Reaction of <Emphasis Type="Italic">N</Emphasis>-Sulfinyltrifluoromethanesulfonamide CF<Subscript>3</Subscript>SO<Subscript>2</Subscript>N=S=O with Carbonyl Compounds

N-Sulfinyltrifluoromethanesulfonamide CF₃SO₂N=S=O reacts with salicylaldehyde, 2-furaldehyde, 2-thiophenecarbaldehyde, 3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, and 2-phenyl-2H-1,2,3-triazole-4-carbaldehyde to afford the corresponding N-aryl(hetaryl)methylidenetrifluoromethanesulfonamides in high yields. Reactions of the latter with aniline give no adducts at the C=N bond but transamination products. The reaction of trifluoromethanesulfonamide with phenyl isocyanate led to formation of N,N′-diphenylurea instead of expected N-phenyl-N′-(trifluoromethylsulfonyl)urea.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1006–1010.Original Russian Text Copyright © 2005 by Shainyan, Tolstikova.     

Adsorption of Some Nitrogen-Containing Compounds and Benzene Derivatives from Aqueous Solutions on Active Carbons

The adsorption from aqueous solutions of benzene derivatives (phenol, benzoic acid, and newly synthesized benzoic acid derivatives containing imidazole heterocycles: hydrazide of 4-(1H-imidazole-1-ylmethyl) benzoic acid and methyl ester of 4-(1H-imidazole-1-ylmethyl)benzoic acid), as well as of imidazole and triazole, on active carbons with various microporous structures is studied. The effect of the nature of adsorbate molecules and the pore sizes of active carbons on the sorption character is analyzed. It is shown that the adsorption from aqueous solutions of the organic derivatives of benzene is determined, on the one hand, by the size of a molecule, and, on the other hand, by its hydration energy.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 3, 2005, pp. 416–420.Original Russian Text Copyright © 2005 by Kharitonova, Krasil’nikova, Vartapetyan, Bulanova.     

1, 5-Rearrangement of enol acylates of aryl 1H.-1, 2, 4-triazol-1-ylmethyl ketones

The rearrangement of enol acylates of aryl 1H-1, 2, 4-triazol-1-ylmethyl ketones at 140–150°C in acetic anhydride is studied. The migration of the acyl group to the C(5) atom of the heterocycle is found to be intramolecular. The characteristics of the original and final products are presented. X-ray structural studies of the enol acetates of 2, 4-dichlorophenyl 1H-1, 2, 4-triazol-1-ylmethyl ketone and 2, 4-dichlorophenyl 5-acetyl-1H-1, 2, 4-triazol-1-ylmethyl ketone are carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 560–564, March, 1993.     

Synthesis and Functionalization of 3-Ethylquinoxalin-2(1<Emphasis Type="Italic">H</Emphasis>)-one

A new and effective procedure was developed for the synthesis of 3-ethylquinoxalin-2(1H)-one from o-phenylenediamine and ethyl 2-oxobutanoate. The latter was prepared by the Grignard reaction of diethyl oxalate with ethylmagnesium bromide or iodide. The ethyl group in 3-ethylquinoxalin-2(1H)-one can readily be converted into various functional groups: α-bromoethyl, α-thiocyanato, α-azidoethyl, α-phenylaminoethyl, acetyl, and bromoacetyl. The reaction of 3-(bromoacetyl)quinoxalin-2(1H)-one with thiourea and hydrazine-1,2-dicarbothioamide gives the corresponding 3-(2-amino-4-thiazolyl) derivatives.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 609–616.Original Russian Text Copyright © 2005 by Mamedov, Kalinin, Gubaidullin, Isaikina, Litvinov.     

Synthesis of new amides of the <Emphasis Type="Italic">N</Emphasis>-methylpiperazine series

New carboxylic acid amides containing an N-methylpiperazine fragment were synthesized by reactions of 1-methylpiperazine or 3- and 4-(4-methylpiperazin-1-ylmethyl)aniline with 4-chlorobenzoyl chloride and of 4-methyl-3-nitroaniline with 4-(4-methylpiperazin-1-ylmethyl)benzoyl chloride or benzotriazol-1-yl 4-(4-methylpiperazin-1-ylmethyl)benzoate. 4-Chloro-N-[4-(4-methylpiperazin-1-ylmethyl)phenyl]benzamide reacted with imidazole, quinolin-5-amine, and 2-methylquinolin-5-amine to give substituted 4-amino-N-[4-(4-methylpiperazin-1-ylmethyl)phenyl]benzamides. 4-Methyl-3-nitrophenyl-4-methylpiperazin-1-yl-substituted benzamides were reduced with hydrazine hydrate over Raney nickel to obtain N-(3-amino-4-methylphenyl)-4-(4-methylpiperazin-1-ylmethyl)benzamide as key intermediate in the synthesis of antileukemic agent imatinib and its isomer with alternative position of the amide group, 4-[(3-amino-4-methylphenylamino)methyl]phenyl-(4-methylpiperazin-1-yl)methanone.     

One Step Synthesis of N-[1-(2-Diethylamino-ethylamino)-7-(H or methoxy)-9-oxo-9H-thioxanthen-4-ylmethyl]-formamides and,Acetamide from Their Corresponding Alcohols,Hycanthone, and 7-Methoxy-hycanthone

Abstract

N-[1-(2-Diethylamino-ethylamino)-7-(H or methoxy)-9-oxo-9H-thioxanthen-4-ylmethyl]-formamides and acetamide were synthesized from their corresponding alcohols, hycanthone and 7-methoxy-hycanthone, in one step procedure and 45% yield.     

Cyclization of 2-Azido-3-(alkyl-<Emphasis Type="Italic">N</Emphasis>-nitrosoamino)-1,4-naphthoquinones to 1-Alkyl-1<Emphasis Type="Italic">H</Emphasis>-naphtho[2,3-<Emphasis Type="Italic">d</Emphasis>][1,2,3]triazole-4,9-dione 2-Oxides

Thermolysis of 2-azido-3-(alkyl-N-nitrosoamino)-1,4-naphthoquinones gives rise to compounds belonging to a new quinoid fused heterocyclic system, 1-alkyl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione 2-oxides.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 926–927.Original Russian Text Copyright © 2005 by Radaeva, Dolgushina, Sakilidi, Gornostaev.     

3-Oxy-5-phenyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazole-4-carboxylic Acid. Synthesis,Structure, and Properties

The structure of 3-oxy-5-phenyl-1H-1,2,3-triazole-4-carboxylic acid was determined both experimentally (by the X-ray diffraction method) and by quantum-chemical calculations. Alkylation of 3-oxy-5-phenyl-1H-1,2,3-triazole-4-carboxylic acid (as crystal hydrate) with methyl iodide, depending on the reactant ratio, gives 1-methoxy-4-phenyl-1H-1,2,3-triazole-5-carboxylic acid and methyl 1-methoxy-4-phenyl-1H-1,2,3-triazole-5-carboxylate. Nitration of the title compound under mild conditions occurs at the 5-phenyl group with formation of meta-nitro derivative, while under more severe conditions 3,5-dinitrobenzoic acid is obtained. 3-Oxy-5-phenyl-1H-1,2,3-triazole-4-carboxylic acid was also converted into the corresponding acid chloride and substituted amide.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 601–608.Original Russian Text Copyright © 2005 by Shtabova, Shaposhnikov, Mel’nikova, Tselinskii, Nather, Traulsen, Friedrichsen.     

Reaction of 2,2,3,3-Tetracyanocyclopropanecarboxylic Acid with Iodides. Synthesis of 3-Cyano-4-dicyanomethylidene-5-oxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrol-2-olates

Reactions of 2,2,3,3-tetracyanocyclopropanecarboxylic acid with potassium, sodium, calcium, strontium, barium, ammonium, N-methylpyridinium, N-methylquinolinium, N,N-dimethyl-1,4-diazabicyclo-[2.2.2]octane-1,4-diium, and N,N-dimethylanilinium iodides afforded the corresponding 3-cyano-4-dicyanomethylidene-5-oxo-4,5-dihydro-1H-pyrrol-2-olates.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 535–538.Original Russian Text Copyright © 2005 by Kayukova, Kayukov, Nikolaev, Tafeenko, Ershov, Nasakin.     

Synthesis,structure, and transformations of <Emphasis Type="Italic">N</Emphasis>-(alkyl-, benzyl-, arylsulfonyl)-<Emphasis Type="Italic">N</Emphasis>-(oxiran-2-ylmethyl)bicyclo[2.2.1]hept-5-en-<Emphasis Type="Italic">exo</Emphasis>-2-ylmethanamines

Reactions of N-(alkyl-, benzyl-, arylsulfonyl)bicyclo[2.2.1]hept-5-en-exo-2-ylmethanamines with 2-(chloromethyl)oxirane in the presence of tetramethylammonium iodide gave a number of cage-like N-(oxiran-2-ylmethyl)sulfonamides, as well as N-(exo-5,6-epoxybicyclo[2.2.1]heptan-exo-2-ylmethyl)-4-nitro-N-(oxiran-2-ylmethyl)benzenesulfonamide. The latter was also synthesized by oxidation of oxiran-2-ylmethyl norbornene derivative with peroxy acids. Opening of the epoxide ring in N-(oxiran-2-ylmethyl) sulfonamides in reaction with benzylamine followed the Krasuskii rule, and the aminolysis of N-(exo-5,6-epoxybicyclo[2.2.1]-heptan-exo-2-ylmethyl)-4-nitro-N-(oxiran-2-ylmethyl)benzenesulfonamide chemoselectively occurred at the side-chain epoxy group.     

Stereoselective Synthesis of (7aS)-1-Methylenehexahydro-1H-pyrrolizine and (?)-Heliotridane from N-Diphenylmethyl-(S)-proline Ethyl Ester

Alkaloid (7aS)-1-methylenehexahydro-1H-pyrrolizine was synthesized from N-diphenylmethyl-(S)-proline ethyl ester by cyclopropanation of the ester group with ethylmagnesium bromide in the presence of titanium tetraisopropoxide, replacement of the protecting group on the nitrogen atom, and cationic cyclopropylallyl isomerization of (S)-1-(1-ethoxycarbonylpyrrolidin-2-yl)cyclopropyl sulfonate into the corresponding allyl bromide. Stereoselective reduction of (7aS)-1-methylenehexahydro-1H-pyrrolizine with sodium tetrahydridoborate in the presence of nickel chloride afforded (−)-heliotridane [(1S,7aS]-1-methylhexahydro-1H-pyrrolizine] in high yield.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 73–77.Original Russian Text Copyright © 2005 by Lysenko, Kulinkovich.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-Arylsulfonyl-α-thienylglycines from <Emphasis Type="Italic">N</Emphasis>-(2,2,2-Trichloro-1-thienylethyl)arenesulfonamides

Reactions of N-(2,2,2-trichloroethylidene)arenesulfonamides with thiophene, 2-chlorothiophene, and 2,5-dichlorothiophene, as well as of N-(2,2,2-trichloro-1-hydroxyethyl)arenesulfonamides with 2-chlorothiophene, lead to formation of the corresponding N-(2,2,2-trichloro-1-thienylethyl)arenesulfonamides. Alkaline hydrolysis of the latter occurs selectively at the trichloromethyl group to give N-arylsulfonyl-α-thienylglycines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 93–96.Original Russian Text Copyright © 2005 by Aizina, Rozentsveig, Ushakova, Levkovskaya, Mirskova.     

Reductive Acylamination of Pyridine <Emphasis Type="Italic">N</Emphasis>-Oxide with Aminopyridines and Their <Emphasis Type="Italic">N</Emphasis>-<Emphasis Type="Italic">p</Emphasis>-Tolylsulfonyl Derivatives

Pyridine N-oxide reacts with 2- and 3-aminopyridines and their N-p-tolylsulfonyl derivatives in alkaline medium in the presence of p-toluenesulfonyl chloride to give N-p-tolylsulfonyl-2,2′- and 2,3′-dipyridylamines, respectively, as a result of reductive acylamination. In the reactions with 4-aminopyridine and 4-p-tolylsulfonyl-aminopyridine, their N-p-tolylsulfonyl- and N,N-bis(p-tolylsulfonyl) derivatives are formed, while reductive acylamination does not occur.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 128–130.Original Russian Text Copyright © 2005 by Solekhova, Kurbatov.     

Synthesis and Characterization of Two vic-Dioximes Containing the 1,3-Dioxolane Ring and 1,4-Diaminobutane and Their Cobalt(II), Nickel(II), Copper(II) and Zinc(II) Metal Complexes

Two new vic-dioxime ligands, (E,E)-N-{4-[(1,4-dioxaspiro[4.4]non-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L¹H₂) and (E,E)-N-{4-[(1,4-dioxaspiro[4.5]dec-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L²H₂) containing two different heteroatoms (N,O) have been prepared from anti-chloroglyoxime, N-(1,4-dioxaspiro[4.4]non-2-ylmethyl)butane-1,4-diamine (3) and N-(1,4-dioxaspiro[4.5]dec-2-ylmethyl)butane-1,4-diamine (4). Co^II, Ni^II and Cu^II complexes of the ligands have a metal:ligand ratio of 1:2 and the ligands coordinate through the two N atoms, as do most of the vic-dioximes. However, Zn^II complexes of the ligands have a metal:ligand ratio of 1:1 and the ligands are coordinated only by the N, O atoms of the vic-dioximes. In the Co^II complexes two water molecules, and in the Zn^II complexes a chloride ion and a water molecule, are also coordinated to the metal ion. The structures of the compounds were determined by a combination of elemental analysis, magnetic moments, molar conductances, thermogravimetric analysis (t.g.a.) and spectroscopic (u.v.–vis., i.r., ¹H- and ¹³C-n.m.r.) data.     

Cycloacylation of <Emphasis Type="Italic">N</Emphasis>-Phenyl-3-oxobutanethioamide with 3-Aryl-2-propenoyl Chlorides

Reactions of N-phenyl-3-oxobutanethioamide with 3-aryl-2-propenoyl chlorides in acetone in the presence of potassium carbonate give rise to 4-aryl-5-acetyl-1-phenyl-6-thioxopiperidin-2-ones, 2-aryl-5-acetyl-6-phenylamino-2,3-dihydro-4H-thiopyran-4-ones, and 6-aryl-2-acetonylidene-3-phenyl-5,6-dihydro-4H-1,3-thiazin-4-ones whose structure was proved both by spectral methods and chemical transformations.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 292–296.Original Russian Text Copyright © 2005 by Britsun, Borisevich, Samoilenko, Lozinskii.     

Oxalylation of the 3-oxo-<Emphasis Type="Italic">N</Emphasis>-phenyl-3-R-propanethioamides

Oxalylation of 3-oxo-N-phenyl-3-R-propanethioamides in aprotic solvents in the temperature range from −40°C to +20°C results in 4-acyl-5-phenylamino-2,3-dihydrothiophene-2,3-diones and 2-(2-oxo-2-R-ethylidene)-3-phenyl-1,3-thiazolidine-4,5-diones, while in the presence of potassium carbonate, potassium 4-acyl-2,3-dioxo-1-phenyl-2,3-dihydro-1H-pyrrole-5-thiolates are formed.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 757-760, March, 2005.     

Reaction of the Reformatskii reagent obtained from bromotetrahydrofuran-2-one with 2-oxochromene-3-carboxylic or 3-oxo-3<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">f</Emphasis>]chromene-2-carboxylic acid derivatives

The Reformatskii reagent obtained from 3-bromotetrahydrofuran-2-one reacts with alkyl esters of 6-bromo- and 6,8-dibromo-2-oxochromene-3-carboxylic acid or alkyl esters and N-benzylamide of 3-oxo-3H-benzo[f]chromene-2-carboxylic acid to form alkyl esters of 6-bromo- and 6,8-dibromo-2-oxo-4-(2-oxotetrahydrofuran-3-yl)chroman-3-carboxylic acid or alkyl esters and N-benzylamide of 2,3- dihydro-3-oxo-1-(2-oxotetrahdrofuran-3-yl)-1H-benzo[f]chromene-2-carboxylic acid as a mixture of two diastereomers.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1513–1515.Original Russian Text Copyright © 2004 by Shchepin, Fotin, Shurov.This revised version was published online in April 2005 with a corrected cover date.     

Halogenation of Imidazo[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-2-one Derivatives

Chlorination and bromination of 2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one and its N-methyl-substituted derivatives in acetic acid at 90–95°C leads to formation of the corresponding 5,6-dichloro(dibromo)-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones. Iodination of the same substrates with ICl under analogous conditions yields 6-iodo derivatives. Chlorination of 6-iodo-1,3-dimethyl-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one is accompanied by replacement of the iodine atom by chlorine with formation of 5,6-dichloro-1,3-dimethyl-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one. Bromination of 6-bromo- and 6-chloro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones gives 5,6-dibromo- and 5-bromo-6-chloro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones, respectively.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 586–589.Original Russian Text Copyright © 2005 by Yutilov, Lopatinskaya, Smolyar, Gres’ko.     

Crystal structure of <Emphasis Type="Italic">N</Emphasis>-Furfuryl-1-(2-Thienyl)but-3-en-1-Ammonium Chloride

The crystal structure of (H₂L)⁺Cl^-(HL is N-furfuryl- 1-(2-thienyl)but-3-en-1-amine) was studied by X-ray diffraction analysis. In the crystal, (H₂L)⁺ cations and Cl^- anions are united through N-HCl hydrogen bonds into polymer chains.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 69–71.Original Russian Text Copyright © 2005 by Antsyshkina, Egorova, Sergienko, Sadikov.     

Synthesis of Heterocycles from Arylation Products of Unsaturated Compounds: XIII. 5-R<Superscript>1</Superscript>-Benzyl-2-(R<Superscript>2</Superscript>-2-pyridylimino)thiazolidin-4-ones

Meerwein reactions of arenediazonium bromides with methyl and ethyl acrylates gave 3-aryl-2-bromopropionic acid esters which were subjected to cyclocondensation with N-(2-pyridyl)- and N-(6-methyl-2-pyridyl) thioureas to obtain 5-R¹-benzyl-2-(R²-2-pyridylimino)thiazolidin-4-ones. The latter were shown to exist in solution as E isomers of the imino form.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1071–1075.Original Russian Text Copyright © 2005 by Matiichuk, Obushak, Tsyalkovskii.