- First preparation and crystal structure of heterocyclic λ6-sulfanenitrile, 2,2′-biphenylylene(phenyl)-λ6-sulfanenitrile
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The first heterocyclic λ6-sulfanenitrile, 2,2′-biphenylylene(phenyl)-λ6-sulfanenitrile is prepared and its molecular and electronic structures are determined by X-ray crystallographic analysis and quantum chemical calculations, respectively.
- Fujii, Takayoshi,Itoh, Akiko,Hamata, Kouki,Yoshimura, Toshiaki
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- EFFECT OF RING SIZE ON PHOTOREACTIVITY OF MEDIUM AND LARGE RING ESTERS.
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Photochemical studies on 7,8,12,14,16 and 20 membered cyclic esters have been carried out in benzene and methanol.Decarboxylation and solvolysis ascribable to β- and α-scission respectively are observed in case of seven and eight membered cyclic esters.Larger rings do not undergo these photoreactions thus demonsrating effect of ring size on photoreactivity.
- Kulkarni, V. S.,Kulkarni, N. N.,Lele, S. R.,Hosangadi, B. D.
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- Efficient synthesis of unsymmetrical dibenzothiophenes by acid-mediated intramolecular cyclization of biaryl methyl sulfoxides
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Aconvenient and high-yielding synthesis of unsymmetrical dibenzothiophenes has been achieved by an acid-mediated ring closure of the biphenyl ring having a sulfoxide substituent at the ortho position. Various functional groups are well tolerated in this methodology. Taylor & Francis Group, LLC.
- Pandya, Vrajesh B.,Jain, Mukul R.,Chaugule, Balaji V.,Patel, Jigar S.,Parmar, Bhavesh M.,Joshi, Jignesh K.,Patel, Pankaj R.
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- Reactivity of sulfur-containing molecules on noble metal surfaces. 4. Benzenethiol on Au(110)
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The adsorption of benzenethiol on clean and sulfided Au(110) surfaces has been investigated with temperature programmed reaction spectroscopy. The monolayer is saturated at an benzenethiol coverage of 0.25 monolayers. About one-half of the thiol adsorbed at 100 K undergoes S-H bond cleavage below 300 K to form phenyl thiolate; H2 and H2S are evolved between 150 and 350 K. Phenyl thiolate decomposes above 400 K on clean Au(110) to yield mainly biphenyl, together with diphenyl sulfide, benzenethiol, and dibenzothiophene. With sulfidation of the Au(110) surface, the yield of biphenyl drops, while that of diphenyl sulfide rises. The range of products formed arises from competing C-S bond cleavage and C-H bond cleavage processes.
- Jaffey, Deborah M.,Madix, Robert J.
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- Refinement of the Catalyst Backbone of Chiral Intramolecular Silicon–Sulfur Lewis Pairs: Improved Enantioselectivity in the Diels–Alder Reaction of Cyclohexa-1,3-diene and Chalcone Derivatives
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The preparation and NMR spectroscopic characterization of a family of axial chiral, sulfur-stabilized silicon cations is reported. These silicon Lewis acids have been applied as catalysts in difficult enantioselective Diels–Alder reactions of cyclohexa-1,3-diene and representative chalcone derivatives. To gain better understanding of the relevant structural elements in these catalysts, their silepine backbone and the aryl thioether group have been systematically modified. These efforts have led to an improved catalyst that induces 53 % ee for chalcone and even 65 % ee for a more hindered derivative. These cyclohexa-1,3-diene Diels–Alder reactions are endo selective. However, the corresponding cyclopentadiene Diels–Alder reactions predominantly yield the exo cycloadducts with no enantioinduction.
- Shaykhutdinova, Polina,Kemper, Sebastian,Oestreich, Martin
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- Palladium(ii)-catalyzed synthesis of dibenzothiophene derivatives via the cleavage of carbon-sulfur and carbon-hydrogen bonds
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A new process has been developed for the palladium(ii)-catalyzed synthesis of dibenzothiophene derivatives via the cleavage of C-H and C-S bonds. In contrast to the existing methods for the synthesis of this scaffold by C-H functionalization, this new catalytic C-H/C-S coupling method does not require the presence of an external stoichiometric oxidant or reactive functionalities such as C-X or S-H, allowing its application to the synthesis of elaborate π-systems. Notably, the product-forming step of this reaction lies in an oxidative addition step rather than a reductive elimination step, making this reaction mechanistically uncommon.
- Tobisu, Mamoru,Masuya, Yoshihiro,Baba, Katsuaki,Chatani, Naoto
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- Copper-Catalyzed Double S-Arylation of Potassium Thioacetate with Dibenziodolium Triflates: Facile Synthesis of Unsymmetrical Dibenzothiophenes
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Much interest has been paid to cyclic diaryliodonium salts as bis(electrophile)s in transition-metal-catalyzed annulation reactions to produce polycyclic (hetero)aromatic hydrocarbons. Herein, we report that dibenziodolium triflates smoothly react with potassium thioacetate in the presence of CuCl2in THF or DMSO at 100–110 °C to afford the corresponding dibenzothiophenes in good-to-high yields. The coupling reaction tolerates reactive functional groups such as chloro and cyano and serves as a facile and reliable method for the synthesis of unsymmetrical dibenzothiophenes.
- Shimizu, Masaki,Ogawa, Mai,Tamagawa, Tomokazu,Shigitani, Ryosuke,Nakatani, Masaki,Nakano, Yoshiki
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- Polar Diels-Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study
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The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.
- Della Rosa, Claudia D.,Mancini, Pedro M.E.,Kneeteman, Maria N.,Lopez Baena, Anna F.,Suligoy, Melisa A.,Domingo, Luis R.
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- Effects of Solvents in Deep Desulfurization of Benzothiophene and Dibenzothiophene
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Solvent effects on hydrodesulfurization of benzothiophene (BT) and dibenzothiophene (DBT) catalyzed by co-Mo/Al2O3 were investigated under deep desulfurization conditions by using Langmuir-Hinshelwood (L-H) rate law.Solvents affected heats of adsorption of thiophenes rather than activation energy of HDS.Activation energies of HDS and heats of adsorption of thiophenes and solvents were estimated from the kinetic data.
- Kabe, Toshiaki,Ishihara, Atsushi,Nomura, Masatoshi,Itoh, Tetsuro,Qi, Pingyen
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- Generation and detection of tellurane [10-Te-4(C4)] and selenurane [10-Se-4(C4)] having alkyl and aryl ligands
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Formation of 2,2′-biphenylylenedimethylselenurane and -tellurane was observed by the 1H, 13C, 77Se, and 125Te NMR studies at low temperature, in the reactions of dibenzoselenophene Se-oxide and 2,2′-biphenylylenedibromotellurane with methyllithium. These hypervalent compounds were unstable and decomposed at room temperature to give the corresponding dibenzochalcogenophenes quantitatively.
- Sato, Soichi,Matsuo, Makoto,Nakahodo, Tsukasa,Furukawa, Naomichi,Nabeshima, Tatsuya
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- Aryl-aryl bond formation by flash vacuum pyrolysis of benzannulated thiopyrans
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(Chemical Equation Presented) In contrast to fully unsaturated 7-membered ring sulfur heterocycles (thiepines), some of which extrude sulfur and give the ring-contracted hydrocarbon even at room temperature in solution, benzannulated thiopyrans (6-membere
- Amick, Aaron W.,Wakamiya, Atsushi,Scott, Lawrence T.
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- Arylation of aryllithiums with: S-arylphenothiazinium ions for biaryl synthesis
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Aryllithiums are one of the most common and important aryl nucleophiles; nevertheless, methods for arylation of aryllithums to produce biaryls have been limited. Herein, we report arylation of aryllithiums with S-arylphenothiazinium ions through selective
- Morofuji, Tatsuya,Yoshida, Tatsuki,Tsutsumi, Ryosuke,Yamanaka, Masahiro,Kano, Naokazu
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- Synthesis of NiMo Catalysts Supported on Gallium-Containing Mesoporous y Zeolites with Different Gallium Contents and Their High Activities in the Hydrodesulfurization of 4,6-Dimethyldibenzothiophene
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Mesoporous MY-xGa zeolites exhibiting both crystallized pore walls and narrowly dispersed mesopores with different Ga content were successfully synthesized. The synthesized samples were characterized by XRD, N2 adsorption desorption isotherms, SEM, TEM, XPS, FTIR, 29Si MAS NMR, 71Ga MAS NMR, and Py-FTIR methods. The results show that the synthesized samples exhibit unique open channel like mesopore systems and outstanding crystallite natures; no nonframework Ga species were observed over the MY-xGa series samples, and their acidic properties can be modulated by varying the Ga/Al ratio in the initial synthesis gel. The corresponding NiMo/HMY-xGa catalysts were prepared via the incipient wetness coimpregnation method; the morphologies of the sulfide catalysts were characterized by HRTEM, and the covalent states of the active metals were characterized by XPS. The catalytic activities of the investigated catalysts for the 4,6-DMDBT HDS reaction were assessed, and the collected products were analyzed by GC and GC-MS methods. The catalyst NiMo/HMY-0.5Ga showed the highest catalytic activity due to the synergistic effect of modulated acidic properties, excellent morphology, highest sulfidation degree, and proper proportion of NiMoS phase. More importantly, 4-MDBT, DBT, and BP were observed and identified as the products of the 4,6-DMDBT HDS reaction, designated as the demethylation pathway (DM) for the 4,6-DMDBT HDS reaction. Finally, a reaction network including DDS, HYD, ISO, and DM pathways for the 4,6-DMDBT HDS reaction over catalyst NiMo/HMY-0.5Ga was proposed.
- Zhou, Wenwu,Liu, Meifang,Zhang, Qing,Wei, Qiang,Ding, Sijia,Zhou, Yasong
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- Iron-catalyzed carbon–sulfur bond formation: Atom-economic construction of thioethers with diaryliodonium salts
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Diaryliodonium salts are characterized by poor atom economy with the formation of one equivalent of an iodoarene as waste. We have developed an atom-economic iron-catalyzed protocol for the synthesis of a variety of thioethers with diaryliodonium salts. Not only cyclic diaryliodonium salts but also linear diaryliodonium salts were found to perform well in the reactions.
- Liu, Li,Qiang, Jian,Bai, Shuhua,Li, Yang,Li, Jian
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- REDUCTION OF SULFOXIDES AND SULFILIMINES CATALYZED BY METALLOPORPHINS
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Reduction of sulfoxides and sulfilimines to the corresponding sulfides by both BNAH and NaBH4 have been found to proceed in the presence of a catalytic amount of metallo-meso-tetraphenylporphins.
- Nagata, Toshiyuki,Yoshimura, Toshiaki,Fujimori, Ken,Oae, Shigeru
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- Towards a general scale of nucleophilicity?
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(Chemical Equation Presented) One for all? The nucleophilicity parameters N, which have been derived from the rate constants k of reactions of nucleophiles with carbocations, also hold for SN2-type reactions (see scheme). A general equation is suggested which includes established correlations (Swain-Scott, Ritchie) as special cases.
- Phan, Thanh Binh,Breugst, Martin,Mayr, Herbert
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- Transition-Metal-Free Diarylannulated Sulfide and Selenide Construction via Radical/Anion-Mediated Sulfur-Iodine and Selenium-Iodine Exchange
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A facile, straightforward protocol was established for diarylannulated sulfide and selenide construction through S-I and Se-I exchange without transition metal assistance. Elemental sulfur and selenium served as the chalcogen source. Diarylannulated sulfides were systematically achieved from a five- to eight-membered ring. A trisulfur radical anion was demonstrated as the initiator for this radical process via electron paramagnetic resonance (EPR) study. OFET molecules [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and [1]benzothieno[3,2-b][1]benzoselenophene (BTBS) were efficiently established.
- Wang, Ming,Fan, Qiaoling,Jiang, Xuefeng
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- Palladium catalyzed syntheses of dibenzothiophenes by ring-closure of 2-iodinated diaryl thioether
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An efficient ring-closure of 2-iodinated diaryl thioethers at the presence of palladium catalyst to form dibenzothiophene is described. After the best condition was set up as Pd3(dba)2 as the catalyst, anhydrous Cu(OAc)2 as additive, PivONa.H2O as base, DMF as solvent, a series of dibenzothiophenes could be successfully obtained through this protocol in moderate to excellent yields.
- Chen, Ya-Fang,Ma, Rui-Yue,Zhou, Lu-Nan,Du, Zhenting,Zhang, Tao
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- Scalable electrochemical reduction of sulfoxides to sulfides
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A scalable reduction of sulfoxides to sulfides in a sustainable way remains an unmet challenge. This report discloses an electrochemical reduction of sulfoxides on a large scale (>10 g) under mild reaction conditions. Sulfoxides are activated using a substoichiometric amount of the Lewis acid AlCl3, which could be regeneratedviaa combination of inexpensive aluminum anode with chloride anion. This deoxygenation process features a broad substrate scope, including acid-labile substrates and drug molecules.
- Kong, Zhenshuo,Pan, Chao,Li, Ming,Wen, Lirong,Guo, Weisi
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supporting information
p. 2773 - 2777
(2021/04/21)
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- Synthesis and properties of thieno[2,3-d:5,4-d']bisthiazoles and their oxidized derivatives: Thionyl chloride as a sulfurative ring-fusing reagent towards thiophene-based ring-fused heteroaromatic compounds
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A new route to thiophene-ring-fused compounds with thionyl chloride as a sulfur source was developed. Use of an excess amount thionyl chloride directly gave the corresponding thiophene-ring-fused compound via further reduction of generated thiophene-S-oxide with excess thionyl chloride in some cases. One-pot reduction with tributylphosphine also gave thiophene-ring-fused compounds in good yields, and oxidation with NaClO·5H2O gave S-dioxides. In addition, one of the obtained thiazole-thiophene ring-fused compounds showed some unexpected mechanochromism behavior.
- Wada, Ryuta,Kaga, Shigesaki,Kawai, Yasuhiro,Futamura, Kimitaka,Murai, Toshiaki,Shibahara, Fumitoshi
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- α-Diazo Sulfonium Triflates: Synthesis, Structure, and Application to the Synthesis of 1-(Dialkylamino)-1,2,3-triazoles
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The one-pot synthesis of a series of sulfonium salts containing transferable diazomethyl groups is described, and the structure of these compounds is elucidated by X-ray crystallography. Under photochemical conditions, reaction of these salts with N,N-dialkyl hydrazones affords 1-(dialkylamino)-1,2,3-triazoles via diazomethyl radical addition to the azomethine carbon followed by intramolecular ring closure. The straightforward transformation of the structures thus obtained into mesoionic carbene–metal complexes is also reported and the donor properties of these new ligands characterized.
- Li, Xiangdong,Golz, Christopher,Alcarazo, Manuel
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p. 6943 - 6948
(2021/02/26)
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- Short syntheses of 1-substituted dibenzothiophene derivatives
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The 1-substituted dibenzothiophene motif is an unusual substitution pattern that has previously been accessedviaa multi-step synthesis. We demonstrate a simple one-pot preparation of 1-lithiodibenzothiophene from commercial materialsviaa cascade of two benzyne additions and conversion to several derivatives by addition of electrophiles. A chiral amine containing the 1-dibenzothiophene motif was also prepared. This work avoids the use of precious metals ortert-butyllithium and is much shorter and more convenient than existing routes to 1-substituted dibenzothiophenes.
- Welsh, Erin N.,Robertson, Katherine N.,Speed, Alexander W. H.
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supporting information
p. 2000 - 2007
(2021/03/16)
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- A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
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A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
- Huang, Binbin,Guo, Lin,Xia, Wujiong
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supporting information
p. 2095 - 2103
(2021/03/26)
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- Nickel-Catalyzed Photodehalogenation of Aryl Bromides
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Herein, we describe a Ni-catalyzed photodehalogenation of aryl bromides under visible-light irradiation that utilizes tetrahydrofuran as hydrogen source. The protocol obviates the need for exogeneous amine reductants or photocatalysts and is characterized by its simplicity and broad scope, including challenging substrate combinations.
- Higginson, Bradley,Sanjosé-Orduna, Jesus,Gu, Yiting,Martin, Ruben
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supporting information
p. 1633 - 1636
(2021/04/23)
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- Facile Synthesis of Thienoacenes via Transition-Metal-Free Ladderization
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Herein, we report a facile transition-metal-free approach to sulfur-containing heteroacenes from fluorinated oligophenylenes. Unlike most existing methods, the presented approach is not restricted to simple dibenzothiophene derivatives and thus appears to
- Akhmetov, Vladimir,Amsharov, Konstantin Yu,Feofanov, Mikhail,Takayama, Ryo
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p. 14759 - 14766
(2021/11/12)
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- Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis
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An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.
- Cao, Fei,Chen, Jinhong,Deng, Jiedan,Deng, Xuemei,Hou, Yongsheng,Shao, Xiangfeng,Shi, Tao,Wang, Yongqiang,Wang, Zhen,Wu, Lingxi,Yang, Jinru,Yang, Yuhang
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p. 2707 - 2712
(2020/03/11)
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- Synthesis of Benzo[b]thiophenes through Rhodium-Catalyzed Three-Component Reaction using Elemental Sulfur
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A benzo[b]thiophene synthesis by Rh-catalyzed three-component coupling reaction of arylboronic acids, alkynes, and elemental sulfur (S8) is developed. A notable feature of this protocol is that the thienannulation (thiophene annulation) proceeds with high regioselectivity via the sequential alkyne insertion, C?H activation, and then sulfur atom transfer to the metallacycle intermediate. In a similar manner, dibenzothiophenes can be synthesized from the parent biarylboronic acids and S8. (Figure presented.).
- Moon, Sanghun,Kato, Moena,Nishii, Yuji,Miura, Masahiro
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supporting information
p. 1669 - 1673
(2020/03/23)
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- Exploiting the radical reactivity of diazaphosphinanes in hydrodehalogenations and cascade cyclizations
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The remarkable reducibility of diazaphosphinanes has been extensively applied in various hydrogenations, based on and yet limited by their well-known hydridic reactivity. Here we exploited their unprecedented radical reactivity to implement hydrodehalogenations and cascade cyclizations originally inaccessible by hydride transfer. These reactions feature a broad substrate scope, high efficiency and simplicity of manipulation. Mechanistic studies suggested a radical chain process in which a phosphinyl radical is generated in a catalytic cycle via hydrogen-atom transfer from diazaphosphinanes. The radical reactivity of diazaphosphinanes disclosed here differs from their well-established hydridic reactivity, and hence, opens a new avenue for diazaphosphinane applications in organic syntheses.
- Cheng, Jin-Pei,Yang, Jin-Dong,Zhang, Jingjing
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p. 4786 - 4790
(2020/06/18)
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- Mo-Based Oxidizers as Powerful Tools for the Synthesis of Thia- and Selenaheterocycles
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A highly efficient synthetic protocol for the synthesis of thia- and selenaheterocycles has been developed. By employing a MoCl5-mediated intramolecular dehydrogenative coupling reaction, a broad variety of structural motifs was isolated in yields up to 94 %. The electrophilic key transformation is tolerated by several labile moieties like halides and tertiary alkyl groups. Due to the use of disulfide or diselenide precursors, a high atom efficiency was achieved.
- Franzmann, Peter,Beil, Sebastian B.,Schollmeyer, Dieter,Waldvogel, Siegfried R.
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p. 1936 - 1940
(2019/01/14)
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- Thiolate-Initiated Synthesis of Dibenzothiophenes from 2,2′-Bis(methylthio)-1,1′-Biaryl Derivatives through Cleavage of Two Carbon-Sulfur Bonds
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A catalytic reaction involving the cleavage of two carbon-sulfur bonds in 2,2′-bis(methylthio)-1,1′-biaryl derivatives is reported. This reaction does not require a transition-metal catalyst and is promoted by a thiolate anion. Notably, based on DFT calculations, the product-forming cyclization step is shown to proceed through a concerted nucleophilic aromatic substitution (CS N Ar) mechanism.
- Chatani, Naoto,Kawashima, Yuki,Kodama, Takuya,Masuya, Yoshihiro,Tobisu, Mamoru
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supporting information
p. 1995 - 1999
(2019/10/22)
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- Cyclization of 2-Biphenylthiols to Dibenzothiophenes under PdCl2/DMSO Catalysis
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A palladium-catalyzed synthesis of dibenzothiophenes from 2-biphenylthiols is described. This highly efficient reaction employs a simple PdCl2/DMSO catalytic system, in which PdCl2 is the sole metal catalyst and DMSO functions as an oxidant and solvent. This transformation has broad substrate scope and operational simplicity and proceeds in high yield. The synthetic utility was demonstrated by the facile synthesis of helical dinapthothiophene 3 and an eminent organic semiconductor DBTDT 4. Importantly, highly strained trithiasumanene 5, a buckybowl of considerable synthetic challenge, was observed under this catalytic system.
- Zhang, Tao,Deng, Guigang,Li, Hanjie,Liu, Bingxin,Tan, Qitao,Xu, Bin
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supporting information
p. 5439 - 5443
(2018/09/13)
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- Palladium(II)-Catalyzed Synthesis of Dibenzothiophenes from 2-Biphenylyl Disulfides by C?H Functionalization
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The palladium-catalyzed oxidative preparation of dibenzothiophene derivatives from 2-biphenylyl disulfides by C?H functionalization is described herein. This procedure shows a high tolerance toward various functional groups and does not require the further addition of a metal oxidant, a base, or a ligand. Also, the present method was applied to the facile preparation of dibenzoselenophene.
- Nishino, Kota,Ogiwara, Yohei,Sakai, Norio
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p. 10971 - 10974
(2018/08/09)
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- Triphenylsulfonium topophotochemistry
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The products from the 193 nm irradiation of triphenylsulfonium nonaflate (TPS) embedded in a poly(methyl methacrylate) (PMMA) film have been characterized. The analysis of the photoproduct formation was performed using chromatographic techniques including HPLC, GPC and GC-MS as well as UV-vis and NMR spectroscopic methods. Two previously unreported TPS photoproducts, triphenylene and dibenzothiophene, were detected; additionally, GPC and DOSY-NMR spectroscopic analyses after irradiation suggested that TPS fragments had been incorporated into the polymer film. The irradiation of acetonitrile solutions containing 10% w/v PMMA and 1% w/v TPS in a 1 cm-path-length cuvette showed only a trace amount of triphenylene or dibenzothiophene, indicating that topochemical factors were important for the formation of these molecules. The accumulated evidence indicates that both products were formed by in-cage, secondary photochemical reactions: 2-(phenylthio)biphenyl to triphenylene, and diphenylsulfide to dibenzothiophene.
- Despagnet-Ayoub,Kramer,Sattler,Sattler,Labeaume,Thackeray,Cameron,Cardolaccia,Rachford,Winkler,Gray
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- A Pd-catalyzed optional approach for the synthesis of dibenzothiophenes
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A direct and practical approach for the construction of DBTs was developed via a Pd-catalyzed tandem reaction, in which commercially available o-bromo-iodobenzenes combined with benzene thiols or iodobenzenes combined with o-bromo-benzene thiols were applied. These two approaches will provide an alternative for the synthesis of DBT derivatives.
- Song, Juan,Wu, Hao,Sun, Wei,Wang, Songjiang,Sun, Haisen,Xiao, Kang,Qian, Yan,Liu, Chao
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supporting information
p. 2083 - 2087
(2018/03/26)
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- Palladium catalysis based one-pot synthesis method for DBTs (dibenzothiophenes)
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The invention discloses a palladium catalysis based one-pot synthesis method for DBTs (dibenzothiophenes). An inorganic base is added to an N,N-dimethylacetamide solution, with a palladium catalyst/ligand as a catalysis system, o-bromoiodobenzene derivatives or iodobenzene derivatives and thiophenol derivatives taken as raw materials are subjected to a reaction in nitrogen atmosphere, and DBTs areobtained through separation. The simple, economical and easily available raw materials are taken as substrates, all-position-substituted DBTs are synthesized on the basis of palladium catalyzed cascade reaction, and DBTs have great application prospect in medical synthesis intermediates and organic optoelectronic material science.
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Paragraph 0039; 0040; 0048-0050
(2020/05/12)
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- Hydroconversion of Oxidation Products of Sulfur-Containing Aromatic Compounds
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Hydroconversion of benzo- and dibenzothiophene sulfone on a Ni–Mo sulfide catalyst based on mesoporous aluminosilicate Al-HMS and on unsupported catalysts prepared in situ in the course of decomposition of poorly soluble precursors (molybdenum hexacarbonyl, nickel naphthenate) was investigated. Hydrogenation of sulfones was performed at 250°С, 340°С, and 380°С and elevated СО pressure in the presence of H2O ensuring in situ generation of H2 via water-gas shift reaction. The products that are formed by oxidation of organic sulfur compounds and remain in the hydrocarbon medium (mainly sulfones) will not significantly affect the subsequent hydrotreatment since under the conditions of hydroprocesses, they transform into the corresponding benzo- and dibenzothiophenes, which undergo the subsequent hydrodesulfurization to form mono- and diaromatic hydrocarbons.
- Vutolkina,Akopyan,Glotov,Kotelev,Maksimov,Karakhanov
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p. 981 - 989
(2018/08/31)
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- Pd-Catalyzed C—S Cyclization via C—H Functionalization Strategy: Access to Sulfur-containing Benzoheterocyclics
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A C—H sulfurated cyclization protocol starting from thioacetates is developed for straightforward construction of sulfur-containing benzoheterocyclics. The diversiform functional dihydrobenzothiophenes and thiochromans were comprehensively achieved through the Pd-catalyzed carbon- sulfur cyclization. Mechanistic studies indicated that C—H bond cleavage was involved in the rate-determining step. [1]Benzothieno-[3,2-b]- [1]benzothiophene (BTBT) and benzo[b]thieno[2,3-d]thiophene (BTT) were efficiently established as the well-known organic field-effect transistor (OFET) material molecules through this methodology.
- Chen, Shihao,Wang, Ming,Jiang, Xuefeng
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supporting information
p. 921 - 924
(2018/09/22)
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- Green Preparation of Dibenzothiophene Derivatives Using 2-Biphenylyl Disulfides in the Presence of Molecular Iodine and Its Application to Dibenzoselenophene Synthesis
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A protocol for the direct preparation of dibenzothiophenes from 2-biarylyl disulfides in the presence of an economic and ecological oxidant, molecular iodine, was explored. This protocol was used for the direct preparation of dibenzoselenophene.
- Nishino, Kota,Ogiwara, Yohei,Sakai, Norio
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p. 5892 - 5895
(2017/10/31)
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- METHOD FOR PRODUCING HETEROCYCLIC COMPOUNDS
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PROBLEM TO BE SOLVED: To provide heterocyclic compounds in high yield and by simple compositions. SOLUTION: The method for producing heterocyclic compounds comprises: a step of heating a raw material solution containing a solvent having a raw material substrate dissolved; and a step of cooling the raw material solution after the heating step where, in the heating step, the state of the solvent is a subcritical fluid or a supercritical fluid. The term supercritical fluid refers to a state of a metrial under the a temperature and pressure of the critical point or more. The term subcritical fluid refers to a liquid under high temperature and high pressure below the critical point. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0046-0048
(2017/10/05)
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- Cu(ii)-catalyzed sulfide construction: both aryl groups utilization of intermolecular and intramolecular diaryliodonium salt
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A sulfur-iodine exchange protocol of diaryliodonium salts with inorganic sulfur salt was developed. Both aryl groups in the diaryliodonium salt were fully exerted in this transformation. Five- to eight-membered sulfur-containing heterocycles were achieved. Note that [1]benzothieno-[3,2-b][1]benzothiophene (BTBT) (an organic field-effect transistor (OFET) material) and Zaltoprofen were efficiently established through this method.
- Wang, Ming,Wei, Jianpeng,Fan, Qiaoling,Jiang, Xuefeng
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supporting information
p. 2918 - 2921
(2017/03/15)
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- Trifluoromethylation of Secondary Nitroalkanes
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Using a commercially available Umemoto's reagent, the metal-free trifluoromethylation of nitroalkanes is now possible. This method provides a general, high-yielding synthesis of α-(trifluoromethyl)nitroalkanes. The quaternary α-(trifluoromethyl)nitroalkanes obtained from this transformation can be elaborated to a variety of complex nitrogen-containing molecules, including α-(trifluoromethyl)amines.
- Gietter-Burch, Amber A. S.,Devannah, Vijayarajan,Watson, Donald A.
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supporting information
p. 2957 - 2960
(2017/06/07)
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- Diaryl ring fused sulfides and diaryl ring fused selenides, and synthesis method and application thereof
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The invention discloses a synthesis method of diaryl ring fused sulfides represented by formula (B) and diaryl ring fused selenides represented by formula (C). The method is characterized in that a reaction of a reaction raw material high-iodine salt is carried out in dimethyl sulfoxide under the action of an inorganic sulfuration reagent or selenylation reagent and an alkali at 60-100 DEG C to obtain the diaryl ring fused sulfides and the diaryl ring fused selenides. Sulfur or selenium is introduced in the later stage in the presence of a nonmetal catalyst, so poisoning of sulfur to a metal catalyst in the early stage reaction is avoided; the above inorganic sulfur source is nontoxic and odorless; and two aryl groups in the high-iodine salt are fully used, so the atom economy and the greenness of the method are fully shown. The diaryl ring fused sulfides and the diaryl ring fused selenides prepared through the method can be applied to synthesize photoelectric materials BTBT and BTBS.
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Paragraph 0033; 0034; 0035; 0036
(2017/06/20)
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- Effect of the nature of sulfur compounds on their reactivity in the oxidative desulfurization of hydrocarbon fuels with oxygen over a modified CuZnAlO catalyst
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The reactivity of thiophene, dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), which are the representatives of the main classes of sulfur compounds that are the constituents of diesel fractions, was studied in the course of their oxidative desulfurization with oxygen on a CuO/ZnO/Al2O3 catalyst modified with boron and molybdenum additives. At T ≥ 375°C, the reactivity increased in the order thiophene 2 from hydrocarbon fuel, which was simulated by a solution of 4,6-DMDBT in toluene, was 80%. Under the assumption of a first order reaction with respect to sulfur compound and oxygen, the apparent activation energies of the test processes were calculated. An attempt was made to reveal the role of the adsorption of sulfur compounds in the overall process of oxidative desulfurization with the use of X-ray diffraction analysis, X-ray photoelectron spectroscopy, and differential thermal and thermogravimetric analysis with the massspectrometric monitoring of gas phase composition.
- Yashnik,Salnikov,Kerzhentsev,Saraev,Kaichev,Khitsova,Ismagilov,Yamin,Koseoglu
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- Bipolar micromolecular luminescent material based on 4-(9H-carbazole-9-yl) aniline and preparation method and application thereof
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The invention discloses a bipolar micromolecular luminescent material based on 4-(9H-carbazole-9-yl) aniline and a preparation method and application thereof. The material is mainly characterized in that the 4-(9H-carbazole-9-yl) aniline is used as a hole transport center unit, and bipolar micromolecules with the 4-(9H-carbazole-9-yl) aniline as the center are obtained by selecting groups with an electron transmission function. The bipolar micromolecules prepared through the method can be used for making a luminescent layer of an organic light emitting diode.
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Paragraph 0064; 0068
(2016/10/09)
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- N-Benzyldithiocarbamate Salts as Sulfur Sources to Access Tricyclic Thioheterocycles Mediated by Copper Species
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Using an easily prepared triethylammonium N-benzyldithiocarbamate salt as a sulfur source, a dual C?S functionalization of cyclic diaryliodoniums to form tricyclic thioheterocycles is realized. Our method uses the readily available copper sulfate to accelerate the chemical transformation under mild conditions. A broad range of cyclic diaryliodoniums with a ring size from 5- to 7-membered can be employed to gain a quick access to tricyclic thioheterocycles including dibenzothiophenes, thioxanthenes, and phenoxathiines. (Figure presented.).
- Luo, Bingling,Cui, Qingbin,Luo, Hongwen,Hu, Yumin,Huang, Peng,Wen, Shijun
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supporting information
p. 2733 - 2738
(2016/09/13)
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- Diaryl thioether compound, and synthetic method and application thereof
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The invention discloses a diaryl thioether compound, and a synthetic method and an application thereof. Various diaryl thioether compounds can be obtained through a reaction of a reaction raw material high iodine salt in dimethyl sulfoxide at 60-100DEG C under the action of an odorless sulfuration reagent, an alkali, a metal catalyst and a ligand for 3-12h. Sulfur is introduced in the later stage, so poisoning of sulfur to the metal catalyst and incompatibility of an oxidant in the early stage reaction are avoided; the above inorganic sulfur source is nontoxic and odorless; and two aryl groups in the high iodine salt are fully used, so the atom economy of the method is fully shown. The diaryl thioether compound prepared through the method can be further used to synthesize a photoelectric material BTBT and an anti-inflammatory drug zaltoprofen.
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Paragraph 0115-0119
(2018/02/04)
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- Photodeoxygenation of dinaphthothiophene, benzophenanthrothiophene, and benzonaphthothiophene: S-oxides
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Photoinduced deoxygenation of dibenzothiophene S-oxide (DBTO) has been suggested to release atomic oxygen [O(3P)]. To expand the conditions and applications where O(3P) could be used, generation of O(3P) at longer wavelengths was desirable. The sulfoxides benzo[b]naphtho-[1,2,d]thiophene S-oxide, benzo[b]naphtho[2,1,d]thiophene S-oxide, benzo[b]phenanthro[9,10-d]thiophene S-oxide, dinaphtho[2,1-b:1′,2′-d]thiophene S-oxide, and dinaphtho[1,2-b:2′,1′-d]thiophene S-oxide all absorb light at longer wavelengths than DBTO. To determine if these sulfoxides could be used to generate O(3P), quantum yield studies, product studies, and computational analysis were performed. Quantum yields for the deoxygenation were up to 3 times larger for these sulfoxides compared to DBTO. However, oxidation of the solvent by these sulfoxides resulted in different ratios of oxidized products compared to DBTO, which suggested a change in deoxygenation mechanism. Density functional calculations revealed a much larger singlet-triplet gap for the larger sulfoxides compared to DBTO. This led to the conclusion that the examined sulfoxides could undergo deoxygenation by two different mechanisms.
- Zheng,Baumann,Chintala,Galloway,Slaughter,McCulla
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p. 791 - 800
(2016/07/06)
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- Rhodium-Catalyzed Sequential Dehydrogenation/Deoxygenation in One-Pot: Efficient Synthesis of Dibenzothiophene Derivatives from Diaryl Sulfoxides
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A novel strategy for the synthesis of dibenzothiophene derivatives is established through a one-pot intramolecular cross-dehydrogenative-coupling reaction of diaryl sulfoxides followed by deoxygenation with a Rh/Ag catalytic system. The yields obtained were good to excellent (up to 96 %), therefore making the described protocol an attractive option for building dibenzothiophene compounds. A novel strategy for the synthesis of dibenzothiophene derivatives was established through a one-pot intramolecular cross-dehydrogenative-coupling reaction of diaryl sulfoxides followed by deoxygenation with a Rh/Ag catalytic system.
- Huang, Qiufeng,Fu, Shurong,Ke, Shaojia,Xiao, Hanbing,Zhang, Xiaofeng,Lin, Shen
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supporting information
p. 6602 - 6605
(2015/10/29)
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- Efficient Oxidation of Sulfides to Sulfoxides and Deoxygenation of Sulfoxides over Carbonaceous Solid Acid
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Carbonaceous Solid Acid (CSA) was found to be a highly efficient, environmentally friendly, recyclable heterogeneous solid acid for the oxidation of sulfides and deoxygenation of sulfoxides, in good to excellent yields under mild reaction conditions.
- Atabaki, Fariborz,Abedini, Ebrahim,Shokrolahi, Arash
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p. 1169 - 1176
(2015/08/04)
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- Hydrodesulfurization of dibenzothiophene, 4,6-dimethyldibenzothiophene, and their hydrogenated intermediates over bulk tungsten phosphide
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The kinetics of the hydrodesulfurization (HDS) of dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), and their hydrogenated intermediates over bulk tungsten phosphide (WP) was studied. WP possessed high hydrogenation/dehydrogenation activity but was highly sensitive to piperidine inhibition. 4,6-DMDBT reacted faster than DBT, and both DBT and 4,6-DMDBT reacted mainly through the hydrogenation pathway. The methyl groups suppressed the direct desulfurization of 4,6-DMDBT but significantly promoted the hydrogenation of 4,6-DMDBT and the dehydrogenation of 1,2,3,4-tetrahydro-4,6-dimethyldibenzothiophene (TH-4,6-DMDBT) and 1,2,3,4,4a,9b-hexahydro-4,6-dimethyldibenzothiophene, but decreased the rate of hydrogenation of TH-4,6-DMDBT. Piperidine inhibited the HDS of 4,6-DMDBT much more strongly than that of DBT. Substantial dehydrogenation of TH-4,6-DMDBT to 4,6-DMDBT and two of its isomers occurred. The formation of these 4,6-DMDBT isomers in the dehydrogenation of TH-4,6-DMDBT and the hydrocracking of 1-methyl-4-(3-methylcyclohexyl)-benzene, as well as the formation of cyclopentylphenylmethane and (cyclopentylmethyl)cyclohexane, is ascribed to the metallic character of WP.
- Yang, Lei,Li, Xiang,Wang, Anjie,Prins, Roel,Chen, Yongying,Duan, Xinping
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p. 330 - 343
(2015/09/01)
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- Palladium-Assisted "Aromatic Metamorphosis" of Dibenzothiophenes into Triphenylenes
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Abstract Two new palladium-catalyzed reactions of aromatic sulfur compounds enabled the conversion of dibenzothiophenes into triphenylenes in four steps. This transformation of one aromatic framework into another consists of 1) 4-chlorobutylation of the dibenzothiophene to form the corresponding sulfonium salt, 2) palladium-catalyzed arylative ring opening of the sulfonium salt with a sodium tetraarylborate, 3) an intramolecular SN2 reaction to form a teraryl sulfonium salt, and 4) palladium-catalyzed intramolecular C-S/C-H coupling through electrophilic palladation. Symmetrical as well as unsymmetrical triphenylenes of interest were synthesized in a tailor-made fashion in satisfactory overall yields. A change of heart: The invention of two palladium-catalyzed arylation reactions of organosulfur compounds enabled the transformation of dibenzothiophenes into triphenylenes and thus a fundamental change in the core aromatic structure (see scheme). Both symmetrical and unsymmetrical triphenylenes were synthesized in a tailor-made fashion in satisfactory overall yield.
- Vasu, Dhananjayan,Yorimitsu, Hideki,Osuka, Atsuhiro
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supporting information
p. 7162 - 7166
(2015/06/08)
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- Synthesis of hindered biaryls via aryne addition and in situ dimerization
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Benzynes generated under Knochel conditions from 2-iodophenylsulfonates and iPrMgCl smoothly add to thiol, selenol, and amine nucleophiles. Treatment of the resulting aryl Grignard intermediate with a copper salt and an organic oxidant then affords symmetrical biaryls in good yield. 3-Substituted arynes undergo regioselective addition, enabling synthesis of atropisomeric biaryls with chelating S, Se, or N groups in the 2,2′ positions.
- García-López, José-Antonio,Cetin, Meliha,Greaney, Michael F.
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supporting information
p. 2649 - 2651
(2015/06/16)
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- Room-temperature carbon-sulfur bond activation by a reactive (dippe)Pd fragment
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The reactivity of [Pd(dippe)(μ-H)]2 (1) and [(μ-dippe)Pd]2 (2) (dippe = 1,2-bis(diisopropylphosphino)ethane) toward C-S bonds in thiophene derivatives and thioethers was investigated, which led to C-S bond activation products. The thiapalladacycles derived from thiophenic substrates were fully characterized by 1H, 31P, and 13C NMR spectroscopy, elemental analysis, and X-ray diffraction. The stability of the C-S insertion products was probed by performing competition experiments which follow the thermodynamic stability order (dippe)Pd(κ2C,S-benzothiophene) (6) > (dippe)Pd(κ2C,S-dibenzothiophene) (8) > (dippe)Pd(κ2C,S-thiophene) (3). The reactivity of the thiapalladacycles with small molecules such as H2, CO, and alkynes was investigated.
- Munjanja, Lloyd,Brennessel, William W.,Jones, William D.
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p. 1716 - 1724
(2015/05/20)
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- Regioselective functionalisation of dibenzothiophenes through gold-catalysed intermolecular alkyne oxyarylation
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A protocol has been developed for direct Csp3-Csp2 bond formation at the 4- and 6-positions of dibenzothiophenes using a gold(i) catalyst with terminal alkynes and dibenzothiophene-S-oxides. The sulfoxide acts as a traceless directing group to avoid the need to prefunctionalise at carbon. The iterative use of this protocol is possible and has been employed in the preparation of novel macrocyclic structures. In addition, a cascade process shows how oxyarylations can be combined with other processes resulting in complex, highly efficient transformations.
- Barrett, Matthew J.,Davies, Paul W.,Grainger, Richard S.
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p. 8676 - 8686
(2015/08/24)
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- Direct C-H Trifluoromethylation of Glycals by Photoredox Catalysis
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A mild, efficient, and practical transformation for the direct C-H trifluoromethylation of glycals under visible light has been reported for the first time. This reaction employed fac-Ir3+(ppy)3 as the photocatalyst, Umemoto's reagent as the CF3 source, and a household blue LED or sunlight as the light source. Glycals bearing both electron-withdrawing and -donating protective groups performed this reaction smoothly. This visible light-mediated trifluoromethylation reaction was highlighted by the trifluoromethylation of the biologically important Neu2en moiety.
- Wang, Bang,Xiong, De-Cai,Ye, Xin-Shan
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supporting information
p. 5698 - 5701
(2015/12/01)
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- Oxidation of plasmalogen, low-density lipoprotein and raw 264.7 cells by photoactivatable atomic oxygen precursors
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The oxidation of lipids by endogenous or environmental reactive oxygen species (ROS) generates a myriad of different lipid oxidation products that have important roles in disease pathology. The lipid oxidation products obtained in these reactions are dependent upon the identity of the reacting ROS. The photoinduced deoxygenation of various aromatic heterocyclic oxides has been suggested to generate ground state atomic oxygen (O[3P]) as an oxidant; however, very little is known about reactions between lipids and O(3P). To identify lipid oxidation products arising from the reaction of lipids with O(3P), photoactivatable precursors of O( 3P) were irradiated in the presence of lysoplasmenylcholine, low-density lipoprotein and RAW 264.7 cells under aerobic and anaerobic conditions. Four different aldehyde products consistent with the oxidation of plasmalogens were observed. The four aldehydes were: tetradecanal, pentadecanal, 2-hexadecenal and hexadecanal. Depending upon the conditions, either pentadecanal or 2-hexadecenal was the major product. Increased amounts of the aldehyde products were observed in aerobic conditions. The photodeoxygenation of dibenzothiophene S-oxide has been suggested to generate ground state atomic oxygen (O[3P]). The reactivity of the putative O(3P) is distinct from other reactive oxygen species (ROS) and little is known about its reactivity with lipids and other biomolecules. In this work, exposure of low-density lipoprotein (LDL) to O(3P) yielded four aldehyde products. The same aldehydes were observed after the oxidation of an isolated plasmalogen by O(3P).
- Bourdillon, Max T.,Ford, Benjamin A.,Knulty, Ashley T.,Gray, Colleen N.,Zhang, Miao,Ford, David A.,McCulla, Ryan D.
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p. 386 - 393
(2014/04/03)
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- Synthesis of dibenzothiophenes by pd-catalyzed dual C-H activation from diaryl sulfides
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Palladium-catalyzed dual C-H functionalization of diaryl sulfides to form dibenzothiophenes (DBTs) by oxidative dehydrogenative cyclization is reported. This protocol afforded various DBTs in moderate to good yields with tolerance of a wide variety of substrates. Benzo[1,2-b:4,5-b]bis[b]benzothiophene was successfully synthesized by this method, which was used as an organic semiconductor for field-effect transistors.
- Che, Rui,Wu, Zhiqing,Li, Zhengkai,Xiang, Haifeng,Zhou, Xiangge
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supporting information
p. 7258 - 7261
(2014/06/23)
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- Regiospecific Synthesis of 1-Trifluoromethylisoquinolines Enabled by Photoredox Somophilic Vinyl Isocyanide Insertion
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A strategy has been developed for the regiospecific synthesis of 1-trifluoromethylisoquinoline derivatives. This strategy is enabled by a photoredox vinyl isocyanide insertion with the help of Umemoto's reagent. The methodology presented here provides an access to highly fuctionalized 1-trifluoromethylisoquinolines regiospecifically under mild conditions in good-to-excellent chemical yields. A detailed mechanism is proposed, which is supported by experiments and theoretical calculations.
- Cheng, Yuanzheng,Yuan, Xiangai,Jiang, Heng,Wang, Ruzhi,Ma, Jing,Zhang, Yan,Yu, Shouyun
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supporting information
p. 2859 - 2866
(2016/02/18)
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- Lewis acid/Broensted acid mediated benz-annulation of thiophenes and electron-rich arenes
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A facile preparation of benz-annulated heterocycles were achieved at rt involving a Lewis acid/Broensted acid mediated annulation of heterocycles using 2,5-dimethoxytetrahydrofuran as a four-carbon synthon. The benz-/naphth-annulation was found to be successful with electron-rich arenes as well.
- Rafiq, Settu Muhamad,Sivasakthikumaran, Ramakrishnan,Mohanakrishnan, Arasambattu K.
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supporting information
p. 2720 - 2723
(2014/06/09)
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