Investigation of the products of the reaction of epichlorohydrin with aromatic amines

5,6-Dichlorobenzo[f]quinoline is formed by the action of thionyl chloride on 3-hydroxy-5-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline hydrochloride. 7-Chlorobenzo[f]quinoline and 7-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline are obtained in good yields by heating 3-hydroxy-7-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline with orthophosphoric acid, while benzo[f]quinoline is also obtained by heating it with polyphosphoric acid.See [1] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 108–111, January, 1971.     

Synthesis of Tetrahydrobenzo[g]Quinoline Derivatives Using Recoverable Carbonaceous Material as Heterogeneous Catalyst

A variety of substituted benzo[g ]quinoline‐5,10‐dione derivatives were synthesized via one‐pot three‐component reaction of 2‐hydroxynaphthalene‐1,4‐dione, aromatic aldehydes, and (E )‐3‐aminobut‐2‐enoates using carbonaceous material as the heterocyclic catalyst. This procedure is simple and efficient owing to short reaction times, easy work‐up, and recovery of heterogeneous catalyst. This procedure develops an efficient and promising synthetic method to construction of the benzo[g ]quinoline‐5,10‐dione skeleton.     

Iodine-Catalyzed Synthesis of 3-Arylbenzoquinoline Derivatives by Three-Component Reactions

A mild, efficient, and general method for the synthesis of benzo[f]quinoline derivatives via three-component reaction of arylaldehyde, naphthalen-2-amine, and acetone or acetophenone is described using iodine as catalyst. The features of this procedure are mild reaction conditions, high yields, and operational simplicity.     

Synthesis of benzo[g]quinoline derivatives

In the condensation of 1, 2, 3, 4-tetrahydro-4-oxobenzo[g]quinollne with ammonia, which leads to the formation of 4-aminobenzo[g]quinoline, the by-products are benzo[g]quinoline (V) and 1, 2, 3, 4-tetrahydrobenzo]quinoline (VI), which are also obtained from 1, 2, 3, 4-tetrahydro-4hydroxybenzo[g]quinoline by its dehydration and the subsequent disproportionation of the dihydrobenzo[g]quinoline formed.For communication II, see [1].     

Chemistry of indole

Indolyl keto acids were synthesized by the action of dinitriles on substituted indoles under the conditions of the Hoesch reaction. The reaction of these keto acids with isatin in alkali leads to quinoline derivatives, whereas pyridazinones of the indole series are obtained with hydrazine hydrate.See [1] for communication XLIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1512–1517, November, 1975.     

Effect of benzo annelation on the Chichibabin reaction

The kinetics of amination with sodium amide (the Chichibabin reaction) for six azines and five azoles and the kinetics of the piperidinolysis of 2-chloro-substituted azole systems were studied. The following orders of reactivities were established for the Chichibabin reaction: isoquinoline > phenanthridine > benzo[h]quinoline > benzo[f]quinoline > pyridine acridine and 1-methylbenzimidazole > 1-methylnaphth[2,3-d]imidazole > 1-methylperimidine > 1-methylnaphth[1,2-d]imidazole > 3-methylnaphth-[1,2-d]imidazole. The changes in the reactivities are explained by the changes in the hydride labilities of the corresponding complexes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp, 257–261, February, 1979.     

Density functional theory study of the styrylbenzoquinoline dyad and the related dibenzoquinolylcyclobutane formed in the [2 + 2] photocycloaddition reaction

The structure and electronic properties of the biphotochromic dyad with two styrylbenzo[f]quinoline photochromes, as well as the corresponding cyclobutane with two benzo[f]quinoline (BQ) substituents, are studied by DFT at the M06-2X/6-31G* level, the cyclobutane being a product of the [2 + 2] photocycloaddition (PCA) reaction of the dyad. According to calculations, the dyad forms π-stacked folded conformers, which, when excited, can form excimers that are precursors of cyclobutane. TD DFT calculations and natural transition orbital (NTO) analysis indicated that the lowest singlet excited S₁ state in the dyad is localized on the SBQ photochrome, including the ethylene group that undergoes PCA. Thus, the conditions for concerted electrocyclic reactions are satisfied, and the direct PCA follows the Woodward–Hoffmann rules. In contrast, in cyclobutane, the S₁ state is localized on the BQ substituent rather than on the cyclobutane core. Therefore, the reverse ring-opening (retro-PCA) reaction cannot follow the Woodward-Hoffmann rules and inevitably involves a step of excitation energy transfer from BQ to cyclobutane, which means the predissociation mechanism.     

Synthesis of nitrogen heterocycles underlain by application of 3-(4-Acetyl[phenyl)-2H-coumarin

3-(4-Acetylphenyl)-2H-chromen-2-one was obtained from 4-acetylphenyldiazonium chloride in the conditions of Meerwein reaction. Reactions of 3-[4-(2-bromoacetyl)phenyl]-2H-chromen-2-one with pyridine, 4-methylpyridine, quinoline, benzo[f]quinoline, and triphenylphosphine afforded quaternary salts, and with thioacetamide, thiourea, 2-aminopyridine, 2-aminopyrimidine, and 6-aminopurine provided the corresponding derivatives of thiazole, imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine, imidazo[2,1-i]purine. In the reaction of the same bromo derivative with thiosemicarbazide and aromatic aldehydes a thiazole ring is built and the corresponding hydrazones are formed.     

A Novel and Facile Synthesis of 2‐(Benzofuran‐2‐yl)benzo[h]quinoline‐3‐carboxylic Acid Derivatives

A simple and concise approach for the synthesis of a series of new heterocyclic systems of 2‐(benzofuran‐2‐yl)benzo[h]quinoline‐3‐carboxylic acid derivatives ( 3a–3g ) is described. The synthetic strategy features the one‐pot reaction of ethyl 2‐(chloromethyl)benzo[h]quinoline‐3‐carboxylate ( 2 ) with various substituted salicylaldehydes as well as 2‐hydroxy‐1‐naphthaldehyde as a key step. The substrate 2 was prepared in good yield by a mild, efficient and direct reaction of 1‐naphthylamine ( 1 ) with Vilsmeier‐Haack reagent. The structures of all the new compounds were identified by spectral data and elemental analysis.     

Heck-like coupling and Pictet-Spengler reaction for the synthesis of benzothieno[3,2-c]quinolines

A series of 6-arylbenzothieno[3,2-c]quinolines were synthesised in three steps from benzo[b]thiophene. After a selective Heck-type coupling of benzo[b]thiophene with different o-nitroaryl bromides to obtain 2-(o-nitroaryl)benzo[b]thiophenes, corresponding 2-(benzo[b]thiophen-2-yl)anilines were involved in a Pictet-Spengler reaction to form the quinoline cycle.     

Theoretical study of aza-polycyclic aromatic hydrocarbons (aza-PAHs), modelling carbocations from oxidized metabolites and their covalent adducts with representative nucleophiles

Protonation of the epoxides, diol epoxides, and dihydrodiols of benzo[h]quinoline (BhQ), benzo[f]quinoline (BfQ), phenanthrene (Phe), benzo[c]phenanthridine (BcPhen), and chrysene (Chry) were studied by DFT at the B3LYP/6-31G* level, and selected cases were calculated with the 6-31+G* diffuse-function augmented basis set for comparison purposes. Bay-region carbocations were formed from O-protonated epoxides via a barrierless processes. Relative carbocation stabilities were determined in the gas phase and with water as solvent (PCM method). The presence of a heteroatom changes the regioselectivity of epoxide ring opening, in some cases favoring non-bay-region carbocations. The epoxide ring opening mode is also greatly influenced by N-protonation. The dications resulting from initial N-protonation followed by epoxide protonation were also studied by DFT. Charge delocalization modes in the resulting mono- and dications were derived by GIAO-NMR (based on Delta delta13C values) and via the NPA-derived changes in charges. Relative aromaticity in different rings in the arenium ions was gauged by NICS. In representative cases, the covalent adducts (syn and anti) formed by reaction of the benzylic carbocations derived from diol epoxides and dihydrodiols with methoxide and methanethiolate anions were studied. Relative energies (in the gas phase and with water as solvent) and geometries of the adducts formed by quenching of the carbocations derived from BhQ and Phe-epoxides with guanine via the exocyclic amino group and via the N-7 were also investigated computationally. Although aqueous phase calculations change the energy for the addition reactions because of greater stabilization of the reactants, relative reactivity trends remain the same. The data are discussed, taking into account the available experimental results concerning the biological activity of these compounds.     

Synthesis and Characterization of New Heterocyclic Compounds Containing Thienylbenzo[h]Quinoline Moiety

In this paper the reaction of 2‐(2′‐thienylmethylene)‐3,4‐dihydronaphthalen‐2(1H)‐one ( 1 ) with cyanothioacetamide gave a mixture of 3‐cyano‐5,6‐dihydro‐4‐(2′‐thienyl)‐benzo[h]quinolin‐2(1H)‐thione ( 2 ) and the related disulfide 3 . Compound 2 was reacted with some halo compounds namely; ethyl chloroacetate, chloroacetamide, chloro(N‐(p‐chlorophenyl))acetamide, N¹‐chloroacetylsulfanilamide, and 2‐chloromethyl‐1H‐benzimidazole to produce a series of 2‐(substituted)methylthio‐3‐cyano‐5,6‐dihydro‐4‐(2′‐thienyl)benzo[h]quinolines 4a , 4b , 4c , 4d , 4e and 11 . Upon heating the latter compounds with sodium ethoxide, they underwent intramolecular Thorpe–Zeigler cyclization to furnish the corresponding 2‐(substituted)‐3‐amino‐5,6‐dihydro‐4‐(2′‐thienyl)‐benzo[h]thieno[2,3‐b]quinolines 5a , 5b , 5c , 5d , 5e and 12 . (3‐Cyano‐5,6‐dihydro‐4‐(2′‐thienyl)‐benzo[h]quinolin‐2‐ylthio)acethydrazide ( 8 ) and the related isomer, 3‐amino‐5,6‐dihydro‐4‐(2′‐thienyl)thieno[2,3‐b]benzo[h]quinoline‐2‐carbohydrazide ( 9 ), were also synthesized. Most of the aforementioned compounds were used as key intermediates for synthesizing other benzo[h]quinolines, benzo[h]thieno[2,3‐b]quinolines as well as benzo[h]pyrimido[4′,5′:4,5] thieno[2,3‐b]quinolines. The structure of all synthesized compounds was confirmed by spectroscopic measurements and analytical analyses.     

Construction of new heteroacenes based on benzo[b]thieno[2,3-d]thiophene / quinoline or 1,8-naphthyridine systems using the Friedländer reaction

Two new classes of heteroacenes, namely benzo[4′,5′]thieno[2′,3′:4,5]thieno[3,2-b]quinolines and benzo[4′,5′]thieno[2′,3′:4,5]thieno[3,2-b][1,8]naphthyridines, have been formed using the Friedländer reaction to annulate the benzo[b]thieno[2,3-d]thiophene scaffold to quinoline or 1,8-naphthyridine fragments. In accordance with this synthetic strategy, benzo[b]thieno[2,3-d]thiophen-3(2H)-ones were treated with 2-aminobenzaldehydes or 2-aminonicotinaldehyde in the presence of pyrrolidine in glacial acetic acid at reflux to give the desired quinoline- or 1,8-naphthyridine-fused compounds, respectively. The optical and electrochemical properties of selected heteroacenes were determined.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

4-Hydroxy- and 4-oxo-1,2,3,4-tetrahydrobenzo[h]quinolines were synthesized. Benzo[h]-quinoline, 1,2,3,4-tetrahydrobenzo[h]quinoline, and a dimeric compound are formed when the 4-hydroxy derivative is heated with hydrochloric acid or without it. The reaction of 4-hydroxy-1,2,3,4-tetrahydrobenzoth]quinoline with thionyl chloride was carried out.See [1] for communication X.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 548–551, April, 1972.     

Condensed pyridine bases synthesis of some benzo[b]furo[2,3-c]-, benzo[b]- thieno[2,3-c]-, and benzo[b]selenopheno[2,3-c]-quinolines

Summary Condensation of benzo[b]furan-3(2H-one, benzo[b]thiophen-3(2H)-one and benzo[b]selenophen-3(2H)-one with dimedone gives 2-(3-heteryl)dimedones. Acylation of the latter leads to the corresponding tetracyclic pyrylium salts, from which condensed quinolines are obtained. Some condensed quinoline derivatives are obtained by reaction of 1-oxo-1,2,3,4-tetrahydroheterene[2,3-c]quinolines with sodium borohydride, hydrazine, and hydroxylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 321–326, March, 1994.     

Reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones

The reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones in the presence of a proton catalyst leads to 1-aryl-3-(3-pyridyl)benzo[f]quinolines. Noncyclic amino ketones — [1-aryl-3-(3-pyridyl)-3-(2-naphthylamino)]-1-propanones — precede the formation of the cyclic products. The IR, UV, PMR, and mass spectra of the synthesized compounds are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 351–354, March, 1989.     

1-Ethyl- and 1,2-dimethyl-3-(p-methoxyphenyl)benzo[f]quinolines and their transformations

Condensation of p-methoxybenzylidene-2-naphthylamine with methyl ethyl ketone leads to a mixture of 1-ethyl- and 1,2-dimethyl-3-(p-methoxyphenyl)benzo[f]quinolines, for which protic and quaternary salts were obtained. Cyanine dyes were synthesized from 1,2-dimethyl-3-(p-methoxyphenyl)benzo[f]quinoline methiodide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1223–1226, September, 1976.     

Catalytic Regio‐ and Enantioselective [4+2] Annulation Reactions of Non‐activated Allenes by a Chiral Cationic Indium Complex

Regio‐ and enantioselective [4+2] annulation between β,γ‐unsaturated α‐keto esters and non‐activated allenes was achieved by using a chiral cationic indium(III)/phosphate catalyst. The reaction affords the corresponding C3‐selective dihydropyrans in good yields and with high enantioselectivity (up to 99 % ee ).     

Synthesis of novel benzo naphtho naphthyridines from 2,4-dicloroquinolines

A schematic study on the condensation of 2,4-dichloroquinolines ( 1 ) with 1-naphthyamine ( 2 ) in the presence of CuI as a catalyst to functionalized mono ( 3 ) and di ( 4 ) substituted naphthylamino quinolines was described. Consequently, these mono- and di-substituted amines on polyphosphoric acid-catalyzed cyclization reaction with p-toluic acid and acetic acid to yield the linear benzo[b]naphtho[2,1-g][1,8]naphthyridines ( 5 ) and angular benzo[b]naphtho[2,1-h] naphthyridines ( 6 ) in good yields. In addition to descried the similar synthesis of benzo[g]naphtho [2,1-b][1,8]naphthyridines ( 12 ) and benzo[h]naphtho[2,1-g][1,8]naphthyridines ( 13 ) from 2,4-dichlorobenzo[h]quinoline ( 8 ) with various anilines ( 9 ) through my intermediates ( 10 and 11 ).