239-35-0Relevant articles and documents
Palladium catalysis based one-pot synthesis method for DBTs (dibenzothiophenes)
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Paragraph 0033-0038, (2020/05/12)
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.
A Pd-catalyzed optional approach for the synthesis of dibenzothiophenes
Song, Juan,Wu, Hao,Sun, Wei,Wang, Songjiang,Sun, Haisen,Xiao, Kang,Qian, Yan,Liu, Chao
supporting information, p. 2083 - 2087 (2018/03/26)
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.
Synthetic Utility of Arylmethylsulfones: Annulative π-Extension of Aromatics and Hetero-aromatics Involving Pd(0)-Catalyzed Heck Coupling Reactions
Sankar, Elumalai,Raju, Potharaju,Karunakaran, Jayachandran,Mohanakrishnan, Arasambattu K.
, p. 13583 - 13593 (2017/12/26)
A straightforward and general method for the synthesis of annulated thiophene, dibenzothiophene, and carbazoles analogues has been achieved involving alkylation of 2-bromo-1-(phenylsulfonylmethyl)arene/heteroarene with arylmethyl bromides/heteroarylmethyl bromides using t-BuOK as a base in DMF, followed by Pd(0)-mediated intramolecular Heck coupling in the presence of K2CO3 in DMF at 80-140 °C. The attractive feature of this protocol is that a wide variety of π-conjugated heterocycles could be readily accessed by an appropriate choice of arylmethylsulfones and benzylic bromides.
METHOD FOR SYNTHESIS OF POLYHETEROAROMATIC COMPOUNDS BY USING VISIBLE LIGHT AND REGIOSELECTIVE POYHETEROAROMATIC COMPOUNDS
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Paragraph 0055-0057, (2017/10/05)
The present invention relates to a method for manufacturing polyheteroaromatic compounds, comprising the following steps: preparing a reaction mixture including an aniline compound or a heteroaryl amine compound having heterocycles on 2-position as a substituent, a heteroaryl alkyne compound and a photocatalyst; and irradiating visible rays to the reaction mixture. The present invention further relates to a polyheteroaromatic compound including a heteroaryl group as a substituent and heterocycle adjacent to the substituent.COPYRIGHT KIPO 2017
Heterotetracenes: Flexible Synthesis and in Silico Assessment of the Hole-Transport Properties
Li, Yifan,Gryn'ova, Ganna,Saenz, Felipe,Jeanbourquin, Xavier,Sivula, Kevin,Corminboeuf, Clémence,Waser, Jér?me
supporting information, p. 8058 - 8065 (2017/06/19)
Thienoacenes and furoacenes are among the most frequent molecular units found in organic materials. The efficient synthesis of morphologically different heteroacenes and the rapid determination of their solid-state and electronic properties are still challenging tasks, which slow down progress in the development of new materials. Here, we report a flexible and efficient synthesis of unprecedented heterotetracenes based on a platinum- and gold-catalyzed cyclization–alkynylation domino process using EthynylBenziodoXole (EBX) hypervalent iodine reagents in the key step. The proof-of-principle in silico estimation of the synthesized tetracenes’ charge transport properties reveals their strong dependence on both the position and nature of the heteroatoms in the ring system. A broad range of mobility is predicted, with some compounds displaying performance potentially comparable to that of state-of-the-art electronic organic materials.
N-Benzyldithiocarbamate Salts as Sulfur Sources to Access Tricyclic Thioheterocycles Mediated by Copper Species
Luo, Bingling,Cui, Qingbin,Luo, Hongwen,Hu, Yumin,Huang, Peng,Wen, Shijun
supporting information, p. 2733 - 2738 (2016/09/13)
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.).
Photodeoxygenation of dinaphthothiophene, benzophenanthrothiophene, and benzonaphthothiophene: S-oxides
Zheng,Baumann,Chintala,Galloway,Slaughter,McCulla
, p. 791 - 800 (2016/07/06)
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.
CO2-promoted oxidative cross-coupling reaction for C-S bond formation via masked strategy in an odourless way
Qiao, Zongjun,Ge, Nanyang,Jiang, Xuefeng
supporting information, p. 10295 - 10298 (2015/06/25)
Cu-catalyzed direct oxidative cross-coupling between boronic acids and masked sulfides delivering thioethers was described, in which the SO3-, as a mask, has shown a distinctive effect on the oxidative cross-coupling condition. Disulfide could be suppressed efficiently via masked strategy under CO2 atmosphere. A broad scope of aromatics and scalable processes indicates its practicality, which could be further applied to drug late-stage modification and unsymmetrical dibenzothiophenes (DBTs) synthesis.
Palladium-Assisted "Aromatic Metamorphosis" of Dibenzothiophenes into Triphenylenes
Vasu, Dhananjayan,Yorimitsu, Hideki,Osuka, Atsuhiro
supporting information, p. 7162 - 7166 (2015/06/08)
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.
A combined experimental and computational study on the cycloisomerization of 2-ethynylbiaryls catalyzed by dicationic arene ruthenium complexes
Yamamoto, Yoshihiko,Matsui, Kazuma,Shibuya, Masatoshi
supporting information, p. 7245 - 7255 (2015/05/05)
Ruthenium-catalyzed cycloisomerization of 2-ethynylbiaryls was investigated to identify an optimal ruthenium catalyst system. A combination of [η6-(p-cymene)RuCl2(PR3)] and two equivalents of AgPF6 effectively converted 2-ethynylbiphenyls into phenanthrenes in chlorobenzene at 120 °C over 20 h. Moreover, 2-ethynylheterobiaryls were found to be favorable substrates for this ruthenium catalysis, thus achieving the cycloisomerization of previously unused heterocyclic substrates. Moreover, several control experiments and DFT calculations of model complexes were performed to propose a plausible reaction mechanism.
