Synthesis of 5-Amino-4-(4-aryl-2-thiazolyl)-2,3-Dihydro-2-Pyrrolones

A method was developed for preparation of 5-amino-4-(4-aryl-2-thiazolyl)-2,3-dihydro-2-pyrrolones by alkylation of 4-aryl-2-thiazolylacetonitriles by N-substituted chloroacetamides in the presence of K₂CO₃. In 1-(1-naphthyl)-substituted pyrrolones atropoisomerism was observed.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 266–269.Original Russian Text Copyright © 2005 by Resnyanskaya, Tverdokhlebov, Tolmachev, Volovenko.     

Reactions of 2-Nitro- and 2-Bromo-2-nitroethenylphosphonates with Anthracene

Bis(2-chloroethyl) 2-nitro- and 2-bromo-2-nitroethenylphosphonates react with anthracene along two competing pathways: [4+2] cycloaddition and electrophilic substitution; in the case of the bromo derivative, the resulting products undergo dehydrobromination under the reaction conditions to form anthracene- and dihydroanthracene-containing nitroethenylphosphonates.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 729–733.Original Russian Text Copyright © 2005 by Anisimova, Kuzhaeva, Berkova, Deiko, Berestovitskaya.     

Synthesis of Substituted 2-Methyl-4-quinolyl Isothiocyanates and 4-Mercaptoquinolines

Synthesis was performed of substituted 2-methyl-4-quinoline thiouronium salts by reaction of 2-methyl-4-chloroquinolines with thiourea. The alkaline hydrolysis of these salts afforded the corresponding 2-methyl-4-quinolyl- isothiocyanates and 2-methyl-4-mercaptoquinolines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 783–785.Original Russian Text Copyright © 2005 by Avetisyan, Aleksanyan, Ambartsumyan.     

Synthesis and Properties of Substituted 2-Amino-5-nitrosobenzylamines

Substituted nitrosobenzylamines were synthesized by cyclocondensation of hydroxyimino-β-diketones with 4-dialkylamino-2-butanones.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 57–59.Original Russian Text Copyright © 2005 by Semichenko, Gavrilova, Suboch.     

Spiroheterocyclic Compounds Based on 2-Bromobutanolides

Bromination of ethyl 5-alkoxymethyl-2-oxotetrahydrofuran-3-carboxylates afforded ethyl 5-alkoxymethyl-3-bromo-2-oxotetrahydrofuran-3-carboxylates which reacted with thiourea, substituted thioureas, benzimidazole-2-thiol, and benzothiazole-2-thiol to give new heterocyclic compounds.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 590–593.Original Russian Text Copyright © 2005 by Kochikyan.     

Regular Trends in Nucleophilic Substitutions in 2-Alkylamino-4-chloronitrobenzenes

The effect of substituents in position 2 on the reactivity of 2-alkylamino-4-chloronitrobenzenes in nucleophilic substitution by N-nucleophiles of various character was studied.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 224–227.Original Russian Text Copyright © 2005 by Zotova, Kushakova, Kuznetsov, Rodin, Garabadzhiu.     

Reaction of 2-Alkoxypropenals with 2-Aminoethanethiol and Ring-Chain Tautomerism of the Resulting 2-(1-Alkoxyvinyl)-1,3-thiazolidines

2-Alkoxypropenals react with 2-aminoethanethiol to give tautomeric mixtures of the corresponding 2-(1-alkoxyvinyl)-1,3-thiazolidines and 2-(2-alkoxy-2-propenylideneamino)ethanethiols in quantitative yield. The state of the ring-chain tautomeric equilibrium depends on the polarity and acidity of the medium and initial reactant ratio, and it does not change on raising the temperature and is only slightly affected by microwave irradiation.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 529–534.Original Russian Text Copyright © 2005 by Keiko, Funtikova, Stepanova, Larina.     

3-Alkyl-2-[3(4)-pyridyl]-5-(2-vinyloxyethoxymethyl)-oxazolidines

1-Alkylamino-3-(2-vinyloxyethoxy)-2-propanols react with 3-and 4-pyridinecarbaldehydes to give equimolar mixtures of cis- and trans-3-alkyl-5-(2-vinyloxyethoxymethyl)-2-[3(4)-pyridyl]oxazolidines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 104–108.Original Russian Text Copyright © 2005 by Kukharev, Stankevich, Lobanova, Klimenko, Kukhareva.     

Nitration of Some 3-(2-Furyl)-2-propenones with Dinitrogen Tetraoxide

Nitration of 3-(2-furyl)-2-propenones with dinitrogen tetraoxide leads to the corresponding 3-(4-nitro-2-furyl)-2-propenones. If the furyl group contains a substituent in position 5, the nitration occurs at the side chain to afford 3-(5-R-2-furyl)-2-nitro-2-propenones.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 3, 2005, pp. 431–436.Original Russian Text Copyright © 2005 by Sitkin, Klimenko.     

Reactions of 2-Butylsulfanyl-2-alkenals with Alcohols and Water

2-Butylsulfanyl-2-alkenals react with alcohols at room temperature in the presence of acid catalysts to give 45–90% of the corresponding acetals. Acetals derived from 2-butylsulfanylpropenal readily undergo hydrolysis at the vinylsulfanyl group (20°C, catalysis by HCl or TsOH) with formation of 2-oxopropionaldehyde O,O- or O,S-acetals in 70–90% yield. Unlike 2-butylsulfanyl-2-propenal O,O-dialkyl acetals, the initial aldehydes and 2,4-dinitrophenylhydrazones derived therefrom are stable to hydrolysis under analogous conditions: the vinyl sulfide moiety remains unchanged even under considerably more severe conditions (100°C, 3 h; HCl, H₂SO₄, CF₃SO₂OH, or TiCl₄).__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 832–836.Original Russian Text Copyright © 2005 by Keiko, Chuvashev, Stepanova, Larina.     

Reduction of Alkyl-2-amino-5,6-dialkyl-3-cyanopyridine-4-carboxylates

Reduction of alkyl-2-amino-5,6-dialkyl-3-cyanopyridine-4-carboxylates with sodium borohydride in protic solvents gave rise to 4-amino-3-imino-6,7-dialkyl-1,3-dihydrofuro[3,4-c]pyridines that at hydrolysis in acid medium afforded the corresponding lactones.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 288–291.Original Russian Text Copyright © 2005 by Vasil’ev, Lyshchikov, Nasakin, Kayukov, Tafeenko.     

Reformatsky Reaction of Methyl α-Bromoisobutyrate with 2-Arylmethylidenemalonic Acid Derivatives

Reformatsky reagent obtained by treatment of methyl α-bromoisobutyrate with zinc reacts with dimethyl 2-arylmethylidenemalonates to give trimethyl 2-aryl-3-methylbutane-1,1,3-tricarboxylates. The reaction of the same compound with ethyl 3-aryl-2-(4-methylphenylcarbamoyl)acrylates yields cyclic products, ethyl 4-aryl-5,5-dimethyl-1-(4-methylphenyl)-2,6-dioxopiperidine-3-carboxylates. Treatment of the latter with morpholine and phenylhydrazine leads to the corresponding 4-aryl-5,5-dimethyl-1-(4-methylphenyl)-2,6-dioxopiperidine-3-carboxylic acid morpholides and phenylhydrazides. The products are formed as a single diastereoisomer.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1034–1038.Original Russian Text Copyright © 2005 by Shchepin, Fotin.     

Synthesis and Transformations of 4-(4-Ethoxycarbonylphenylamino)- and 4-(2-Carboxyphenylamino)quinolines

Synthesis was performed of 4-(4-ethoxycarbonylphenylamino)- and 4-(2-carboxyphenylamino)-2-methylquinolines by reaction of 2-methyl-4-chloroquinoline with anesthesin and anthranilic acid. In concentrated sulfuric acid 4-(2-carboxyphenylamino)-2-methylquinoline underwent cyclization into 6-hydroxy-7-methylquinolino[3,2-c]quinoline, and the alkaline hydrolysis of 4-(4-ethoxycarbonylphenyl-amino)quinoline afforded 2-methyl-4-(4-carboxyphenylamino)quinoline.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 786–787.Original Russian Text Copyright © 2005 by Avetisyan, Aleksanyan, Ambartsumyan.     

Polyfunctional Derivatives of Isocytosine. Effect of Hydration on Prototropic Tautomerism of 2-(2-Hydroxyethyl)amino-6-methylpyrimidin-4(3<Emphasis Type="Italic">H</Emphasis>)-one

Hydration of 2-(2-hydroxyethyl)amino-6-methylpyrimidin-4(3H)-one forms an equilibrium mixture of 4-oxo-3,4-dihydro and 4-hydroxy tautomers. The intermediate in mutual transitions of these tautomers has a zwitter ionic structure. The equilibrium shifts to the 4-oxo-3,4-dihydro form as the polarity of the medium decreases.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 677–682.Original Russian Text Copyright © 2005 by Erkin, Krutikov.     

On the Mechanism of Intramolecular Cyclization of Dialkyl(2-propynyl)[3-alkenyl(or aryl)-2-propynyl]-ammonium Salts

Given are experimental data indicating that base-catalyzed intramolecular cyclization of ammonium salts containing a 2-propynyl-like group together with a 3-alkenyl- or 3-aryl-2-propynyl group follows a concerted mechanism involving the 3-alkenyl- or 3-aryl-2-propynyl moiety as π⁴-fragment.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 3, 2005, pp. 369–371.Original Russian Text Copyright © 2005 by E. Chukhadzhyan, Gevorkyan, El. Chukhadzhyan, Kinoyan.     

Acylation and Carbamoylation of 2-Hydrazinothiazole Derivatives. Identification of Isomeric Structures

Acylation and carbamoylation of 2-(arylmethylidenehydrazino)- and 2-(aroylhydrazino)thiazoles was performed, and structure of the products was established.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 594–600.Original Russian Text Copyright © 2005 by Denisova, Bakulev, Dehaen, Toppet, Van Meervelt, Kodess.     

Synthesis of 4-amino-substituted but-2-en-4-olides

Previously unknown 4-amino derivatives of spiro-annelated Δ²-butenolide were synthesized by the addition of various amines at the activated triple bond of 4-hydroxy-2-alkynoic esters. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2761–2770, December, 2005.     

Synthesis of Dimethyl 2-(2-Alkyl-1,3-diaryl-3-oxopropyl)malonates and Their Reactions with Amines

Zinc enolates generated from 1-aryl-2-bromoalkanones and zinc react with dimethyl 2-(1-arylmethylene)malonate to form dimethyl 2-(2-alkyl-1,3-diaryl-3-oxopropyl)malonates. The latter react with benzylamine or cyclohexylamine to form the corresponding disubstituted amides, while the reactions with piperidine, morpholine, and p-methoxyaniline provide monosubstituted amides of the corresponding target derivatives.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 636–641.Original Russian Text Copyright © 2005 by Shchepin, Korzun, Poroshina.     

Synthesis of Secondary Alcohols and Their Esters from 4-Alkoxy-4-acetyl-1-(2-ethoxyethyl)piperidines

4-Alkoxy-4-(1-hydroxyethyl)-1-(2-ethoxyethyl)piperidines were prepared by reduction of 4-alkoxy-4-acetyl-1-(2-ethoxyethyl)piperidines. The esters of the hydroxyethyl derivatives were prepared. The presence of an asymmetric carbon atom in the molecules of the carbinols and their esters results in complication of their ¹H NMR spectra.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 456–460.Original Russian Text Copyright © 2005 by Praliev, Poplavskaya, Nauyryzova, Baimurzina, Botbaeva.     

Coordination Polymers of Scandium Sulfate. Crystal Structures of (H2Bipy)[Sc(H2O)(SO4)2]2 · 2H2O and (H2Bipy)[HSO4]2

Compounds with the general formula Cat_x[Sc(H₂O)_z(SO₄)_y] · nH₂O (Cat = NH₄, H₂Bipy (Bipy is 4,4′-bipyridine), and HEdp (Edp is ethylenedipyridine) are synthesized and identified by elemental analysis and IR spectral data. The X-ray diffraction analysis of (H₂Bipy)[Sc(H₂O)(SO₄)₂]₂ · 2H₂O shows that in the structure of this compound, the chains of ScO₆ octahedra and SO₄ tetrahedra are united to form ribbons due to the tridentate coordination of the sulfate ion. The ribbons form a framework, whose infinite cavities contain H₂Bipy²⁺ cations.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 8, 2005, pp. 576–582.Original Russian Text Copyright © 2005 by Petrosyants, Ilyukhin, Sukhorukov.