Synthesis of pyrrolo[2,1-a]isoquinolines

Enamine derivatives of 3,4-dihydroisoquinoline obtained by the Ritter reaction form 2,3-dioxo-5,5-RR¹-1-R²-2,3,5,6-tetrahydropyrrolo[2,1-a]isoquinolines with oxalyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 963–965, July, 1987.     

An unusual reaction of 2-(2-pyridylcarbonyl)- and 2-(2-quinolylcarbonyl)benzoyl chlorides with p-nitroaniline

In the reaction of 2-(2-pyridylcarbonyl)benzoyl chloride, which exists in the form of 6,11-dioxo-6,11dihydrobenzo[b]quinolizinium chloride, with p-nitroaniline, 2-(4-nitrophenylimino)-6, 11-dihydro-2H-benzo-[b]quinolizine-6, I I -dione is unexpectedly formed. When it reacts with water or methanol there is an opening of the quinolizine ring and aromatization of the quinoid fragment with the formation of 2-[4-(4nitrophenylamino)-2-pyridylcarbonyl]benzoic acid or its methyl ester. Under the action of antimony pentachloride, 2- 2-quinolylcarbonyl)benzoylchloride-3 (2-quinolyl)-3-chloro- 1, 3-dihydrobenzo[c]furan-1 -one -is converted to 3-(2-quinolyl)-1,3-dihydrobenzo[c]furan-1-on-3-ylium hexachlorantimonate, which undergoes isomerizing recyclization upon heating to 7,12-dioxo-7,12-dihydrobenzo[b/ hexachloroantimonate. The latter enters into an analogous reaction with p-nitroaniline, thereby forming 5-(4-nitrophenylimino)-7,12-dihydro-5H-dibenzo[b,f]quinolizine-7,2-dione.Riga Technical University, Riga LV-1048. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 938–944, July, 1995. Original article submitted May 31, 1995.     

Synthesis and transformations of 2,3-dioxo-2,3-dihydroimidazo [1,2-a]-benzimidazole derivatives

9-(H)Alkyl-2,3-dioxo-2,3-dihydroimidazo[1,2-a]benzimidazoles were synthesized by the action of oxalyl chloride on 2-amino-1(H)alkylbenzimidazoles and subsequent cyclization of the resulting 2-amino-1-(H)alkyl-3-chlorooxalylbenzimidazolium chlorides in the presence of triethylamine. The behavior of the synthesized benzimidazoles with respect to the action of alkalis, lithium aluminum hydride, and ethylmagnesium bromide was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1391–1395, October, 1976.     

Synthesis of nitro-substituted dioxotetrahydrodioxapyrenes and 6H-dibenzo[b,d]pyran-6-one

Methods for the synthesis of tri- and tetranitro-substituted 5,9-dioxo-4,5,9,10-tetrahydro-4,10-dioxapyrenes, 5,10-dioxo-4,5,9,10-tetrahydro-4,9-dioxapyrenes, and 6H-dibenzo[b,d]pyran-6-one were developed in a search for effective sensitizers for electrophotographic layers based on carbazole-containing polymers. The possibility of the production of nitro compounds that contain three vicinal nitro groups was demonstrated. Under severe nitration conditions 2,4,8-trinitro-6H-dibenzo[b,d]pyran-6-one is cleaved to give 2-hydroxy-2-carboxy-3,5,4-trinitro-biphenyl, which is resistant to cyclization to give the starting compound, evidently because of the existence of an intramolecular hydrogen bond between the hydroxy group and the nitro group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 463–467, April, 1985.     

Reaction of 2,3-dioxo-4-(N,N-dimethylaminomethylene)hexahydroazepine with hydrazine and its derivatives

8-Oxo-8H-4,5,6,7-tetrahydropyrazolo[5,4-c]azepine and a mixture of 2-phenyl-8-oxo-8H-4,5,6,7-tetrahydro [3,4-c]azepine and 2,3-dioxo-4-formylhexahydroazepine 4-phenylhydrazone were obtained in the reactions of 2,3-dioxo-4-(N,N-dimethylaminomethylene)-hexahydroazepine with hydrazine and phenylhydrazine, respectively. Cyclization of 2,3-dioxo-4-formylhexahydroazepine 4-phenylhydrazone gave 1-phenyl-8-oxo-8H-4,5,6,7-tetrahydropyrazolo [5,4-c]azepine. The reaction of 2,3-dioxo-4-(N,N-dimethylaminomethylene)hexahydroazepine with semicarbazide and thiosemicarbazide gives 2,3-dioxo-4-formylhexahydroazepine 4-semicarbazone and 4-thiosemicarbazone.Communication XXX from the series Research on Lactams. See [1] for communication XXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1248–1251, September, 1978.     

Conversion of 2-amino-3-phenyl-4-quinolone to 1H-2,3-dihydro-2,9-dioxo-10-phenylimidazo[1,2-a]quinoline

1H-2,3-Dihydro-2,9-dioxo-10-phenylimidazo[1,2-a]quinoline has been obtained from 2-amino-3-phenyl-4-quinolone by acylation with chloroacetyl chloride and cyclization of the intermediate 2-di(chloroacetyl)amino-3-phenyl-4-chloroacetoxyquinoline. The reaction of the latter with morpholine was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 388–390, March, 1990.     

Condensed isoquinolines 23. Reaction of <Emphasis Type="Italic">o</Emphasis>-bromomethylphenyl-acetonitrile with anthranilic acids: Synthesis of 6H, 12H,17H-dibenzo[3,4:6,7][1,8]-naphthyridino[1,8-<Emphasis Type="Italic">ab</Emphasis>]quinazoline-6,17-diones

The direction of the reaction of anthranilic acids with o-bromomethylphenylacetonitrile upon fusion depends on the temperature and nature of the substituent in the anthranilic acid. The reaction may lead to three types of products: Derivatives of 7,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-ones below 150°C and to 6,11-dihydro-13H-isoquino[3,2-b]quinazolin-13-one or derivatives of 6H,12H,17H-dibenzo[3,4:6,7][1,8]naphthyridino[1,8-ab]quinazoline-6,17-diones above 150°C depending on the nature of the substituent in the anthranilic acid. A study was carried out on the mechanism for the formation of 6H,12H,17H-dibenzo[3,4:6,7][1,8]naphthyridino[1,8-ab]quinazoline-6,17-diones, which permitted the preparation of 6-(4-methylphenyl)-6,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-one. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1059–1067, July, 2007.     

1,2,3,9a-Tetrahydro-9H-imidazo[1,2-a]indoles

When derivatives of 1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one or 1-carbamoylmethyl-2-methylene-2,3-dihydroindole are reacted with lithium aluminum hydride, derivatives of 1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indole are formed. Under the same conditions 1-(N-phenylcarbamoylmethyl)-2-methylene-2,3-dihydroindole is not cyclized to an imidazo[1,2-a]indole. WHen treated with proton acids imidazo[1,2-a]indoles are converted to 3H-indolium salts. Opening of the imidazolidine ring is also found when imidazo[1,2-a]indole is acylated with benzoyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 227–230, February, 1987.     

Synthesis of 2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine and its 1-α-L-arabinopyranoside

A new type of isatin analog-2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine — was obtained by oxidation of 4-methyl-6-chloro-1H-pyrrolo(2,3-b]pyridine. Condensation of L-arabinose with 4-methyl-6-chloro-2,3-dihydropyrrolo[2,3-b]pyridine and subsequent acetylation and dehydrogenation gave 1-(2,3,4-tri-O-acetyl--L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine, which served as the starting compound for the synthesis of 1--L-arabinopyranosyl-4-methyl-6-chloropyrrolo[2,3-b]pyridine. Oxidation of 1-(2,3,4-tri-O-acetyl-L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine gave 1-(2,3.4-tri-O-acetyl--L-arabinopyranosyl)-2,3-dioxo-2,3-dihydro-4-methyl-6-chloropyrrolo [2,3-b]pyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1083–1086, August, 1977.     

Investigation of phenanthridone and dioxotetrahydrodiazapyrene. 3. Investigation of the nitration of 5H-phenanthridin-6-one and its derivatives

The nitration of 5H-phenanthridin-6-one (I), 5H-phenanthridin-6-one-10-carboxylic (II) and 5H-phenanthridin-6-one-1-carboxylic acids (III), 4H-cyclopenta[k,l,m]-phenanthridine-5,9-dione (IV), 4H-cyclopenta[k,l,m]phenanthridine-5-one (V), 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene (VI), and 5,9-dioxo-4,5,9,10-tetrahydro-4,10-diazapyrene (VII) with nitric acid (sp. gr. 1.42–1.51) and a nitrating mixture of 0–120 °C was investigated. The orientation and sequence of incorporation of nitro groups in I-VII are determined by the presence of a phenanthridone structure in them. Mono-, di-, tri-, and tetranitro-substituted I-VII were obtained and characterized.See [l] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 388–393, March, 1981.     

Saturated heterocycles, 75. Preparation of tetracyclic thiophene derivatives with bridgehead nitrogen. Synthesis of polymethylenethieno[2,3—d]dihydropyrrolo-, tetrahydropyrido- and tetrahydroazepino[1,2—a]pyrimidin-4-ones and -4-thiones

The following tetracyclic ring systems and their derivatives have been synthesized for pharmacological investigations: Trimethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and -4-thione (1 a, 5 a); Tetramethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and -4-thione (1 b, 1 j, 5 b); Pentamethylenethieno[2,3—d]dihydropyrrolo[1,2—a]pyrimidin-4-one and-4-thione (1 c, 5 c); Trimethylenethieno[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one and -4-thione (1 d, 5 d); Tetramethylenethieno[2,3—d]tetrahydropyrido[1,2,—a]pyrimidin-4-one and -4-thione (1 e, 5 e); Pentamethylenethieno[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one and -4-thione (1 f, 5 f); Trimethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one and -4-thione (1 g, 5 g); Tetramethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-on and -4-thione (1 h, 5 h); Pentamethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one and -4-thione (1 i, 5 i); Tentamethylenethieno[2,3—d]tetrahydroazepino[1,2—a]pyrimidin-4-one (7 b); Pentamethylenethieno-[2,3—d]tetrahydropyrido[1,2—a]pyrimidin-4-one (7 c).Compounds1 a–i were synthesized from 2-amino-3-ethoxycarbonyl-4,5-polymethylenethiophene2 a–c with the corresponding lactim ethers (3 a–c) in chlorobenzene in the presence of polyphosphoric acid (PPA). Compounds7 b and7 c were obtained in the reaction of -amino acid esters2 b and2 c with 2-bromopyridine (6). The thione derivatives (5 a–i) were prepared from compounds1 a–i with phosphorus(V) sulphide.Part 74:Szabó J, Fodor L, Szcs E, Bernáth G, Sohár P (1984) Pharmazie 39: 347.     

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 new pyrido[2,3-d]pyrimidine derivatives

The mutual condensation of 4-aminouracil or 2,4-diamino-6-hydroxypyrimidine with bisacetonitrile and aldehydes was used to synthesize 2,4-dioxo-5-R-7-methyl-6-cyano-1,2,3,4,5,8-hexahydropyrido[2,3-d]pyrimidine and 2-amino-4-oxo-5-R-7-methyl-6-cyano-3,4,5,8-tetrahydropyrido[2,3-d]pyrimidine derivatives, which were oxidized with chromic anhydride to the corresponding 2,4-dioxo-5-R-7-inethyl-6-eyano-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine and 2-amino-4-oxo-5-R-7-methyl-6-cyano-3,4-dihydro[2,3-d]pyrimidines. The IR and UV spectra of the synthesized compounds were recorded.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 422–425, March, 1972.     

Condensed imidazo-1,2,4-azines. 21. Synthesis of 2-arylfuro(pyrrolo-, thieno-)[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles by cyclization of 2-aroyl-1,2,4-triazino[2,3-a]benzimidazol-4H-3-ones

2-[(-Ethyl-, arylimino)phenethyl]-1,2,4-triazino[2,3-a]benzimidazoles were obtained by reaction of 2-aroylmethyl-1,2,4-triazino[2,3-a]benzimidazol-4H-3-ones with ethyl(aryl)amines or urea. By the action of phosphorus oxychloride, these benzimidazoles cyclize into substituted pyrrolo[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles, heating of which in polyphosphoric acid leads to the formation of furo[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles, while by the action of P₄S₁₀, they are transformed into thieno[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles.For Communication 20, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1109–1113, August, 1989.     

Dioxodihydrobenzo[b]furoindoles

The synthesis and some properties of the isomeric 2,3-dioxo-2,3-dihydro-1H-benzo[b]furo[2,3-g]- and 2,3-dioxo-2,3-dihydro-1H-benzo[b]furo[3,2-g]indoles are described. Georgian Technical University, Tbilisi 380075. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, 627–630, May, 1999.     

Oxidative transformations of 2,4-dioxo-3-(3-hydroxybutyl)-1,2,3,4,6,7-hexahyidro-11bH-benzo[a]quinolizine

Conclusions The oxidation of 2,4-dioxo-3-(3-hydroxybutyl)-1,2,3,4,6,7-hexahydro-11bH-benzo[a]quinolizine with either the Sarett complex or Jones reagent gives predominantly 5-oxo-2-methyl-2,3,7,8-tetrahydro-4H,5H-benzo[a]pyrano[2,3-g]quinolizine, while oxidation with CrO₃ in AcOH solution gives 8,9,14-trioxo-12-methyl-5,6,8,9,10,11,15,15a-octahydro-13-oxa-12H,14H-azepino[2,1-a]isoquinoline.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1611–1614, July, 1973.     

Polyfuryl(aryl)alkanes and their derivatives. 8. Synthesis of benzofuro[2,3-h]-1-oxaazulenium salts. molecular and crystal structures of 2,4-dimethylbenzo[b]furo[2,3-h]-1-oxaazulenium perchlorate

The first representatives of a new heterocyclic system — benzofuro[2,3-h]-1-oxaazulenium salts — were synthesized. Diverse variations of the synthesis of these compounds are proposed. The molecular and crystal structures of 2,4-dimethylbenzo[b]furo[2,3-h]-1-oxaazulenium perchlorate were studied.See [1] for our preceding communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 627–632, May, 1993.     

Investigation of phenanthridone and dioxotetrahydrodiazapyrene. 4. Synthesis of amino-substituted phenanthridones and dioxotetrahydrodiazapyrenes

The corresponding mono-, di-, and triamino derivatives substituted in the 2, 4, and 8 positions of the phenanthridone ring were obtained by reduction of mono-, di-, and trinitro-substituted phenanthridone (I), phenanthridone-10-carboxylic acid (II), phenanthridone-1-carboxylic acid (III), 4H-cyclopenta[k,l,m]phenanthridine-5,9-dione (IV), 4H-cyclopenta[k,l,m]phenanthridin-5-one (V), 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene (VI), and 5,9-dioxo-4,5,9,10-tetrahydro-4,10-diazapyrene (VII) with powdered iron in an electrolyte medium, with hydrogen in the presence of a nickel catalyst, or with stannous chloride. The 2,4,7,9-tetraamino derivative of VI was similarly obtained. 1-Amino-, 7-amino-, and 10-amino-phenanthridones were obtained by the Schmidt reaction from the corresponding carboxylic acids. 1,10-Diamino-, and 3,8-diaminophenanthridones were similarly obtained from the corresponding aminofluorenones.See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 394–397, March, 1981.     

Alkylation of 1,2,3,4,10,10a-hexahydropyrimido[1,2-a]indol-2-one

A mixture of N- and O-alkylation products is formed in the reaction of 1,2,3,4,10,-10a-hexahydropyrimido[1,2-a]indol-2-ones with ethyl iodide, allyl bromide, or benzyl chloride in DMFA (dimethylformamide) in the presence of potassium hydroxide. In the presence of aqueous solutions of acids with subsequent treatment with bases, the alkylation products are converted to 1-[2-(alkoxycarbonyl)-ethyl]-2-methylene-2,3-dehydro-1H-indoles. The reaction of 1,2,3,4,10,10a-hexahydropyrimido[1,2-a]indol-2-one with triethyloxonium fluoroborate gives 1-[2-(ethoxycarbonyl)ethyl]-2-methylene-2,3-dihydro-1H-indole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1224–1227, September, 1989.     

Study of Nitrogen- and Sulfur-Containing Heterocycles. 57. Synthesis and Conversion of 4′-Substituted 5-(5-Amino-6-Pyrimidylthio)-2,2-Dimethyl-4,6-Dioxo-1,3-Dioxanes

By reaction of 4-substituted 5-amino-6-mercaptopyrimidines with 5-bromo-2,2-dimethyl-4,6-dioxo-1,3-dioxane, we have obtained 4′-substituted 5-(5-amino-6-pyrimidylthio)-2,2-dimethyl-4,6-dioxo-1,3-dioxanes. We have studied diazotization of these compounds by isoamyl nitrite. In the case of 4′-methoxy- and 4′-dimethylamino-substituted derivatives, we have obtained derivatives of novel heterocyclic systems: pyrimido[5,4-e][1,3,4]thiadiazine and pyrimido[5,4-e][1,3,4]thiadiazine-7-spiro-5′-1,3-dioxane, and in the case of the 4′-isopropylamino-substituted derivative we obtained 4-isopropyl-7-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)-1,2,3-triazolo[5,4-d]pyrimidin-7-ylidene.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 613–623, April, 2005.