Reactions of benzo-1,2,3-dithiazolium salts and their selenium analogs with amines

The corresponding 6-arylamino derivatives were obtained by reaction of 6-chloro, 6-bromo, and 6-methoxy derivatives of benzo-1,2,3-dithiazolium and their selenium analogs — benzo-1,2,3-thiaselenazolium, benzo-2,1,3-thiaselenazolium, and benzo-1,2,3-diselenazolium salts — with aromatic amines. The 6-methoxy derivatives also react with acetates of secondary aliphatic amines, whereas in the case of the chloro derivatives attack is directed to the heteroring. 6-Aryl(dialkyl)amino derivatives of dithiazolium and 1,2,3-thiaselenazolium salts are protonated in concentrated sulfuric acid at the exocyclic nitrogen atom. The analogous derivatives of 2,1,3-thiaselenazolium and diselenazolium salts under the same conditions form a tautomeric mixture of dications, the position of the equilibrium between which depends on the substituent. The electronic and PMR spectra of the amination products are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1499–1502, November, 1977.     

Synthesis and some properties of benzo-1,2,3-thiaselenazolium salts

The reaction of selenious acid on benzo-1,2,3-dithiazolium salts (Herz salts) gives benzo-1,2,3-thiaselenazolium salts, which were previously obtained from o-aminothiophenols. This reaction, which involves exchange of sulfur by selenium in the heteroring, occurs only under conditions in which the products of hydrolysis of the Herz salts —benzo-3H-1,2,3-dithiazole 2-oxides- are in equilibrium with them.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1361–1364, October, 1976.     

Reaction of benzo-1,2,3-dithiazolium salts with aromatic amines

The character of a displaceable group depends substantially on the rate of reaction of substituted 6-chloro and 6-methoxy derivatives of benzo-1,2,3-dithiazolium salts, which gives the corresponding 6-phenylaminobenzo-1,2,3-dithiazolium salts. In 4,6-disubstituted benzo-1,2,3-dithiazolium salts, an aniline residue displaces only the substituent in the 6 position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 183–185, February, 1976.     

Mass spectrometric study of methyl-substituted 4-azaphenanthrenes and their nitration products

The mass spectral behavior of five derivatives of the 4-azaphenanthrene series — 1,3-dimethyl-(I), 2,3-dimethyl-(II), 1,2,3,-trimethyl-(III), 1,2,3-trimethyl-8-nitro-(IV), and 1,3-dimethyl-6,7-dinitro-4-azaphenanthrene (V) — was studied. The stabilities of the molecular ions with respect to gragmentation (W_M) are higher by a factor of two or more for the methyl-substituted I–III than for nitro derivatives IV and V. The intensity of the [M-H]⁺ ion peak in the mass spectra of I–V does not depend on the number of methyl groups but only on their positions: the presence of a CH₃ group in the 2 position leads to an [M-H]⁺ ion that is 1.5 times more intense than when there is a methyl group in the 1 position. The molecular ions of I–V do not eliminate HCN molecules; this constitutes evidence for the absence of randomization of their methyl groups. The presence of a CH₃ substituent in the 1 or 2 position does not affect the intensity of the [M-CH₃]⁺ ion peaks, while the simultaneous presence of CH₃ groups attached to the C₁ and C₂ atoms increases the intensity of the [M-CH₃]⁺ fragment peak by a factor of two. In the mass spectra of nitro derivatives IV and V, [M-O]⁺, [M-OH]⁺, [M-NO]⁺, and [M-NO₂]⁺ fragments are observed in the first step of the fragmentation of the M⁺ ion, whereas the [M-CO]⁺ ion peak characteristic for the dissociative ionization of 1-nitronaphthalene is also observed for 8-nitro-substituted IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1365–1369, October, 1977.     

Reactivities,Conformational Properties,and Molecular Structures of σ-Bonded Cyclic Selenurane Dications

Abstruct:

The synthesis of σ-selenurane dication salts via transannular interactions and the reactivities of these dication salts are described. The X-ray crystallographic analyses of the dication salts show that the dications have selenium atoms in a trigonal-bipyramidal bonding environment. Ab initio calculations carried out for the dication revealed that the selenium atoms exclusively carry the positive charge. The interesting conformational properties of these dications are also described.     

Electroreduction of benzo-1,2,3-dithiazolium salts and their selenium analogs in nonaqueous solution

The electroreduction of benzo-1,2,3-dithiazolium cations and their selenium analogs in aprotic solvents takes place in two steps. The first step is a reversible, one-electron transfer leading to the formation of stable radicals detected by EPR. As a result of further electroreduction, the radicals obtained combine with six electrons to form the corresponding o-aminothio(seleno)phenols. Analysis of the reduction potentials of the compounds studied shows that the substitution of a selenium atom for a sulfur in these cations, especially in the 2 position of the heterocycle, facilitates their electrochemical reduction. The electrochemical activity and the kinetics of nulceophilic substitution in the cations studied are compared.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 219–222, February, 1985.     

Heterocyclic analogs of pleiadiene

The behavior of N-methyl derivatives of perimidine (I), aceperimidine (VI), aceperimidylene (VII), naphth[2,3-d]imidazole (V), benzimidazole (II), and 1H- and 3H-naphth[1,2-d]imidazoles (III, IV) with respect to n-butyllithium was studied. Compounds I and V–VII add n-butyllithium to the C=N bond to give 2-n-butyl-2,3-dihydro derivatives, whereas II–IV are metallated to give 2-lithio derivatives. The different reactivities of I, V–VII, and II–IV are explained by the reduced aromatic character and high polarization of the C=N bond in I and V–VII. The investigated compounds are arranged in the following order with respect to the ease of undergoing basic deuterium exchange at the C-H bond V>II>III>IV>VII>I>VI. There is no correlation between the rate of deuterium exchange and the behavior of I–VII with respect to butyllithium.See [1] for communication XXX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1544–1548, November, 1977.     

Reactions of N-alkylazinium cations. Reaction of acridinium salts with enamines

The reaction pyridinium N-methylazinium salts and their benzo analogs — quinolinium, isoquinolinium, and acridinium ions — with enamines was investigated. Acridanyl-substituted enamines, their iminium salts, and the corresponding ketones were obtained by reaction of the N-methylacridinium salts with the enamines in dimethyl sulfoxide at room temperature. The quinolinium and isoquinolinium salts have lower activities; the N-methylpyridinium cation does not react at all under the indicated conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 666–669, May, 1979.     

A study of the tautomerism of the N-butyl-4(2)-methoxycarbonyl-pyrrolid-3-ones and their hydrochlorides

The tautomerism of N-butyl-2-methoxycarbonyl-4-methylpyrrolid-3-one (I), N-butyl-4-methoxycarbonylpyrrolid-3-one (II), N-butyl-4-methoxycarbonyl-2-methylpyrrolid-3-one (III), N-butyl-4-methoxycarbonylpyrrolid-3-one hydrochloride (IV), and N-butyl-4-methoxy-carbonyl-2-methylpyrrolid-3-one hydrochloride (V) has been studied by UV and IR spectroscopy. It has been found that the esters I–V are highly ionized in aqueous and ethanolic solutions at concentrations of 10^–2–10^–3 M. On passing from methyl cyclopentran-1-one-2-carboxylate to the esters II and III the position of the equilibrium in heptane and CCl₄ shifts in the direction of the keto form. On passing from the esters II and III to the esters IV and V, the position of the equilibrium shifts in the direction of the enol. Meyer's relationship is not satisfied for the esters II and III, while it is satisfied for the esters IV and V. Hypotheses have been put forward on the causes of the phenomena mentioned.     

13C NMR spectra of handelin and its derivatives

The¹³C spectra of the diguaiane lactone handelin (I), deacetylhandelin (II), handelin diacetate (III), and deacetyldehydrohandelin (IV), and also cumambrin A (V) — a known sesquiterpene lactone that is a component part of the molecule of the compound (I) and is isolated together with it from a single source — have been studied. The identification of the resonance lines was based on a comparison with one another of the¹³C NMR spectra of compounds (I–IV) and (V) obtained under conditions of complete and partial decoupling from protons, and an analysis of the chemical shifts of certain carbon atoms of the model lactone cumambrin A and their comparison with the analogous parameters of handelin and its derivatives. The -, -, and -contributions of the neighboring groups to the chemical shifts of the carbon atom considered, and, in individual cases, the contributions due to steric factors, were also taken into account. A complete assignment of the lines of the spectra has been made on the basis of the comparative consideration performed.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 329–334, May–June, 1979.     

2-Oxo-2,3-dihydroimidazo[2,1-a]isoquinoline and its transformations

2-Oxo-2,3-dihydroimidazo[2,1-a]isoquinoline (I) was synthesized by the action of -haloacetic acids on 1-aminoisoquinoline esters. The reactions of I with nitrous acid, acylating agents, aromatic aldehydes, p-nitrosodimethylaniline, and arenediazonium salts were studied. 3,3-Dihalo derivatives of this system with high reactivities of the halogen atoms were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1666–1671, December, 1976.     

Electronic and steric factors in reactions involving the formation of spiropyrans

A study of the properties of six-membered heterocyclic cations with a methyl group in the position makes it possible to reveal the relative roles played by electronic and steric factors for the conversion of the corresponding o-oxidostyryl derivatives to spiropyrans. The positive charge on the carbon atom in the investigated bicyclic heterocations increases in the order 1,2-dimethylisoquinolinium <1,2-dimethylquinolinium <1,2,3-trimethylquinolinium <1,2-dimethyl-3,4-dihydroisoquinolinium, whereas the rates of reaction with p-dimethylaminobenzaldehyde follow a different sequence — 1,2-dimethylisoquinolinium <1,2,3-trimethylquinolinium <1,2-dimethyl-3,4-dihydroisoquinolinium <1,2-dimethylquinolinium. The ability of o-oxidostyryl isoquinolinium and 1,3-dimethylquinolinium derivatives to form spiropyrans, in contrast to 1-methylquinolinium derivatives, is due to the steric effect of the hydrogen atom in the peri position or of the methyl group near the reaction center, which leads to disruption of the coplanarity and a decrease in the stabilities of the corresponding merocyanine molecules.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 818–827, June, 1976.     

Synthesis and spectral-generational characteristics of pentamethylidynecyanine dyes from 1-methyl-3-arylbenzo[f]quinolinium salts

Pentamethylidynecyanine dyes were synthesized by the reaction of 1-methyl-3-(R-phenyl)benzo[f]quinolinium quarternary salts with 1,3,3-triethoxy-1-propene, Pentamethylidynecyanines substituted in the meso position of the polymethine chain were obtained by condensation of these salts with 1-anilino-2-methyl-3-dimethoxy-1-propene hydrobromide. The spectral and generational characteristics of the dyes were determined. It was shown that the presence of a phenyl group in the benzo-[f]quinoline ring of the dyes gives rise to a bathochromic shift of the absorption and generation maxima. The investigated dyes have high generation efficiencies that lie in the 20–30% range and in the 940–1010 nm spectral range.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1523–1527, November, 1982.     

Neues Grisoumeter zur Bestimmung des Methans in Grubenwettern

Ohne Zusammenfassung(Hierzu Tafel I, Figure I–IV.)Trynietz in österr. Schlesien, am 24. Juli 1886.     

Benzo-1,2,3-oxadiazole and 6-Diazocyclohexa-2,4-dienone: Structures and Relative Energies of Molecules

Structural parameters, IR spectra, ionization potentials, relative energies, isomerization barriers, and solvation energies have been calculated for the aromatic benzo-1,2,3-oxadiazole (prevalent tautomer in the gas phase) and zwitterionic 6-diazocyclohexa-2,4-dienone (prevalent tautomer in a polar solvent) molecules. Similar calculations indicated that unsubstituted 1,2,3-oxadiazole is unstable in all solvents.Original Russian Text Copyright © 2004 by S. G. Semenov and Yu. F. Sigolaev__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1128–1131, November–December, 2004.     

Synthesis of benzimidazole derivatives

New bases and quaternary salts — 2-methylbenzimidazole derivatives — containing 2-pyridyl residues as a substituent in various positions of the benzimidazole ring were synthesized. Benzimidazolium salts of a new type with hetaryl groups attached to both nitrogen atoms were obtained. Imidacyanines were synthesized from the quaternary salts of pyridyl-substituted 2-methylbenzimidazoles, and the chief light-absorption maxima of these dyes were determined.See [1] for communication IVTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 687–690, May, 1972.     

New conducting salts containing unsymmetricalπ-donors

This communication describes the synthesis and the electrochemical properties of a new type of donor containing sulfur or selenium atoms: the dimethyltetramethylenetetraselenafulvalene 1 and the dimethyltetramethylenetetrathiafulvalene 2. The electrical conductivity of their charge transfer complexes and of some of their radical cation salts are reported.     

Mass spectrometric study of 9-substituted 10-sila-2-azaanthracenes

The dissociative ionization of 10 derivatives of 10-sila-2-azaanthracene, containing cyanoethyl (I–III), aminopropyl (IV), amino (V, VI), and amide (VII–X) groups at the C₍₉₎ atom, was investigated. It was shown that for all the compounds the general direction of decomposition is elimination of substituents from the silicon and carbon C₍₉₎ atoms. The stability of the compounds to electron impact is determined chiefly by the nature of the substituent at the C₍₉₎ atoms and depends weakly on the type of substituent at the silicon atom. In the case of amino-derivatives V–X, fragmentation of the molecular ions is determined by the method of localization of the positive charge in the molecular ion. This determines the occurrence of specific decompositions, which permits reliable identification of the compounds studied according to their mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1071–1076, August, 1984.     

Nucleophilic substitution in 1,2,3-thiadiazoles

By reactions of nucleophilic substitution of the halogen atom in 5-halo-1,2,3-thiadiazoles (IV), we have obtained 5-amino- (I, V), hydrazino-(VI, VII, IX, X), and mercapto- (VIII) 1, 2, 3-thiadiazoles. We show that upon reaction with amines, a mixture of 5-amino-1, 2, 3-thiadiazoles (I) and 5-mercapto-1, 2, 3-triazoles (II) is formed, and also the reaction product of compounds I and IV,: the selectivity of this process depends only on the type of solvent.Organic Synthesis Technology Department, Urals State Technical University—UPI, Ekaterinburg 620002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 554–559, April, 1994. Original article submitted February 28, 1994.     

Trifluoromethyl-containing cumulated 1,3-oxathiols and 1,4-oxathians

In the course of acid catalysis, ortho-(1-trifluoromethylvinylthio)phenols cyclize into benzo-1,3-oxathiols, and on treatment with aqueous alkali — into benzo-1,4-oxathians. The characteristic features of these transformations and the oxidative reactions of oxathians were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1625–1630, July, 1991.