Bisindoles. 20. Synthesis of 3H,8H-indolo[4,5-e]- and -[5,4-e]indole systems

New heterocyclic systems, viz., 3H,8H-indolo[4,5-e]indole and 3H,8H-indolo-[5,4-e]indole, which were also obtained from the corresponding pyruvic acid dihydrazones, were synthesized by cyclization of ethyl pyruvate 2,7- and 2,6-naphthylenedihydrazones and subsequent saponification and decarboxylation of the cyclization products. The syn-syn, syn-anti, and anti-anti forms of the dihydrazones were isolated and characterized.See [1] for Communication 19.Translated from Khimiya Geterotsiklcheskikh Soedinenii, No. 3, pp. 352–357, March, 1984.     

Imidazoindoles. 3. Alkylation of 7,8-dimethylimidazo[4,5-e] indole

It is demonstrated that products of monoalkylation of 7,8-dimethylimidazo[4,5-e]-indole at the N₃ atom are formed in dioxane in the presence of sodium alkoxide or an aqueous solution of potassium hydroxide in the case of alkylation with alkyl halides, ethylene oxide, and acrylonitrile. The structures were proved by alternative synthesis and comparison of the UV spectra with the spectra of model structures.See [1] for Communication 2.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1369–1373, October, 1980.     

Pyrroloindoles. 14. Synthesis of dimethyl substituted pyrrolo[2,3-e]indole,indolo[4,5-e]indole,and some ditetrahydrocarbazolocarbazoles

Cyclization of the m-phenylen- and 2,7-naphthylendihydrazones of acetone leads to formation of dimethyl substituted, angular pyrrolo- and indolo-indoles. Cyclization of the 2,7-naphthylendihydrazone of cyclohexanone gives the linear 1H,12H-2,3,4,5,8,9,10,11-octahydrocarbazolo[3,4-d]carbazole. A further impurity of an angular ditetrahydrocarbazolocarbazole is also formed.For Communication 13 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 346–348, March, 1990.     

Sequence of the conversion of pyrimido [5,4-e]-1,2,4-triazinediones to imidazo[4,5-e]-1,2,4-triazinones

The conversion of pyrimido[5,4-e]-1,2,4-triazinediones to imidazo[4,5-e]-1,2,4-triazinones is a multistage process including the hydrolysis of the C₍₅₎-N₍₆₎ amide bond, the closure of the ureido group to the imidazolidinone ring, decarboxylation, acid oxidation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1252–1259, September, 1987.     

Bisindoles 34. Preparation and reactions of dehydrazides of the benzo[e]pyrrolo[3,8-g]-indole and indolo[4,5-e]indole series

Summary 2, 9 -Di (carbohydrazide)-1 H, IOH-benzo[elpyrrolo[3, 2-g]indole and 2, 9-di (carbohydrazide)-3H, 8H-indolo[4, 5-e]indole have been prepared. Nitrosation of the dihydrazides has been effected. The aryl azides do not undergo the curtius rearrangment.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1048-1051, August, 1994.Communication 33, see [1].     

Synthesis of crown containing imidazo[4,5-e] and-[5,4-e][1,4]diazepines

Starting from benzocrown substituted 4(5)-aminoimidazole-5(4)-carboxamides we have, for the first time, prepared benzocrown imidazo[4,5-e]-and-[5,4-e][1,4]diazepines-cyclic homologs of the corresponding xanthines.A. V. Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa 270080. Translated from Khimiya Geterotsiklicheskikh Soedinenii No. 6, pp 828–831, June, 1998.     

Pyrroloindoles. 8. Electrophilic substitution in the 1H,5H-pyrrolo[2,3-f]indole and 3H,6H-pyrrolo[3,2-e]indole series

The principles of the electron density distribution in 1H,5H-pyrrolo [2,3-f]indole and 3H,6H-pyrrolo[3,2-e]indole molecules were determined on the basis of quantumchemical calculations. These results were confirmed by the results of the investigated electrophilic-substitution reactions. The reaction centers of these compounds proved to be the same positions as in indole, viz., the 3 and 7 and 1 and 8 positions, respectively. The impossibility of 1,8-disubstitution in the angular heteroring was demonstrated in the case of bulky substituents; this was explained by a steric effect.See [1] for communication 7.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1086–1091, August, 1983.     

Diethylamine and triethylamine as sources of the dienophile component in the reverse azadiene synthesis with dimethylpyrimido[4,5-e]- and-[5,4-e]-1,2,4-triazinediones and 1,2,4,5-tetrazines

Diethylamine (DEA) and triethylamine (TEA) can function as sources for the two-carbon component in the reverse azadiene synthesis. Reaction of 5,7-dimethylpyrimido[4,5-e]-1,2,4-triazine-6,8-dione, 6,8-dimethylpyrimido-[5,4-e]-1,2,4-triazine-5,7-dione, or 1,2,4,5-tetrazine with an excess of DEA or TEA gives, respectively, the pyrido[2,3-d]pyrimidine-2,4-dione,pyrido[3,2-d]pyrimidine-2,4-dione, or pyridazine. The presence of an oxidant (atmospheric oxygen, MnO₂, or an electron-acceptor solvent) is required for the reaction to occur. Reaction of 5,7-dimethylpyrimido[4,5-e]-1,2,4-triazinedione with piperidine, morpholine, or under certain conditions DEA, results in opening of the triazine ring to give uracils with an amidine group in the 6-position.For preliminary communication, see [1, 2].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1545–1558, November, 1990.     

Condensed heterocycles with a thiazole nucleus. 8. Thiazolo[4,3-a]pyrimido[5,4-e]pyrimidines

Condensation of 4-amino-2-methylthiothiazolium salts with 2,4,6-trichloro-5-formylpyrimidine or 3-R-2,4-dioxo-6-chloro-5-formyl-1,2,3,4-tetrahydropyrimidines yielded mesoionic derivatives of a new heterocyclic system — thiazolo[3,4-a]pyrimido[5,4-e]-pyrimidine — which can be used for the synthesis of polymethine dyes. The absorption maxima of these dyes are bathochromically shifted by 10–20 nm relative to the maxima of the thiazolopyrimidine analogs. The structure of the compounds synthesized was demonstrated by the PMR and IR spectra.For communication 7, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1126–1128, August, 1984.     

Synthesis of furo[2,3-f]- and furo[3,2-e]indole derivatives

Two compounds — the diethylamides of 1,2-dimethyl-3-carbethoxy-6-carboxyfuro[2,3-f]- and 1,2-dimethyl-3-carbethoxy-5-carboxvfuro[3,2-e]indoles — are formed in the reaction of 1,2-dimethyl-3-carbethoxy-5-hydroxyacetic acid (I) with dimethylformamide and phosphorus oxychloride as a result of subsequent intramolecular cyclization of the intermediates. This constitutes evidence for formylation of the starting acid in the 6 and 4 positions. Formylation of the ethyl ester of acid I gives only the 6-formyl derivative, the intramolecular cyclization of which under the influence of sodium ethoxide gives 1,2-dimethyl-3,6-dicarbethoxyfuro[2,3-f]-indole. Hydrolysis of the latter with alcoholic alkali gives the corresponding dicarboxylic acid. The structures of the synthesized compounds were confirmed by the PMR, IR, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 766–769, June, 1977.     

1,2,3-Triazolo[4,5-e]-1,2,4-triazolo[3,4-c]pyrimidines

Some new 1,2,3-triazolo[4,5-e]-1,2,4-triazolo[3, 4 -c]pyrimidmes were prepared starting from the corresponding 1,2,3-triazolo[4,5-d]pyrimidines via the formation of the 1,2,4-triazole ring. Thus suitable hydrazino derivatives 6 were condensed with triethyl orthoformate, triethyl orthoacetate and triethyl orthobenzoate to give the expected tricyclic derivatives 7 , 8 and 9 . Intramolecular cyclization of the ethoxycarbonylhydrazino derivatives 10 gave the tricyclic compounds 11 bearing an hydroxyl group in the 3 position. The v-triazolo-s-triazolopyrimidine derivatives were tested towards the A₁ and A_2A adenosine receptors in binding assays, but they did not show any receptor affinity.     

Synthesis of perfluoroalkyl-substituted 4,5-dihydro-3H-pyrazolo[4,3-a]phenazines and tetrahydroimidazo[4,5-e]indazoles

Oxidation of 1-aryl-3-perfluoroalkyl-6,7-dihydro-1H-indazol-4(5H)-ones with selenium dioxide in the presence of sulfuric acid in glacial acetic acid, followed by treatment of 6,7-dihydro-1H-indazole-4,5-diones thus obtained with an equimolar amount of o-phenylenediamine in ethanol or with a mixture of 4-fluorobenzaldehyde and ammonium acetate in acetic acid, gave 3-aryl-1-perfluoroalkyl-4,5-dihydro-3H-pyrazolo-[4,3-a]phenazines and 6-aryl-2-(4-fluorophenyl)-8-perfluoroalkyl-1(3),4,5,6-tetrahydroimidazo[4,5-e]indazoles, respectively.     

Synthesis of imidazo[4,5-e][1,4]diazepine-8-one

We have developed a method for synthesis of 1-methyl-4,5,7, 8-tetrahydro-6H-imidazo[4,5-e][1,4]diazepin-8-one. We have shown that in intramolecular cyclization of N-(2-hydroxyethyl)- or N-(2-chloroethyl)amides of 1-methyl-4-aminoimidazolyl-5-carboxylic acids it is not the corresponding tetrahydroimidazo[4,5-e][1,4]diazepin-8-ones which are formed but rather the isomeric 4-amino-5-(oxazolin-2-yl)imidazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1203–1206, September, 1993.     

Pyrroloindoles. 6. New synthesis of 1H, 5H-pyrrolo[2,3-f]indole and 3H,6H-pyrrolo[3,2-e]indole

Ethyl pyruvate 1-acetyl-5-indolinylhydrazone was obtained by diazotization of 1-acetyl-5-aminoindoline with subsequent reduction of the diazonium salt and condensation of the hydrazine with ethyl pyruvate. A mixture of hydrogenated derivatives of linear and angular pyrroloindoles is formed as a result of cyclization of the hydrazone in polyphosphoric acid esters. Subsequent hydrolysis, decarboxylation, and dehydrogenation lead to 1H,5H-pyrrolo[2,3-f]indole and 3H,6H-pyrrolo-[3,2-e]indole.See [1] for Communication 5.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 504–507, April, 1982.     

Synthesis of 3H[1,2]diazepino[5,6-b]indole and 3H[1,2]diazepino[4,5-b]indole derivatives

The synthesis of two new derivatives of 3H[1,2]diazepino[5,6-b]indole, 5 and 11 , and one new derivative of 3H[1,2]diazepino[4,5-b]indole, 16 , are described. Compound 5 was obtained by the reaction of methyl 2-(3-methoxycarbonyl-1-methylindole)acetate 2 , with hydrazine. Compound 11 was obtained in two ways from ethyl 2-(1-methylindole)acetate ( 8 ) by formylation and reaction with hydrazine. Compound 16 was obtained treating 3-(2-ethoxycarbonylindole)acetonitrile ( 14 ) with hydrazine.     

Synthesis and Properties of Derivatives of the new Heterocyclic System Benz[4,5]imidazo[1,2-c]pyrido[3',2';4,5]thieno[2,3-e]pyrimidine

Derivatives of a new heterocyclic system - benz[4,5]imidazo[1,2-c]pyrido[3',2';4,5]thieno[2,3-e]pyrimidine have been obtained by successive reactions in three stages - alkylation of 3-cyanopyridine-2(1H)-thiones with 2-chloromethylbenzylimidazole to give 2-benzimidazolylmethylthio-3-cyanopyridines, closing the thiophene ring in the latter to form 3-amino-2-(benzimidazolyl-2)thieno[2,3-b]pyridines, and cyclization of the pyrimidine ring by acylation with carboxylic acid anhydrides or chlorides.     

Synthesis of dithieno[2,3-b:3′,2′-e]-8H-thiopyran-8-thione and dithieno[2,3-b:3′,2′-e]-8H-thiopyran-8-one

This paper describes the reaction of 2,2-di-(3- thienyi) -1,3-dioxalane with butyllithium and sulphur resulting in the formation of the dithieno-dithiopyrone 3, the dithieno - thiopyran -dioxolane 4 and the dithieno - thiopyrone 5.The diminished carbonyl character of the carbonyl group was studied in connection with the possibility of the dithienothiopyrone systems to form thiopyrilium structures.Investigations for the existance of these charged structures were performed with UV and PMR spectroscopy of the thiopyrones in acidic media. By oxidation of the pyrones with hydrogen peroxide the sulphones were synthesized in which the carbonyl character was restored as was shown by the formation of the oximes. The assymetry introduced by the oximidogroup was demonstrated by the PMR spectra.