An efficient one-pot synthesis of bisalkylthioarenes

Charoonniyomporn, Porntip; Thongpanchang, Tienthong; Witayakran, Suteera; Thebtaranonth, Yodhathai; Phillips, Karen E. S.; Katz, Thomas J.

doi:10.1016/j.tetlet.2003.11.015

Cited by 16 publications

(5 citation statements)

References 22 publications

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“…The 1,4‐quinone methodology, which combines the above two methodologies, has turned out to be the most versatile so far . The direct synthesis of aryl/alkylthio‐substituted acenes is limited to smaller anthracenes only, and may be realized by the following transformations: sulfenylation of the middle, most reactive anthracene ring, X/RS exchange reactions (X=OH, OMe, OAc, Br, Cl, NO 2 ), Br/RS double exchange in 9,10‐dibromoanthracene, alkylation of anthracenethiols and bis‐anthryl disulfides, arylation of anthracenethiols, as well as conversions of anthraquinones, anthrones, and dithioanthraquinones leading to mono‐ or di‐aryl/alkylthio‐substituted anthracenes.…”

Section: Introductionmentioning

confidence: 99%

Mono‐Aryl/Alkylthio‐Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio‐Friedel–Crafts/Bradsher Cyclization Reaction

Bałczewski

Kowalska

Różycka‐Sokołowska

et al. 2019

Chemistry A European J

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The highly substituted mono‐aryl/alkylthio‐(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp.=331–354 °C) than the known di‐aryl/alkylthio‐substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio‐anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG‐substituted anthracenes (EDG=electron‐donating group, EWG=electron‐withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio‐Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o‐(1,3‐dithian‐2‐yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono‐aryl/alkylthio‐substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD‐DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono‐aryl/alkylthio‐substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen.

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Section: Introductionmentioning

confidence: 99%

Mono‐Aryl/Alkylthio‐Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio‐Friedel–Crafts/Bradsher Cyclization Reaction

Bałczewski

Kowalska

Różycka‐Sokołowska

et al. 2019

Chemistry A European J

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“…The methoxy groups were demethylated by BBr 3 in CH 2 Cl 2 . A known reaction of hydroxyarenes with alkylthiols with acid catalyst yields thioethers . We initially used that reaction to synthesize 9,10‐dimethylanthracene‐2,3,6,7‐tetra( n ‐propylthioether), but the reductive cleavage of the propyl groups by Na/NH 3 led to hydrogenation of the anthracene at the 9 and 10 positions, and we were unable to oxidatively remove those hydrogen atoms.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 9,10‐Dimethyl‐2,3,6,7‐Anthracenetetra(thioacetate) and Benzenepentathiol; Improved Syntheses of 1,2,4,5‐Benzenetetra(thioacetate) and Benzenehexathiol

Singh

Baghel

et al. 2016

ChemistrySelect

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A synthesis is reported for 9,10‐dimethyl‐2,3,6,7‐anthracenetetra(thioacetate), an anthracenetetrathiol derivative that may find use in molecular electronics and conducting metal‐organic frameworks (MOFs). The easily accessible 2,3,6,7‐tetrahydroxy‐9,10‐dimethylanthracene was treated with 2‐(4‐pyridyl)ethanethiol in molten p‐toluenesulfonic acid to yield the tetra(thioether), which was methylated and then deprotected with triethylamine in the presence of acetic anhydride to yield 9,10‐dimethyl‐2,3,6,7‐anthracenetetra(thioacetate), a protected form of the tetrathiol. Separately, the first synthesis of benzenepentathiol and streamlined syntheses of 1,2,4,5‐benzenetetra(thioacetate) and benzenehexathiol are reported.

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“…Synthesis of 1,4-bisalkanethionaphthalene: 1,4-Bisalkanethionaphtalene (1,4-bisethanethionaphtalene (NpEDT) or 1,4-bisdecanethionaphtalene (NpDDT)) were prepared by previously reported. [19] Under an N 2 atmosphere, 1,4-dihydroxynaphthalene (0.81 g, 5.0 mmol), p-toluenesulfonic acid (0.48 g, 2.5 mmol) and alkanedithiol (1, or 1,10-decanedithiol (DDT), 46 mmol) were dissolved in benzene (50 mL), and the mixture was heated at reflux (80 8C) for 1 h. After aqueous workup, the product was purified by column chromatography on silica gel by using ethyl acetate as an eluent. The collected product was crystallized from a mixture of ethyl acetate and n-hexane to give NpEDT or NpDDT as a white solid, respectively.…”

Section: Synthesis Of Au Nanoparticlesmentioning

confidence: 99%

Enhanced Magneto‐optical Properties of Semiconductor EuS Nanocrystals Assisted by Surface Plasmon Resonance of Gold Nanoparticles

Kawashima

Nakanishi

Shibayama

et al. 2013

Chemistry A European J

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Remarkable magneto-optical properties of a new isolator material, that is, europium sulfide nanocrystals with gold (EuS-Au nanosystem), has been demonstrated for a future photo-information technology. Attachment of gold particles that exhibit surface plasmon resonance leads to amplification of the magneto-optical properties of the EuS nanocrystals. To construct the EuS-Au nanosystems, cubic EuS and spherical Au nanocrystals have been joined by a variety of organic linkers, that is, 1,2-ethanedithiol (EDT), 1,6-hexanedithiol (HDT), 1,10-decanedithiol (DDT), 1,4-bisethanethionaphthalene (NpEDT), or 1,4-bisdecanethionaphthalene (NpDDT) . Formation of these systems was observed by XRD, TEM, and absorption spectra measurements. The magneto-optical properties of the EuS-Au nanosystem have been characterized by using Faraday rotation spectroscopy. The Faraday rotation angle of the EuS-Au nanosystem is dependent on the Au particle size and interparticle distance between EuS and Au nanocrystals. Enhancement of the Faraday rotation of EuS-Au nanosystems was observed. The spin configuration in the excited state of the EuS-Au nanosystem was also investigated using photo-assisted electron paramagnetic resonance.

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An efficient one-pot synthesis of bisalkylthioarenes

Cited by 16 publications

References 22 publications

Mono‐Aryl/Alkylthio‐Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio‐Friedel–Crafts/Bradsher Cyclization Reaction

Mono‐Aryl/Alkylthio‐Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio‐Friedel–Crafts/Bradsher Cyclization Reaction

Synthesis of 9,10‐Dimethyl‐2,3,6,7‐Anthracenetetra(thioacetate) and Benzenepentathiol; Improved Syntheses of 1,2,4,5‐Benzenetetra(thioacetate) and Benzenehexathiol

Enhanced Magneto‐optical Properties of Semiconductor EuS Nanocrystals Assisted by Surface Plasmon Resonance of Gold Nanoparticles

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