Synthesis of macrocyclic lactones with methoxysulfonyl side chain

Two representative macrocyclic lactones with methoxysulfonyl side chain（5a and 5b）were synthesized employing Michael addition with acrolein and ring enlargement as the key steps,starting from potassium,α-oxocycloaikylsulfonates（1）in total yields of 45 and 57%,respectively.     

Synthesis of α-tocopherol analogs with unsaturated side chain and their transformation into the corresponding chromans with ω-functionalized side chain

-Tocopherol analogs with double bond-containing side chains were synthesized by condensation of trimethylhydroquinone with optically active (3R/S,4S)-3,4,8-trimethylnona-1,7-dien-3-ol and linalool in the presence of the zeolite-containing Tseokar-10 aluminosilicate. Ozonolysis of these compounds gave the corresponding chromans with -formyl or (after hydride reduction) -hydroxyl groups in the side chain.     

Synthesis and photovoltaic properties of phthalocyanine end-capped copolymers with conjugated dithienylbenzothiadiazole–vinylene side chains

Two phthalocyanine end-capped copolymers with conjugated dithienylbenzothiadiazole–vinylene side chains, PHY1 and PHY2, have been synthesized according to the Stille–Coupling polymerization method. The structures, thermostability, optical and electrochemical properties of the copolymers were characterized via NMR, GPC, TGA, DSC, UV–vis, photoluminescence (PL) spectroscopy, and cyclic voltammetry (CV), respectively. The two copolymers exhibit excellent film-forming ability and good thermostability in a wide temperature range. PHY1 and PHY2 end-capped with different phthalocyanines showed broad absorption bands ranging from the ultraviolet to the red/near-infrared (IR) region of the solar spectrum and deep HOMO energy levels. Bulk heterojunction polymer solar cells were fabricated based on PHY1 and PHY2 with [6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) as the electron acceptor and showed power conversion efficiencies (PCE) of 1.56% and 1.26%, respectively, under the illumination of AM 1.5, 100 mW/100 cm².     

Investigation of side chain liquid crystal polymers bearing cholesterol and bile acid derivatives

Cholic acid (or 3α,7α,12α-trihydoxyl-5β-cholan-24-oic acid) and lithocholic acid (or 3α-hydroxyl-5β-cholanic-24-oic acid) are commonly occurring bile acids synthesized from cholesterol in the liver in mammals. They all possess a steroid skeleton containing four rings, three with six carbons and one with five carbons. The transformation of cholesterol to cholic acid results in two major structural changes that affect the steroid skeleton. The first is the hydrogenation of the double bond …     

Synthesis of pH-responsive polysilane with polyelectrolyte side chains through γ-ray-induced graft polymerization

Polysilanes with polyelectrolyte side chains are synthesized by two methods utilizing γ-ray-induced grafting and the pH responsiveness for one of those polymers is revealed mainly by investigating interfacial behavior of its monolayer at the air/water interface. In the first synthetic method, poly(methyl acrylate) is grafted onto poly(methyl-n-propylsilane) (PMPrS) through γ-ray-induced grafting, and then the PMA chains are hydrolyzed to poly(acrylic acid) resulting in the yield of ca. 97%. Thus PMPrS with polyelectrolyte side chains is successfully synthesized by the graft chain hydrolysis. The other method is the direct grafting of electrolyte monomers. Poly(methacrylic acid)-grafted PMPrS (PMPrS-g-PMAA) can be obtained through γ-ray-induced grafting of methacrylic acid monomers onto PMPrS chains, which shows the effectiveness of radiation grafting for the synthesis of polyelectrolyte graft copolymers. PMPrS-g-PMAA exhibits pH responsive behavior. In addition to the pH-dependence of water solubility, interfacial behavior also depends on the pH. Langmuir monolayers of PMPrS-g-PMAA exhibit different surface pressure-area isotherms according to the grafting yield and the pH of the subphase water. This result suggests that radiation modification is useful for fabricating polysilane-based ordered materials responsive to outer stimuli.     

Synthesis and magnetooptical properties of mesomorphic complexes of lanthanides with β-aminovinyl ketones

Complexes of the composition L(LH)₂Ln(NO₃)₂ (Ln = La, Dy, Gd, Er, Eu, or Tb) were obtained by the reaction of -aminovinyl ketone (LH) with rare earth metal nitrates. All the compounds synthesized are thermotropic liquid crystals having the smectic S_A phase. The values of magnetic anisotropy of these complexes measured by magnetic birefringence are fairly high.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2331–2333, September, 1996.     

Synthesis and characterization of organic–inorganic macrocyclic molecular brushes with poly(ε-caprolactone) side chains

In this work, we reported the synthesis of a dodecahydroxyl-functionalized macrocyclic oligomeric silsesquioxane (MOSS). The novel 24-membered hydroxyl-functionalized MOSS was employed as a macroinitiator for the ring-opening polymerization of ε-caprolactone (CL) and the organic–inorganic macrocyclic molecular brushes with poly(ε-caprolactone) (PCL) side chains were successfully synthesized. The organic–inorganic macrocyclic molecular brushes were characterized by means of nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). The results of wide angle X-ray diffraction (XRD) indicate that the architecture of the organic–inorganic macrocyclic molecular brushes did not alter the structure of PCL crystals. Differential scanning calorimetry (DSC) shows that the architecture of organic–inorganic macrocyclic molecular brushes significantly affected the rearrangement of PCL crystals. Compared to linear PCL, the organic–inorganic macrocyclic molecular brushes possessed the improved thermal stability in terms of the temperatures at the maximum of degradation rate and the yields of degradation residues.     

Synthesis and structural studies of homooligomers of geminally disubstituted β(2,2)-amino acids with carbohydrate side chain

A new class of geminally disubstituted C-linked carbo-β(2,2)-amino acids (β(2,2)-Caa) were prepared from d-glucose. The structures of homooligomeric di-, tetra-, and hexapeptides prepared from (S)-β(2,2)-Caa were studied with NMR (in CDCl(3)), CD, and Molecular Dynamics calculations. These β(2,2)-peptides have shown the presence of stable 6-membered (6-mr) NH(i)···CO(i) intra-residue H-bonded (C(6)) strands. It was found that the strand structures realized in these systems were additionally stabilized by the electrostatic interaction arising due to the proximity of amide proton (NH(i)) to the oxygen of the preceding methoxy group (O(Me)(i-1)) at the C3 carbon of the carbohydrate ring. The new β(2,2)-Caa residues with additional support to H-bonding considerably expand the domain of foldamers.     

Infrared spectroscopic study of a phenyl benzoate side group—methacrylate main chain polymeric liquid crystal

Abstract

The temperature dependence of the infrared dichroism of a side chain polymeric liquid crystal was investigated for two homogeneously oriented samples, one aligned with a PVA coating and the other aligned by a magnetic field. From the apparent order parameters, it was found that the rotation of the mesogenic side group was restricted. Not only the rigid part of the side group, but also the alkyl chains were found to be partly ordered. Realignment of the side groups was observed in the case of the magnetically aligned sample at the smectic-nematic transition temperature. Unlike the other absorption bands, the C?O bond vibration band shifted to higher wavenumbers with increasing temperature. This behaviour was explained by the influence of the neighbouring mesogenic groups on the conjugation existing between the π-electron cloud of the benzene rings and the π-electrons of the C?O bond.     

Polytungstates with the organic cation—I. Synthesis and chemical properties of sodium—tetramethylammonium decatungstate

Sodium-tetramethylammonium decatungstate has been obtained and investigated. On the basis of X-ray, thermogravimetric and IR spectroscopic measurements its chemical formula has been discussed.     

Synthesis and characterization of side‐chain liquid‐crystalline poly(ethyleneimine)s with cyanobiphenyl groups

A series of polyethyleneimine‐based side‐chain liquid‐crystalline polymers substituted with different ratios of cyanobiphenyl as pendent mesogenic groups has been synthesized in which the spacer length varies between two and six methylene units. The structures of the synthesized polymers are confirmed by infrared and ¹H nuclear magnetic resonance spectroscopy. The thermal properties of these polymers have been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. The results indicate that the thermal behaviour of the polymers is strongly dependent on the degree of substitution. Polymers containing more than 69% of mesogenic groups exhibit nematic‐type thermotropic liquid‐crystalline behaviour with schlieren textures. Below this limit, the polymers are amorphous. Polymers with a higher degree of substitution present the crystalline states. The phase transition temperatures increase and the mesomorphic temperature ranges widen with increasing degree of substitution. The clearing temperatures decrease as the spacer length increases. An odd–even effect in the clearing temperatures is observed and the odd members display the higher values.     

Thermotropic liquid-crystal polymers—25. A Mössbauer spectroscopy study of molecular mobility

The Mössbauer label variant of the Mössbauer spectroscopy method is employed to study intramolecular mobility in comb-shaped liquid-crystal (LC) polymer, poly{I-[II-(4′-cyano-4-biphenyloxy)undecyloxycarbonyl]ethylene}(CBO-II-PM) and also in the PA-4 (polybutylacrylate) polymer and 4-hexyloxy-4′-cyanodiphenyl (CBO-6), a low-molecular-weight LC compound, as model systems. Ferrocene and ferrocenealdehyde were used as molecular labels. Measurements were taken between 90 and 390 K. Temperature dependences of the dynamic parameters of the Mössbauer spectra of the labels localized in various polymer matrix microregions were analyzed to estimate characteristic Debyc temperatures and mean square vibrational amplitudes of label molecules. These quantities reflect “rigidity” of the corresponding microregions in the vitreous and LC phases.     

Synthesis of novel non-proteinogenic α-amino acids with charged imidazolium fragment in the side chain

Zwitterionic imidazolium and benzimidazolium salts bearing chiral amino acid moiety were synthesized using chiral Ni^II complexes. Different N-derivatives of the synthesized enantiomerically pure amino acids were prepared; their zwitterionic structures were confirmed by X-ray analysis.     

Synthesis with organoboranes. 21. Synthesis of α- and gd-bamascone

Selective syntheses of α- and gd-damascone, using allylic organoboranes as the key intermediates, are described.     

Synthesis and characteristic of double hydrophilic block copolymer with amine pendant chains

Novel double hydrophilic block copolymers with amine pendant chains were synthesized by polymerization of 4-vinyl benzylamine hydrochloric salt using 4,4′-azo-bis[4-cyanopentanoate poly（ethylene glycol） ester] as macroazoinitiator. The structures of the copolymers were characterized by ^1H NMR, FTIR spectra and acid-base titration, GPC-MALS techniques.     

Synthesis and crystal structures of two new Zn(II) coordination polymers with 4,4′-dipyridyl disulfide and dicarboxylate acid

The title compounds, Zn(C₅H₆O₄)(Dpds) · 5H₂O (I) and Zn(C₆H₈O₄)(Dpds) (II) (C₅H₈O₄ = glutaric acid, Dpds = 4,4??-dipyridyl disulfide, and C₆H₁₀O₄ = adipic acid), are two-dimensional metal-organic coordination polymers. In I, the tetrahedra coordinated Zn atoms are bridged by glutarate anions and Dpds ligand to form a 2D layer parallel to (001) plane, which are connected by the 1D water tape notated as T4(2)₅(2) to build up 3D supramolecular architecture. In II, both Dpds ligands and adipate anions act as bidentate bridges, connecting the Zn(II) centers in a tetrahedral coordination geometry into a two-dimensional (4,4) layer. Each layer polycatenates adjacent layers, exhibiting the rare combination of 2D ?? 2D parallels interpenetration.     

Synthesis and characterization of a novel main chain oxadiazole-based copolymer for n-type solar cell material

A novel oxadiazole-based copolymer has been successfully synthesized through the palladium-catalyzed cross-coupling polycondensation method.The copolymer P is soluble in common organic solvents.Its structure has characterized by ~1H NMR,~(13)C NMR,gel permeation chromatagraphy (GPC),UV-vis absorbance (Abs) and photoluniminescence (PL) spectroscopy,and cyclic voltammetry (CV).Investigation of its optical properties revealed that it is yellow emitting material,and the electrochemical analysis showed that P was well suited poly (2,5-dioctyloxy-p-phenylenevinylene) (PDOCPV) for photovoltaic devices,so the copolymer P is able to act as an electron acceptor in combination with PDOCPV as the electron donor to quench photoluminescence of the copolymer in the blend,indicative of the efficient photoinduced electron transfer from the PDOCPV to the P.     

Synthesis and mesomorphic behaviour of wedge‐shaped nematic liquid crystals with flexoelectric properties

The synthesis and mesomorphic behaviour of a series of wedge‐shaped liquid crystals and some reference compounds are reported. These unusual liquid crystals possess smectic C, smectic A and nematic phases. These new wedge‐shaped materials with a high degree of shape anisotropy and a large dipole moment can be used to induce an increase in the flexoelectric effects of nematic guest–host mixtures as dopants at low concentrations.