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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. 相似文献
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《Green Chemistry Letters and Reviews》2013,6(1):19-26
Abstract An efficient one-pot synthesis of β-hydroxy sulfides from thiophenol and cyclic carbonates catalyzed by large-pore zeolites has been reported. Reaction of thiophenol with ethylene carbonate in the presence of the Na-X zeolite catalyst gave the highest yield of 2-(phenylthio)ethanol (100%), while reaction with propylene carbonate a highest yield of regioselective product 1-(phenylthio)propan-2-ol was obtained (97%). Enantiomerically pure 1,2-propylene carbonate gave highly regioselective and stereospecific phenylthiopropanol, demonstrating that original chirality of propylene carbonate is retained. A plausible mechanism has been proposed for zeolite-catalyzed transformation involving a chemoselective nucleophilic attack of thiophenoloxide ion onto the less-substituted carbon of cyclic carbonate. The Na-X zeolite catalyst is recyclable and provides advantages of green chemistry approach to the synthesis of β-hydroxy sulfides without the use of any solvent. 相似文献
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Filipe Belarmino de Lima Gessenildo Pereira Rodrigues Juracy Regis de Lucena Júnior Elizete Ventura Rui Fausto Igor Reva Silmar Andrade do Monte 《International journal of quantum chemistry》2020,120(16):e26263
Multi-reference configuration interaction, MR-CI (including extensivity corrections, named +Q), calculations were performed on the S0–S3 states of cyclohexa-2,4-diene-1-thione (thione 24 ) and cyclohexa-2,5-diene-1-thione (thione 25 ), which are thione isomers of thiophenol. Several types of uncontracted MR-CIS and MR-CISD wavefunctions were employed, comprising MR-CI expansions as large as ~365 × 106 configuration state functions. The nature of the studied excited states was characterized. Vertical excitation energies (ΔE) and oscillator strengths (f) were computed. The most intense transitions (S0 → S2 for 24 and S0 → S3 for 25 ) did not change with the wavefunction, although a variation as large as ~1 eV was obtained for the S3 state of 24 , at the highest (MR-CI+Q) level. On the other hand, ΔE changed at most by ~0.56 eV for 25 as the wavefunction changes, at the same level. The S1 state of both thiones was found to have nπ* character and is in the visible region. For 24 , S2 and S3 are ππ* and nπ* states, respectively, while for 25 the reverse order is obtained. S2 and S3 are in the range ~3.5 to 5.2 eV, again at the highest level. It is the first time that the excited states of the title molecules are studied. The computed results agree with the experimental onset of photoreactions of thiones 24 and 25 found by Reva et al (Phys. Chem. Chem. Phys., 2015 , 17, 4888). 相似文献
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Remziye Güzel Haslet Ekşi Zafer Üstündağ Ali Osman Solak 《Surface and interface analysis : SIA》2013,45(13):1821-1829
In this study, 4‐thiophenol modified glassy carbon electrode was prepared by the reduction of 4‐diazothiophenol tetrafluoroborate salt. Silver nanoparticles were attached to the thiophenol modified surface to prepare a thiophenol‐silver nanoparticle composite film. 4‐Aminothiopenol molecules were deposited by self‐assembling technique to form multi‐layered nanofilms of TP/SNP/PhNH2 on glassy carbon substrate. These surfaces were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, X‐ray photoelectron spectroscopy, reflectance‐absorption infrared spectroscopy, and ellipsometry at each multilayer film growth process. Atomic force microscopic images of GC/TP/SNP/PhNH2 surfaces were also acquired. The characterization methods show that the amine group containing surface permits the subsequent modification by a variety of coupling reactions for the immobilization of more complex systems. An application of the electrode modification for the determination of uric acid with a significantly lower detection limit is described. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Yaoli Wang Yan Liang Huixiang Sheng Jin Wang Junjie Wang Shunhao He Mengdan Guan Yaqi Chen Prof. Gang Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(2):e202103709
Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts. 相似文献
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Dr. Xin Chen Peter Denninger Dr. Tanja Stimpel-Lindner Prof. Erdmann Spiecker Prof. Georg S. Duesberg Dr. Claudia Backes Dr. Kathrin C. Knirsch Prof. Andreas Hirsch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(29):6535-6544
Two-dimensional (2D) molybdenum disulfide (MoS2) holds great promise in electronic and optoelectronic applications owing to its unique structure and intriguing properties. The intrinsic defects such as sulfur vacancies (SVs) of MoS2 nanosheets are found to be detrimental to the device efficiency. To mitigate this problem, functionalization of 2D MoS2 using thiols has emerged as one of the key strategies for engineering defects. Herein, we demonstrate an approach to controllably engineer the SVs of chemically exfoliated MoS2 nanosheets using a series of substituted thiophenols in solution. The degree of functionalization can be tuned by varying the electron-withdrawing strength of substituents in thiophenols. We find that the intensity of 2LA(M) peak normalized to A1g peak strongly correlates to the degree of functionalization. Our results provide a spectroscopic indicator to monitor and quantify the defect engineering process. This method of MoS2 defect functionalization in solution also benefits the further exploration of defect-free MoS2 for a wide range of applications. 相似文献
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İsa Karaman Hayreddin Gezegen Mustafa Ceylan Merve Dilmaç 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):580-586
Abstract In this study, a series of novel β-mercapto carbonyl derivatives (3a–j) was prepared by addition of thiophenol (2) to chalcones (1a–j) in the presence of catalytic amount of iodine (10 mol%) in CH2Cl2. Antibacterial and antifungal in vitro properties of the synthesized compounds were tested against some human pathogenic microorganisms by employing the disk diffusion technique. For the most active compounds, also minimum inhibitory concentrations (MICs) were determined. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
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Humeyra Mert Umit Tunca Gurkan Hizal 《Journal of polymer science. Part A, Polymer chemistry》2006,44(20):5923-5932
The copper‐catalyzed living radical polymerization (LRP) of styrene (St) was carried out in the presence of thiophenol derivative such as sodium thiophenolate (PhSNa) or p‐methoxythiophenol as a reducing agent for Cu(II) by using either 1‐chloro‐1‐phenyl ethane or ethyl‐2‐bromoisobutyrate as an initiator and N,N,N′,N″,N″‐pentamethyldiethylenetriamine as ligand at 110 °C. Kinetic experiments were carried out to reveal the effect of PhSNa concentration on copper‐catalyzed LRP of St. This technique was successfully applied for the preparation of both chain‐extended polymer and block copolymer polystyrene‐b‐poly(methyl methacrylate). The obtained polymers were characterized using GPC, 1H‐NMR, and MALDI‐TOF measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5923–5932, 2006 相似文献