Anthracene derivatives of benzo[f]quinoline. Synthesis,spectra, and luminescence

By condensation of 9-[N-(2-naphthyl)formimidoyl]anthracene with methyl ketones under conditions of acid catalysis, 1-R-3-(9-anthryl)benzo[f]quinolines have been obtained. The byproducts of the reaction have been identified: 1-R-3-(9-anthyl)-2-propen-1-ones and N-[1-(p-aminophenyl)-3-(9-anthryl)-2-propen-1-ylidene]-2-naphthylamines. The spectral and luminenscence properties of these compounds have been examined critically.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1536–1541, November, 1985.     

水介质中三组分一锅合成1-芳基苯并[f]喹啉衍生物

以芳醛、2-萘胺和Meldrum酸为原料, 以水为溶剂, 在回流条件下以三乙基苄基氯化铵为催化剂通过三组分一锅反应, 合成了一系列的1-芳基苯并[f]喹啉衍生物. 该方法具有反应条件温和、产率较高(79%～87%)、环境友好等优点. 产物的结构通过熔点, IR, ¹H NMR和元素分析表征.     

Crystal structure and luminescence property of ternary terbium p-aminobenzoic acid complexes with different second ligands

Ternary terbium complexes with p-aminobenzoic acid (HL), [TbL₃(DMSO)(H₂O)]₂ (1), [TbL₃(DMF)(H₂O)]₂ (2) and [TbL₃(Bpy)(H₂O)]₂·2H₂O (3) (DMSO=dimethyl sulfoxide, DMF=N, N- dimethylformamide, Bpy=2, 2′- bipyridyl) have been synthesized, and their crystal structures determined. The luminescence properties of these complexes, including both the emission quantum yield and the fluorescence lifetime, have been investigated. The effect of a second ligand on the crystal structure and luminescence property of the ternary terbium p-aminobenzoic acid complexes, and the relationship between luminescence properties and crystal structure, including coordination mode of the L⁻ ligand and the characteristics of a second ligand, are discussed.     

Synthesis and luminescence of benzo[f]quinoline derivatives with fused alicyclic rings

Cyclic ketones react with N-(2-naphthyl)formimidoyl-4-pyridine in refluxing aliphatic alcohol to form 1,2-(1,2-cycloalkylene)-3-(4-pyridyl)benzo[f]quinolines. Under mild conditions, cyclopentanone and cyclohexanone gave dihydrobenzo[f]quinoline derivatives — 1,2-(1,2-cycloalkylene)-3-(4-pyridyl)-3,4-dihydrobenzo[f]quinolines, whereas cycloheptanone gave an aminoketone — 2-[(4-pyridyl) (2-naphthylamino)methyl]cycloheptanone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 947–950, July, 1986.     

Cyclometallation reactions : VII. Reactions of benzo[h]quinoline

Reactions between benzo[h]quinoline (BqH) and M(CO)₅Me (M = Mn, Re), M₃(CO)₁₂ (M = Ru, Os) and [Rh(CO)₂Cl]₂ have given the complexes M(CO)₄Bq (M = Mn, Re), M(CO)₂Bq₂ (M = Ru, Os), and Bq₂RhCl₂Rh(CO)₂, respectively; Cr(CO)₃ (π-BqH) is metallated on reaction with Mn(CO)₅Me, affording [π-BqMn(CO)₄]Cr(CO)₃. Spectroscopic evidence was obtained for the formation of Mo(CO)₂Bq(π-C₅H₅). Reactions of some complexes to give bi(benzo[h]quinolyl) are also reported. Characteristic changes in the IR and NMR spectra which occur as a result of metallation of the ligand are reported.     

Synthesis of benzo[g]quinoline derivatives. XII. 1,2,3,4-Tetrahydro-4-oxo-10-chlorobenzo[g]quinoline

1,2,3,4-tetrahydro-4-oxobenzo[g]quinoline was halogenated with elementary chloride. The structure of the product — 1,2,3,4-tetrahydro-4-oxo-10-chlorobenzo[g]quinoline — was established by alternative synthesis.     

DFT-calculated structure of protonated tetraphenyl p - tert -butylcalix[4]arene tetraketone

Using DFT calculations, two of the most probable structures (A, B) of the tetraphenyl p-tert-butylcalix[4]arene tetraketone·H₃O⁺ cationic complex species were derived. The hydroxonium ion H₃O⁺, placed in the coordination cavity formed by the calix[4]arene lower-rim groups, is bound by strong hydrogen bonds to the phenoxy oxygen atoms of the calix[4]arene ligand (structures A, B) and also to one carbonyl oxygen (structure B).     

A highly selective method for the synthesis of 1,3-diarylbenzo[f]quinoline derivatives catalyzed by silver triflate

Abstract  

The three-component reactions of aromatic aldehydes, naphthalen-2-amine, and phenylacetylene catalyzed by AgOTf in toluene selectively gave 1,3-diarylbenzo[f]quinolines in high yields. This procedure provides an efficient method for the synthesis of benzo[f]quinolines under mild reaction conditions and with high yields, high selectivity, and operational simplicity.     

Spectral luminescence properties of 1- and 2-alkyl(cycloalkyl) derivatives of benzo[f]quinoline

The absorption and fluorescence spectra of alcohol solutions of 3-aryl-substituted benzo[f]-quinolines were investigated, and the fluorescence quantum yields were measured. It was established that the indicated compounds have intense absorption in the UV region and fluorescence at 350–450 nm. The fluorescence quantum yields range from 5 to 70%, depending on the substituents. The introduction of aromatic substituents in the 1 and 3 positions of benzo-[f]quinoline ring raises the fluorescence quantum yields. A methyl group in the 2 position of the molecule leads to a decrease in the fluorescence quantum yield. Benzo[f]quinoline derivatives that contain a cyclopentene ring in the 1 and 2 positions fluoresce intensely (=40–60%), while cyclohexene and cycloheptene condensed in the same positions cause a decrease in the fluorescence yield to 7–13%; this is associated with the three-dimensional structure of these molecules.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1237–1240, September, 1977.     

Synthesis and cytotoxicity of two novel alcohols based on a benzo[c]phenanthrene moiety

Synthetically, 1-(benzo[c]phenanthren-2-yl)ethanol and 1-(benzo[c]phenanthren-2-yl)-3-phenylpropane-1,3-diol were successfully obtained from 2-acetylbenzo[c]phenanthrene and methyl benzo[c]phenanthrene-2-carboxylate, respectively, and fully characterized. The desired compounds were purified by silica gel column chromatography, and their structures were characterized by melting points, ¹H NMR, ¹³C NMR, and mass spectroscopy. Next, the in vitro cytotoxicity of the new polyaromatic alcohols was evaluated against two human carcinoma cell lines (Hep-2 and Caco-2) using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay method. Consequently, the 1,3-diol derivative displayed the highest cytotoxicity against both cell lines (IC₅₀ = 0.7 and 0.6 μg/mL). This allowed us to infer that the effect of intramolecular hydrogen bond seems to be important for the cytotoxic activity.     

Simple synthesis of quinolines and dibenzo[b,f][1,5]diazocines under microwave irradiation

Quinolines 3a–f, 5a–f, and dibenzo[b,f][1,5]diazocines 4, 6 were synthesized in the presence of 0.5 equiv. of diphenyl phosphate (DPP) under microwave irradiation. The obtained yield of 6,12-diphenyl-dibenzo[b,f][1,5]diazocine 4 was higher when using anhydrous DPP than when using HCl, H₃PO₄, and CH₃COOH.     

Protonated Tetramethyl p - tert -Butylcalix[4]arene Tetraketone: NMR Evidence and Probable Structures

Both NMR spectra in nitrobenzene-d ₅ and high-precision quantum mechanical DFT calculations proved that tetramethyl p-tert-butylcalix[4]arene tetraketone binds hydroxonium cation H₃O⁺ quite strongly to form an equimolar complex. Three different structures of the resulting complex species were indicated by the NMR spectra and the DFT calculations.     

Measurement of benzo[a]pyrene,benzo[k]fluoranthene and benzo[g,h,i]perylene by ultraviolet spectroscopy

Microchimica Acta - The technique for determining benzo[a]pyrene, benzo[k]fhuoranthene, and benzo[g,h,i]perylene respectively inμg amounts by UV absorption measurements is described. The...     

Benzocyclobutenes-x : Synthesis of cyclobuta[l]phenanthrene derivatives from [2 + 2]photoadducts of chlorinated ethenes and phenanthrene

UV irradiation of phenanthrene and 1,1-dichloro-, 1,2-dichloro-, and 1,1,2-trichloroethenes resulted m [2+2]cycloaddition to give cyclobutane derivatives. Treatment of the 1,2-dichloro-adducts with N-bromosuccinimide resulted in aromatisation to yield cis- and tras-l,2-dichloro-1,2- dihydrocyclobuta[l)phenanthrene, whereas the 1,1-dichloro-adduct resulted in aromatisation and hydrolysis to give cyclobuta[l]phenanthrene-l(2H)-one. The trichloroethene adducts gave 1,2-dichloro-2a,10b-dihydrocyclobuta [l)phenanthrene upon treatment with base, and reaction with N- bromosuccinimide resulted in bromine substitution in the cyclobutane ring. The stereochemistry of the adducts and the stereoselectivity of the bromination reactions are discussed.     

Synthesis and spectral characteristics of acenaphthene derivatives of benzo[f]quinoline

The catalytic interaction of 5-acetylacenaphthene with arylidene-2-naphthylamines leads to the formation of adducts to the C=N bond (aminoketones) or 1-(5-acenaphthenyl)-3-aryl-(heteroaryl) benzo[f]quinolines. In several instances they are accompanied by 1-(5-acenaphthenyl)-3-R-2-propen-1-ones or N-substituted 2-naphthylamines. The ratio of the products depends on the condensation conditions and the structure of the starting azomethine. Using the 3-(p-fluorophenyl)-substituted derivative as an example, it has been shown that in the absence of dihydrogenating agents -aminoketones undergo dehydrocyclization with formation of benzoquinolines and 1,2,3,4-tetrahydroquinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1102–1106, August, 1986     

Studies of imidazo[4, 5-f]quinoline

The UV absorption spectra of imidazo[4, 5-f]quinoline and its quaternary salts were examined. The causes of the development of luminescence in solutions of the quaternary salts of imidazo[4, 5-f]quinoline were elucidated.For part I, see [6].     

杯芳烃多齿水杨醛亚胺衍生物的合成

以对叔丁基杯[n]芳烃1a～1b (n＝6, 8)为原料, 经过三步反应, 以较高产率合成了一系列含多个水杨醛亚胺端基的西佛碱衍生物5a～5f. 对叔丁基杯[n]芳烃用溴乙酸乙酯进行烃基化反应, 生成杯芳烃氧代乙酸乙酯2a～2b, 后者与过量脂肪族二胺NH₂(CH₂)_mNH₂ (m＝2, 4, 6)反应, 生成含有游离氨基的杯芳烃酰胺衍生物4a～4f, 再与水杨醛在乙醇中反应生成目标产物席夫碱衍生物.     

Transformations of imidazo[4, 5-f]quinoline

Treatment of imidazo[4, 5-f]quinoline and some of its 3-substitmion products with methyl halides and methyl benzenesulfonate gives as the main reaction products N-methylimidazoquinolinium salts, which can also be synthesized from 5, 6-dimainoquinolines. Methylation at the N atom of the imidazole ring is only a side reaction. Treatment with trimethylphenylammonium hydroxide introduces a methyl radical into the NH group of imidazoquinoline, giving a mixture of 1-and 3-substitution products.