Nitro derivatives of isomeric methyldiazaphenanthrenes

The synthesis of four isomeric nitro derivatives of methyldiazaphenanthrenes (DAP) has been described. The UV spectra of these compounds have been recorded and compared with those of parent diazaphenanthrenes. The biological data of methylnitrodiazaphenanthrenes and of other derivatives of diazaphenanthrenes are presented. Institute of Chemistry, Pedagogical University, 42-201 Czestochowa, Poland Babimost School, 66-110 Babimost, Poland. Microbiology Department Agricultural Academy 50-375 Wroclaw, Poland. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1396–1403, October, 1999.     

Nitro derivatives of 1-picrylbenzotriazole

The synthesis of the isomeric 4,6-, 5,6-, and 5,7-dinitro-1-picrylbenzotriazoles has been accomplished. The nmr spectra of these compounds and the mononitro derivatives of 1-picrylbenzotriazole were determined and the substituent effects of the nitro and picryl groups on the chemical shifts of the various benzotriazole protons are discussed.     

Nitro derivatives of phenyl-1,2,3-triazole

A number of tri- and tetranitro-N-phenyl-1,2,3-triazolyl compounds were synthesized by a combination of condensation, cycloaddition, and nitration reactions, and their crystal densities, impact sensitivities, and thermal stabilities were determined.     

Mass spectrometry of 8-hydroxyquinoline derivatives

In contrast to the fragmentation of the corresponding alkyl aryl ethers, characteristic [M-H]⁺ and [M-H, -CO]⁺ fragments were observed in the fragmentation of 5-nitro(halo)-substituted 8-alkoxyquinolines. It was found by means of deuterium labeling that a hydrogen atom is split out primarily from the alkoxy group. It was demonstrated that an [M-H, -CO]⁺ fragment was formed from the [M-H]⁺ ion, which has a three-ring structure and a quaternary nitrogen atom. The formation of an [M-CO]⁺ fragment is characteristic for the fragmentation of 5(7)-nitro(halo)-substituted 8-hydroxyquinolines. The interrelationship between the intensities of the [M-H]⁺, [M-H, -CO]⁺, and [M-CO]⁺ ion peaks and the protonation constants (pK_a) of the investigated compounds is discussed.Communication 4 from the series Mass spectrometry of biologically active substances, See [1] for communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 786–791, June, 1984.     

Spectrophotometric determination of halogenated 8-hydroxyquinoline derivatives

A spectrophotometric method is proposed for the determination of 8-hydroxyquinoline and three of its iodinated derivatives: 5-chloro-7-iodo-8-hydroxyquinoline (clioquinol), 5,7-di-iodo-8-hydroxy-quinoline (iodoquinol) and 8-hydroxy-7-iodo-quinolone-5-sulphonic acid (chinoform). The suggested method depends on the reaction with 4-aminoantipyrine in the presence of an alkaline oxidizing agent. A red antipyrine dye with an absorption peak at 500 nm is produced in all cases. The reacting ratio has been determined and a reaction mechanism is presented. The proposed method can be applied to the analysis of pharmaceutical preparations containing the compounds studied, and the results obtained compare favourably with those obtained with the standard methods.     

Proton magnetic resonance studies of 8-hydroxyquinoline derivatives

The PMR spectra of 8-hydroxyquinoline and eighteen derivatives have been obtained at 220 MHz. For several of the compounds, PMR spectra have not been reported previously. The use of 220-MHz frequency considerably facilitates the interpretation of spectra from such complex derivatives as 2-(2'-pyridyl) and 2-(2'-thienyl)-8-hydroxyquinoline.     

IR spectra and structures of 3-hydroxyquinoline, 4-hydroxyisoquinoline,and their derivatives

From an examination of the frequencies, integral intensities, and half-widths of the absorption bands of the stretching vibrations of the hydroxyl groups in the IR spectra, it was concluded that 3-hydroxyquinoline, 4-hydroxyisoquinoline, and their derivatives exist in the phenol form in dilute CCl₄ solutions. Strong intermolecular hydrogen bonds, which are destroyed on dilution, exist in 3-hydroxyquinoline, 4-methyl-3-hydroxyquinoline, 4-hydroxyisoquinoline, and 1-chloro-3-methyl-4-hydroxyquinoline at concentrations above 10² M in CCl₄. From an examination of the values of halo derivatives of 3-hydroxyquinoline and 4-hydroxyisoquinoline, it was concluded that an intramolecular hydrogen bond of the OH...Hal type is present in these compounds. The shift in the OH band increases in the order Cl< Br< I. Weak bands of a free OH group that pertain to the s-trans form are observed in the spectrum. Strong intramolecular hydrogen bonds exist in 3-nitro-4-hydroxyisoquinoline and 3-piperidinomethyl-4-hydroxyisoquinoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1535–1539, November, 1971     

Nitro and bromo derivatives of a highly fluorinated thiobenzoate

Several compounds derived from monosubstituted thiobenzoates, with substituents in the meta- or para-position, have been prepared; these contain a thioester spacer between a semifluorinated chain and the rigid core unit. The substituent is either a bromo or a nitro group. Their mesomorphic properties were evaluated using polarizing optical microscopy and differential scanning calorimetry. The influence of the different substituents on the phenyl core was considered. No mesomorphic behaviour was seen except for one nitro derivative. The introduction of the nitro group in the para-position of the thiobenzoate core leads to a LC transition on heating. As with previous studies, these results show that substitution at the 4 position on a monophenyl core can lead to liquid crystallinity, whereas substitution in the meta-position does not; this supports the view that meta-substitution is not a necessary condition for obtaining a LC phase.     

8-羟基喹啉衍生物及其锌配合物的合成

<正>自从1987年美国Kadak公司C.W.Tang及其合作者[1]首次用8-羟基喹啉铝(Alq3)作为发光层,得到了在较低直流电压(约10V)驱动下高亮度(1000cd/m2)的有机电致发光材料以来,以8-羟基喹啉为配体的有机金属电致发光材料的研究就一直成为人们重点关注的内容[2-5];近年来,人们不断对8-羟基喹啉配体进行化学修饰[6-12],在喹啉环结构上引入不同基团,改变分子轨道中HOMO和LUMO能级差,使配合物发光峰改变,成功合成出各种发不同荧光的有机电致发光材料。     

Nitro derivatives of cyclic sulfoximides of the 1,2-benzoisothiazole series

Nitro derivatives of 1-R-1,2-benzoisothiazol-3-one 1-oxide were synthesized by the reactions of 2-alkyl(phenyl)thio-4-nitro- and 4,6-dinitro-2-(phenylthio)benzamides with chlorine in 60% acetic acid. Analogous reactions of 2-(n-butylthio)-4-nitro- and 2-(tert-butylthio)-4-nitrobenzamides with chlorine afforded 2-butyl- and 2-H-1,2-benzoisothiazol-3-one 1-oxides, respectively. The proposed reaction mechanism includes the formation and subsequent transformations of S-alkyl-S-aryl- and S,S-diarylchlorosulfonium chlorides.     

Nitro derivatives of 2-(1-naphthyl) thiophene

2-[1-(3, 4-Dihydronaphythyl)]thiophene, 2-(1-naphthyl)thiophene, 3, 4, 5-triacetoxymercuri-, 3, 4-diacetoxymercuri-5-nitro-, 4, 5-diacetoxymercuri-3-nitro-2-(1-naphthyl)thiophenes and 3, 3, 4-triacetoxymercuri-2[1-(4-nitronaphthyl)]thiophene are synthesized and characterized. Nitration of 2-(1-naphthyl)thiophene with copper nitrate in acetic anhydride leads to formation of two isomeric mono-nitro derivatives, 4-nitro- and 5-nitro-2-(1-naphthyl)thiophene.     

CH3和CN取代8-羟基喹啉电子光谱性质的含时密度泛函理论研究

对8－羟基喹啉QH及其代衍生物MQH和CNQH用密度泛函方法（DFT）在B3LYP／6－31G＊水平上进行理论计算，探讨了供电子取代基（－CH3）和吸电子取代基（－CN）对分子电子结构，前线分子轨道能和光谱性质等的影响规律，在此基础上采用含时密度泛涵方法（TD－DFT）计算了电子光谱，计算结果表明，MQH，QH和CNQH的最低激发单重态都是A，激发能分别为3．58，3．72和3．74eV，在高激发态，无论是供电子基团（－CH3）还是拉电子基团（－CN），都导致取代衍生物的电子光谱红移。     

Properties of 4-nitro-3-hydroxyquinoline

It was found that the nitro group in 4-nitro-3-hydroxyquinoline readily undergoes exchange in acidic media; the corresponding 4-halo-, 4-mercapto, 4-phenylsulfonyl, and p-tolylthio derivatives of 3-hydroxyquinoline were obtained.