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Transition-Metal-Free Synthesis of Carbazoles and Indoles by an SNAr-Based “aromatic Metamorphosis” of Thiaarenes

Dibenzothiophene dioxides, which are readily prepared through oxidation of the parent dibenzothiophenes, undergo nucleophilic aromatic substitution with anilines intermolecularly and then intramolecularly to yield the corresponding carbazoles in a single operation. The “aromatic metamorphosis” of dibenzothiophenes into carbazoles does not require any heavy metals. This strategy is also applicable to the synthesis of indoles. Since electron-deficient thiaarene dioxides exhibit interesting reactivity, which is not observed for that the corresponding electron-rich azaarenes, a combination of a thiaarene-dioxide-specific reaction with the SNAr-based aromatic metamorphosis allows transition-metal-free construction of difficult-to-prepare carbazoles.

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A novel aggregation-induced emission platform from 2,3-diphenylbenzo[b]thiophene S,S-dioxide

New aggregation-induced emission (AIE) luminogens with high solid-state emission efficiencies are developed by adopting a benzo[b]thiophene S,S-dioxide core, and steric and electronic effects on the AIE property are elucidated.

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Dihydropyridines useful in the treatment of angina and stroke

This invention provides certain substituted dihydropyridines, their pharmaceutical formulations, and their use for causing vasodilation in mammals.

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Synthesis and Reactions of 2,3,5,6-Tetrahydro-2,5-ethano-3-benzazocin-4(1H)-one and a Thieno-extended Analogue: X-Ray Structure of 3-Methyl-2,3,5,6-tetrahydro-2,5-ethano<1>benzothieno<3,2-d>azocin-4(1H)-one

5,6,7,8,9,10-Hexahydro-6,9-methanobenzocyclo-octen-11-one (3) was prepared through condensation of o-xylene-alpha,alpha’-diyl dibromide with N-cyclopentylidenepyrrolidine and converted by Beckmann rearrangement of its oxime (4) into 2,3,5,6-tetrahydro-2,5-ethano-3-benzazocin-4(1H)-one (6). 2,3-Bis(bromomethyl)benzothiophene was converted similarly into a mixture of 1,4,5,6-tetrahydro-2,5-ethano<1>benzothieno<2.3-d>azocin-3(2H)-one (15) and the isomeric lactam (19).Lactam (6) was N-methylated and both the parent lactam (6) and the N-methyl derivative (23) were reducedwith lithium aluminium hydride to the saturated products (24) and (25), respectively.Conversion of lactam (6) into the corresponding thiolactam (26) with phosphorus pentasulphide followed by alkylation of the latter compound gave an N-(29) or S-alkylated derivative, (27) or (28), depending on the reagent and reaction conditions.Similar reactions are reported also for lactams (15) and (19).The 4(1H)-one structures of compounds (15) – (22) are based on an X-ray analysis of 3-methyl-2,3,5,6-tetrahydro-2,5-ethano<1>benzothieno<3,2-d>azocin-4(1H)-one (20).We also report syntheses of 2-azido-5,6,7,8,9,10-hexahydro-6,9-methanobenzocyclo-octen-11-one (33) and 3-nitro(and 1,3-dinitro)-6,7,8,9,10,11-hexahydro-7,10-methanocyclo-octa<1>benzothiophen-12-one, (36) and (37), respectively.

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Photochromic dihetarylethenes 10. Photochromic 1,2-bis[2-(benzothiazol-2-yl)-3-thienyl]- and 1,2-bis[2-(benzothiazol-2-yl)benzothiophen-3-yl]ethenes

Dithienylethenes containing the thiophene rings with benzothiazolyl substituent in position 2 were synthesized. 1,2-Bis[2-(benzothiazol-2-yl)benzothiophen-3-yl]hexafluorocyclopentene and 1,2-bis[2,5-di(benzothiazol-2-yl)-3-thienyl]hexafluorocyclopentene possess photochromic properties. The open forms of 1,2-bis(2-benzothiazolylhetaryl)ethenes fluoresce, but introduction of the benzothiazole rings into dihetarylethenes significantly lowers the fatigue resistance of photochromes and favors thermal reversibility.

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Fischer dinuclear and mononuclear bis-carbene complexes of thiophene and thiophene derivatives

The reaction of dilithiated thiophene and thiophene derivatives with group 6 transition metal carbonyl precursors and subsequent alkylation afforded linearly arranged Fischer 2,5-bis-carbene and the rare unsymmetrical 2,3-bis-carbene chelated complexes. The latter requires a second lithiation to occur at an adjacent, less reactive site on the thiophene ring. The control of reactivity sites was investigated and achieved by either blocking more reactive positions with substituents or activating less reactive positions by lithium-halogen exchange reactions. A series of Fischer bis-carbene chelates were synthesized by manipulating the above variables. Structural features of Fischer mono-carbene, mononuclear bis-carbene, and bis-carbene chelated complexes were studied by IR, NMR, and single-crystal X-ray diffraction.

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Benzothiophene – Wikipedia,
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Benzo[b]thiophenium S,C-Ylides: Preparation, structure and comparison with thiophenium analogues

A series of new S,C-ylides derived from benzo[b]thiophene and beta-dicarbonyldiazocompounds were prepared and characterised. NMR (1H,13C) studies revealed that ylides substituted additionally at position 2 of the thiophene ring can exist as pairs of diastereoisomers, not interchangeable at room temperature. The slow exchange between two sites was attributed to the restricted rotation about the ylidic S-C bond. The crystal structure determined for one ylide demonstrated different molecular environment for two parts of the beta-dicarbonyl ylidic substituent with respect to the benzothiophene ring. The prepared ylides were found to be much less reactive than the previously studied thiophenium S,C-ylides.

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Benzothiophene – Wikipedia,
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The Chemistry of Thieno[c]pyrrolones, Dihydrothieno[c]pyrrolones, and Their Fused Derivatives

The chemistry of the known thieno[c]pyrrolones and dihydrothieno[c]pyrrolones as well as ring-fused analogs is reviewed up to mid-2018 with 120 literature references. For each system, the properties, reactivity, synthesis, and applications are systematically covered.

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Photon-quantitative reaction of a dithiazolylarylene in solution

Ready for action: An excellent quantum yield was observed for a photocoloration reaction of a photochromic molecule based on a triangular terarylene structure. The molecule is brought into a conformation favorable for photocyclization by multiple intramolecular interactions, including CHi-N hydrogen bonding and Si-N and CHi-pi interactions (see picture).

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Benzothiophene – Wikipedia,
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The considerable photostability improvement of photochromic terarylene by sulfone group

Photochromic terarylene derivative 4 which has a sulfone group at the upper benzothiophene ring is readily synthesized using Suzuki coupling reaction. It exhibits good photochromic properties. Interestingly, the closed form of the compound 4 shows a good photostability as well as a thermal stability compared with its reduced analog 3, that provides a method to enhance the photostability of versatile photochromic terarylenes under UV.

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Benzothiophene – Wikipedia,
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