1-Acyldeoxyvasicinone salts as effective intermediate C-and N-acylating agents for alkaloids and amino acids

The reaction of deoxyvasicinone with acid chlorides of aliphatic (acetylbromide) and aromatic (benzoyl-, o-, p-methoxy-, p-nitrobenzoylchlorides) acids was studied. It was shown that 1-deoxyvasicinone salts were formed at room temperature; α-aroyloxymethylidenedeoxyvasicinones, in the presence of triethylamine at 80–85°C. It was found that acid chlorides cause 1-acyldeoxyvasicinone salts to transform into α-hydroxy-or α-aroyloxyarylidenedeoxyvasicinones, which indirectly confirmed their acylating properties. It was found that 1-acyldeoxyvasicinone salts were effective acylating agents for alkaloids (cytisine, 1,2-dihydrodeoxyvasicinone) and amino acids (glycine, β-alanine, α-aminobutyric acid) and can be used to acylate primary and secondary aliphatic and heterocyclic amines. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 585–589, November–December, 2006.     

Effect of the trifluoroacetyl group on the direction of the recyclization of the pyrazine ring in 6-trifluoroacetylpyrrolo[1,2-a]pyrazinium salts

A cyclotransformation of 6-trifluoroacetylpyrrolo[1,2-a]pyrazinium salts involving the trifluoroacetyl group carbon atom was discovered and investigated. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1714–1719, November, 2007.     

Transformations of sym-octahydroxanthene-1,8-diones and 1,8-dioxo-sym-octahydroxanthylium salts in recyclization under the influence of amines

The chemical behavior of 9-R-sym-octahydroxanthene-1,8-diones and salts based on them in recyclization reactions under the influence of amines was studied. The effect of the basicity of the amines on the direction of recyclization was established. A method is proposed for the single-stage synthesis of sym-octahydroacridine-1.8-dione oximes based on 1,8-dioxo-sym-octahydroxanthenes. Conditions were worked out for the oxidation of sym-octahydroxanthene-1,8-diones and N-R-decahydroacridinediones to the corresponding salts. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 32–38, January, 2006.     

The investigations in 2,3′-biquinoline series. 25*. Synthesis of 4-(2-quinolinyl)-pyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinolines and 4-(2-quinolyl)-imidazo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinolines

A method has been developed for the synthesis of 4-(2-quinolinyl)-1,2,3,3a-tetrahydropyrrolo-[1,2-a]quinolines based on the 1,3-dipolar cycloaddition reaction of α,β-unsaturated carbonyl compounds to 2,3′-biquinolinium salts. Oxidation in benzene using MnO₂ gave 4-(2-quinolinyl)-pyrrolo[1,2-a]quinolines. It was found that a side product of the 1,3-dipolar cycloaddition is 7,14-di-benzoyl-6,13-di(2-quinolyl)-6a,7,13a,14-tetrahydro-7a,14a-diazadibenzo[a,h]anthracene. Reaction of 1′-phenacyl-2,3′-biquinolinium salts with hydroxylamine in acetic acid gave 4-(2-quinolyl)imidazo-[1,2-a]quinolines. *For Communication 24 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 433–439, March, 2009.     

Alkylation of toluene with methanol on microporous MxH3?XPW12O40 [M=K+, Cs+, NH4+ and Tl+]

Alkylation of toluene was carried out on microporous salts of phosphotungstic acid. Among the systems studied, M_2.5H_0.5PW₁₂O₄₀ showed maximum catalytic activity.p-Xylene selectivity was evaluated as a function of x. A linear correlation was observed betweenpara-selectivity and number of strong acid sites with strength of H₀≤−5.6.     

Electrooxidative coupling of salts of nitro compounds with halide,nitrite, cyanide,and phenylsulfinate anions

Electrolysis of salts of primary and secondary nitro compounds (nitroethane, 1- and 2-nitropropanes, nitrocyclohexane, and nitrocycloheptane) in the presence of excess halide, nitrite, cyanide, and phenylsulfinate anions under undivided and divided amperostatic electrolysis conditions in a two-phase medium (CH₂Cl₂/H₂O) produces geminal nitrohalides (35–85% yields), dinitro compounds (15–51%), nitronitriles (6–27%), and nitrosulfones (50–70%). The salts of secondary nitro compounds form the products of oxidative coupling with halide and phenylsulfinate anions under the undivided electrolysis conditions. In all other cases, divided electrolysis is required. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1539–1546, July, 2005.     

The reaction of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with dihalomethanes

Methylene-bis[N′-oxydiazene-N-(β-hydroxyalkyl)N-oxides] were synthesized by the reaction of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with diahalomethanes. The effect of the nature of the starting reagents and the reaction condtions on the yields of the target compounds was studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2269, November, 1998.     

<Emphasis Type="Italic">N</Emphasis>-(3-Phosphonopropyl)-substituted α-amino acids and their phosphine oxide analogs

A facile method was developed for the synthesis of N-(3-phosphonopropyl)-substituted α-amino acids and their phosphine oxide analogs based on hydrolysis of 2-oxo-1,2-azaphospholanes and 1,2-azaphospholanium salts prepared from readily available reagents. A chelate Cu^II N-[(3-diphenylphosphoryl)propyl]glycinate was isolated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2551–2556, November, 2005.     

Pyrano[4,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidinium salts

5-Aroyl-1,3,6-trimethyluracils were converted to pyrano[4,3-d]pyrimidinium salts. Reactions of the salts obtained with ammonia, primary amines, and hydrazine were studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2251–2257, November, 2007.     

Methods for the synthesis of cinnolines (review)

This review analyses the principal approaches to the synthesis of the cinnoline nucleus, used as synthetic precursors of arenediazonium salts, arylhydrazones, and arylhydrazines, and also reductive methods for the synthesis of polycondensed derivatives of cinnoline. The mechanisms of the transformations and the possibilities and limitations of the various methods are discussed. Special attention is paid to methods based on the cyclization of derivatives of arenediazonium salts, which have been developed substantially in recent years. In memory of A. A. Potekhin __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 643–667, May, 2008.     

Synthesis and structure of di(NON-azoxy)formals and some relatedN-alkyl-N′-alkoxydiazeneN-oxides

A series of di(NON-azoxy)formals and some relatedN-alkyl-N′-alkoxydiazeneN-oxides were prepared by the reaction ofN-nitrosohydroxylamine salts with dihaloalkanes. The dependence of the yield of di(methyl-NON-azoxy)formal on the reaction conditions and the nature of the cation was studied. The structure of di(methyl-NON-azoxy)formal and di(phenyl-NON-azoxy) formal as well as of the coppertert-butylnitrosohydroxylaminate was established by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1486–1493, August, 1997.     

Reactions of functionalized alkyl halides withN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxide salts

Some characteristic features of reactions ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxide salts with various α- and β-functionalized alkyl halides were established. Some α-and β-functionalizedN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides and e ethylenebis[N-(β-hydroxyalkyl)-N′-oxydiazeneN-oxides] were synthesized for the first time. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 123–129, January, 1999.     

Synthesis of 2-substituted 6,8-dinitro[1,2,4]triazolo[1,5-a]pyridines and the formation of the related zwitterionic σ-adducts

A method for the synthesis of 2-substituted 6,8-dinitro[1,2,4]triazolo[1,5-a]pyridines is proposed. The method includes the reaction of 2-chloro-3,5-dinitropyridine with the corresponding 5-substituted tetrazoles. The resulting compounds react with anhydro bases of α- and γ-methylazinium salts to give zwitterionic σ-adducts. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1405–1407, July, 1999.     

Alkaloids from <Emphasis Type="Italic">Papaver angrenicum</Emphasis>. II. Crystal and Molecular Structure of the New Diisoquinoline Alkaloid Pangrenine

The structure of pangrenine, a new diisoquinoline alkaloid representing salts of protoberberine bases that was isolated from the aerial part of Papaver angrenicum as the nitrate, was established. Spectral and x-ray structural data of the isolated compound were presented. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 357–359, July–August, 2005.     

Formation of cation–radical anion pairs derived from carboxybenzophenone–tetrabutylammonium salts. Pulse radiolysis studies

Pulse radiolysis of acetonitrile solutions of tetra-n-butyl ammonium salts of 2- and 4-carboxybenzophenones [BP-COO⁻···N⁺(C₄H₉)₄] were performed in order to generate directly the reduced forms of the benzophenone moieties within pre-formed ion pairs. In earlier studies on photochemical electron transfer reactions, ion pairs containing a tetraalkyl ammonium cation and a benzophenone radical anion were formed in an electron transfer to the triplet BP from a quencher consisting of a tetraalkyl ammonium salt of (phenylthio)acetic acid. In the current work, the [BP^•−COO⁻···N⁺(C₄H₉)₄] ion pairs were formed by direct reduction of the salts without the complication of a third moiety, i.e., the (phenylthio)acetic anion. The spectra and kinetic parameters of the radiolytically-reduced salts were compared to the behavior of reduced forms of the 2- and 4-COOH substituted benzophenones. The results from the pulse radiolysis and photochemistry were compared and explained in terms of the different structures of the ion pairs.     

Pyrano[4,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidinium salts

Reactions of 5-aryl- and 5,7-diaryl-1,3-dimethyl-2,4-dioxopyrano[4,3-d]pyrimidinium salts with hydrazine were studied. In the former case, the reaction products were the 6-amino-1,3-dimethyl-2,4-dioxopyrido[4,3-d]pyrimidinium salts. 5,7-Diarylpyrano[4,3-d]pyrimidinium salts were transformed into either the corresponding pyridinium salts or 1H-pyrimido-[5,4-d][1,2]diazepine-2,4(3H,9H)-diones, depending on the hydrazine concentration and the reaction time. For Part 1, see Ref. 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1720–1725, May, 2008.     

Reactions of α-pentafluorophenylpyrylium salts with hydroxylamine

The reactions of α-pentafluorophenylpyrylium salts with hydroxylamine in ethanol afford isoxazoline derivatives and/or pyridine N-oxides depending on the steric characteristics of the substituent in the second α position. The structure of 2-hydroxy-2-pentafluorophenyl-4-phenyl-2,3,5,6,7,8-hexahydroquinoline 1-oxide, which was synthesized by the reaction of 2-pentafluorophenyl-4-phenyl-5,6,7,8-tetrahydrobenzopyrylium perchlorate with NH₂OH, was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 402–407, February, 2008.     

Combined study of thermochemical properties of nitroform and its salts

A combined method for determination of the standard enthalpies of formation of nitroform and its salts was proposed. The enthalpies of dissolution of nitroform and its ammonium, hydrazinium, guanidinium, and potassium salts in water were measured. The enthalpy of combustion of hydrazinium salt of nitroform was determined by a combustion calorimetry, and its standard enthalpy of formation was calculated. The enthalpy of formation of trinitromethyl anion in indefinitely diluted aqueous solution −24.94±0.79 kJ mol⁻¹, was calculated on the basic of the data obtained for enthalpies of formation and dissolution of ammonium and hydrazinium salts of nitroform. Standard enthalpies of formation of nitroform and its salts were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2451–2454, December, 1998.     

Synthesis, properties, and structures of ammonium 4-aryl-5-cyano-2-oxo-1,2,3,4-tetrahydropyridine-6-thiolates

The reaction of arylcyanomethylenethiocetamides with Meldrum, acid gave Michael adducts as ammonium salts. When heated in alcohol, these salts undergo cyclization to ammonium 4-aryl-5-cyano-2-oxo-1,2,3,4-tetrahydropyridine-6-thiolates. The structure ofN-methylmorpholinium 4-(2′-chlorophenyl)-5-cyano-2-oxo-1,2,3,4-tetrahydropyridine-6-thiolate was established by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1029–1034, May, 1997.     

Structures of deoxypeganine salts

The structures of deoxypeganine (DOP) hydrochloride and oxalate were solved by x-ray structure analysis. An infinite chain along the crystallographic c axis was formed in the crystal structure of DOP oxalate. A molecular framework consisting of Cl anions and DOP cation protonated at N1 was found in the structure of unhydrated DOP hydrochloride. The molecular packing of the “host” (DOP cation) was pseudoisostructural in the studied ion-molecular crystals but differed from other known DOP salts. The “guest” molecules (acid anions) in the studied and known DOP salts formed different intermolecular contacts. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 280–283, May–June, 2006.