Reaction of alkenynylamines with 2-aminoresorcinol as a method for the synthesis of 2-(2-alkenyl)-4-hydroxybenzoxazoles

The reaction of 1-diethylamino-(4-methyl)-3-penten-1-ynes with 2-aminoresorcinol leads to the formation of 2-(2-alkenyl)-4-hydroxybenzoxazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 231–232, February, 1992.     

Three-dimensional structures of phosphorus-containing heterocycles 50. 2-dimethylamino-2-oxo- and -2-thiono-1,3,2-oxathiaphosphorinanes

Conclusions A chair conformation with an axial orientation of the phosphoryl or thiophosphoryl group is preferable for 2-dimethylamino-2-oxo- and-2-thiono-1,3,2-oxathiaphosphorinanes. The cis isomer of 2-dimethylamino-2-oxo-4-methyl-1,3,2-oxathiaphosphorinane has a similar structure with an equatorial orientation of the 4-methyl group, while the corresponding sulfide is characterized by a trans configuration with a reoriented positioning of the substituents attached to the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1369–1374, June, 1989.The authors thank I. A. Litvinov and V. A. Naumov for carrying out the x-ray diffraction analysis.     

Synthesis of 2-phenylethynyl-1,3-dioxanes and their hydrolysis

2-Phenylethynyl substituted 1,3-dioxanes were obtained by the reaction of 1,3-dioxanium salts with an lotsich reagent. It was shown that they are readily hydrolyzed with the formation of a-acerylenic ketones. A simple new method is proposed for the synthesis of the latter without isolating the intermediate 1,3-dioxanes using the reaction of 4 substituted 2-methyl(phenyl, furyl)-1,3-dioxanium salts with hydroxymethyl- and phenylethynylmagnesium bromide as examples.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 193–197, February, 1996.     

Dipole moments,kerr constants,and conformations of some substituted methyl cyclopropyl ketones

Conclusions The acetyl group in a substituted cyclopropane ring has an s-cis conformation that is distorted by either 15–20° (cis-2-halo-cis-3-methyl derivatives) or by 55–70° (cis-2-halo-1-methyl derivatives).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1174–1177, May, 1977.     

Friedel-Crafts acylation of 5-hydroxybenzimidazole derivatives

The Friedel-Crafts acylation of 5-hydroxybenzimidazole and its 2-methyl and 1-ethyl-2-methyl derivatives proceeds exclusively at C⁴ and only with aliphatic acid derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1928–1931, August, 1991.     

2-R-7-Hydroxy-8-methyl-3-(2-quinolyl)chromones

By condensation of 2-methyl resorcinol with 2-quinolyl acetonitrile, we have synthesized α-(2-quinolyl)-2,4-dihydroxy-3-methylacetophenone, which when reacted with carboxylic acid anhydrides followed by hydrolysis yields 2-R-7-hydroxy-8-methyl-3-(2-quinolyl)chromones.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 407–415, March, 2005.     

Synthesis of N-vinyl derivatives of 2-methyl- and 4(5)-methylimidazoles

Conclusions The reaction of 2-methyl and 4(5)-methylimidazoles with acetylene in the presence of Gu₂Cl₂ leads to the corresponding N-vinyl derivatives. 1-Vinyl-4(5)-methylimidazole is formed as a mixture of two isomers differing in the position of the methyl group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2122–2124, September, 1987.     

Gas-Chromatographic Determination of Sarin, Soman, and O-Isobutyl S-2-(N,N-Diethylamino)ethyl Methylphosphonothioate (a VX-Like Compound) Traces in Water

A gas-chromatographic procedure for the determination of O-isobutyl S-2-(N,N-diethylamino)ethyl methylphosphonothioate (VX), sarin, and soman in water at levels of 2 × 10^–6, 5 × 10^–5, and 2 × 10^–6 mg/L, respectively, was proposed. The procedure includes liquid–liquid extraction with the use of salting-out agents, back extraction, and evaporation. In this case, the VX compound was converted into O-isobutyl O-methyl methylphosphonate (a substance convenient for chromatographic determination) by the reaction with hydrochloric acid, methanol, thriethylamine, and silver nitrate.     

Synthesis of fluorine-containing tetrasubstituted pyrimidines from 1-cyano-2-chloro-2-trifluoromethylethylenes

The condensation of 1,1-dicyano- and 1-trifluoromethylthio-1-cyano-2-chloro-2-trifluoromethylethylenes with amidines of trifluoro- or trichloroacetic acid gave 2,4-bis(trifluoromethyl)(or 2-trichloromethyl-4-trifluoromethyl)-5-cyano(or 5-trifluoromethylthio)-6-aminopyrimidines. The corresponding substituted 1-methyl(or 1-phenyl)-6(1H)-pyrlmidineimines were synthesized by condensation of the same ethylenes with N-methyl (or N-phenyl)benzamidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1680–1681, December, 1981.     

2-Amino-6-phenyl-7,8-dihydroindazolo[4,5-d]thiazoles

Treatment of 4-oxo-l -phenyl-4,5,6,7-tetrahydroindazole and its 3-methyl, 6-phenyl, and 3-methyl-6 phenyl substituted derivatives with pyridinium bromide-perbromide and subsequent reaction of the 5-brorno derivatives obtained with thiourea gave 2-amino-6 phenyl-7, 8-dihydroindazolo[4,5-d]thiazole and its corresponding substituted derivatives. The condensation of these products with 2 formyldimedone led to their 4, 4-dimethyl-2, 6-dioxocyclohexylidene derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 497–500. April, 1966.     

Synthesis of 2-methyl-4,6-diarylpyrilium tetrafluoroborates

Condensation of acetophenones with acetic anhydride in the presence of boron trifluoride etherate has given some 2-methyl -4,6-diarylpyrilium tetrafluoroborates. The optimum conditions for the synthesis of 2-methyl-substituted pyrilium salts have been established.Translated from Khimiya Geterotsiklicheskikh Soedenii, No. 2, pp. 173–176, February, 1985.     

Indole derivatives. 124. 5-(2-phenylethenyl)indolines and 5-(2-phenylethenyl)indoles

5-(2-Phenylethenyl)indolines, the dehydrogenation of which leads to the formation of the corresponding compounds of the indole series, were obtained from 5-formyl-1-methyl(or benzyl)indolines via the Grignard reaction with benzyl-magnesium chloride and subsequent dehydration. The hormonal activity of the synthesized compounds was studied.See [1] for communication 123.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 4, pp. 466–469, April, 1984.     

Radical arylation of acetyl-substituted thioureas

Conclusions The reaction of N-acetylthiourea with phenyl and p-tolyl radicals leads to diaryl disulfides and 2-methyl -4-thioaryl-6-acetamido-s-triazines.A scheme was proposed for the formation of substituted s-triazines by the successive transformation of the intermediate radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2591–2593, November, 1982.     

Synthesis of 2-(pyridylazo)-2-furyl-and 2-(pyridylazo)-2-thienylmethines and other heterocyclic Schiff bases in the presence of molecular sieves

The reactions of 2-furaldehyde, 2-thiophenecarbaldehyde, and their 5-methyl derivatives with 2-aminopyridines and some other amines in the presence of molecular sieves as a dehydrating agent and acid catalyst have been studied. A series of new heterocyclic azomethines was synthesized. Proposals were made for the mechanism of the condensation involving 2-aminopyridines and the structure of the intermediates in these processes.Latvian Institute of Organic Synthesis, Riga LV-1006, Latvia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 890–897, July, 2000.     

Enantioselective syntheses of no-carrier-added (n.c.a.) (s)-4-chloro-2-[f] fluorophenylalanine and (s)-(α-methyl) -4-chloro-2-[f]fluorophenylalanine

(S)-4-Chloro-2-fluorophenylalanine and (S)-(α-methy)-4-chloro-2-fluorophenylalanine were synthesized and labeled with no carrier added (n.c.a.) fluorine-18 through a radiochemical synthesis relying on the highly enantioselective reaction between 4-chloro-2-[¹⁸F]fluorobenzyl iodide and the lithium enolate of (2S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3-methyl-1,3-imidazolidine-4-one for (S)-4-chloro-2-[¹⁸F]fluorophenylalanine and (2S,5S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3,5-dimethyl-1,3-imidazolidine-4-one for (S)-(α-methyl) -4-chloro-2-[¹⁸F] fluorophenylalanine. Quantities of about 20–25 mCi were obtained at the end of sy nthesi s, ready for injection after hydrolysis and high performance liquid chromatography (HPLC) purification, with a radiochemical yield of 17%–20% corrected to the end of bombardment after a total synthesis time of 90–105 min from [¹⁸F] fluoride. The enantiomeric excesses were shown to be 97% or more for both molecules without chiral separation and the radiochemical and chemical purities were 98% or better.     

Investigation of the reactivities and tautomerism of azolidines. 40. 2-iminothiazolidin-4-one in the mannich reaction

It is shown that the aminomethylation of 2-iminothiazolidin-4-one and its 5-methyl and 5-arylidene derivatives in an alcohol medium leads to the formation of 6-oxo-2,3,4,5,6,7-hexahydrothiazolo [3,2-a]-1,3,5-triazines. The structures of the compounds obtained were confirmed by their IR, PMR, and UV spectra.See [1] for Communication 39.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 477–480, April, 1981.     

Spectrophotometric behaviour of quinolinium oxime-palladium(II) complexes

Summary It has been established that 1-(2-phenyl-2-hydroxyiminoethyl)-1-quinolinium chloride, 1-(2-phenyl-2-hydroxyiminoethyl)-1-isoqui-nolinium chloride, 1-(2-phenyl-2-hydroxyiminoethyl)-1-(4-methyl)-quinolinium chloride and 1-(2-phenyl-2-hydroxyiminoethyl)-1-(6-methyl)quinolinium chloride react with palladium(II) chloride in the pH range 3.3–7.1 and form yellow water-soluble 11 complexes with maximum absorbance at 413 nm. The conditional stability constants of the complexes at the optimum pH of 6.5 are all about 10^4.7, and the molar absorptivities are in the range 2.2–2.6×10³ l·l mole^–1·cm^–1 at pH 6.5 and 413 nm. Beer's law is obeyed up to 3–4×10^–4 M oxime concentration, depending on the oxime determined.     

Indolizines

A comparative study was made of electrophilic substitution reactions of isomeric 2-methyl(aryl)-7-ethoxycarbonyl- and 2-methyl(aryl)-6-ethoxycarbonylindolizines, and it was shown that 6-ethoxycarbonylindolizines have higher reactivities.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 348–351, March, 1976.     

Reaction of 1-alkyl-2-aryl-3-(2-methyl-2,3-epoxypropionyl)aziridines with boron trifluoride etherate in methanol

The reaction of boron trifluoride etherate in methanol with trans-1-methyl(ethyl)-or cis-1-cyclohexyl-2-aryl-3-(2-methyl-2,3-epoxypropionyl)aziridines leads to the formation of the corresponding boron fluoride complexes on the nitrogen atom of the aziridine ring. Reaction with trans-1-cyclohexyl-2-phenyl-3-(2-methyl-2,3-epoxypropionyl)aziridines occurs with stereospecific opening of the aziridine ring to give diastereomeric 2-methyl-5-methoxy-5-phenyl-4-cyclohexylamino-1,2-epoxypen-tan-3-ones, as well as products from the opening of the epoxide and aziridine rings — tetrahydrofuranones and tetrahydropyranones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 596–600, May, 1986.     

Iodocyclization of 2-allylcyclohexanols

Iodination of 2-allylcyclohexanol and its 1-methyl and 1-phenyl derivatives gives the corresponding 2-(iodomethyl)octahydrobenzofurans. These are reduced by to the stereoisomeric 2-methyloctahydrobenzofurans. The rate of iodination of 2-allylcyclohexanols is largely independent of their configuration.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 170–172, February, 1985.