A chemo-enzymatic route to enantiomerically pure cyclic tertiary amines

Deracemization of racemic chiral tertiary amines has been achieved by combination of an enantioselective amine oxidase, obtained through directed evolution, and ammonia borane in a one-pot process.     

Synthesis of non-natural cyclic amino acids from available unsaturated tertiary amines

New approach is developed to the synthesis of cyclic amino acids derivatives. Unsaturated tertiary amines react with ethyl diazoacetate under the catalysis by copper catalyst Cu(F₃acac)₂ leading to the formation of products of [2,3]-sigmatropic rearrangement which via the metathesis of double bonds undergo a ring closure. The subsequent hydrogenation of compounds obtained furnished esters of 6- and 7-membered cyclic α-amino acids. Besides the racemic also optically active compounds were obtained, in particular, esters of (R)- and (S)-pipecolic acid.     

Splitting of perfluorinated tertiary cyclic amines by the action of SbF5

It was shown that perfluorinated tertiary cyclic amines are dealkylated by the action of SbF₅ with the formation of cyclic azomethines. The presence of a perfluoroalkyl substitutent in the -position to the nitrogen atom in the amine molecule considerably decreases its stability to the action of antimony pentafluoride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1616–1619, July, 1990.     

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.     

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.     

Reaction of 2,3-dichloro-5,6-dicyanopyrazine with enamines and some tertiary amines

The reaction of 2,3-dichloro-5,6-dicyanopyrazine ( 1 ) with enamines as well as a few tertiary amines as enamine precursors was investigated. Both reactions gave aminovinyl-substituted pyrazine derivatives. During the attempted purification of 3c or 3d by column chromatography on silica gel, 2-chloro-5,6-dicyano-3-(1′-oxocyclopent-2′-yl)pyrazine ( 4 ) was obtained, apparently by hydrolytic cleavage. The products prepared are all of interest as potential pesticides.     

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.     

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.     

Electrochemical chlorination of amines

We have studied the laws governing the electrochemical chlorination of primary and secondary amines in aqueous solution on a ruthenium-titanium anode under conditions of diaphragm electrolysis. It was found that in order to ensure the most complete conversion of the amines into the corresponding chloramines it is necessary to add NaHCO₃ to the electrolyte [amine:NaHCO₃=1(1.5–3)]. Under the conditions of electrolysis primary amines are converted almost quantitatively into dichloramines. High yields of the N-chloro-derivatives of secondary amines can be obtained with high current densities and concentrations of NaCl.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 620–625, March, 1990.     

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.     

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.     

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.     

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.