Mesogenic and optical properties of α,α′‐bis(4‐alkoxyphenylethynyl)oligothiophenes

Liquid crystalline α,α′‐bis(4‐alkoxyphenylethynyl)oligothiophenes (bi‐ and ter‐thiophene) have been synthesized and their mesogenic behaviour and optical properties investigated. They all exhibited a nematic mesophase, and compounds with long alkoxy chains also showed lamellar phases. Increasing the number of thiophene units increased both the transition temperatures and the mesophase ranges. As for their optical properties, incorporating more thiophene units results in red‐shifted absorption and emission spectra, slightly enhanced quantum efficiency, and a larger Stoke's shift. Most importantly, in terms of the absorption and emission maxima, the incorporation of one 4‐alkoxyphenylethynyl moiety was found to be equivalent to adding one thiophene ring.     

Dipole moments of phenyl,benzo, and benzo[b]thiopheno derivatives of thiophene; 1, 4-dithiin,and thianthrene and their sulfones

The dipole moments of a series of phenyl, benzo-, and benzo[b]thiopheno-derivatives of thiophene, 1,4-dithiin, and thianthrene have been determined. An increase in the dipole moments of the phenyl derivatives of thiophene with an increase in the number of phenyl groups is connected with the existence of conjugation between the thiophene and benzene rings, a quantitative evaluation of the nature of which is given. It is suggested that the structure of the 1, 4-dithiin ring is close to coplanar.     

The synthesis and reactions of 4-(2- and 3-thienyl)-tetrahydroisoquinolines

Tetrahydroisoquinoline derivatives substituted in the 4-position by either a 2- or 3-substituted thiophene ring have been synthesised. Simple electrophilic substitution reactions of these systems take place as expected in the α-position of the thiophene ring. Metalation reactions are more complex and take place at the benzylic 4-position of the tetrahydroisoquinoline nucleus in the case of the 2-substituted thiophene derivatives or at either the thiophene α-positions or the benzylic 4-position depending on the nature of the attacking electrophile in the case of the 3-substituted thiophene system.     

Conformational isomerism of electroactive calix[4]arenes: influence of the electronic state in the flexibility of thiophene-containing calix[4]arene

The cone-to-paco conformational isomerism of 11,23-bis(thiophen-5-yl)-26,28-dimethoxycalix[4]arene-25,27-diol, a calix[4]arene with thiophene substituents in para position with respect to the hydroxyl groups, has been investigated using ab initio and DFT quantum mechanical methods. This compound models a molecular device constituted by small oligomers of thiophene and calix[4]arene units, whose actuation mechanism is promoted by the conformational flexibility of the latter. To examine the influence of the electronic structure of this electroactive calix[4]arene, three different states have been considered: (i) neutral state; (ii) oxidized state, in which one electron is extracted from each thiophene ring; and (iii) oxidized-deprotonated state, in which the two hydroxyl groups of the oxidized compound are deprotonated. Results are discussed and compared with those obtained for the same molecule but without thiophene substituents, 25,27-dihydroxy-26,28-dimethoxycalix[4]arene. Although the influence of the thiophene substituents is negligible in the neutral state, they play a crucial role in the rotational isomerism of both the oxidized and deprotonated-oxidized states.     

Synthesis and Crystal Structure of 2,3-Diethoxycarbonyl-4-phenyl-5-morpholinyl Thiophene

1INTRoDUCTIONa-Thiocarbonylthioformamidesweresynthesizedin198o[l~2i,however,thereisnoreportofthesecompoundsconcerningtheirpropertiesandreactionactivitiest33.Accordingtotheirstructure,theyseemtohavereactionwithdienophi1es,likesubsti-tutedolefinicandacetylenicdienophilestoleadcorrespondingDiels-Alderproduct.xylene(15ml),diethylbutynedioicester(O.2g,1.2mmol)wasadded,themix-turewasrefluxedfor20h,thencooledtoroomtemperatureandconcentrated.Theresiduewaspurifiedbysilicagelcolumnusingacetone/petr…     

Tuning the Spectroscopic,Electrochemical, and Photovoltaic Properties of Triaryl Amine Based Sensitizers through Ring‐Fused Thiophene Bridges

The ring‐fused thiophene derivatives benzo[c]thiophene and its precursor bicyclo[2.2.2]octadiene (BCOD) have been introduced as π‐conjugated spacers for organic push–pull sensitizers with dihexyloxy‐substituted triphenylamine as donor and cyanoacrylic acid as acceptor ( OL1 , OL2 , OL3 , OL4 , OL5 , OL6 ). The effects of the fused ring on the spectroscopic and electrochemical properties of these sensitizers and their photovoltaic performance in dye‐sensitized solar cells have been evaluated. Introduction of a binary benzo[c]thiophene and ethylenedioxy thiophene as π bridge caused a significant red shift of the characteristic intramolecular charge‐transfer band to 642 nm. It is found that the sensitizer OL3 , which contains one benzo[c]thiophene unit as π linker, gives the highest overall conversion efficiency of 5.03 % among all these dyes.     

Synthesis of new 4-quinolone-type compounds in the benzo[b]thiophene series

Some new derivatives of 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid (quinolone-type compounds) 5 and 13 have been prepared in the benzo[b]thiophene series. The key step was the construction of the pyridine ring starting from 2-aminobenzo[b]thiophene derivatives. The synthesis of amine 9 , was performed by using an original “animation” reaction.     

4-Methylthionaphthenopyridines

4-Methylthionaphtheno[2, 3-b]pyridine and 4-methylthionaphtheno[3, 2-b]pyridine, new organic bases with a condensed thiophene ring, are synthesized. The physical constants of these new heterocyclic bases are quite close to those of the isosteric 4-methylnaphthoquinoline bases.     

Synthesis of 5, 7-dimethylthieno-, 3, 1-dimethylthionaphtheno-, and 6, 4-dimethylthienothienopyridines

New heterocyclic compounds with a condensed thiophene ring are synthesized.     

Synthesis of 5, 7-dimethylthieno-, 3, 1-dimethylthionaphtheno-, and 6, 4-dimethylthienothienopyridines

New heterocyclic compounds with a condensed thiophene ring are synthesized.     

Liquid crystalline compounds in the thiophene series. VIII. Synthesis and characterization of liquid crystalline vinylenes with thiophene moieties and carbaldehyde groups

New thermotropic liquid crystal compounds, with one and two mesogenic groups, have been synthesized and characterized. The structural elements of the compounds consist of thiophene ring systems, vinylene units and, for some compounds, carbaldehyde groups. Mesogenic groups involving three thiophene ring systems are normally not liquid crystalline. Only in the case of E,E-5-[5-(5-butyl-2-thienylvinyl)-2-thienylvinyl]-2-thiophenecarbaldehyde could a monotropic nematic phase be easily observed. By replacing thiophene ring systems in the core with a benzene ring system, or by attaching one carbaldehyde group at the moieties, or by doubling the mesogenic groups via an alkylene spacer, the temperature ranges of the mesophases of the compounds with thiophene ring systems can be enlarged or liquid crystal phases induced. The small values for δS_NI, which have been observed for the low molecular weight compounds, indicate a very low order in the nematic phases.     

The effect of the nature of the substituent on the structure of a 1,3,4-oxathiazol-2-one ring

A series of 5-aryl(thienyl) substituted 1,3,4-oxathiazol-2-ones has been synthesized. The molecular structures of 5-(4-nitrophenyl)-, 5-(5-ethylthieno[2,3-b]thiophen-2-yl)-, 5-(5-ethyl-2-ethylsulfanylthiophen-3-yl)-, and 5-(5-methylsulfonylthiophen-2-yl)-1,3,4-oxathiazol-2-ones have been investigated by X-ray analysis. The thiophene and oxathiazolone fragments are coplanar. The geometric parameters of the oxathiazolone ring are discussed. Electron acceptor substituents in the para position of the benzene ring and in the 5 position of the thiophene ring have the greatest effect on the system conjugation in the oxathiazolone ring.     

A plethora of carbene interconversions on the C(5)H(4)S energy surface: a computational study

The potential energy surface for the reaction of atomic carbon with thiophene has been studied computationally. Intermediates which are energetically viable include the 2- and 3-thienylcarbenes 8 and 11, thiacyclohexa-3,5-dien-2-ylidene, 10, and thiacyclohexa-2,3,5-triene, 6. In accord with experimental data, 6 and 8 are in equilibrium. The lowest-energy pathway for rearrangement of 6 to 8, which is endothermic by 14.5 kcal/mol, involves ring opening to Z-2-penten-4-ynthial which then recloses to carbene 8. A 1,4 addition of C across the diene system in thiophene generates an ylid which rearranges with little or no barrier to cyclopentadienethione, the global minimum on this potential energy surface.     

Novel thiophene-based cycloruthenated compounds: synthesis, characterization, and reactivity

The reactions between a series of thiophene-based imines with [(η(6)-C(6)H(6))RuCl(μ-Cl)](2), in a basic medium, and in MeCN give a family of ruthenacycles of stoichiometry [Ru(C^N)(NCMe)(4)]PF(6) (C^N = orthometalated thiopheneimine). In these species, the C-H activation process is produced in most cases at the thiophene ring. When two C-H bonds are competing (thiophene vs aryl), the cyclometalation can be driven regioselectively to the thiophene unit or to the aryl ring as a function of the location of the iminic C=N bond. Cyclometalation can also be oriented to positions 2 or 3 of the thiophene depending on the situation of the imine in the heterocycle (3 or 2, respectively). In all studied cases, the η(6)-C(6)H(6) ligand was substituted by acetonitrile. The X-ray structures of two representative complexes have been determined. These thiophene-based metallacycles react with iodine under very mild conditions affording, after hydrolysis, substituted 3-iodo-2-formyl(benzo)thiophenes or substituted 2-iodo-3-formyl(benzo)thiophenes, as a function of the organometallic precursor.     

Reaction of 2-methyl-3-ethoxycarbonyl-4-hydroxythiophene with hydrazines

2-Methyl-3-ethoxycarbonyl-4-(N,N-dimethylhydrazino)thiophene (II) and 2-methyl-3-ethoxy-carbonyl-4-(N-phenylhydrazino)thiophene (III) are formed by the action of substituted hydrazines — N,N-dimethylhydrazine and phenylhydrazine — on 2-methyl-3-ethoxycarbonyl-4-hydroxythiophene (I). At the same time, the thiophene ring of hydroxythiophene I undergoes hydrazinolysis under the influence of hydrazine hydrate to form 3-mercaptomethyl-4-ethoxycarbonyl-5-methylpyrazole (IV). Structure IV was proved by IR, UV, and PMR spectroscopy and by hydrogenolysis of IV to the known 3,5-dimethyl-4-ethoxycarbonylpyrazole (V).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 759–761, June, 1971.     

Studies in sulphur heterocycles. Part 7 . Tricyclic compounds related to 5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophene

Synthesis of a number of tricyclic compounds with a fused thiophene ring starting from 5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophen-4-one and benzosuberone is described. Biological testing of these compounds for their antiparasitic activities has been carried out.     

Mechanism of the aromatic hydroxylation of thiophene by acid-catalyzed peracid oxidation

The oxidation of thiophene (1) with peracids in a strongly acidic environment yielded thiophen-2-one (4) as the product of an apparent direct hydroxylation of the thiophene aromatic ring together with the anticipated thiophene-S-oxide dimers, 2a,b, as the main products. Formation of the latter dimers can be rationalized in a straightforward manner by initial oxidation at the sulfur atom of thiophene (1) to yield thiophene-S-oxide followed by subsequent dimerization in a Diels-Alder type reaction. Trapping experiments in the presence of a competing dienophile indicated that thiophen-2-one (4) did not originate from the monomeric thiophene-S-oxide but was the product of an independent reaction pathway. The extent of thiophen-2-one (4) formation correlated with the acidity of the reaction medium and was suppressed in the presence of water, the latter presumably acting as a competing base. As evidenced by the use of 2,5-dideuterated thiophene (1-D), its mechanism of formation involved a 1,2-hydride shift, a feature commonly described in the peracid-mediated epoxidation of aromatic hydrocarbons and indicative for the occurrence of cationic intermediates. In agreement with all these observations we propose a mechanism involving initial protonation of thiophene followed by nucleophilic attack of the peracid in position 2 of the thiophene ring. Intramolecular epoxidation may lead to the formation of thiophene 2,3-epoxide as a highly reactive intermediate that then undergoes heterolytic ring opening and a 1,2-hydride shift to yield thiophen-2-one (4) after a final, acid-catalyzed, isomerization of the double bond.     

NMR studies on 4‐thio‐5‐furan‐modified and 4‐thio‐5‐thiophene‐modified nucleosides

Systematic NMR characterization of 4‐thio‐5‐furan‐pyrimidine nucleosides or 4‐thio‐5‐thiophene‐pyrimidine nucleosides (ribonucleosides and 2′‐deoxynucleosides) was performed. All proton and carbon signals of 4‐thio‐5‐thiophene‐ribouridine and related analogues were unambiguously assigned. The orientations of the base (4‐thiouridine or its deoxy analogue) relative to the ring (furan or thiophene) are explored by a NMR approach and further supported by X‐ray crystallographic studies. The procedures presented here would be applicable to other modified nucleosides and nucleotides. Copyright © 2016 John Wiley & Sons, Ltd.     

A DFT Study of Thiophene Adsorption on the Rh（111） Surfaces

Thiophene adsorption on the Rh(111) surfaces has been investigated by density functional theory.The results show that the adsorption at the hollow and bridge sites is the most stable.The molecular plane of the thiophene ring is distorted,the C=C bond is stretched to 1.448  and the C-C bond is shortened to 1.390.The C-H bonds tilt 22～42oaway from the surface.The calculated adsorption geometries are in reasonable agreement with population analysis and density of states.The thiophene molecule obtains 0.74 electrons,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.The reaction paths and transition states for desulfurization of the molecule have been investigated.The bridge adsorption structure of thiophene leads to a thiol via an activated reaction with an energetic barrier of 0.30 eV.This second step is slightly difficult,and dissociation into a C4H4 fragment and a sulfur atom is possible,with an energetic barrier of 0.40 eV.