Bisindoles. 38. Synthesis of Some Derivatives of 1H,6H-Indolo[7,6-g]indole

1H,6H,2,3,7,8-Tetramethylindolo[7,6-g]indole and 1H,8H,2,3,4,5,9,10,11,12-octahydrocarbazolo[3,2-c]carbazole were synthesized by the condensation of 1,5-naphthylenedihydrazine with alkyl ketones followed by cyclization of the obtained hydrazones without isolation. The respective N,N-dibenzyl derivatives were obtained by benzylation of the alkyl-substituted compounds. A new spirocyclic system was synthesized by nucleophilic addition of 2,3,3,7,8,8-hexamethylindolenino[7,6-g]indolenine to 2',3'-dimethoxycarbonylspirofluorenecyclopropene.     

Pyrroloindoles. 12. Synthesis of 1H, 10H-benzo[e]pyrrolo[3,2-g]indole

Cyclization of ethyl pyruvate 2,3-naphthylenehydrazone in polyphosphate ester gives 2,9-diethoxycarbonyl-1H,10H-benzo[e]pyrrolo[3,2-g]indole, which on hydrolysis and decarboxylation of the resulting acid affords the unsubtituted 1H,10H-benzo[e] pyrrolo[3,2-g]indole.For communication 11, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1222–1224, September, 1985.     

Bisindoles. 6, Synthesis and investigation of some properties of 2-formyl-, 3-formyl-, and 3,8-diformyl-1H,6H-indolo[7,6-g]indoles

The formylation of 1H,6H-indolo[7,6-g]indole under the conditions of the Vilsmeier reaction at a molar ratio of the indoloindole and the Vilsmeier complex of 11 has made it possible to raise the yield of 3-formyl-1H,6H-indolo[7,6-g]indole to 43% and to also isolate 2-formyl-1H,6H-indolo[7,6-g]indole. The 1H,6H-indolo[7,6-g]indole molecule was subjected to quantum-chemical calculation by the CNDO (complete neglect of differential overlap) MO method. The formylindoloindoles were condensed with aniline, thiosemicarbazide, nitromethane, nitroethane, and hydroxyl-amine. The configurations of the isomeric dioximes of 3,8-diformyl-1H, 6H-indole[7, 6-g]indole were established by PMR spectroscopy.See [1] Communication 5.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1501–1507, November, 1980.     

Total assignment of the 1H NMR spectra of 5H-indolo[1,7-ab] [1]benzazepine,6,7-dihydro-5H-indolo[1,7-ab][1]benzazepine and pyrrolo[3,2,1-kl ] phenothiazine

The total assignment of the ¹H nmr spectrum of the three tetracyclic compounds: 5H -indolo[1,7-ab][1]benzazepine,6,7-dihydro-5H -indolo[1,7-ab ][1]benzazepine and pyrrolo[3,2,1-kl ]phenothiazine is described. Assignments were based on decoupling experiments and the spectrum of 1,10-dideuteriopyrrolo[3,2,1-kl]phenothiazine and the spectral parameters were verified by spin-simulation techniques. A temperature study of 6,7-dihydro-5H -indolo[1,7-ab][1]benzazepine was also performed.     

Pyrroloindoles. 13. Properties of 1H,10H-benzo[e]-pyrrolo[3,2-g]indole

1H,10H-Benzo[e]pyrrolo[3,2-g]indole reacts with the Vilsmeier and Mannich reagents to give disubstituted compounds, whereas monosubstitution products are formed in the case of diazo coupling.See [1] for communication 12.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 603–607, May, 1988.     

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.     

Anthra[1,2-b]furan and 1h-naphth[2, 3-g]indole derivatives

A number of previously inaccessible anthra[1,2-b]furan and 1H-naphth[2,3-g]indole derivatives were obtained by condensation of 1,4-anthraquinone with acetoacetic ester and its analogs. Quinones of the anthra[1,2-b]furan series were obtained by oxidation of the methoxy derivatives of anthra[1,2-b]furan.Translated from Khimiya Geterotsiklicheskikh Soedtaenii, No. 8, pp. 1027–1029, August, 1972.     

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.     

Pyrroloindoles. 18. An Unexpected Chlorination Reaction During the Synthesis of 2,7-Diethoxycarbonyl-1H,8H-pyrrolo[3,2-g]indole

During the E. Fischer type synthesis of 2,7-diethoxycarbonyl-1H,8H-pyrrolo[3,2-g]indole there was discovered an unusual chlorination reaction of the benzene ring in 7-amino-2-ethoxycarbonylindole. It is suggested that the reaction occurs via an electrophilic substitution mechanism.     

Synthesis of 11,12,12a,13-tetrahydro-6H-indolo[1,2-b]-[2,4]benzodiazepines

Alkylation of 2,3,3-trimethyl- and 2,3,3,5-tetramethyl-3H-indoles with 2-bromomethylbenzonitrile gave 2-methylene-1-(2-cyanobenzyl)-2,3-dihydro-1H-indoles. When treated with lithium aluminum hydride the latter are cyclized to 11,12,12a,13-tetrahydro-6H-indolo[1,2-b][2,4]benzodiazepines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 815–817, June, 1990.     

Synthesis of 4-amino[1] benzofuro[3,2-g] cinnolines

The synthesis of the new heterocycles, 4-amino[1]benzofuro[3,2-g]cinnolines, was accomplished by the intramolecular cyclization of the Z -configuration of cyanoarylhydrazones. The latter compounds were obtained via interaction between the diazonium salt of 3-amino-dibenzofuran and various active methylene compounds via the Japp-Klingemann reaction. The alkaline treatment of azo intermediates 4 , which may be isolated in the course of condensation, gave the corresponding cyanoarylhydrazones 5 . A study of the configuration and possible isomerisations is reported.     

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 study of 3-methyl-6H-indolo[2,3-b]quinoxalines

By the condensation of isatin, N-methyl-, N-propyl-, N-benzoylisatin with 4-methyl-1,2-benzeneldiamine 3-methyl-6H-indolo[2,3-b]quinoxalines were obtained in high yields. The reaction occurs stereoselectively, in the mixture only one of possible isomers is present. By the oxidation of methyl group of the quinoxaline fragment new carbonyl derivatives were obtained, and by the reduction of nitro group, the corresponding indoloquinoxalinamines.     

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.     

Synthesis, spectra, and theoretical investigations of the triarylamines based on 6H-indolo[2,3-b]quinoxaline

Triarylamines containing a 6H-indolo[2,3-b]quinoxaline core and aromatic units such as phenyl, naphthyl, pyrene, anthracene, or fluorene have been synthesized by employing palladium-catalyzed C-N and C-C coupling reactions and characterized by optical absorption and emission spectra, electrochemical behavior, and thermal studies. Even though the electronic absorption spectra of the compounds were influenced by the nature of the peripheral amines, the emission spectra indicated close similarity for the excited states in these compounds. For the derivatives in which the amines were directly anchored on the 6H-indolo[2,3-b]quinoxaline nucleus, the emission appeared to be dominated by the state localized on the 6H-indolo[2,3-b]quinoxaline chromophore, while in the compounds containing the extended conjugation the fluorescence originated from the polyaromatic linker. The compounds displayed green or yellow emission depending on the nature of the amine segment. All of the dyes displayed one-electron quasi-reversible oxidation couple in the cyclic voltammograms, which is attributable to the oxidation of the peripheral amines at the 6H-indolo[2,3-b]quinoxaline core. An additional one-electron oxidation process observable at the high positive potentials for the compounds 7 and 8 probably arises from the oxidation of the arylthiophene segment. The enhanced thermal stability and relatively higher glass transition temperatures observed for these compounds were attributed to the presence of dipolar 6H-indolo[2,3-b]quinoxaline segment. The origin of the optical spectra and the trends observed therein were rationalized using TDDFT simulations.     

6-萘氧甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸衍生物的合成（英文）

介绍了通过6-氯甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯与1-和2-萘酚的Williamson醚合成反应及其随后的酯水解反应,"一锅法"高收率的合成了结构新颖的含有萘环结构的喹啉化合物,即2-(萘氧甲基)喹啉-3-羧酸.这种新合成的化合物可以为开发有用的药物活性先导化合物提供很好的底物.     

Synthesis of 7-substituted 1H-indolo[3,2-d][1,2]benzoxazepines

The synthesis of the novel 7-substituted 1H-indolo[3,2-d][1,2]benzoxazepine ring system is described. Fischer indolization of 2-fluoroacetophenone phenylhydrazone provided the starting material 2-(2-fluorophenyl)-1H-indole. An acyl group was then introduced at the 3-position of the indole nucleus and the resulting ketone was converted to the ketoxime. Upon treatment with sodium hydride to form the oxanion of the ketoxime, an intramolecular cyclization took place via displacement of fluoride from the adjacent 2-fluorophenylsubstituent. This ring closure completed the construction of the 1H-indolo[3,2-d][1,2]benzoxazepine ring system.