- 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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- 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 0033-0038
(2020/05/12)
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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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p. 5439 - 5443
(2018/09/13)
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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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- 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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supporting information
p. 5892 - 5895
(2017/10/31)
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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 0069; 0070; 0071; 0072
(2017/06/20)
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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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supporting information
p. 5756 - 5759
(2016/11/17)
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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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- 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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p. 497 - 505
(2011/11/29)
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- Palladium-catalyzed double C-H activation directed by sulfoxides in the synthesis of dibenzothiophenes
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S=O shows where to go: A novel double C-H activation of aromatic compounds with a sulfoxide as a directing group results in the highly regioselective synthesis of polysubstituted dibenzothiophenes (see scheme). The reaction cascade consists of palladium-catalyzed double C-H activation and a Pummerer rearrangement followed by palladium-catalyzed C-S bond formation. Copyright
- Samanta, Rajarshi,Antonchick, Andrey P.
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p. 5217 - 5220
(2011/07/08)
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- Formation of dibenzofurans by flash vacuum pyrolysis of aryl 2-(allyloxy)benzoates and related reactions
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Flash vacuum pyrolysis (FVP) of aryl 2-(allyloxy)benzoates 5 and of the corresponding aryl 2-(allylthio)benzoates 6 at 650°C, gives dibenzofurans 19 and dibenzothiophenes 20, respectively. The mechanism involves generation of phenoxyl (or thiophenoxyl) radicals by homolysis of the O-allyl (or S-allyl) bond, followed by ipso attack at the ester group, loss of CO2 and cyclisation of the resulting aryl radical. Synthetically, the procedure works well for p-substituted substrates, which lead to 2-substituted dibenzofurans 19b-f (73-90%) and dibenzothiophenes 20b-c (90-94%). Little selectivity is shown in the cyclisation of m-substituted substrates and competing interactions of the radical with the substituent - and ipso-attack - complicate the pyrolyses of o-substituted substrates. FVP of related radical precursors including 2-(allyloxy)phenyl benzoates 43 gave no dibenzofurans, whereas 2-(allyloxy-5-methyl)azobenzene 44 gave a much reduced yield. No carbazoles were obtained by FVP of 4-methylphenyl 2-(allylamino)benzoate 42.
- Black, Michael,Cadogan,McNab, Hamish
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experimental part
p. 2961 - 2967
(2010/09/06)
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- SCHWEFELVERBINDUNGEN DES ERDOELS XVI. DIBENZOTHIOPHENE MIT EINEM UNVERZWEIGTEN C1-C5-ALKYLREST
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The preparation of all position isomers of dibenzothiophenes with a linear C1-C5-side chain and of the corresponding 5,5-dioxides is described. (1)H-NMR data and GC-purities are given. Key words: Monoalkyldibenzothiophenes; methyldibenzothiophenes; ethyldibenzothiophenes; propyldibenzothiophenes; butyldibenzothiophenes; pentyldibenzothiophenes; monoalkyldibenzothiophene-5,5-dioxides.
- Boberg, Friedrich,Bruns, Wolfgang,Musshoff, Dagmar
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- Gas phase generation and cyclisation reactions of some o-substituted phenyl radicals
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Flash vacuum pyrolysis of the allyl esters 2 (X=O, S, CH2, CO) at 900°C (10-2 Torr) gives dibenzofurans, dibenzothiophenes, fluorenes, and fluorenones respectively as the major products. The mechanism involves the phenyl radical intermediates 1 which equilibrate by intramolecular hydrogen transfer via six-membered transition states, prior to cyclisation.
- Cadogan,Hutchison,McNab
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p. 7747 - 7762
(2007/10/02)
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- A Short Synthesis of Dibenzofurans and Dibenzothiophenes
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An afficient synthesis of dibenzofurans and dibenzothiophenes from aryl salicylates is described, which involves a novel rearrangement-extrusion-cyclisation sequence of o-substituted phenoxyl and thiophenoxyl radicals.
- Black, Michael,Cadogan, J. I. G.,McNab, Hamish
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p. 395 - 396
(2007/10/02)
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