Photon‐Quantitative 6π‐Electrocyclization of a Diarylbenzo[b]thiophene in Polar Medium

The high reactivity of 6π‐electrocyclization in polar solvents has remained one of the important challenges for diarylethenes because of the emergence of a twisted intramolecular charge transfer (TICT) state at the excited state in such polar media, which usually quenches the photocyclization reaction. Herein we report on the preparation and highly efficient photocyclization of 2,3‐diarylbenzo[b]thiophenes with nonsymmetric side‐aryl units in a polar solvent. While the dithiazolylbenzo[b]thiophene showed a suppressed quantum yield of 6π‐electrocyclization of 54 % in methanol, the replacement of a thiazole unit with a thiophene ring led to a photon‐quantitative 6π‐cyclization reaction. The nonsymmetrical modification into the side‐aryl units was considered to enhance the CH/π interactions between side‐aryl units to support a photoreactive conformation in methanol. The stabilization of the photochromic reactive conformation is expected to suppress the formation of the TICT state at the excited state, leading to highly efficient photoreactivity.     

Electronic modulation of fused oligothiophenes by chemical oxidation

The reaction of pentathienoacene (f-5T) with mCPBA produced a series of oxidized derivatives containing one or two thiophene- S, S-dioxide rings. The regioselectivity of the oxidation reflects the aromaticity of each thiophene ring in the f-5T skeleton, and the extent of the oxidation significantly affects the fluorescence and redox properties.     

Solvent effect on photochromism of a dithienylperfluorocyclopentene having diethylamino group

Some photochromic diarylethenes having polar substituents were synthesized, and their photochromic behavior was examined. They exhibited photochromism with the similar photoreactivity in a non-polar solvent. However, the photocyclization quantum yield of dithienylperfluorocyclopentene having diethylamino group was found to decrease in polar solvents. The yield in acetonitrile was estimated to be 60 times smaller than that in hexane. The yields determined in various solvents were found to be correlated with the solvent polarity parameter E_T(30). Such an effect was not observed in dithienylfluorocyclopentenes bearing methoxy or acetoxy group and in non-fluorinated dithienylcyclopentene bearing diethylamino group.     

Photochromism of a diarylethene having an azulene ring

Diarylethene derivatives incorporating an azulene ring at the ethene moiety were synthesized. One derivative having thiazole rings showed the expected coloration reaction by excitation at 313 nm (to a higher singlet state) but not when excited at 635 nm (S(0) to S(1) excitation). The system demonstrates that the cyclization reaction can be controlled by selective excitation at different wavelengths of the absorption spectrum. On the other hand, another derivative having thiophene rings did not show any photochromism. The results clearly show the importance of the coplanarity of the system for the photoisomerization.     

Modular Synthesis of Phenanthro[9,10‐c]thiophenes by a Sequence of CH Activation,Suzuki Cross‐Coupling and Photocyclization Reactions

A total number of 15 different 3,4‐diarylthiophenes were synthesized, which bear a chlorine atom in ortho‐position of one of the aryl substituents. One aryl group was introduced by an oxidative cross‐coupling reaction, involving a C?H activation at C4(3) of the thiophene core. The other aryl group was in most cases introduced by a Suzuki cross‐coupling reaction, which succeeded the oxidative cross‐coupling step. Photocyclization reactions of the 3,4‐diarylthiophenes were performed in a solvent mixture of benzene and acetonitrile (50:50 v/v) at λ=254 nm and proceeded to the title compounds in yields of 60–82 %. The selectivity of the photocyclization was determined at the ortho‐chloro‐substituted aryl ring by the position of the chlorine substituent. At the other ring, a single regioisomer was observed for phenyl and para‐substituted phenyl groups. For 2‐naphthyl and ortho‐substituted phenyl rings a clear preference was observed in favor of a major regioisomer, while meta‐substitution in the phenyl ring led to a about 1:1 mixture of 5‐ and 7‐substituted phenanthro[9,10‐c]thiophenes. Mechanistically, the photocyclization is likely to occur as a photochemically allowed, conrotatory [(4n+2)π] process accompanied by elimination of HCl. It was shown for two phenanthro[9,10‐c]thiophene products that they can be readily brominated in positions C1 and C3 (74–77 %), which in turn allows for further functionalization at these positions, for example, in the course of halogen–metal exchange and polymerization reactions.     

Nucleophilic addition to benzo[b]thieno[2,3-b]benzo[b]thiophene S,S,S′,S′-tetroxide

The reaction of benzo[b]thieno[2,3-b]benzo[b]thiophene S,S,S′,S′-tetroxide with primary and secondary amines and with alcohols gave 10 b-amino- and 10 b-alkoxy-5a, 10b-dihydro-benzo[b]thieno[2,3-b]benzo[b]thiophene S,S,S′,S′-tetroxides. These nucleophilic reagents do not add to benzo[b]thieno[2,3-b]benzo[b]thiophene S,S-dioxide.     

Invisible photochromism of diarylethene derivatives

Diarylethene derivatives with oxidized thiophene rings shift their absorption band to a shorter wavelength in the UV region upon photocyclization; no color change was observed during the photochromic reaction, and the invisible photochromism is advantageous for devices used under room light.     

Studies on the structure behavior of triphenyldichlorophosphorane in different solvents

Triphenyldichlorophosporane, which was prepared according to Appel reaction, was an efficient reagent for alkyl halide synthesis by virtue of having two replaceable groups on "pentavalent" phosphorus. The reaction of triphenylphosphine with hexachloroethane was investigated in different solvents and 31P NMR traced the processes of these reactions. As results, it was found that there was similar high coordinated phosphorus species formed in aromatic solvents and in ring ether type solvents, which had large 1J(P-C) (about 140 Hz) according to 13C NMR experiments. It is indicated that, for some solvent such as benzene or dioxane, solvent molecules might be locked in the high coordinated phosphorus compounds, which in turn would affect the triphenyl groups situated at the equatorial position.     

Regioselective Photocyclizations of Di(quinolinyl)arylamines and Tri(quinolinyl)amine with Emission Color Changes and Photoreaction‐Induced Self‐Assemblies

Bis[2,4‐di(trifluoromethyl)quinoline‐7‐yl]amine ( 1 ), bis[2,4‐di(trifluoromethyl)quinoline‐7‐yl]methylamine ( 2 ), bis[2,4‐di(trifluoromethyl)quinoline‐7‐yl]phenylamine derivatives, Q₂NPhX; X=NO₂ ( 3 a ), I ( 3 b ), H ( 3 c ), OMe ( 3 d ), and NH₂ ( 3 e ), tris[2,4‐di(trifluoromethyl)quinoline‐7‐yl]amine ( 4 ), and bis[2,4‐di(pentafluoroethyl)quinoline‐7‐yl]‐4‐nitrophenylamine ( 5 ) were prepared as functional fluorophores. On irradiating the solution samples, 1 showed no noticeable alteration, whereas 2 , 3 a – d , and 4 showed emission color changes from yellowish green to blue, indicating that a photoreaction took place. Analyses of the photoproduct based on absorption and emission spectra, ¹H NMR spectra, and X‐ray crystallography indicated that photocyclization reactions occurred regioselectively and quantitatively to form bent–bent dipyridocarbazoles. In 3 a – d , the reaction rates depended on the solvent polarity and the substituent on the benzene ring. The photoreactions were accelerated with decreasing solvent polarity and with increasing electron‐withdrawing character of the substituents. The photocyclization of triquinolineamine 4 was faster than that of 3 a in all solvents. The results of semiempirical quantum‐chemical PM6 calculations suggested that the observed regioselective photocyclization could be explained by stabilization of the excited triplet transition state for the bent–bent form because of the molecular geometry with the CH?NQ hydrogen bonds. The solution of 5 in MeOH displayed photoreaction‐induced self‐assembly behavior to form twisted tape‐like fibers of width 200 nm, as determined by TEM imaging.     

Spectroscopic investigation of 3-pyrazolyl 2-pyrazoline derivative in homogeneous solvents

How solvent conditions such as solvent polarity and hydrogen-bonding affect the fluorescence of a newly synthesized 3-pyrazolyl 2-pyrazoline derivative (Pyz) having pharmaceutical activity has been explored. The solvatochromic effect of Pyz is due to a change in dipole moment of the compound in the excited state. The relaxation of S1 state is perturbed in hydrogen-bonding solvents. The fluorescence properties of the systems are strongly dependent on the polarity of the media. The non-radiative relaxation process is facilitated by an increase in the polarity of the media. The photophysical response of Pyz in different solvents has been explained considering solute-solvent interactions.     

Activity of catalysts in thiophene synthesis from furan and hydrogen sulfide

Thiophene synthesis from furan and H₂S over acid catalysts is reported. Proton donor catalysts are low-active, nonselective, and prone to deactivation. Alumina-supported catalysts having Lewis acid sites, such as alumina-supported catalysts, are more efficient. With these catalysts, the thiophene formation rate per Lewis acid site increases with increasing site strength. It is assumed that the reaction proceeds via the formation of a surface intermediate consisting of an acid site bonded to an α carbon atom of the furan ring and an H₂S molecule nondissociatively adsorbed on a basic site. At atmospheric pressure, T = 250–450°C, initial furan concentrations of 1–20 vol %, and H₂S/furan = 0.4–20 (mol/mol), the thiophene formation reaction is first-order with respect to both reactants and its rate constant increases with increasing temperature. The thiophene formation rate depends on the H₂S/furan molar ratio. Under optimal conditions, the thiophene yield is 95–98 mol % and the thiophene formation rate is high.     

Photochromic properties of diarylethene derivatives having chryso[b]thiophene rings

Diarylethene derivatives having one or two chryso[b]thiophene ring(s) have been synthesized. In solution the derivatives underwent photochromism and the derivative with one chryso[b]thiophene ring exhibited photochromism even in the single crystalline phase. The color of the UV irradiated single crystal changed from blue to green by rotation the sample under polarized light.     

The synthesis of 8-oxoberbines containing a heterocyclic D-ring by enamide photocyclizations

The photocyclization of 2-heteroyl-1-methyleneyl-3,4-dihydro-6,7-dimethoxyisoquinolines, where heteroyl = benzofuran, benzo[b]thiophene, coumarin and nicotinoyl, leads to the corresponding 8-oxoberbines containing a heterocyclic D-ring. Dehydrogenation can accompany photocyclization depending on the reaction conditions employed, or alternatively DDQ can be used to effect this dehydrogenation.     

Hexitol derivatives containing a 1,4-oxathiane ring—III : Rearrangement of a sulfone on treatment with LAH

Treatment of 2,5 - anhydro - 3,4 - di -O- mesyl - 1,6 - thioanhydro - D - glucitol S,S-dioxide (1) with LAH afforded (1S,6R)-2-thiabicyclo[4.1.0]heptane S,S-dioxide (2) and its (4R) - 4 -hydroxy derivative 3 in a ratio of 46:6. Sodium - dihydro - bis(2 - methoxy - ethoxy) - aluminate afforded the same compounds in a ratio of 15:22. The corresponding sulfide 5 underwent no rearrangement under similar conditions. The structure of the products was established by IR, PMR, CMR and MS. A probable reaction mechanism is discussed.     

Intramolecular charge transfer assisted by conformational changes in the excited state of fluorene-dibenzothiophene-S,S-dioxide co-oligomers

The strong solvatochromism observed for two fluorene-dibenzothiophene-S,S-dioxide oligomers in polar solvents has been investigated using steady-state and time-resolved fluorescence techniques. A low-energy absorption band, attributed to a charge-transfer (CT) state, is identified by its red shift with increasing solvent polarity. In nonpolar solvents, the emission of these conjugated luminescent oligomers shows narrow and well-resolved features, suggesting that the emission comes from a local excited state (LE), by analogy to their conjugated fluorene-based polymer counterparts. However, in polar solvents, only a featureless broad emission is observed at longer wavelengths (CT emission). A linear correlation between the energy maximum of the fluorescence emission and the solvent orientation polarizability factor Deltaf (Lippert-Mataga equation) is observed through a large range of solvents. In ethanol, below 230 K, the emission spectra of both oligomers show dual fluorescence (LE-like and CT) with the observation of a red-edge excitation effect. The stabilization of the CT emissive state by solvent polarity is accompanied/followed by structural changes to adapt the molecular structure to the new electronic density distribution. In ethanol, above 220 K, the solvent reorganization occurs on a faster time scale (less than 10 ps at 290 K), and the structural relaxation of the molecule (CT(unrelaxed) --> CT(Relaxed)) can be followed independently. The magnitude of the forward rate constant, k(1)(20 degrees C) approximately 20 x 10(9) s(-1), and the reaction energy barrier, E(a) approximately 3.9 kcal mol(-1), close to the energy barrier for viscous flow in ethanol (3.54 kcal mol(-1)), show that large-amplitude molecular motions are present in the stabilization of the CT state.     

[4+2]-Cycloaddition of sterically hindered thiophene S-oxides to alkenes and SO extrusion reactions of the cycloadducts

Cycloaddition reactions of 2,5-di-tert-butylthiophene S-oxide and 2,3,4,5-tetrakis(p-tolyl)thiophene S-oxide with alkenes are described. The reactivity of 2,5-di-tert-butylthiophene S-oxide as diene in Diels–Alder reactions is compared with 2,5-di-tert-butylthiophene S,S-dioxide. The thermal and photochemical SO extrusion reactions of the cycloadducts under formation of highly substitutedaromatic compounds are exemplified.     

Concise Access to the Skeleton of Protoilludane Sesquiterpenes through a Photochemical Reaction Cascade: Total Synthesis of Atlanticone C

In a single photochemical operation (λ≥350 nm) an easily accessible indanone derivative was converted into a structurally complex precursor of the protoilludane sesquiterpenes. The product (60 % yield) contains all 15 carbon atoms of the skeleton in the required connectivity and was transformed into the natural product atlanticone C (9 steps, 6 % overall yield). In addition, it was shown that other protoilludanes, such as Δ⁶‐protoilludene and paesslerin A, can be prepared in a concise fashion via the photochemical key intermediate. The photochemical reaction cascade comprises an ortho photocycloaddition, a thermal disrotatory ring opening and a regioselective disrotatory [4π] photocyclization.     

Synthesis of thiophene/phenylene co‐oligomers. IV. 6‐ to 8‐ring molecules

We report the synthesis of various thiophene/phenylene co‐oligomers with a total number of thiophene and benzene (phenylene) rings of 6 to 8. These compounds include a phenyl‐capped sexithiophene, a thienyl‐capped quaterphenylene, as well as block and alternating co‐oligomers. The synthesis is based on either the Suzuki coupling reaction or the direct dimerization coupling. The latter method produces symmetric molecules with an even total ring number. These reaction schemes enabled us to obtain the target compounds in high quality. Although the resulting materials are difficult to dissolve in organic solvents and therefore difficult to identify by usual ¹H nmr spectroscopy, they have successfully been identified through Fourier‐transform ir spectroscopy. The specific group frequencies of ring‐stretching and out‐of‐plane deformation modes are characteristic of the substitution pattern of the individual thiophene and benzene rings.     

Poly (3-substituted) thiophenes electroactive in water

Three thiophene rings bearing n-ethoxy arylsulfonamide pendant groups were synthesized and their electropolymerization was performed at a platinum electrode. The electrochemical behaviour of the polythiophene matrix was studied both in organic and in aqueous solvent. If all polymers present a reversible n- and p-doping process in organic solvents, only one of them particularly possess a reversible p-doping in aqueous media. This phenomenon was shown to be directly related to the nature of the spacer between the thiophene ring and the aryl sulfonamide unit.     

Photoinduced intramolecular charge transfer of sodium 4-(N,N-dimethylamino) benzenesulfonate

A new dual fluorescent N,N-dimethylaniline derivative, sodium 4-(N,N-dimethylamino)-benzenesulfonate (SDMAS), is reported. In SDMAS, the electron acceptor is linked to the phenyl ring via a sulfur atom at the para-position of the electron donor. It was found that SDMAS emits dual fluorescence only in highly polar solvent water but not in organic solvents such as formamide, methanol and acetonitrile. In organic solvents only a single-band emission at ca.360 nm was observed in the short wavelength region. The dual fluorescence of SDMAS in water was found at 365 and 475 nm, respectively. Introduction of organic solvent such as ethanol, acetonitrile, and 1,4-dioxane into aqueous solution of SDMAS leads to blue-shift and quenching of the long-wavelength emission. Measurements of steady-state and picosecond time-resolved fluorescence indicate that the long wavelength fluorescence is emitted from a charge transfer (CT) state that is populated from the locally excited (LE) state, with the latter giving off the