The synthesis and characterization of a mesomorphic brush type polycarbosilane: poly[1,1-bis(4′-biphenyl)silabutane]

Summary Poly[1,1-bis(4-biphenyl)silabutane] (II) has been prepared by the anionic ring opening polymerization of 1,1-bis(4-biphenyl)silacyclobutane. II shows mesomorphic behavior by DSC. The¹³C NMR T₁ relaxation times have been measured. These are found to be smaller than those of poly(1,1-dimethylsilabutane)by an order of magnitude. This may result from interaction of the highly rigid biphenyl side chain moieties. The thermal stability of II is higher than that for other 1,1-disubstituted polysilabutanes.     

Synthesis of poly(acrylonitrile‐co‐divinylbenzene‐co‐vinylbenzyl chloride)‐derived hypercrosslinked polymer microspheres and a preliminary evaluation of their potential for the solid‐phase capture of pharmaceuticals

Poly[acrylonitrile (AN)‐co‐divinylbenzene (DVB)‐co‐vinylbenzyl chloride (VBC)] terpolymers were synthesized by precipitation polymerization in the form of porous polymer microspheres. The poly(AN‐co‐DVB‐co‐VBC) polymers were then hypercrosslinked, via a Friedel‐Crafts reaction with FeCl₃ in nitrobenzene, to provide a significant uplift in the specific surface areas of the polymers. FTIR spectra of the hypercrosslinked poly(AN‐co‐DVB‐co‐VBC)s showed that the chloromethyl groups derived from VBC were consumed by the Friedel‐Crafts reactions, which was consistent with successful hypercrosslinking. Hypercrosslinking installed a number of new, small pores into the polymers, as evidenced by a dramatic increase in the specific surface areas upon hypercrosslinking (from ～530 to 1080 m² g^?1). The hypercrosslinked polymers are very interesting for a range of applications, not least of all for solid‐phase extraction (SPE) work, where the convenient physical form of the polymers (beaded format), their low mean particle diameters, and narrow particle size distributions, as well as their high specific surface areas and polar character (arising from the AN residues), make them attractive candidates as SPE sorbents. In this regard, in a preliminary study one of the hypercrosslinked polymers was utilized as an SPE sorbent for the capture of the polar pharmaceutical diclofenac from a polar environment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45677.     

Two Organic Phase Suspension Polymerization for Novel Hypercrosslinked Resin Bead by Polycondensation of CMB

The suspension polymerization with two organic phases was adopted to prepare spherical hyper- crosslinked resin by self-polycondensation of 4,4＇-bis-（chloromethyl）- 1, 1＇-biphenyl （CMB）. The chemical structure,morphology and pore characteristics of the novel spherical resin were characterized with Fourier transform infrared spectroscopy （FTIR）, micrograph and Brunauer-Emmett-Teller （BET）. It is found that the suspension system and stirring speed impose a great influence upon the regularity and size distribution of hypercrosslinked beads. To prepare CMB resin beads with diameter of about 300 μm, the optimal condition is as follows： stirring speed 300 r·min^-1, and the volume ratio of the two organic phases （nitrobenzene/dimethyl silicon oil） 1 ： 5. After the self-polycondensation and sqccedent post-crosslinking of CMB monomer, the spherical adsorbent presents high spec~al surface area （1190 m^2· g^-1） and abundant pore~volume （0.714 cm^3· g^-1）, and could be potentially applied qn the adsorption of various organic molecules and synthesis of porous ion exchanger.     

Synthesis and properties of novel poly(aryl ether ketone)s containing imide linkages in the main chains

A new monomer containing imide linkages, bis[4-(p-phenoxybenzoyl)-1,2-benzenedioyl]-N,N,N′,N′-4,4′-diaminodiphenyl ether (BPBDADPE), was prepared by the Friedel–Crafts reaction of bis(4-chloroformyl-1,2-benzenedioyl)-N,N,N′,N′-4,4′-diaminodiphenyl ether (BCBDADPE) with diphenyl ether (DPE). Novel poly(aryl ether ketone)s containing imide linkages in the main chains (PEK-I) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of terephthaloyl chloride (TPC) with a mixture of DPE and BPBDADPE. The polymers were characterized by different physico-chemical techniques. The polymers with 10–40 mol% BPBDADPE are semicrystalline and had increased T _gs over commercially available poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK) (70/30) due to the incorporation of imide linkages in the main chains. The polymers IV and V with 30–40 mol% BPBDADPE had not only high T _gs of 182–183 °C, but also moderate T _ms of 341–343 °C, having good potential for melt processing and exhibited high thermal stability and good resistance to common organic solvents.     

Heterogeneous membranes based on a composite of a hypercrosslinked microparticle adsorbent and polyimide binder

This paper deals with the preparation and characterization of heterogeneous membranes based on microparticle hypercrosslinked polymeric adsorbents with a polyimide binder. The polyimide based membrane extension is hindered by their low permeability. We enhanced the permeability of polyimide membranes by changed chemical structure and by adding of the new type fillers. Hypercrosslinked polystyrene microparticles of diameter 1–5 μm were prepared by SnCl₄-catalyzed Friedel–Crafts reaction of polystyrene with chloromethyl methyl ether in 1,2-dichlorethane solution. The precursor polyamic acid (PAA) was synthesized by the reaction of equimolar amounts of 4,4′-oxy(bis(phthalic anhydride)) (ODPA) and bis(4,4′-oxydianiline) (ODA) or 4,4′-[(1,4-phenylene)dipropane-2,2-diyl]dianiline (BIS P) in N-methylpyrrolidone (content 10 wt.%). A PAA solution in N-methylpyrrolidone with the adsorbent was spread onto a glass substrate and kept at 60–240 °C for 12 h. Heterogeneous membranes were characterized by thermal, mechanical and separation measurements. The permeability for membrane ODPA–BIS P filled with 10 wt.% of hypercrosslinked adsorbent was 3.5 × 10⁻¹¹ cm³(STP) cm cm⁻² s⁻¹ cmHg⁻¹ for nitrogen and 4 × 10⁻⁹ cm³(STP) cm cm⁻² s⁻¹ cmHg⁻¹ for hydrogen. The permeability of homogeneous polyimide membranes is up to one order of magnitude lower. The diffusion coefficient of heterogeneous membranes increased in the order CH₄ < N₂ < O₂ < CO₂ < H₂. The selectivity of hydrogen–nitrogen separation with the amount of adsorbent decreased from 164 to 69. The prepared membranes are intended for separation of gases and low organic molecules even at enhanced temperature. The present paper aims at giving information on the influence of hypercrosslinked adsorbents and polyimide binding materials on the gas separation properties of membranes.     

Ionic Liquids as Exceedingly Convenient Solvents for the Friedel–Crafts Monoalkylation of Electron-Rich Arenes with Paraformaldehyde Using HCl as Catalyst

Friedel–Crafts hydroxyalkylation of 2-methoxynaphthalene, anisole and 2-methylfuran with paraformaldehyde has been carried out in N-ethyl-N-methylimidazolium chloride (1⁺Cl^-) or N-butyl-N-methylimidazolium hexafluorophosphate (2⁺PF^- ₆) or ethanol using concentrated aqueous HCl as catalyst. The results have shown an extraordinary activity and selectivity towards the formation of the corresponding hydroxymethyl derivative using 2⁺PF^- ₆ as solvent. This sharply contrasts with the case of the ethanol as solvent wherein the reaction is much slower and diarylation products are largely formed.     

Polybinaphthyls incorporating chiral 2,2′-binaphthyl and isoquinoline moieties by Sonogashira reaction

Polymers P-1, P-2, P-3, P-4 and P-5 were synthesized by the polymerization of 5,8-bis(ethynyl)isoquinoline (M-1) with (R)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((R)-M-2), (S)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((S)-M-2), (R)-6,6′-dibromo-2,2′-bisbutoxy-1,1′-binaphthyl ((R)-M-3), (S)-6,6′-dibromo-2,2′-bisbutoxy-1,1′-binaphthyl ((S)-M-3), and rac-6,6′-dibromo-2,2′-bisbutoxy-1,1′-binaphthyl (M-4) under Sonogashira reaction, respectively. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and circular dichroism (CD) spectroscopy. CD spectra of polymers P-1 and P-2, P-3 and P-4 are almost identical except that they gave opposite signals at each wavelength. The long wavelength CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure in the repeating unit and the helical backbone in the polymer chain. All five polymers have strong blue-green fluorescence due to the efficient energy migration from the extended π-electronic structure of the repeating unit of the polymers to the chiral binaphthyl core and are expected to provide understanding of structure-property relationships of the chiral conjugated polymers.     

Water resistant sulfonated polyimides based on 4,4′-binaphthyl-1,1′,8,8′-tetracarboxylic dianhydride (BNTDA) for proton exchange membranes

A series of sulfonated polyimides (SPIs) were synthesized in m-cresol from 4,4′-binaphthyl-1,1′,8,8′-tetracarboxylic dianhydride (BNTDA), 4,4′-diaminodiphenylether-2,2-disulfonicacid (ODADS), and 4,4′-diamino-diphenyl ether (ODA) in the presence of triethylamine and benzoic acid. The resulted polyimides showed much better water resistance than the corresponding sulfonated polyimides from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and ODADS, which is contributed to the higher electron density in the carbonyl carbon atoms of BNTDA. Copolyimides S-75 and S-50 maintained their mechanical properties and proton conductivities after aging in water at 100 °C for 800 h. The proton conductivity of these SPIs was 0.0250-0.3565 S/cm at 20 °C and 100% relative humidity (RH), and increased to 0.1149-0.9470 S/cm at 80 °C and 100% RH. The methanol permeability values of these SPIs were in the range of 0.99-2.36 × 10⁻⁷ cm²/s, which are much lower than that of Nafion 117 (2 × 10⁻⁶ cm²/s).     

Ortho alkyl substituents effect on solubility and thermal properties of fluorenyl cardo polyimides

Five fluorenyl cardo diamines containing different alkyl substituents were synthesized and characterized. A series of fluorenyl cardo polyimides were prepared by polycondensation of these cardo diamines with 4,4′-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3′,4,4′-biphenyl tetracarboylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA). Most of fluorenyl cardo polyimides exhibited excellent solubility in common organic solvents such as m-cresol, chloroform, tetrahydrofuran (THF), N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAC) etc. and intrinsic viscosity in N,N-dimethylacetamide (DMAC) ranged from 0.31 to 0.92 dl/g. T_g of polyimides based on ODPA decrease with the number and size of alkyl substituents on fluorenyl cardo diamine. The results show that the incorporation of noncoplanar structure led by the introducing alkyl substituents on fluorenyl cardo diamines improves the solubility of cardo polyimides in organic solvents without sacrificing thermal properties.     

Hypercrosslinked microporous organic polymer networks derived from silole-containing building blocks

Three silole-containing hypercrosslinked microporous organic polymer networks were designed and synthesized via Friedel–Crafts alkylation promoted by anhydrous FeCl₃. The results demonstrated that the substitution of methyl group connected with silicon atom by benzene has negligible effect on the surface area and gas uptake ability of the polymer networks. The network-1 produced from 1,1-dimethyl-2,3,4,5-tetraphenylsilole shows a surface area up to 1236 m² g⁻¹ with the hydrogen uptake ability of 1.33 wt% (77.3 K/1.13 bar) and a carbon dioxide capture capacity of 2.94 mmol g⁻¹ at 273 K/1.13 bar. The isosteric heats of carbon dioxide sorption for all of the polymer networks exceed 25 kJ/mol at the zero coverage because the introduction of silicon atom into the polymer skeleton enhanced the binding affinity between the adsorbent and CO₂ molecules. In addition, the selectivity of the polymer networks for CO₂/N₂ and CO₂/CH₄ were found to be around 35 and 6 at 273 K, respectively. These results show that these materials are potential candidates for applications in post-combustion CO₂ capture and separation.     

Synthesis and characterizations of a polyimide containing a triphenylamine derivative as an interlayer in polymer light-emitting diode

Polyimide containing triphenylamine derivative (TPD-PI) was synthesized to prepare a polymer interlayer having insolubility in common nonpolar solvent for light-emitting polymers. N,N′-diphenyl-N,N′-bis(4-aminophenyl)-1,1-biphenyl-4,4′-diamine, as a new triphenylamine-containing diamine monomer, was synthesized by the palladium-catalyzed amination reaction between 4-nitrodiphenylamine and 4,4′-dibromobiphenyl and subsequent reduction of the nitro-intermediate. The TPD-PI was prepared from the synthesized diamine monomer and 4,4′-(hexafluoropropylidene)-diphthalic anhydride by the standard two-step polymerization method, which involved ring-opening polymerization and subsequent cyclodehydration. The structures and properties of the monomer and the resulting polyimide were characterized with ¹H and ¹³C NMR, elemental analysis, gel permeation chromatography, UV-visible spectroscopy, etc. The TPD-PI is readily soluble in aprotic polar solvents such as N-methyl-2-pyrrolidinone and N,N-dimethylformamide and insoluble in nonpolar solvents such as toluene and xylene. The highest occupied molecular orbital (HOMO) level of the TPD-PI was measured to be 5.5 eV by a photoelectron spectrometer in air, and the band gap was calculated as 3.1 eV from the onset of UV-vis spectrum. The polymer light-emitting diode with the thin TPD-PI layer between a hole injection layer and an emitting polymer layer was fabricated to examine the performance of the polyimide as an polymer interlayer. Although the luminous efficiency of the device is lowered by the introduction of the TPD-PI interlayer, the lifetime of the device is improved.     

Poly(arylene ether)s with trifluoromethyl groups via meta-activated nitro displacement reaction

New poly(arylene ether)s with pendent trifluoromethyl groups were synthesized from 2,2′-bis(trifluoromethyl)-4,4′-dinitro-1,1′-biphenyl with several bisphenols. The nitro leaving group activated by the trifluoromethyl group at meta position was quantitatively displaced with phenolate ions, resulting in high molecular weight polymers. The quantum mechanical calculation of the energy state suggested that the nitro displacement reaction activated by the trifluoromethyl group at meta position is an energetically favorable process. The polymers having weight average molecular weight of 42,100-95,000 g/mol and molecular weight distribution of 2.65-2.95 were obtained. The polymers were amorphous and dissolved in a wide range of organic solvents. Transparent and flexible films were obtained by solution casting. The resulting polymers are thermally stable, and T_gs of the polymers are in the range of 176-199 °C depending on their molecular structure. All of the synthesized polymers show refractive indices in the range of 1.592-1.624 with low birefringence below 0.006.     

Synthesis and properties of amphotropic hydrogen bonded liquid crystalline (LC) poly(ester amide)s (PEA): effect of aromatic moieties on LC behavior

Twelve hydrogen bonded aromatic-aliphatic poly(ester amide)s differing in the structures of their aromatic moieties (isophthalic, terephthalic, 2,6-naphthyl and 4,4′-biphenyl moieties of the dicarboxylic acid and phenylene and xylylene moieties of the amido diol part) were prepared by the polycondensation of amido diols with acid chlorides of isophthalic acid, terephthalic acid, 2,6-naphthalic dicarboxylic acid and 4,4′-biphenyl dicarboxylic acid, respectively. The amido diols were prepared by the aminolysis of γ-butyrolactone with hexamethylene diamine, para phenylene diamine and para xylylenene diamine, respectively. The PEAs were characterised for elemental analysis, FTIR, ¹³C NMR, TGA, DSC, POM, isothermal viscosity measurements and WAXD. Here we are presenting the effect of aromatic moieties on the thermotropic and lyotropic (amphotropic) properties of PEAs. These PEAs are essentially constituted of six types of structural entities, i.e. isophthalic, terephthalic, 2,6-naphthalic and 4,4′-biphenyl moieties containing dicarboxylic acid and the aliphatic, aromatic (phenylene and xylylene moieties) of the di-amide linkage of the amido diol part. The structure of the polymers even in the mesophase is dominated by hydrogen bond interaction between the adjacent chains and also inter plane mesogenic interaction between the rigid aromatic group. It was observed morphologically that the formation of different forms of nematic/smectic/columnar/spherullitic phases in PEAs are due to the delicate balance of self assembling through hetero intermolecular hydrogen bonded amide-amide and amide-ester net works and also inter-plane mesogenic interactions.     

Cyclic hyperbranched polyesters derived from 4,4-bis(4′-hydroxyphenyl)valeric acid

Three monomers were prepared from 4,4-bis(4′-hydroxyphenyl)valeric acid (BHVA) namely its methylester (BHVAM), its bis-acetylated methylester (BAVAM) and its 4,4-bis(4′-acetoxyphenyl)valeric acid (BAVA). All three monomers were polycondensed in bulk at various temperature profiles using Ti(OBu)₄, Co(OAc)₂, Mn(OAc)₂, Sn(OAc)₂ or Bu₂Sn(OAc)₂ as transesterification catalysts. The structure of the resulting ‘hyperbranched’ polyesters were characterized by ¹H NMR spectroscopy, MALDI-TOF mass spectroscopy and in selected cases by SEC. Regardless of the reaction conditions only low oligomers almost free of cycles were obtained from the methylesters BHVAM and BAVAM. Higher molecular weights and high contents of cycles were obtained from polycondensations of BAVA. The content of cycles increased with the conversion. Hyperbranched polyesters with cyclic core were detected up to masses around 10,000 Da. The reactivities of the three hyperbranched monomers were compared with those of bisphenol-A plus dimethyl sebacate or acetylated bisphenol-A plus sebacic acid in ‘linear polycondensations’ and close analogies were found.     

The preparation of α‐bis and α,ω‐tetrakis aromatic oxazolyl‐ and carboxyl‐functionalized polymers using 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

The preparation of new compounds, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethanol and a new symmetrically disubstituted 1,1‐diphenylethylene derivative, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene, is described. 1,1‐Bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene was utilized as a dioxazolyl initiator precursor for the polymerization of styrene by atom transfer radical polymerization (ATRP) methods to produce α‐bis(oxazolyl) polystyrene. The kinetic study of the polymerization process indicated that the free radical polymerization reaction for the preparation of α‐bis(oxazolyl) polystyrene follows first‐order rate kinetics with respect to monomer consumption. α,ω‐Tetrakis(oxazolyl) polystyrene was prepared by a new, in situ, controlled/living, post‐ATRP chain‐end‐functionalization reaction which involves the direct addition of 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene to the ω‐terminus of the α‐bis(oxazolyl) polystyrene derivative, without the isolation and purification of the polymeric precursor. α‐Bis(carboxyl) and α,ω‐tetrakis(carboxyl) polystyrene derivatives were obtained by the quantitative chemical transformation of the oxazoline groups of the respective aromatic oxazolyl chain‐end‐functionalized polystyrene derivatives to the aromatic carboxyl groups. The organic precursor compounds, the dioxazolyl‐functionalized 1,1‐diphenylethylene derivative and the functionalized polymers were characterized using ¹H NMR and ¹³C NMR spectrometry and Fourier transform infrared spectroscopy, size‐exclusion and thin‐layer chromatography and non‐aqueous titration measurements. © 2014 Society of Chemical Industry     

Synthesis and memory characteristics of polyimides containing noncoplanar aryl pendant groups

A series of soluble aromatic polyimides were prepared from 2,2′-diphenyl-4,4′-biphenyl diamine (DPBD), 2,2′-bis(biphenyl)-4,4′-biphenyl diamine (BBPBD), 2,2′-bis[4-(naphthalen-1-yl)phenyl]-4,4′-biphenyl diamine (BNPBD) and 2,2′-bis(3,5-dimethoxyphenyl)-4,4′-biphenyl diamine (BMPBD) by polycondensation with 2,2′-bis[4′-(3′′,4′′,5′′-trifluorophenyl)phenyl]-4,4′,5,5′-biphenyl tetracarboxylic dianhydride via a two-step procedure. The resulting polymers were fully characterized and they exhibited excellent organosolubility, high thermal and dimensional stability. Resistive switching devices with the configuration of Al/polymer/ITO were constructed from these polyimides by using conventional solution coating process. Devices with the active layer based on DPBD, BBPBD and BNPBD exhibited nonvolatile and rewritable flash type memory characteristics with the turn-on voltage at ?2.0 to ?3.0 V and the turn-off voltage at 2.0–3.0 V. Whereas, device based on BMPBD demonstrated a bipolar write-once read-many times (WORM) memory capability with the writing voltage around ±3.0 V. The ON/OFF current ratio of these devices was of about 10⁶ and the retention times can be as long as 10⁴ s.     

Synthesis of 1,9-bis[glycidyloxypropyl]penta(1′H,1′H,2′H,2′H-perfluoroalkylmethylsiloxane)s and copolymerization with piperazine

A series of 1,9-bis[glycidyloxypropyl]pentasiloxanes (IV-VI) were prepared by the platinum catalyzed hydrosilylation of 1,9-dihydridodecamethylpentasiloxane (I), 1,9-dihydrido-3,5,7-tris(3′,3′,3′-trifluoropropyl)heptamethylpentasiloxane (II), and 1,9-dihydrido-3,5,7-tris(1′H,1′H,2′H,2′H-perfluorooctyl)heptamethylpentasiloxane (III) with allyl glycidyl ether. Subsequently, IV-VI were copolymerized with piperazine to form high molecular weight copoly(carbosiloxane)s (VII-IX). The structures of the 1,9-bis[glycidyloxypropyl]penta-siloxanes (IV-VI) and copoly(carbosiloxane)s (VII-IX) were determined by ¹H, ¹³C, ²⁹Si, and ¹⁹F NMR as well as IR spectroscopy. The molecular weight distributions (M_w/M_n) of VII-IX have been characterized by gel permeation chromatography and their thermal properties measured by differential scanning calorimetry and thermal gravimetric analysis.     

Viscometric behavior of disulfonated poly(arylene ether sulfone) random copolymers used as proton exchange membranes

tert-Butylphenyl-terminated disulfonated poly(arylene ether sulfone) random copolymers with a sulfonation degree of 35 mol% (BPS35) and controlled molecular weights (M_n), 20-50 kg mol⁻¹, were successfully prepared by direct copolymerization of the two activated halides, 4,4′-dichlorodiphenyl sulfone (DCDPS) and 3,3′-disulfonate-4,4′-dichlorodiphenyl sulfone (SDCDPS) with 4,4′-biphenol and the endcapper, 4-tert-butylphenol. Dilute viscosity measurements of the BPS35 random copolymers were successfully conducted in NMP containing various concentrations of LiBr from 0.01 to 0.2 M and mostly at 0.05 M according to the measured theory. The effects of salt concentration and molecular weights of the copolymers on the viscometric behavior were studied and compared with published data for sulfonated polystyrene. The charge density parameter (ξ) for the BPS35 copolymers was determined to be smaller than 1, suggesting that no counterion condensation occurs. Studies of the effect of ionic strength (I) on the intrinsic viscosities ([η]) under theta condition were obtained by plotting [η] vs. I^−1/2 and extrapolating to infinite ionic strength. For salt-free BPS35 solutions, the viscometric behavior was shown to fit well with the Liberti-Stivala equation, providing a way to determining intrinsic viscosity when the copolymer charge is fully screened. Intrinsic viscosity and molecular weight characterization of BPS35 copolymers by SEC and static light scattering are also presented. The results are very useful for characterizing polymeric electrolyte membrane (PEM) for fuel cells, reverse osmosis and ionic transducer membranes.     

Electrochemical syntheses of heterocyclic compounds—III. Anodic oxidation of chalcone phenylhydrazone

Anodic oxidations of chalcone phenylhydrazone were performed in acetonitrile-lithium perchlorate electrolyte solution at platinum using controlled potentials. By means of TLC the following products were isolated: 1,3,5-triphenylpyrazole (1), 1,3,5-triphenyl-Δ²-pyrazoline (2a), 1,3,5-triphenyl-Δ²-pyrazolinium perchlorate (2), 4,4′-bis[3,5-diphenyl-Δ²-pyrazolynil(1)]-biphenyl (3a), protonated form of the compound 3a as a diperchlorate (3) and 4,4′-bis-[3,5-diphenylpyrazolyl-(1)]-biphenyl (4). A mechanism rationalizing these products as well as cyclic voltammetric and chronoamperometric data is proposed.     

Polybinaphthyls incorporating chiral (R) or (S)-2,2′-binaphthyland oxadiazole moieties by Stille reaction

Chiral polymers P-1 and P-2 were prepared by the polymerization of (R)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((R)-M-1) and (S)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((S)-M-1) with 2,5-bis[(4-tributylstannyl)phenyl]-1,3,4-oxadiazole (M-2) via Pd(PPh₃)₄ catalyzed Stille coupling reaction. 1,3,4-Oxadiazole unit not only has high electron affinity, high thermal and oxidative stability, but also serves as a good chromophore. Polymers have strong blue fluorescence due to the efficient energy migration from the extended π-electronic structure of the polymers to the chiral binaphthyl core and can be expected to have potential application in the materials of fluorescent sensors. Circular dichroism (CD) spectra of polymers P-1 and P-2 are almost identical except that they gave opposite signals at each wavelength. The long wavelengths CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure in the repeating unit and a high rigidity of the polymer backbone.