- New 3,1,2,4-benzothiaselenadiazines, related π-heterocycles including Herz cations, radicals and molecular complexes, and Bunte salts
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New chalcogen-nitrogen π-heterocycles covering 3,1,2,4-benzothiaselenadiazines, 1,3,2,4-benzodithiadiazines and 1,2,4,3,5-benzotrithiadiazepines were synthesized via the electrophilic cyclization of compounds Ar-NSN-SiMe3 under the action of SeCl2, SeCl4/FeCp2, SCl2 and S2Cl2. Heterocycles obtained were thermolyzed into persistent 2,1,3-benzothiaselenazolyls and 1,2,3-benzodithiazolyls (Herz radicals), which were characterized using EPR spectroscopy and DFT calculations. Reaction of the archetypal 3,1,2,4-benzothiaselenadiazine with SCl2 afforded 2,1,3-benzothiaselenazolium chloride (Herz salt), whereas that of sterically hindered 1,3,2,4-benzodithiadiazine resulted in a complex of the corresponding Herz salt with unexpected carbocycle-chlorinated and non-chlorinated 3,3-dioxides of the starting material, which is a rare example of a molecular complex involving a Herz cation. Formation of the dioxides can be explained through intermediate participation of the benzodithiadiazine radical cation. Hydrolysis of 3,1,2,4-benzothiaselenadiazine or 1,3,2,4-benzodithiadiazine led to Se-(2-aminophenyl)selenosulfate (Se-Bunte salt) or S-(2-aminophenyl)thiosulfate (Bunte salt), respectively. This journal is
- Bagryanskaya, Irina Yu.,Gatilov, Yuri V.,Irtegova, Irina G.,Makarov, Alexander Yu.,Nefedov, Andrey A.,Volkova, Yulia M.,Zibarev, Andrey V.,Zikirin, Samat B.
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p. 3687 - 3696
(2022/03/07)
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- Catalytic antioxidant activity of bis-aniline-derived diselenides as GPx mimics
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Herein, we describe a simple and efficient route to access aniline-derived diselenides and evaluate their antioxidant/GPx-mimetic properties. The diselenides were obtained in good yields via ipso-substitution/reduction from the readily available 2-nitroaromatic halides (Cl, Br, I). These diselenides present GPx-mimetic properties, showing better antioxidant activity than the standard GPx-mimetic compounds, ebselen and diphenyl diselenide. DFT analysis demonstrated that the electronic properties of the substituents determine the charge delocalization and the partial charge on selenium, which correlate with the catalytic performances. The amino group concurs in the stabilization of the selenolate intermediate through a hydrogen bond with the selenium.
- Barbosa, Flavio A. R.,Bettanin, Luana,Botteselle, Giancarlo V.,Braga, Antonio L.,Canto, R?mulo F. S.,Ciancaleoni, Gianluca,Domingos, Josiel B.,Elias, Welman C.,Gallardo, Hugo,Rafique, Jamal,Saba, Sumbal,Salin, Drielly N. O.
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- Green preparation method of aryl diselenium ether type organic selenium compound
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The invention discloses an aryl diselenium ether compound synthesis method. The synthesis method comprises the following steps: taking the compound represented by the formula (I) as a reaction raw material, CuBr as a catalyst, KOH in the condition Se, a reducing agent, a disproportionation reaction, water or ethanol as a solvent, and 60 °C. After completion of the reaction, the obtained reaction solution is subjected to post-treatment (if ethanol is recovered as solvent) to obtain the aryl diselenoether compound represented by the formula (II), the yield is close 100%, the subsequent treatment is simple, and a complex separation and purification method is not needed to obtain a pure product. The solvent is recovered as a solvent such as ethanol. , It is preferable. The method is more green. Economy, high efficiency, environmental protection.
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Paragraph 0066-0070
(2021/11/14)
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- Janus -faced oxidant and antioxidant profiles of organo diselenides
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To date, organoseleniums are pre-eminent for peroxide decomposition and radical quenching antioxidant activities. On the contrary, here, a series of Janus-faced aminophenolic diselenides have been prepared from substituted 2-iodoaniline and selenium powder using copper-catalyzed methodology. Subsequently, condensation with substituted salicylaldehyde afforded the Schiff base, which on reduction, yielded the desired substituted aminophenolic diselenides in 72%-88% yields. The generation of reactive oxygen species (ROS) from oxygen gas by the synthesized aminophenolic diselenides was studied by analyzing the oxidation of dichlorofluorescein diacetate (DCFDA) dye and para-nitro-thiophenol by fluorescence and UV-Visible spectroscopic methods. Furthermore, density functional theory calculations and crystal structure analysis revealed the role of functional amine and hydroxyl sites present in the Janus-faced organoselenium catalyst for the activation of molecular oxygen, where NH and phenolic groups bring the oxygen molecule close to the catalyst by N-H?O and O-H?O intermolecular interactions. Additionally, these functionalities stabilize the selenium-centered radical in the formed transition states. Antioxidant activities of the synthesized diselenides have been explored as the catalyst for the decomposition of hydrogen peroxide using benzenethiol sacrificial co-reductant by a well-established thiol assay. Radical quenching antioxidant activity was studied by the quenching of DPPH radicals at 516 nm by UV-Visible spectroscopy. The structure activity correlation suggests that the electron-rich phenol and electron-rich and sterically hindered selenium center enhance the oxidizing property of the aminophenolic diselenides. Janus-faced diselenides were also evaluated for their cytotoxic effect on HeLa cancer cells via MTT assay, which suggests that the compounds are effective at 15-18 μM concentration against cancer cells. Moreover, the combination with therapeutic anticancer drugs Erlotinib and Doxorubicin showed promising cytotoxicity at the nanomolar concentration (8-28 nM), which is sufficient to suppress the growth of the cancer cells. This journal is
- Batabyal, Monojit,Dutta, Tanoy,Koner, Apurba Lal,Kumar Jha, Raushan,Kumar, Sangit,Upadhyay, Aditya
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p. 14576 - 14594
(2021/11/03)
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- Benzo five-membered ring aza derivative containing benzophenone group as well as preparation method and application of benzo five-membered ring aza derivative
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The invention discloses a benzo five-membered ring aza derivative containing a benzophenone group as well as a preparation method and application of the benzo five-membered ring aza derivative. The benzo five-membered ring aza derivative containing the benzophenone group has a unique benzophenone group and benzo five-membered ring aza structure, has unique intramolecular twisted charge transfer (TICT) and aggregation-induced emission (AIE) effects, has high luminous intensity, red light emission and delayed fluorescence, and can be well used as a luminous layer in a red light OLED. Controllable preparation of the benzo five-membered ring aza derivative containing the benzophenone group is achieved, the preparation cost is low, the raw material source is wide, and large-scale production can be achieved. The benzo five-membered ring aza derivative containing the benzophenone group can be widely applied to the fields of color display and solid-state illumination, is used for preparing luminous materials, luminous devices or intelligent materials, and is particularly used for preparing OLED devices.
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Paragraph 0119; 0123-0126
(2021/08/25)
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- Non-covalent bridging of bithiophenes through chalcogen bonding grips
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In this work, chalcogen functionalized dithiophenes, equipped on both extremities with chalcogen-bonding recognition heterocycles, have been prepared following two synthetic pathways. The insertion of the chalcogenazolo[5,4-β]pyridine allows the control of the organization at the solid state. X-Ray diffraction analysis of the single crystals, showed that the Te-doped derivatives give the most persistant assemblies, with the molecules arranging at solid-state in wire-like polymeric structures through Te?N interactions. As expected, the introduction of the Se and Te atoms, dramatically decreases the emission properties, with the Te-bearing congeners being virtually non emissive.
- Babudri, Francesco,Biot, Nicolas,Bonifazi, Davide,Romito, Deborah
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supporting information
p. 6732 - 6738
(2020/05/16)
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- Emission color-tunable oxazol(in)yl-substituted excited-state intramolecular proton transfer (ESIPT)-based luminophores
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Oxazolinyl- and arylchalcogenazolyl-substituted hydroxyfluorenes exhibiting excited-state intramolecular proton transfer (ESIPT) are described as potent and highly modular luminophores. Emission color tuning was achieved by varying the π-expansion and the
- Bigall, Nadja C.,Duvinage, Daniel,G?bel, Dominik,Nachtsheim, Boris J.,Rusch, Pascal
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supporting information
p. 15430 - 15433
(2020/12/25)
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- Isolation and structure of an 18-membered macrocycle containing two diselenide linkages and its precursor
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The structures of the 18-membered diselenide-linked macrocycle 10,27-di-tert-butyl 11,28-dioxo-2,3,19,20-tetraselena-10,12,27,29-tetraazapentacyclo-[28.4.0.04,9.013,18.021,26]tetratriaconta-1(30),4(9),5,7,13,15,17,21,23,25
- Raju, Saravanan,Butcher, Ray J.,Singh, Harkesh B.
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p. 336 - 341
(2019/02/27)
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- Se-mediated one-pot synthesis of 2-substituted benzoselenazole derivatives from 2 to iodoanilines and arylacetic acids/arylmethyl chlorides
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A general approach to the formation of 2-substituted benzoselenazoles from the three-component reactions of 2-iodoanilines, selenium powder, arylacetic acids or benzyl chlorides is described. The use of copper salt as catalyst and dimethyl sulfoxide (DMSO) as solvent are crucial to afford the title compounds in moderate to good yields (45–88%) with good functional group tolerance on the aromatic and heteroaromatic substrates.
- Gu, Ren,Wang, Xin,Yang, Zhao,Han, Shiqing
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supporting information
p. 2835 - 2838
(2018/06/25)
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- An Organodiselenide with Dual Mimic Function of Sulfhydryl Oxidases and Glutathione Peroxidases: Aerial Oxidation of Organothiols to Organodisulfides
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A novel organodiselenide, which mimics sulfhydryl oxidases and glutathione peroxidase (GPx) enzymes for oxidation of thiols by oxygen and hydrogen peroxide, respectively, into disulfides has been presented. The developed catalyst oxidizes an array of organothiols into respective disulfides in practical yields by using aerial O2 to avoid any reagents/additives, base, and light source. The synthesized diselenide also catalyzes the reduction of hydrogen peroxide into water by following the GPx enzymatic catalytic cycle with a reduction rate of 49.65 ± 3.7 μM·min-1.
- Rathore, Vandana,Upadhyay, Aditya,Kumar, Sangit
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supporting information
p. 6274 - 6278
(2018/10/05)
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- A One-Pot Access to Benzo[b][1,4]selenazines from 2-Aminoaryl Diselenides
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Different 2-sulfonylaminoaryl diselenides substituted with electron-withdrawing or -donating groups are transformed in one pot into benzo[b][1,4]selenazines. The reaction uses a substoichiometric amount of Cu(OTf)2, and the mechanism involves a base-mediated 1,4-elimination at selenium with the generation of an o-iminoselenoquinone and a 2-sulfonylaminoselenolate anion. The former is a dienic species that can react with electron-rich dienophiles to give the target cycloadducts. The latter is oxidised by air back to the starting diselenide, allowing its complete consumption. A preliminary investigation of the GPx-like activity of a selected selenazine is also described.
- Menichetti, Stefano,Capperucci, Antonella,Tanini, Damiano,Braga, Antonio L.,Botteselle, Giancarlo V.,Viglianisi, Caterina
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supporting information
p. 3097 - 3102
(2016/07/14)
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- Walking Down the Chalcogenic Group of the Periodic Table: From Singlet to Triplet Organic Emitters
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The synthesis, X-ray crystal structures, ground- and excited-state UV/Vis absorption spectra, and luminescence properties of chalcogen-doped organic emitters equipped on both extremities with benzoxa-, benzothia-, benzoselena- and benzotellurazole (1
- Kremer, Adrian,Aurisicchio, Claudia,Deleo, Federica,Ventura, Barbara,Wouters, Johan,Armaroli, Nicola,Barbieri, Andrea,Bonifazi, Davide
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supporting information
p. 15377 - 15387
(2015/11/02)
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- Copper-catalyzed three-component one-pot synthesis of substituted 2-aryl-1,3-benzoselenazoles
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A simple copper-catalyzed, one-pot synthesis of 2-aryl-1,3-benzoselenazole derivatives was developed using inexpensive, readily available 2-iodoanilines, selenium powder, and aromatic aldehydes as the starting materials. The mild reaction conditions and simple procedure without ligands and other additives make this methodology an alternative for preparing these potential selenium-containing compounds very conveniently.
- Su, Tao,Xie, Shishun,Li, Bifu,Yan, Jun,Huang, Ling,Li, Xingshu
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supporting information
p. 215 - 220
(2015/03/03)
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- Synthesis of 2-Substituted 1,3-Benzoselenazoles from Carboxylic Acids Promoted by Tributylphosphine
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We report a general, practical, and simple metal-free method for the synthesis of 2-substituted 1,3-benzoselenazoles by the reaction of bis(2-aminophenyl)diselenide with a wide range of carboxylic acids, promoted by tributylphosphine. This efficient reaction furnishes 2-aryl-1,3-benzoselenazoles in good yields and tolerates a variety of substituents at the aryl moiety of carboxylic acids. For the first time, 2-alkyl-1,3-benzoselenazoles could be obtained from aliphatic carboxylic acids and thiazolidine-4-carboxylic acid in high chemical yields. The use of focused microwave irradiation considerably decreased the reaction time from 48 to 2 h. The experimental data provide insights into the mechanism of the reaction. A metal-free synthesis of 2-substituted 1,3-benzoselenazoles by the reaction of bis(2-aminophenyl)diselenide with carboxylic acids, promoted by tributylphosphine is reported. For the first time, 2-alkyl-1,3-benzoselenazoles could be obtained from aliphatic carboxylic acids and thiazolidine-4-carboxylic acid in high chemical yields. Microwave irradiation reduced the reaction time.
- Schwartz Radatz, Cátia,Rampon, Daniel S.,Balaguez, Renata A.,Alves, Diego,Schneider, Paulo Henrique
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supporting information
p. 6945 - 6952
(2016/02/19)
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- Direct synthesis of 2-aryl-1,3-benzoselenazoles by reaction of bis(2-aminophenyl) diselenides with aryl aldehydes using sodium metabisulfite
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We present here a general and easy method for the synthesis of several 2-aryl-1,3-benzoselenazoles from the reaction of bis(2-aminophenyl) diselenides with different aryl aldehydes, promoted by the non-toxic inorganic reducing agent sodium metabisulfite (Na2S2O5) in DMSO at 120 °C. This efficient method furnishes in high yields the corresponding 2-aryl substituted 1,3-benzoselenazoles and tolerates a range of substituents at the aryl ring of aldehydes. The use of focused microwave irradiation decreases drastically the reaction time from 48 to 2 h.
- Radatz, Cátia Schwartz,Alves, Diego,Schneider, Paulo Henrique
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p. 1316 - 1321
(2013/02/23)
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- Microwave-assisted one-pot synthesis of symmetrical diselenides, ditellurides and disulfides from organoyl iodides and elemental chalcogen catalyzed by CuO nanoparticles
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In this study CuO nanoparticles were applied as a catalyst for CSe, CTe, and CS bond formation. The reaction was performed with organoyl iodides and elemental selenium, tellurium or sulfur under microwave irradiation in the presence of a base and solvent at 80 °C. This novel protocol allowed the synthesis of a variety of diselenides, ditellurides and disulfides in good to excellent yields in a very short reaction time.
- Botteselle, Giancarlo V.,Godoi, Marcelo,Galetto, Fabio Z.,Bettanin, Luana,Singh, Devender,Rodrigues, Oscar E.D.,Braga, Antonio L.
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p. 186 - 193
(2013/01/14)
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- Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones
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Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.
- Balkrishna, Shah Jaimin,Bhakuni, Bhagat Singh,Kumar, Sangit
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experimental part
p. 9565 - 9575
(2011/12/15)
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- Synthesis of arylseleno-1,2,3-triazoles via copper-catalyzed 1,3-dipolar cycloaddition of azido arylselenides with alkynes
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The use of organoselenium compounds in the copper-catalyzed Huisgen 1,3-dipolar cycloaddition of azido arylselenides with various alkynes is described. Arylseleno-1,2,3-triazoles are prepared in excellent yields via reaction of amino arylselenides with is
- Deobald, Anna M.,Camargo, Leandro R.S.,Hoerner, Manfredo,Rodrigues, Oscar E.D.,Alves, Diego,Braga, Antonio L.
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scheme or table
p. 2397 - 2406
(2011/09/15)
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- Synthesis of azido arylselenides and azido aryldiselenides: a new class of selenium-nitrogen compounds
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We present here our results of the efficient synthesis of azido arylselenides and azido aryldiselenides under mild conditions. Starting from nitrogen-substituted benzenes, we incorporated selenium atom at aromatic ring and obtained amino arylselenides and diselenides in satisfactory yields. Treatment of these compounds with iso-pentyl nitrite (i-C5H11ONO) and azido trimethylsilane (Me3SiN3) in THF affords a variety of azido arylselenides and diselenides in good to excellent yields.
- Deobald, Anna Maria,Simon de Camargo, Leandro R.,Tabarelli, Greice,H?rner, Manfredo,Rodrigues, Oscar E.D.,Alves, Diego,Braga, Ant?nio L.
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scheme or table
p. 3364 - 3367
(2010/08/19)
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- An efficient one-pot synthesis of symmetrical diselenides or ditellurides from halides with CuO nanopowder/Se0 or Te0/base
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(Equation Presented). A CuO nanopowder-catalyzed coupling reaction of aryl, alkyl, and heteroaryl iodides with elemental selenium and tellurium takes place in the presence of KOH at 90 °C in DMSO. A wide range of substituted symmetrical diselenides and ditellurides were afforded with good to excellent yields.
- Singh, Devender,Deobald, Anna M.,Camargo, Leandro R.S.,Tabarelli, Greice,Rodrigues, Oscar E.D.,Braga, Antonio L.
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supporting information; experimental part
p. 3288 - 3291
(2010/09/30)
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- Bis(2-aminophenyl) diselenide derivatives with amino acids moieties as potential antivirals and antimicrobials
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The seleno-organic compounds based on bis(2-aminophenyl) diselenide-1 are potential antiviral, antibacterial and antifungal agents.1 In this work, we reported synthesis of bis(2-aminophenyl) diselenide derivatives 2, 3 having amino acid and dipeptide moieties. This process was realized by acylation of amine groups in 1 with N-blocked amino acids, using the active esters method (with DCC and HOBT). After removing protective groups successive N-blocked amino acids were added the same way as previously. All compounds have been tested against broad spectrum of pathogenic microorganisms (Staphylococcus aureus, Staphylococcus simulans, Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Candida albicans, Aspergillus niger) and viruses (HSV-1, EMCV, VSV), in vitro. Most of them exhibited high activity against EMCV. Some of tested compounds were active against gram-positive bacteria species (Staphylococcus aureus, Staphylococcus simulans) and yeast Candida albicans.
- Dbrowska, Ewa,Ptka-Ottlik, Magdalena,Palus, Jerzy
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experimental part
p. 1082 - 1086
(2009/04/10)
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- Functionalized alkyl and aryl diselenides as antimicrobial and antiviral agents: Synthesis and properties
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The different dialkyl and diaryl diselenides with carbamoyl and sulfamoyl moieties 2, 3, 5 and other substituents in the ortho position of benzene ring 4, 7, 8 as well as derivatives of 1,2,4-benzoselenadiazine (6) were designed as antiviral and antimicrobial agents and synthesized. Some of them, particularly 8a and 8b, were found in the antiviral assay in vitro to be strong inhibitors of cytopathic activity encephalomyocarditis virus (EMCV). The compound 4a and 8a were found to have a broad spectrum of acivity against bacteria, yeasts and pathogenic fungi in vitro.
- Wojtowicz,Chojnacka,Mlochowski,Palus,Syper,Hudecova,Uher,Piasecki,Rybka
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p. 1235 - 1242
(2007/10/03)
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- New heterocyclic selenenamides: 1,2,4-benzoselenadiazin-3(4H)-ones and 1,3,2-benzodiselenazoles
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Two groups of selenium-containing heterocycles having new, unique 1,2,4-benzoselenadiazine and 1,3,2-diselenazole ring systems with an endocyclic selenenamide C-N moiety are presented. The first type was obtained by oxidative cyclization of 2,2′-diselenobis(phenylureas) and the second type by the reaction of 1,2-di(bromoseleno)benzene with primary amines.
- Kloc, Krystian,M?ochowski, Jacek,Osajda, Karol,Syper, Ludwik,Wójtowicz, Halina
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p. 4071 - 4074
(2007/10/03)
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- STUDIES ON LONG-RANGE COUPLINGS BETWEEN 77Se AND 13C IN SOME ARYL SELENIDES, DICHLORIDES, AND SELENOXIDES. THE INVERSE EFFECT ON COUPLINGS IN THE SELENOXIDE FORMATION.
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Long-range coupling constants between **7**7Se and **1**3C in selenoanisole, diphenyl selenide, diphenyl diselenide, and their 2-mono- and 2,2 prime -disubstituted derivatives, selenoxanthone, selenanthrene, dichlorides, and selenoxides were measured to disclose predominant factors governing the magnitude of the coupling. Extraordinary large values for two- and three-bond couplings are found in selenoxanthone. Three factors are operative: the orientational effect, the coordination number, and the effect of ring formation. The last factor accompanies a stronger inverse effect on the coupling of selenoxides than on that of selenides.
- Nakanishi,Ikeda
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p. 1661 - 1664
(2007/10/02)
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