Investigations in the area of functionally substituted azines. Synthesis and thermolysis of chlorethoxypyrimidines

The 2-amino-4-(2-chlorethoxy)-6-methyl- and 2-(2-chlorethoxy)-4-methoxy-6-methylpyrimidines were synthesized. Depending on the position of the chlorethoxy group in the ring, their therniolysis results in the formation of the oxazolopyrimidinium chloride or the N₍₁₎-(2-chlorethyl) derivative.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 237–239, February, 1996.     

Investigations in the area of functionally substituted azines. 5.* Reactions of azines with nucleophiles and hydrogen chloride

It was shown that oxazolopyrimidinium and sym-triazinium chlorides give N₍₃₎-(2-Y-ethyl)-substituted azines with nucleophiles. Oxazolo-sym-triazine also reacts analogously, being converted by hydrogen chloride to the N₍₃₎-(2-chloroethyl) derivative.Armenian Agricultural Academy, Yerevan, 375009. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1417–1420, October, 1996. Original article submitted April 15, 1996.     

Research in the field of functionally substituted azines. Syntheses of imidazolidinyl-sym-triazines

New approaches have been developed for the application of cyanamino-sym-triazines in the synthesis of imidazolidinyl-sym-triazines.     

Geometrical structures of the azines of substituted acetophenones

Conclusions By drawing on measured values of dipole moments and Kerr constants and a study of vibrational spectra, it has been shown that the molecules of the symmetrical azines of the acetophenones exist as EE forms of the s-trans conformer, the angle of rotation of the azomethylidyne fragments around the N-N bond being 130±5° with the phenyl rings displaced out of the C=N bond planes by 35±5°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1996–1999, September, 1977.     

Synthesis of functionally substituted benzaldehydes

A new method of synthesis of functionally substituted benzaldehydes by catalytic debromometoxylation of dibromomethylarenes with benzaldehyde dimethyl acetal has been suggested. Anhydrous zinc chloride has been used as a catalyst. Being soft Lewis acid, it formed no strong complex with aldehyde group and other functional groups. The initial acetal has been readily recovered by the treatment of benzaldehyde isolated from the reaction mixture with trimethyl orthoformate.     

Synthesis of functionally substituted cyanoacetates

Some new cyanoacetates were synthesized and characterized. They are precursors for -cyanoacrylates used as rapidly polymerized, cold-hardening adhesives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 523–525, March, 1993.     

Tetrazoles. 33. New method for obtaining functionally substituted tetrazoles

The interaction of 5-methylsulfonyl-1-phenyltetrazole with C-, N-, and O-nucleophiles at 18–20°C gives high yields of 1-phenyltetrazoles that are functionally substituted on the carbon atom of the heteroring. Prospects are examined for the use of 5-methylsulfonyl-1-phenyltetrazole as a universal synthon in the synthesis of tetrazoles with various types of structure.     

Porphyrins. 29. Mass spectra of functionally substituted tetraarylporphyrin derivatives

The mass spectral behavior of functionally substituted meso(p-adamantylphenyl)triphenylporphyrins and their p-methoxy-substituted analogs was studied. Breakdown of the M⁺ ions of these compounds proceeds chiefly-with a loss of the functional substituent in the adamantane ring with the formation of ions, which make it possible to determine the nature of this substituent.For Communication 28, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1642–1644, December, 1993.     

Synthesis of functionally substituted 5-phenylthiazoles

The reaction of esters and amides of 3-phenyl-3-chloro-2-oxopropionic acid with thioamides and thiourea gave new 5-phenylthiazoles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2854–2856. December, 1990.     

Synthesis of functionally substituted 2-cyanoacrylates

The conditions for the Knoevenagel synthesis of 2-cyanoacrylates containing double and triple bonds in the alkoxycarbonyl group have been studied. It was found that the esters are formed in 10–70 % yields by the condensation of the respective cyanoacetates with formaldehyde in the 11 ratio in the presence of piperidine, followed by the pyrolysis of the oligomers formedin vacuo at 170–200 °C in the presence ofpara-toluenesulfonic acid. The compounds synthesized readily undergo polymerization at room temperature and can be used as the basis for thermostable rapidly polymerizing adhesives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 646–649, April, 1994.     

Electrochemical synthesis of functionally substituted sulfides

A method of synthesis of functionally substituted sulfides by cathode electrolysis of thiols on platinum or carbon glass electrodes in the presence of organyl halides was developed. The method of the rotating disk electrode with ring showed that this process passes through the intermediate formation of a thiolate anion on the cathode, and its reaction with the organyl halide results in a high yield of sulfides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1605–1609, July, 1990.     

Synthesis of new functionally substituted fullerenopyrrolidines

New fullerenopyrrolidines were synthesized by the three-component reactions of fullerene C₆₀, N-methylglycine, and aromatic aldehydes, viz., N,N-bis(2-chloroethyl)-4-aminobenzaldehyde, N-(2-chloroethyl)-N-methyl-4-aminobenzaldehyde, indole-3-carbaldehyde, 4-phenylbenzaldehyde, and anthracene-9-carbaldehyde. The structures of the resulting compounds were established by spectroscopic methods.     

Hypohalogenation of functionally substituted acetylenic norbornenes

Hypohalogenation of norbornenes containing a triple bond and various functional groups in the side chain was performed using mixtures of aqueous solutions of hydrochloric or hydrobromic acid (or sodium or potassium bromide) and hydrogen peroxide. The reaction was found to involve addition of electrophilic reagent generated in situ (HOBr or HOCl) at the endocyclic double bond with formation of the corresponding halohydrins. The latter underwent dehydrohalogenation by the action of alklai to give exo-5,6-epoxybicyclo[2.2.1]-heptane derivatives in high yields. Kinetic relations holding in the hypobromination process were established, and the initial rates and activation parameters were calculated.     

Studies with 1‐functionally substituted alkyl azoles: Novel synthesis of functionally substituted azolylbenzimidazoles and functionally substituted azolyl‐1,2,4‐triazoles

ω‐Azolylacetophenones 1 and 2 react with dimethylformamide dimethylacetal to yield enaminones 7,8 that were converted into azolylazoles via reaction with hydrazine and with hydroxylamine. Compounds 1,2 also coupled with aromatic diazonium salts to yield arylhydrazones and reacted with nitrous acid to yield corresponding oximes.     

Functionally substituted azines. 1. Synthesis and reactions of 2-(N-cyano-N-carbethoxmethylamino)-4,6-dimethylpyrimidine

Treatment of 2-(N-potassium-N-cyanamino)-4,6-dimethylpyrimidine with ethyliodoacetate produces 2-(N-cyano-N-carbethoxymethylamino)-4,6-dimethylpyrimidine. Alkaline hydrolysis of the last gives 2-(3-potassium-2,4-dioxoimidazolidinyl-1)-4,6-dimethylpyrimidine. Ammonolysis and hydrazinolysis give imino- or amino-imidazolidinylpyrimidine, respectively.Armenian Agricultural Institute, Erevan 375009. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1241, September, 1994. Original article submitted August 9, 1994.     

Structure and properties of functionally substituted azothiazoles

Absorption and luminescence spectra of a series of functionally substituted azothiazoles in dimethylformamide and transparent polymeric matrix (bulk copolymer of methyl methacrylate and methacrylic acid) were studied. Kinetics of decolorization of liquid and solid solutions under the action of the integral light of a mercury lamp was measured to evaluate their lightfastness.