Study of nitrogen- and sulfur-containing heterocycles. 46. New heterocyclic systems — Derivatives of pyrido[3′,2′∶5,6][1,4]thiazino[3,4-c]- and pyrimido-[5′,4′∶5,6][1,4]thiazino[3,4-c][1,2,4]triazines. Synthesis,properties

Representatives of new heterocyclic systems were obtained — pyrido[3,25,6][1,4]thiazino[3,4-c]- and pyrimido[5,45,6][1,4]thiazino[3,4-c][1,2, 4]triazines. Hydrazides of N-(pyrid-3-yl)- and N-(pyrimid-5-yl)oxamic acids were isolated and characterized. Their acylation products were investigated.For communication 45, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 559–562, April, 1993.     

Research on imidazo[1,2-a] benzimidazole derivatives

,-Unsaturated ketones of the imidazo[1,2-a]benztmidazole series were synthesized from 3-formyl- and 3-acetyl-substituted imidazo[1,2-a]benzimidazoles by crotonic condensation in the presence of alkaline catalysts. The ,-unsaturated ketones can also be obtained by direct acylation of 3-unsubstituted imidazo[1,2-a]benzimidazoles with the chlorides of unsaturated acids. The properties and pharmacological activity of the ketones obtained were studied.See [1] for communication XIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1660–1665, December, 1976.     

Studies of imidazo[1,2-a]benzimidazole derivatives. 21. Synthesis of haloketones in the imidazo[1,2-a] benzimidazole series

Methods for the synthesis of imidazo[1,2-a]benzimidazole haloketone derivatives have been investigated. It has been found that -bromoketone derivatives of this heterocycle can be prepared either by bromination of 3-acylimidazo[1,2-a]benz-imidazoles with bromine in glacial acetic acid or by acylation of 3-unsubstituted imidazo[1,2-a]benzimidazoles with haloanhydride derivatives of -bromoalkanoic acids. Treatment of imidazo[1,2-a]benzimidazoles with 3-chloropropionyl chloride results in the formation of imidazo[1,2-a]benzimidazolyl-3-propionyl chloride and bis(imidazo[1,2-a]benzimidazolyl)propan-3-one derivatives as side products. Reaction of 2-phenylimidazo[1,2-a]benzimidazoles with 3-bromopropionic acid in polyphosphoric acid gives benzocyclohepten[5,6:4,5]imidazo[1,2-a]benzimidazole derivatives.For Communication 20, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 339–345, March, 1986.     

Acetals of lactams and acid amides. 35. Synthesis of condensed two- and three-ring pyridine systems on the basis of enamino amides

The synthesis of 2,3,5,6-tetrahydropyrrolo[3,2-c]pyrid-6-one was accomplished by rearrangement of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1, 2-c]pyrimidine. Pyrrolo[3,2-c]pyrimidine, 1,6-naphthyridine, and pyrimido[4,3-b]-azepine derivatives were synthesized on the basis of enamino dinitriles. The hydrolysis of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1,2-c]-pyrimidine in 50% CH₃COOH leads to a pyrrolo[1,2-c]pyrido[4,3-d]pyrimidine derivative. A similar dipyrido[4,3-d-1,2-c]pyrimidine derivative was obtained from 1-cyano-9-dimethylaminomethylene-2,5,6,7,8,9-hexahydropyrido[1,2-c]pyrimidine under these conditions, and 3,4-dioxo-3,4,7,8,9,10-hexahydropyrido[1,2-c]pyrano[4,3-d]-pyrimidine was synthesized bytreatment with a 1 N solution of HCl.See [1] for Communication 34.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 518–522, April, 1982.     

N-acetylindoxyl in the synthesis of new condensed heterocycles

Derivatives of a new heterocyclic system thieno[2,35,6]pyrimido[3,4-a]indole, were obtained by the reaction of substituted N,O-diacetylindoxyls with excess N-(2-methyl-3-ethoxycarbonyl-4-thienyl)hydrazine. The reaction of N-acetylindoxyl and 4-hydrazinouracil forms 12-amino-1,3-dioxo-2,4,6-trimethylpyrimido[5,45,6]pyrimido[3,4-a]indole.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1343–1345, October, 1987.     

Transformation of β-(5-bromouracil-1-yl)-α-alanine into an imidazo[1,2-c]pyrimidine

In the reaction of -(5-bromouracil-1-yl)--analine with primary or secondary amines an imidazo[1,2-c]pyrimidine is formed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 538–540, April, 1980.     

Investigations in the imidazole series

The reactions of 2-mercaptonaphth[1,2-d]imidazole with 1,2-dichloro- and 1,2-dibromoethanes and the cyclization of 3-(-hydroxyethyl)- and 2-(-hydroxyethyl)mercaptonaphth[1,2-d]imidazoles were studied. 2,3-Dihydro derivatives of naphth[1,2-d]imidazo[1,2-b]thiazole and naphth[1,2-d]imidazo[3,2-b]thiazole were obtained.See [1] for communication LXX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 257–259, February, 1972.     

Polynuclear heterocyclic compounds based on the adduct of o-cinnamoylbenzoic acid and cyclohexanone

The product of addition of cyclohexanone to o-cinnamoylbenzoic acid, which has the 4-phenyl-8a-hydroxyperhydrochroman-2-spiro-3-phthalide structure, reacts with nitrogen-containing nucleophiles to give hydrogenated derivatives of oxa-(aza, thia)indolizinespirophthalide and pyrido[1,21,2]imidazo[2,3-a]-isoin-dole, as well as 4-R-1-phthalazones. An isoindolo[1,2-a]quinoline derivative and a compound with a 7,8-diaza-D-homosteroid skeleton were obtained from the latter.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1280–1285, September, 1986.     

Condensation of 2-amino-3, 4, 5, 6-tetrahydroimidazo[4,5,1-ij]quinolinium and 2-amino-2-pyrrolinium salts with β- dike tones

The corresponding 12,l,2,3-tetrahydropyrimido[2,12,3]imidazo[4,5,1-ij]quinolinium and 7,8-dihydro-6H-pyrrolo[1,2-a]pyrimidinium salts were obtained by the condensation of 2-amino-3,4,5,6-tetrahydroimidazo[4,5,1-ij]quinoline hydrochloride and 2-amino-2-pyrroline hydrochloride with -diketones. The structures of the products of condensation with unsymmetrical diketones were determined from their PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 419–421, March, 1972.     

Kinetic behavior of ethylene polymerization in the presence of highly active titanium-magnesium catalysts

The influence of the composition of highly active titanium-magnesium catalysts (TiCl₄ supported on MgCl₂ and a TiCl₃·nMgCl₂ catalyst), the nature and concentration of organoaluminium cocatalyst, the concentration of catalyst and monomer on the activity and the shape of the kinetic curves during ethylene polymerization has been studied.

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(TiCl₄, MgCl₂ TiCl₃·nMgCl₂), , .

     

Chloral as a formylating agent for some bridge heterosystems

The interaction of condensed nitrogen-containing bridge systems with chloral has been studied and the high sensitivity of the reaction to the -excess of the initial heteroaromatic system has been established. It has been shown that chloral is a convenient formylating agent for systems with a moderate -excess —imidazo[l,2-a]imidazole, 9H-imidazo[1,2-a]benzimidazole, imidazo[1,2-a]pyridine, imidazo[1,2-a]naphtho[2,3-d]imidazole. Heterocycles with a high -excess (indolizine, pyrrolo[1,2-a]benzimidazole) form cyanine dyes under the action of chloral. Systems with a lowered -excess (1H-imidazo[1,2-a]benzimidazole, imidazo[1,2-a]quinoline, imidazo[2,1-a]isoquinoline, imidazo[1,2-a]perimidine, imidazo[5,1-b]benzoxazole, imidazo[1,2-a]benzothiazole, and imidazo[1,2-a]pyrimidine) do not react with chloral in a neutral medium. However, in a number of cases their foraylation can be carried out in an acid medium.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 528–537, April, 1980.     

The products of the photolysis of 2-(4-alkyI(or phenyl)piperazino)-3-amino-1,4-naphthoquinones,their structures and subsequent thermal transformations

Photolysis of 2-(4-alkyI(phenyl)piperazino)-3-amino-1,4-naphthoquinones affords 2-alkyl (phenyl)-1,2,3,4,12,12a-hexahydronaphtho[2,34,5]imidazo[1,2-a]pyrazine-6,11-diols which recyclize at elevated temperatures to yield 1,2,3,4-tetrahydro-13-alkyl(phenyl)-3,1-(iminoethano) benzo[g]quinoxaline-5,10-diols. The latter are oxidated with atmospheric oxygen to the corresponding diones. On the basis of deuterium exchange data a mechanism for the recyclization is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 944–949, May, 1993.     

Infrared and mass spectroscopic evidence for hydrocarbon formation on a supported cobalt catalyst

Interrupting the surface carbonyl development at 345 K on an aerosilsupported cobalt oxide catalyst in CO/H₂ atmosphere at maximum surface concentration of linear carbonyl species by heating to 475 K results in the formation of Fischer-Tropsch type products detectable by combined IR and MS measurements.

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345°K , , CO/H₂ , 475° -, .

     

Photoinduced oxygen adsorption of AgBr crystals at 77 K

Photoinduced adsorption (PIA) of oxygen molecules on AgBr films at 77 K has been experimentally observed and investigated. Lifetimes of PIA centers and desorption activation energies of O₂ molecules have been determined. The process is suggested to compete with the ionic step of AgBr photolysis.

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- () - AgBr 77 K. - O₂. , , - AgBr.

     

Comparison of the acid strength of solid catalysts

The catalytic activity of some solid acidic catalysts was tested in the depolymerization of paraldehyde. It was found that the activities of sulfonated ion exchange resin and mounted phosphotungstic acid strongly exceed the activity of silica-alumina and other oxide catalysts. By means of Brönsted relationship, the differences in H_O of the surfaces were estimated.

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. , - - . H_O .

     

Synthesis of imidazo[1,2-c]pyrimidine derivatives from 4-aminopyrimidines,methyl ketones,and halogens

Imidazo[1,2-c]pyrimidine derivatives were synthesized from C-substituted 4-aminopyrimidines by the King method. The corresponding 8-bromoimidazo[1,2-c]pyrimidines are formed by reaction of 4-aminopyrimidines without substituents in the 5 position with methyl ketones and bromine in a ratio of 112.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 93–94, January, 1975.     

Steroid glycosides XXI. The structure of polygonatoside E′ and protopolygonatoside E′ from the leaves ofPolygonatum latifolium

Summary The chemical structures of two new steroid glycosides from the leaves ofPolygonatum latifolium have been shown. Polygonatoside E is 3-[0--D-glucopyranosyl-(1 3)-0--D-glucopyranosyl-(1 4)-0--d-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-spirost-5-ene, and protopolygonatoside E is 26--D-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-furost-5-en-22-ol.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishenev. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 350–354, May–June, 1978.     

Investigations in the imidazole series

2,3-Dihydro derivatives of naphth[1,2-d]imidazo[3,2-b]imidazole were synthesized by the reaction of 2-chloro-3-(-haloalkyl)naphth[1,2-d]imidazole with ammonia and primary amines and by the reaction of 2-chloro-3-(-hydroxyaIkyl)naphth[1,2-d]imidazole with ammonia and amines with subsequent cyclization of the resulting 2-amino(alkylamino, arylamino)-3-(-hydroxyalkyl)naphth[1,2-d]imidazoles under the influence of thionyl chloride or phosphorus oxychloride. Dihydro derivatives of the condensed naphth[1,2-d]imidazo[3,2-b]imidazole system have not been described in the literature.See [1] for communication LX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1125–1127, August, 1971.     

Synthesis of 1,2-diamino imidazole derivatives by the reaction of benzaldehyde guanylhydrazone with α-haloalkyl aryl ketones

2-Amino-1-benzylideneamino-4-arylimidazoles were obtained by the reaction of benzaldehyde guanylhydrazone with 4-alkyl- and 4-aryl--haloacetophenones. Side products of this reaction were cis- and trans-1,1-bis(benzylideneamino)-4,4-diaryl-2,2-azoimidazoles. The corresponding 2-amino-1-benzylideneaminoimidazole and 1-benzyl-ideneaminoimidazo[l,2-a]imidazole were obtained in the reaction of -bromopropiophenone with benzaldehyde guanylhydrazone. The 2-amino-1-benzylideneamino-4-arylimidazoles were converted by successive reactions to 1,2-diatnino-4-arylimidazoles and then to imidazo[1,2-b]-1,2,4-triazine derivatives —dyes for liquid crystals with positive dichroism.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 236–241, February, 1982.     

Comportement thermique des benzènesulfonates de lithium,sodium et potassium

Résumé Le comportement thermique des benzènesulfonates de lithium, sodium et potassium a été étudié par TG et ATD à l'air et sous atmosphère d'azote.Dans la zone de stabilité des sels anhydres, nous avons mis en évidence des transformations réversibles (changements de phase cristalline) dont certaines ont fait l'objet de mesures calorimétriques.L'étude des résidus solides de la décomposition a montré une proportion importante de sulfates dans les produits obtenus dans l'air, alors que sous azote, il s'agissait surtout de sulfures. Les sulfites ne se présentent qu'en très faible quantité dans les deux cas.

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The thermal behaviour of benzènesulphonates of lithium, sodium and potassium has been investigated by TG and DTA in air and in an atmosphere of nitrogen.We have shown in the stability interval of the anhydrous salts reversible transformations (phase transitions), some of which were quantitatively studied by calorimetry.The radiocristallographic study of the solid residues has shown an important proportion of sulphates in the residues in air and of sulphides in an inert atmosphere. The sulphites were found in very small quantity in both cases.

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Zusammenfassung Das thermische Verhalten der Benzolsulfonate von Lithium, Natrium und Kalium wurde durch TG und DTA in Luft und in Stickstoff untersucht.Im Stabilitätsbereich der wasserfreien Salze wurden reversible Umwandlungen (Phasenübergänge) nachgewiesen, von denen einige quantitativ durch Kalorimetrie untersucht wurden.Das radiokristallographische Studium der festen Rückstände zeigte, daß in Luft ein bedeutender Anteil der Rückstände aus Sulfaten und in inerter Atmosphäre aus Sulfiden besteht. Sulfite wurden in beiden Fällen in sehr geringen Mengen gefunden.

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, . , , ( ), . , , - . .