Synthesis of <Emphasis Type="Italic">N</Emphasis>-[4-hydroxy(alkoxy,acyloxy)-3-alkoxy-benzylidene]-1-(1-adamantyl)ethanamines from 1-(1-adamantyl)ethanamine hydrochloride (Rimantadine)

Reactions of 1-(1-adamantyl)ethanamine with vanillin, vanillal, veratraldehyde, 3-ethoxy-4-methoxybenzaldehyde, and 4-formyl-2-methoxy(ethoxy)phenyl esters gave previously unknown Schiff bases containing an adamantane fragment.     

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 of 2,4-substituted 5,6-benzoquinolines

By the catalytic condensation of azomethines with aliphatic-aromatic and heterocyclic ketones, derivatives of 5,6-benzoquinoline containing thiophene or pyridine rings as substituents have been synthesized.     

Synthesis and Properties of Copper,Mercury, and Silver (2-Naphthyl)acetylenides

(Z)-2-Naphthylacetylene was synthesized by the reaction of (Z)-3-(2-naphthyl)-3-chloropropenal (prepared from 2-acetylnaphthalene) with aqueous NaOH in dioxane. The reactions of 2-naphthylacetylene with CuCl, [Ag(NH₃)₂]NO₃, and K₂[HgI₄] gave copper, silver, and mercury 2-naphthylacetylenides, respectively. Silver naphthylacetylenide reacts with iodine to give the iodoethynyl derivative, which readily takes up bromine across the triple bond.     

Facile syntheses of unsolvated UI3 and tetramethylcyclopentadienyl uranium halides

In the course of comparing the reaction chemistry of (C5Me5)3U, 1, and its slightly less crowded analogue (C5Me4H)3U, 2, new syntheses of UI3, (C5Me4H)3U, (C5Me4H)3UCl, 3, and (C5Me5)3UCl, 4, have been developed. Additionally, (C5Me4H)3UI, 5, and (C5Me4H)2UCl2, 6, have been identified for the first time. A facile synthesis of unsolvated UI3 is reported that proceeds in high yield with inexpensive equipment from iodine and hot uranium turnings. Both UI3 and UI3(THF)4 react with KC5Me4H in toluene to make unsolvated (C5Me4H)3U in higher yield than in previous reports that involve reduction of tetravalent (C5Me4H)3UCl, 3. A more atom-efficient synthesis of complex 3 is also reported that proceeds from reduction of t-BuCl, PhCl, or HgCl2 by 2. Similarly, (C5Me4H)3U reacts with PhI or HgI2 to generate (C5Me4H)3UI. These studies also provided a basis to improve the synthesis of (C5Me5)3UCl from 1 by employing t-BuCl or HgCl2 as the halide source. Like (C5Me5)3UCl, the (C5Me4H)3UCl complex reacts with HgCl2 to form (C5Me4H)2 and (C5Me4H)2UCl2, 6, but unlike (C5Me5)3UX (X = Cl or I), the less substituted (C5Me4H)3UX complexes do not reduce t-BuCl or PhX. The synthesis of 6 from (C5Me4H)MgCl x THF and UCl4 is also included.     

The Tricyclooctanone Approach to the Total Synthesis of Steroids. The Cyclization of the A-CD Unit

The first steps of a novel approach to the total synthesis of 9, 11-dehydroestrone via tricyclo[3.3.0.0^2,8]octan-3-one (2) are described. One route involves a tandem-type transformation of the key intermediate 3 (A-CD unit) consisting of cyclopropane cleavage and ring B closure to afford C, 18-bisnor-13 α, 17 α-estradiol derivatives. E.g. the 3-methoxy-9 ζ-hydroxy-17 α-methanesulfonyloxy derivative (-)- 6 has been synthesized in 8 steps and 10% overall yield from 1,3-cyclohexadiene. As an alternative, the A-CD type intermediate 4b has been prepared and could be used for a ring C enlargement prior to cyclization.     

“Superslow” processes in the Ge-GeO2 system

A study was made of the charged state on a natural or an oxidized germanium surface during heat-and-field treatment. This study dealt with the kinetics of charging and discharging of superslow surface states. The thermal activation energy of these charging and discharging processes has also been evaluated. Conclusions are drawn about the possible nature of superslow traps in the Ge-GeO₂ system.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No.2, pp.79–86, February, 1976.In conclusion, the authors thank V. F. Kiselev for the useful discussion of this report and his valuable comments.     

Conjugates of Iron-Transporting N-Hydroxylactams with Ciprofloxacin

Screening of a library of novel N-hydroxylactams amenable by the Castagnoli-Cushman reaction identified four lead compounds that facilitated ⁵⁵Fe transport into P. aeruginosa cells (one of these synthetic siderophores was found to be as efficient at promoting iron uptake as the natural siderophores pyoverdine, pyochelin or enterobactin). Conjugates of the four lead siderophores with ciprofloxacin were tested for antibacterial activity against P. aeruginosa POA1 (wild type) and the ∆pvdF∆pchA mutant strain. The antibacterial activity was found to be pronounced against the ∆pvdF∆pchA mutant strain grown in CAA medium but not for the POA1 strain. This may be indicative of these compounds being ‘Trojan horse’ antibiotics. Further scrutiny of the mechanism of the antibacterial action of the newly developed conjugates is warranted.     

Synthesis of Cobalt Bis(Dicarbollide)—Curcumin Conjugates for Potential Use in Boron Neutron Capture Therapy

A series of novel cobalt bis(dicarbollide)—curcumin conjugates were synthesized. Two conjugates were obtained through the nucleophilic ring-opening reaction of the 1,4-dioxane and tetrahydropyran derivatives of cobalt bis(dicarbollide) with the OH group of curcumin, and using two equiv. of the oxonium derivatives, two other conjugates containing two cobalt bis(dicarbollide) units per molecule were obtained. In contrast to curcumin, the conjugates obtained were found to be non-cytotoxic against both tumor and normal cell lines. The analysis of the intracellular accumulation of the conjugates by flow cytometry showed that all cobalt bis(dicarbollide)—curcumin conjugates entered HCT116 colorectal carcinoma cells in a time-dependent manner. New non-cytotoxic conjugates contain a large amount of boron atoms in the biomolecule and can potentially be used for further biological research into boron neutron capture therapy (BNCT).     

New Derivatives of 5-Substituted Uracils: Potential Agents with a Wide Spectrum of Biological Activity

Pyrimidine nucleoside analogues are widely used to treat infections caused by the human immunodeficiency virus (HIV) and DNA viruses from the herpes family. It has been shown that 5-substituted uracil derivatives can inhibit HIV-1, herpes family viruses, mycobacteria and other pathogens through various mechanisms. Among the 5-substituted pyrimidine nucleosides, there are not only the classical nucleoside inhibitors of the herpes family viruses, 2′-deoxy-5-iodocytidine and 5-bromovinyl-2′-deoxyuridine, but also derivatives of 1-(benzyl)-5-(phenylamino)uracil, which proved to be non-nucleoside inhibitors of HIV-1 and EBV. It made this modification of nucleoside analogues very promising in connection with the emergence of new viruses and the crisis of drug resistance when the task of creating effective antiviral agents of new types that act on other targets or exhibit activity by other mechanisms is very urgent. In this paper, we present the design, synthesis and primary screening of the biological activity of new nucleoside analogues, namely, 5′-norcarbocyclic derivatives of substituted 5-arylamino- and 5-aryloxyuracils, against RNA viruses.