because they could not function as a capping ligand of the nanoparticles due to their weak coordination to silver. In addition, the heat treatment of silver nanoparticles in solution rather than in the solid state was effective for the growth of particles while maintaining narrow size distributions.     

Novel synthesis of enamines by iridium-catalyzed dehydrogenation of tertiary amines

A novel route to enamines is reported, the dehydrogenation of tertiary amines catalyzed by a "pincer-ligated" iridium catalyst.     

Addition of pyridine and isoquinoline to benzoylcarbonitrile oxide

Addition of pyridine to benzoylcarbonitrile oxide affords a fragile zwitterionic adduct, which slowly reverts to the addends, leading ultimately to benzoyl isocyanate and products deriving from it. A moderately stable cycloadduct is obtained in the reaction with isoquinoline.     

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.     

1,2,3-Triazole as a safer and practical substitute for cyanide in the Bruylants reaction for the synthesis of tertiary amines containing tertiary alkyl or aryl groups

Tertiary amines containing tertiary alkyl or aryl groups were synthesized by the reaction of a ketone with an amine and 1,2,3-triazole followed by substitution of the triazole adduct with a Grignard reagent. Thus, 1,2,3-triazole serves as a safer and practical alternative to cyanide in the Bruylants reaction.     

Novel synthesis of tertiary alkyl,secondary and tertiary benzyl,and allyl selenides from the corresponding alcohols

We report an efficient synthesis of the title compounds from alcohols and selenols. The scope and limitations of the new method are disclosed.     

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).