620-94-0Relevant academic research and scientific papers
Relaxation processes of some aromatic sulfides, sulfoxides, and sulfones in a polystyrene matrix
Desando, M. A.,Walker, S.,Baarschers, W.H.
, p. 3460 - 3466 (1980)
Dielectric absorption studies have been made of a number of aromatic sulfides, sulfoxides, and sulfones in a polystyrene matrix at a variety of temperatures in the frequency range of 102-105 Hz, and in three cases between 104-107 Hz.One compound, bis (4-pyridyl) sulfide, was also examined as a pure compressed solid in the frequency range of 104-107 Hz.The Eyring parameters have been determined and used to characterize the relaxation processes.Low enthalpies of activation (ca.15 kJ mol-1) have been estimated for an intramolecular relaxation process of diphenyl, bis (4-tolyl) and bis (4-pyridyl) sulfide, and rotation about the C-S bond in these symmetrical aromatic sulfides would, thus, be expected to occur quite readily.These low barriers are to be contrasted with those for the molecular relaxation values of 60-78 kJ mol-1 for diphenyl, bis(4-tolyl) and bis(4-chlorophenyl) sulfoxides and sulfones.The enthalpies of activation (ca.39 kJ mol-1) for the molecular relaxation of the disklike molecules, dibenzothiophene and its oxides, are also lower than those for the corresponding nonplanar diphenyl sulfur oxides.
Copper based on diaminonaphthalene-coated magnetic nanoparticles as robust catalysts for catalytic oxidation reactions and C-S cross-coupling reactions
Yarmohammadi, Nasrin,Ghadermazi, Mohammad,Mozafari, Roya
, p. 9366 - 9380 (2021/03/16)
In this work, the immobilization of copper(ii) on the surface of 1,8-diaminonaphthalene (DAN)-coated magnetic nanoparticles provides a highly active catalyst for the oxidation reaction of sulfides to sulfoxides and the oxidative coupling of thiols to disulfides using hydrogen peroxide (H2O2). This catalyst was also applied for the one-pot synthesis of symmetrical sulfidesviathe reaction of aryl halides with thiourea as the sulfur source in the presence of NaOH instead of former strongly basic and harsh reaction conditions. Under optimum conditions, the synthesis yields of sulfoxides, symmetrical sulfides, and disulfides were about 99%, 95%, and 96% respectively with highest selectivity. The heterogeneous copper-based catalyst has advantages such as the easy recyclability of the catalyst, the easy separation of the product and the less wastage of products during the separation of the catalyst. This heterogeneous nanocatalyst was characterized by FESEM, FT-IR, VSM, XRD, EDX, ICP and TGA. Furthermore, the recycled catalyst can be reused for several runs and is economically effective.
Preparation of Recyclable and Versatile Porous Poly(aryl thioether)s by Reversible Pd-Catalyzed C–S/C–S Metathesis
Morandi, Bill,Rivero-Crespo, Miguel A.,Toupalas, Georgios
supporting information, p. 21331 - 21339 (2021/12/17)
Porous organic materials (polymers and COFs) have shown a number of promising properties; however, the lability of their linkages often limits their robustness and can hamper downstream industrial application. Inspired by the outstanding chemical, mechanical, and thermal resistance of the 1D polymer poly(phenylene sulfide) (PPS), we have designed a new family of porous poly(aryl thioether)s, synthesized via a mild Pd-catalyzed C–S/C–S metathesis-based method, that merges the attractive features common to porous polymers and PPS in a single material. In addition, the method is highly modular, allowing to easily introduce application-oriented functionalities in the materials for a series of environmentally relevant applications including metal capture, metal sensing, and heterogeneous catalysis. Moreover, despite their extreme chemical resistance, the polymers can be easily recycled to recover the original monomers, offering an attractive perspective for their sustainable use. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new, recyclable materials.
Palladium-catalysed thioetherification of aryl and alkenyl iodides using 1,3,5-trithiane as sulfur source
Kollár, László,Pongrácz, Péter,Rajat Rao, Yalamarti Venkat,Zugó, Alexandra
, (2021/12/17)
Thioetherification reaction of aryl iodides catalysed by palladium(II) complexes in the presence of 1,3,5-trithiane as sulphur source is reported. The paper presents the first homogeneous catalytic application of 1,3,5-trithiane in synthesis. Detailed optimization steps, the frames of the novel reaction are described, as well as the limitations and the substrate scope are also demonstrated. Moderate to good thioether yields were achieved in the presence of various substituted iodobenzenes and some alkenyl iodides, using palladium-xantphos catalyst system. Competitive reactions in the presence of mixed substrates were also performed and mechanistic considerations were assumed.
Cu attached functionalized mesoporous MCM-41: a novel heterogeneous nanocatalyst for eco-friendly one-step thioether formation reaction and synthesis of 5-substituted 1H-tetrazoles
Molaei, Somayeh,Ghadermazi, Mohammad
, p. 4557 - 4581 (2021/07/28)
In the current study, a mesoporous copper-attached functionalized MCM-41 with the DL-Pyroglutamic acid framework has been produced through a post-synthetic method. The MCM-41 functionalization technique has been used to synthesize this novel heterogeneous catalyst. The material has been identified fully using XRD, FT-IR, BET, EDX, elemental mapping, SEM, and TGA. This catalyst displays high catalytic performance in the one-step thioether formation (C–S) reaction and synthesis of 5-substituted 1H-tetrazoles. The main aspects of this economical copper-catalyzed procedure are green synthesis, slighter experimental conditions, and less reaction time with no additives. Further benefits comprise experimental comfort of handling, secure replacement to dangerous, damaging, and poisoning regular Lewis’s acid catalysts, and reusability with constant catalytic performance. Graphic abstract: [Figure not available: see fulltext.]
Heterogeneously Ni-Pd nanoparticle-catalyzed base-free formal C-S bond metathesis of thiols
Mitamura, Kanju,Yatabe, Takafumi,Yamamoto, Kidai,Yabe, Tomohiro,Suzuki, Kosuke,Yamaguchi, Kazuya
supporting information, p. 3749 - 3752 (2021/04/21)
This study rationally designed a heterogeneously catalyzed system (i.e., using Ni-Pd alloy nanoparticles supported on hydroxyapatite (Ni-Pd/HAP) under an H2atmosphere) achieving an efficient base-free formal C-S bond metathesis of various thiolsviasuppression of the Ni catalysis deactivation.
Coupling of thiols and aromatic halides promoted by diboron derived super electron donors
Franco, Mario,Vargas, Emily L.,Tortosa, Mariola,Cid
supporting information, p. 11653 - 11656 (2021/11/12)
We have proven that pyridine-boryl complexes can be used as superelectron donors to promote the coupling of thiols and aromatic halides through a SRN1 mechanism. The reaction is efficient for a broad substrate scope, tolerating heterocycles including pyridines, enolizable or reducible functional groups. The method has been applied to intermediates in drug synthesis as well as interesting functionalized polythioethers through a controlled and consecutive intramolecular electron transfer process.
A Visible-Light-Harvesting Covalent Organic Framework Bearing Single Nickel Sites as a Highly Efficient Sulfur–Carbon Cross-Coupling Dual Catalyst
Chen, Hui,Liu, Wanlu,Laemont, Andreas,Krishnaraj, Chidharth,Feng, Xiao,Rohman, Fadli,Meledina, Maria,Zhang, Qiqi,Van Deun, Rik,Leus, Karen,Van Der Voort, Pascal
supporting information, p. 10820 - 10827 (2021/04/09)
Covalent Organic Frameworks (COFs) have recently emerged as light-harvesting devices, as well as elegant heterogeneous catalysts. The combination of these two properties into a dual catalyst has not yet been explored. We report a new photosensitive triazine-based COF, decorated with single Ni sites to form a dual catalyst. This crystalline and highly porous catalyst shows excellent catalytic performance in the visible-light-driven catalytic sulfur–carbon cross-coupling reaction. Incorporation of single transition metal sites in a photosensitive COF scaffold with two-component synergistic catalyst in organic transformation is demonstrated for the first time.
Methods, Syntheses and Characterization of Diaryl, Aryl Benzyl, and Dibenzyl Sulfides
Zhou, Wen-Yan,Chen, Min,Zhang, Pei-Zhi,Jia, Ai-Quan,Zhang, Qian-Feng
, p. 301 - 310 (2020/09/07)
Twenty-four aryl benzyl sulfides, diaryl sulfides and dibenzyl sulfides were synthesized by four methods and characterized by 1H NMR, FT-IR and Gas chromatography. The reaction conditions of different synthesis methods were studied from the aspects of time, solvent, base and dispersant. The molecular structures of benzylphenyl sulfide (2S), (4-tert-butylbenzyl)(4-methylphenyl) sulfide (4S), (4-methylbenzyl)(4-methylphenyl) sulfide (9S), di(4-methylphenyl) sulfide (11S), (3,5-dimethylphenyl)(4-methyl phenyl) sulfide (15S), and dibenzyl sulfide (19S) [22] have been determined by single-crystal X-ray crystallography. Compounds 2S and 15S crystallize in the monoclinic space group P21/c, with a = 12.278(3), b = 15.894(3), c = 5.6056(11) ?, β = 94.532(2)°, and Z = 4 for 2S, and a = 9.800(9), b = 7.950(7), c = 16.690(15) ?, β = 100.890(12)°, and Z = 4 for 15S. The unit cell of 4S has a triclinic Pī symmetry with the cell parameters a = 6.0436(10), b = 8.7871(14), c = 15.535(2) ?, α = 81.921(2)°, β = 81.977(2)°, γ = 80.889(2)°, and Z = 2. Compounds 9S and 11S both crystallize in the orthorhombic space group P212121, with a = 6.188(3), b = 8.041(4), c = 26.005(14) ?, and Z = 4 for 9S, and a = 5.835(2), b = 8.010(3), c = 25.131(9) ?, and Z = 4 for 11S. Graphic Abstract: Twenty-four aryl sulfide compounds with different substituents were synthesized and characterized, and the molecular structures of six different sulfide compounds have been determined by single-crystal X-ray crystallography.[Figure not available: see fulltext.]
Photoredox Nickel-Catalyzed C-S Cross-Coupling: Mechanism, Kinetics, and Generalization
Qin, Yangzhong,Sun, Rui,Gianoulis, Nikolas P.,Nocera, Daniel G.
supporting information, p. 2005 - 2015 (2021/02/06)
Photoredox-mediated nickel-catalyzed cross-couplings have evolved as a new effective strategy to forge carbon-heteroatom bonds that are difficult to access with traditional methods. Experimental mechanistic studies are challenging because these reactions involve multiple highly reactive intermediates and perplexing reaction pathways, engendering competing, but unverified, proposals for substrate conversions. Here, we report a comprehensive mechanistic study of photoredox nickel-catalyzed C-S cross-coupling based on time-resolved transient absorption spectroscopy, Stern-Volmer quenching, and quantum yield measurements. We have (i) discovered a self-sustained productive Ni(I/III) cycle leading to a quantum yield φ > 1; (ii) found that pyridinium iodide, formed in situ, serves as the dominant quencher for the excited state photocatalyst and a critical redox mediator to facilitate the formation of the active Ni(I) catalyst; and (iii) observed critical intermediates and determined the rate constants associated with their reactivity. Not only do the findings reveal a complete reaction cycle for C-S cross-coupling, but the mechanistic insights have also allowed for the reaction efficiency to be optimized and the substrate scope to be expanded from aryl iodides to include aryl bromides, thus broadening the applicability of photoredox C-S cross-coupling chemistry.
