The solubilities of zinc complexes of 8-quinolinol and some derivatives of 8-quinolinol

The solubilities of bis-8-quinolinolo-zinc^II, bis-2-methyl-8-quinolinolo-zinc^II and bis-5 : 7-dibromo-S-quinolinolo-zinc^II have been measured over the pH range of 4.5 to 9 at ionic strengths of 0.114 and 0.230 and at 25° and 40°. A mathematical treatment of the results gave nearly constant solubility products only when a dissolved but undissociated molecule, in addition to all of the dissociated and partly dissociated species, was considered. The relative abundance of each species of molecule in solution has been calculated.     

Absorption spectra of some pyridine and pyridine N-oxide derivatives in oleum

The absorption spectra of a number of pyridlne and pyridine N-oxide derivatives in media of different acidity functions have been investigated. The bathochromic shift of the shortwave absorption band in oleum is interpreted as a consequence of the addition of a proton to the conjugate acid. The formation of a hydrogen bond between the 3-hydroxy derivative of the heterocyclic compounds investigated and the oleum, appearing as a hypsochromic shift of the long-wave absorption band, has been detected. This phenomenon is absent in the case of the 2-methoxy derivative.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 963–966, July, 1973.     

Redox properties of 8-quinolinol and implications for its mode of action

8-Quinolinol (oxine, 8-hydroxyquinoline) is a simple aromatic alkaloid with allelopathic, antibacterial, antifungal, and cytotoxic activities. Generally, it is assumed that 8-quinolinol toxicity depends on transition metal chelation that negatively affects their availability for metalloenzymes in the cell or reactive oxygen species generation (ROS), which are formed following reduction of molecular oxygen by autoxidation of the redox active metal central atom of the 8-quinolinol complex. On the contrary, beneficial effects of 8-quinolinol and its derivatives in the medication of certain degenerative diseases are known. In this context, the activity of 8-quinolinol derivatives is attributed to their antioxidant activity following iron complex formation. To address this controversial issue, we explore the possible anti- or pro-oxidant effects of 8-quinolinol and its iron complexes in the deoxyribose degradation assay, by cyclic voltammetry and in a biological assay. The antibacterial effects of 8-quinolinol and its complex with iron were evaluated on Curtobacterium flaccumfacies and Paenibacillus amylolyticus. 8-Quinolinol showed strong antioxidant activity in the deoxyribose degradation assay. This activity may not depend exclusively on iron chelation, but probably more on the notable reducing properties of 8-quinolinol; it proved to be a more efficient antioxidant than the flavonoids catechin and quercetin. By contrast, 8-quinolinol showed no pro-oxidative effects in the deoxyribose degradation assay, both in free form and in complex with iron, as it may occur with redox cyclers. Cyclic voltammetry confirmed this too. 8-Quinolinol significantly inhibited bacterial growth and respiration. Idiosyncratically, its 50:1 mixture with iron(III) ions was less active compared with free 8-quinolinol; it even caused a U-shaped nonlinear hormetic effect on growth and failed to inhibit respiration as totally as the pure mixture; the respiration was even accelerated compared with the control as a result of lower stress. Our results support the notion that complex formation with either iron or other transition metals affects the reducing power of 8-quinolinol, but, in contrast to general assumptions, this study finds no support that complex formation with iron represents the major mode of action.     

The structure of the nickel—8-quinolinol complex in some organic solvents

The ultraviolet and visible absorption spectra of the nickel—8-quinolinol complex in chloroform are significantly affected by traces of water. Absorption spectra of the complex in mixed solvents, e.g. dioxane—water, dioxane—methanol and chloroform-methanol, and in chloroform solution containing water, pyridine, or 8-quinolinol are compared. An addition compound is formed in which the mole ratio of the nickel-8-quinolinol complex to the solvent or the base is 1:1 or 1:2. Polymerization occurs by mutual interaction between the nickel-8-quinolinol complexes. A degree of polymerization of 2.2 was obtained; this indicates that the binuclear compound predominates. The structure of the nickel—8-quinolinol complex in organic solvents is discussed.     

Solvent extraction of cobalt(II) with 8-quinolinol and its analogues in the presence of some heterocyclic nitrogen bases

Summary Pyridine and its 2-methyl, 2,4-dimethyl and 2,4,6-trimethyl derivatives enhance the extraction of cobalt(II) into chloroform in the presence of 8-quinolinol and its 2-methyl, 4-methyl, 5-chloro and 5-nitro analogues. Adduct formation constants were determined for the cobalt(II) chelates, which formed diadducts with the pyridine bases. The special role of steric factors is discussed. The results are consistent with Lewis acid-base concepts.     

Extraction of tungsten with 8-hydroxyquinoline and some of its derivatives

The extraction of tungsten by chloroform solutions of 8-hydroxyquinoline(I), 2-methyl-8-hydroxyquinoline(II), 5,7-dibromo-8-hydroxyquinoline(III) and 8-mercaptoquinoline(IV), as a function of the concentration of tungsten and reagent and the acidity of the aqueous phase, has been studied. Evidence was obtained for the quantitative extraction of tungsten over a wide range of acidity. The degree of extraction of tungsten at 10(-5)M concentration with I,III and IV gives two maxima when plotted against acidity. The extraction maximum for the more acidic solutions lies in the region where the reagents exist in the protonated form and its position depends on the reagent used. It is suggested that different tungsten complexes are extracted, depending on the acidity of the aqueous phase.     

The synthesis of xanthine-8-acetic acid and some of its derivatives

Condensation of 5,6-diaminouracil with ethyl cyanoacetate yields xanthine-8-acetonitrile which is hydrolyzed by alkalis to xanthine-8-acetic acid. Also synthesized were its ethyl ester, acid chloride, and bis(2-hydroxyethyl)amide.     

Spectrophotometric studies of the complexes of group IIIa metal ions with some phenylazo-8-quinolinol dyes

A new rapid precise method for the spectrophotometric microdetermination of group IIIA metal ions with 5-phenylazo-8-quinolinol (I) and 5-(p-chlorophenylazo)-8-quinolinol (II) is given. The optimum conditions favouring the formation of the complexes are reported, as are the compositions of the complexes, their stabilities, and the ranges for obedience to Beer's law. Spectrophotometric titration methods for Al, Ga and In with EDTA in presence of ligand I or II as indicator are also described.     

Oxide formation in the synthesis and hydrolysis of some fluorides and phosphate esters

Investigation of several routes to fluoro-carbohydrates and sugar phosphates has shown that appreciable formation of internal ethers may occur in certain cases.     

Organogels of 8-quinolinol/metal(II)-chelate derivatives that show electron- and light-emitting properties

8-quinolinol/copper(II)-, palladium(II)-, and platinum(II)-chelate-based organogelators (1 M) and their nongelling reference compounds (2 M) were synthesized. Complexes 1 M could gelate various organic solvents at very low concentrations. Electron microscope measurements gave visual images of well-developed fibrous structures characteristic of low-molecular-weight organogels. UV/Vis and FTIR spectroscopy revealed that the good gelation ability of 1 M arises from the pi-pi interactions of the chelate moieties and the hydrogen-bond interactions among the amide groups. Very interestingly, field emission performances of the nanofibers prepared from the 1 M gels are evidently different depending on the electronic states of the three kinds of central metals. In addition, the 1 Pt gel shows unique thermo- and solvatochromism of visible and phosphorescent color in response to a sol-gel phase transition. Furthermore, the 1 Pt gel possesses an attractive ability to inhibit dioxygen quenching of excited triplet states, which increases the phosphorescence quantum yield of this gel. This effect is attributed to the isolation effect of the phosphorescent chelate moiety from the dioxygen-containing solution phase.     

Preparation of benzoate esters of morphine and its derivatives

Abstract  

Sustained analgesia is crucial for patients suffering from long-acting pain. Ester derivatives of morphine could enhance the lipophilicity of morphine; consequently its transdermal delivery as well as its duration of action are also increased. Therefore, twenty-one 3-O-, 6-O-, and 14-O-benzoate esters of morphine and their derivatives were synthesized in order to elaborate different synthetic methods suitable for esterification of these widely used compounds. Schotten–Baumann reaction was applied with sodium hydrogen carbonate, triethylamine, or pyridine in methylene chloride or 1,2-dichloroethane as solvents. The presence of 4-dimethylaminopyridine catalyst was also successfully utilized mainly in the case of tertiary alcohols. A novel synthesis of dihydromorphine via diacetyl morphine free of by-products is also presented. Structures of all synthesized compounds were elucidated by ¹H nuclear magnetic resonance (NMR), ¹³C NMR, high-resolution mass spectrometry (HRMS), and electron ionization mass spectrometry (EI-MS). The log D (pH 7.4) values of the synthesized compounds were determined by a reversed-phase high-performance liquid chromatography (HPLC)–MS-based method, and calculated hydrolysis rate constants are also provided. The synthesized benzoate esters are potential prodrugs of the parent morphine with enhanced lipophilicity, derivatives which can also be used in transdermal drug delivery as prospective long-acting narcotic analgesics.     

Shedding light on octathio[8]circulene and some of its plate-like derivatives

A quantum chemical investigation is made on the recently synthesized octathio[8]circulene (C16S8), an exotic molecule, the first fully heterocyclic circulene, from the structural and electronic properties and some charge-transport parameters viewpoints. Since the molecule consists of eight thiophene rings fused together, we have chosen to compare it with the acyclic (octathienoacene) analogue and to some relatives thereof, in which the sulfur atoms are substituted by Se, NH, CH2 and O. C16S8, C16Se8 and C16S4Se4 are found to show a low reorganization energy comparable or lower than that for already well known field-effect transistor (FET) materials, a promising property which, combined to some others revealed by this study, makes these compounds potential candidates for FET use. In addition, the twist angle is found to be tightly linked to the peripheral bonds lengths, the least twisted structures showing the most interesting properties for organic FET use.     

Strain in biphenylene and some of its derivatives

The strain energies in biphenylene and some of its bridged derivatives have been calculated by using a high-level ab initio method (G3MP2//B3LYP-6-31G*) in order to resolve the long-standing discrepancy in the previously reported values. The results show that the strain energy of biphenylene is approximately 222 kJ/mol, which is lower than the previously reported values. The strain energies in 1,8-bridged biphenylene derivatives were also calculated and turned out to be larger than previously suggested. Our results highlight the need to use thermodynamic information in conjunction with structural data when discussing strain energy or molecular deformation.     

Proton NMR spectra and structure of chlorotin(IV) ternary complexes of 8-quinolinol and its 5,7 dichloro and 2 methyl-5,7 dichloro derivatives

The low temperature ¹H NMR spectra in d-chloroform of the ternary complexes bis-(8-quinolinato) tin(IV) dichloride, bis-(5,7 dichloro-8-quinolinato) tin(IV) dichloride, and bis-(2 methyl-5,7-dichloro-8-quinolinato) tin(IV) dichloride have been obtained. The spectra showed that for the three complexes, only two configurations were appreciably populated, their free energy differences being equal to 0.28, 0.08 and ?0.04 kcal/mol respectively. The proton chemical shifts, the ¹H-¹H coupling constants and some of the ¹H-¹¹⁹Sn coupling constants have been obtained for each complex in the two configurations. An approximate computation of chemical shifts, including aromatic ring magnetic anisotropies and electric effects from polar groups, allowed the identification of the two configurations as the cis-cis-trans and the cis-trans-cis (with respect to Cl, N and O atoms), the former being the more populated one.     

Partial synthesis of 6-methyl-9-ergolen-8-beta-acetic acid and some of its derivatives

The transformation of lysergic acid and 1-methyllysergic acid into their homologous acids, i.e. 6-methyl-9-ergolen-8β-acetic acid and 1,6-dimethyl-9-ergolen-8β-acetic acid, and the synthesis of some of their derivatives are described.     

The anodic oxidation of fluorene and some of its derivatives: Conditions for the formation of a new conducting polymer

Quinones undergo a one-step two-electron reduction in molten acetamide at the mercury and platinum electrodes. The reversibility of reduction increases in the order benzoquinone < napthaquinone = phenanthrquinone < anthraquinone.