Synthesis,methylation, and acylation of 1,2-dihydrodeoxyvasicinones and their homologs

2,3-Trimethylene- and 2,3-pentamethylene-1,2,3,4-tetrahydro-4-quinazolones and their 6-methyl and 6-bromo derivatives have been obtained by the reduction of deoxyvasicinone and its 6-methyl and 6-bromo derivatives and also their seven-membered homologs at the cycloalkane ring with sodium tetrahydroborate in ethanol. The alkylation and acylation reactions of the above-mentioned reducing compounds have been studied. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 659–663, September–October, 1990.     

Some methyl and bromo derivatives of 9-amino-6-nitroacridine

2-Methyl, 4-methyl, and 2-bromo derivatives of 9-amino-6-nitroacridine and of 9-(-diethylamino--hydroxypropylamino)-6-nitroacridine, and a number of intermediates in their synthesis, have been obtained.     

Synthetic analogues of Peganum alkaloids. III. Pentamethylenequinazolones

Monosubstituted 5-, 6-, and 8-methoxy-3,4-dihydro-2,3-pentamethylenequinazolones (1–3) have been syntehsized by the condensation of monosubstituted methoxyanthranilic acids with caprolactam. Demethylation with hydrobromic acid gave the corresponding hydroxy compounds [4–6]. When the 6- and 8-methoxy- and 6- and 8-hydroxy-3,4-dihydro-2,3-pentamethylenequinazolones (2, 3, 5, and 6) were reduced with zinc in hydrochloric acid, the corresponding quinazoline derivatives (7–10) were obtained. The melting points of the basis and their hydrochlorides are given. Some features of their UV, mass, and PMR spectra are reported.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 465–469, July–August, 1986.     

Bromination,nitration, and azo coupling of substituted 3-ethoxycarbonyl-5-hydroxybenzofurans

The bromination and nitration of 2-methyl-3-ethoxycarbonyl-5-hydroxybenzofuran (I) leads to 6-bromo and 6-nitro derivatives, while azo coupling results in substitution of the hydrogen in the 4 position. The structures of the compounds obtained were confirmed by IR and PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1443–1446, November, 1971     

Reaction of ketenes with N,N-disubstituted α-aminomethyleneketones. XX. Synthesis of 2H-pyrano[2,3-f]quinazoline derivatives

The polar 1,4-cycloaddition of dichloroketene to N,N-disubstituted (E)-6-aminomethylene-7,8-dihydro-(2-methyl)(2-phenyl)quinazolin-5(6H)-ones III , prepared in good yields from 7,8-dihydro-(2-methyl)-(2-phenyl)quinazolin-5(6H)-ones via their 6-hydroxymethylene derivatives I and II , gave in satisfactory to excellent yields N-N-disubstituted 4-amino-3,3-dichloro-3,4,5,6-tetrahydro-(8-methyl)(8-phenyl)-2H-pyrano- [2,3,-f]quinazolin-2-ones IV , which are derivatives of the new heterocyclic system pyrano[2,3-f]quinazoline. This cycloaddition occurred both in the case of aliphatic and aromatic N-substitution only with 2-phenyl-enaminones III , whereas with 2-methyl derivatives III the reaction took place only in the case of aromatic N-monosubstitution. Dehydrochlorination of IV with DBN afforded, generally in excellent yields, N,N-disubstituted 4-amino-3-chloro-5,6-dihydro-(8-methyl)(8-phenyl)-2H-pyrano[2,3-y]quinazolin-2-ones, which were dehydrogenated with DDQ to give N,N-disubstituted 4-amino-3-chloro-(8-methyl)(8-phenyl)-2H-pyrano[2,3-f]quinazolin-2-ones in excellent yields.     

Dipole moments,kerr constants,and conformations of some substituted methyl cyclopropyl ketones

Conclusions The acetyl group in a substituted cyclopropane ring has an s-cis conformation that is distorted by either 15–20° (cis-2-halo-cis-3-methyl derivatives) or by 55–70° (cis-2-halo-1-methyl derivatives).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1174–1177, May, 1977.     

Synthesis,spectral-luminescence,and acid-base properties of 3-halo-7-aminocoumarins

The reactions of substituted coumarins with a variety of halogenating agents, leading to the formation of the corresponding 3-chloro-, 3-bromo-, and 3-iodo-7-aminocoumarins, have been studied. It has also been shown, based on the results of studies of the spectral-luminescence and acid-base characteristics of these 3-halo-7-aminocoumarins, that their basicity increases as the electron-donating nature of the substituent in the 4-position increases, and is also greater, as expected, for 3-iodo- and 3-chloro derivatives than for 3-bromo derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1600–1609, December, 1990.     

Chemistry of benzo[6-b]selenophene III. Selenoindoxyl derivatives

3-Acetoxybenzo[b]selenophene and its 2-methyl derivative, respectively, were synthesized by the cyclization of o-carboxyphenylselenoacetic and-(o-carboxyphenyl)selenopropionic acids. 3-Hydroxy-2,3-dihydrobenzo[b]selenophene and its 2-methyl derivatives were obtained by the reduction of selenoindoxyl and 2-methylselenoindoxyl with sodium borohydride. 3-Methyl-3-hydroxy-2,3-dihydrobenzo[b]selenophene was synthesized by the reaction of selenoindoxyl with methylmagnesium iodide.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1640–1644, December, 1971.     

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.     

Heterocyclic diazo compounds

Benzothiazole-2-diazonium tetrafluoroborate and its 6-bromo, 6-methyl, and 6-methoxy derivatives are relatively stable and have high electrophilicities. They are rapidly converted in weakly alkaline media to the corresponding anti-diazotates, from which primary nitrosoamines can be obtained by acidification.     

Synthesis and membrane activity of new derivatives of 2,3-benzo-18-crown-6

The acylation of 2,3-benzo-18-crown-6 with carboxylic acids in the presence of polyphosphoric acid has given new acyl derivatives which have been reduced to the corresponding alkyl derivatives. The ionophoric activities of the compounds have been investigated on mitochondrial membranes.Institute of Biochemistry, Academy of Sciences of the Uzbek SSR, Tashkent. Institute of Bioorganic Chemistry, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 634–637, September–October, 1983.     

Nitrosation and bromination of 6-(2'-furyl)imidazo[2,1-b]thiazole and its derivatives

The action of nitrosating agents and bromine on 6-(2-furyl)imidazo[2,1-b]thiazole and its 3-methyl, 5-bromo, and 5-nitro derivatives was studied. The structures of the products were proved by UV, IR, and PMR spectroscopy and thin-layer chromatography.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1353–1358, October, 1972.     

Bis(2,4–pentanedionato)vanadium(IV) aryloxides

Complexes of composition [VCl(acac)2(OAr1–4)] and [V(acac)2(OAr1–4)2] (HOAr1=HOC6H4NO2–4, HOAr2= HOC6H4OMe-4, HOAr3=HOC6H4But-4 and HOAr4= HOC6H2But-2,6–Me-4; acac=2,4–pentanedionato ion) have been synthesized by the reaction of [VCl2(acac)2] with the respective phenols or their trimethylsilyl derivatives. The complexes have been characterized by physicochemical and spectroscopic techniques. They are non-electrolytes in nitrobenzene. Room temperature magnetic moments in the 1.71–1.82B range are consistent with the VIV system. The reactions of [VCl(acac)2(OAr2)] and [VCl(acac)2(OAr3)] with chloride acceptors have been studied by conductance techniques and the formation of ionic complexes of the types [V(acac)2(OAr2,3)][MCl4] (M=Fe, Al or Sb) and [V(acac)2(OAr2,3)][MCl6] (M=P or Sb) is indicated by the conductance composition curves. Several of these complexes have been isolated and characterized.     

Investigations in the fie ld of substituted furanurona ldehydes steric directivity of the nitromethane condensation

Summary 1. The condensation of the anomeric methyl 2,3-di-O-benzyl-D-xylofuranosiduronaldehydes with nitromethane has been studied.2. It has been shown that the position of the substituent at the glycosidic center has an influence on the steric directivity of this reaction.3. The structure of the 6-nitro-6-deoxyhexofuranosides synthesized has been confirmed by their conversion into known derivatives of methyl D-glucofuranosides.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 8–12, January–February, 1972.     

11H-Pyrido[3',2':4,5]pyrrolo[2,3-g]isoquinoléines (aza-7 ellipticines) substituées sur leur position 6

6-Dialkylaminoalkylamino substituted 11H-pyrido[3',2':4,5]pyrrolo[2,3-g]isoquinolines (7-aza ellipti-cines) were obtained by a six step synthesis starting from 2-chloro-3-nitro pyridine and 6-amino-5-methyl (and 5,8-dimethyl) isoquinoline-1-2H-ones already described. A brief survey of biological results shows that derivatives of this new heterocyclic ring system are less interesting than their 5H-pyrido(3',4':4,5]pyrrolo[2,3-g]isoquinolines (9-aza ellipticines) and pyrido[4,3-b]carbazoles (ellipticines) analogues.     

Chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H,1,5-benzodiazepin-2-one

The results of the chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H,1,5-benzodiazepin-2-ones are compared with the results of quantum-chemical calculations of 4-methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones with various substituents in the benzene ring in the case of homolytic halogenation. The chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H-1,5-benzodiazepin-2-one (I) with N-chlorosuccinimide leads to 3-chloro- and 3,3-dichloro-4-methyl-8-methoxy-2,3-dihydro-1H-1,5-benzodiazepin-2-ones, whereas chlorination with sulfuryl chloride leads to 4-chloromethyl and 3,3-dichloro-4-methyl derivatives. The IR, PMR, and mass spectra of the synthesized compounds are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1272–1274, September, 1981.     

Synthesis of 1,3-dioxanes from furan aldehydes

Six new cyclic acetals have been synthesized by the reaction of furfural and its 5-methyl, 5-bromo, 5-chloro, and 5-nitro derivatives and furyl-acrolein with 1,1,1-tris(hydroxymethyl)propane. Their UV and IR spectra are given.     

Synthesis of 5-glycopyranosylamino-pyrano[2,3-d]pyrimidin-2-one derivatives

Summary Three series of 3-substituted 5-glycopyranosylamino pyrano[2,3-d]pyrimidin-2-one derivatives,3 a–c,4 a–c, and5 a–c have been prepared by treatment of the corresponding 1,4-dihydro-6-glycopyranosylamino pyrimidin-4-ones1 a–c with malonic, methyl malonic and ethyl malonic acids, respectively.

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Synthese von Derivaten des 5-Glucopyranosylaminopyrano[2,3-d]pyrimidin-2-on

Zusammenfassung Es wurden drei Serien von 3-substituierten 5-Glucopyranosylaminopyrano[2,3-d]pyrimidin-2-onen (3 a–c,4 a–c und5 a–c) mittels Behandlung der entsprechenden 1,4-Dihydro-6-glucopyranosylamino-pyrimidin-4-one (1 a–c) mit Malon-, Methylmalon- bzw. Ethylmalonsäure dargestellt.

     

The synthesis of monomethoxynaphtho[1′,2′:4,5]thieno[2,3-c]quinolines

A series of monomethoxynaphtho[1′,2′:4,5]thieno[2,3-c]quinolines has been prepared by photocyclization of the appropriate N-methoxyphenyl-1-chloronaphtho[2,1-b]thiophene-2-carboxamides. Some of the lactams obtained were converted into the thiolactams and their S-methyl derivatives. The lactams were also converted into the corresponding 6-chloro derivatives. Some of these were catalytically dechlorinated into the monomethoxynaphtho[1′,2′:4,5]thieno[2,3-c]quinolines which were then quaternized into the N-methyl quaternary salts.     

A facile synthesis of the novel thiazolo[3,2-a]pyrimidine derivatives

2-Bromomethyl- and 2-iodomethyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-5-ones are prepared via the reaction of 3-allyl-2-thiouracil derivatives with bromine or iodine chloride, respectively. The 6-bromo and 6-nitro derivatives are synthesized by an electrophilic substitution at C-6 of the thiazolopyrimidine system. As a result, novel 2,3-dihydrothiazolo[3,2-a]pyrimidin-5-one derivatives are obtained. Hydrogen halide elimination from the 2-halomethyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-5-ones is also reported.