New polysilalkylenes: synthesis and gas-separation properties

A series of polysiltrimethylenes with different substituents at the silicon atom, as well as new polydimethylsilmethylene, were synthesized by the ring-opening polymerization of the corresponding sila- and disilacyclobutanes. For the first time, the copolymerization of dimethylsila- and tetramethyldisilacyclobutanes was carried out with formation of permethylsilalkylene elastomers containing a controlled number of silmethylene and siltrimethylene units in the main chain. Permeability coefficients of n-alkanes C₁-C₄ were measured for the prepared silalkylene homopolymers and copolymers by mass spectrometric and barometric techniques. An analysis of the permeability, solubility, and diffusion coefficients indicated that the separation of hydrocarbons proceeded according to a solubility-controlled mechanism. Polysilalkylenes with various structures of radicals at the Si atom were applied onto the surface of porous hollow fibers. The study of gas-separation parameters of the obtained composite membranes showed that they dramatically depended on the type of substituents at the Si atom. The series of polypermethylsilalkylenes are promising as membrane materials for the separation of hydrocarbon gases.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2497–2503, November, 2004.     

Discotic liquid crystalline hydrazone compounds: synthesis and mesomorphic properties

[reaction: see text] 1,3,5-Trisacetoacetamidobenzene with three 1,3-diketo groups was synthesized by the reaction of 1,3,5-triaminobenzene with diketene. Discotic hydrazone compounds were prepared by the diazo coupling reaction between 1,3,5-trisacetoacetamidobenzene and diazonium salts of 4-alkyloxyphenylamines. The compounds existed in hydrazone forms exclusively, being stabilized by the intramolecular hydrogen bonds, and showed discotic nematic or columnar hexagonal mesophases.     

Allyl strontium compounds: synthesis, molecular structure and properties

The synthesis and attempted isolation of neutral bis(allyl)strontium [Sr(C(3)H(5))(2)] (1) resulted in the isolation of potassium tris(allyl)strontiate K[Sr(C(3)H(5))(3)] (2). In situ generated 1 shows a pronounced Br?nsted basicity, inducing polymerisation of THF. Ate complex 2 crystallises as [K(THF)(2){Sr(C(3)H(5))(3)}(THF)](∞) (2·(THF)(3)). The salt-like solid state structure of 2·(THF)(3) comprises a two-dimensional network of (μ(2)-η(3):η(3)-C(3)H(5))(-) bridged potassium and strontium centres. Synthesis of allyl complexes 1 and 2 utilised SrI(2), [Sr(TMDS)(2)] (3) (TMDS = tetramethyldisilazanide), and [Sr(HMDS)(2)] (HMDS = hexamethyldisilazanide) as strontium precursors. The solid state structure of previously reported [Sr(TMDS)(2)] (3) was established by X-ray single crystal analysis as a dissymmetric dimer of [Sr(2)(TMDS)(4)(THF)(3)] (3·(THF)(3)) with multiple Si-HSr agostic interactions. The presence of ether ligands (THF, 18-crown-6) influenced the Si-HSr resonances in the NMR spectra of the amido complex 3.     

New aromatic azo compounds: syntheses and liquid-crystalline properties

The chemical syntheses of 12 new azo dyes are reported. The optically active compounds were prepared by the Mitsunobu reaction, amide formation, and esterification with optically active alcohols or acids. Several new compounds showed liquid-crystalline properties, and their phase transition behavior was investigated.     

New 1,2,4-triazine-containing podands: synthesis and properties

A method of one-step C-C coupling of 1,5-bis(2,6-dimethylphenoxy)-3-oxapentane (1a) and 1,8-bis(2,6-dimethylphenoxy)-3,6-dioxaoctane (1b) with 3-methylthio- (2) and 3-amino-1,2,4-triazine (3) and 3-aryl-1,2,4-triazin-5-one (6-8) has been described. The reaction of compounds 1a,b with compounds 2 and 3 in the presence of trifluoroacetic acid results in the addition of the dimethylphenoxy group to the unsubstituted C(5) carbon atom of the triazine ring. The reactions of triazinones 6-8 with compounds 1a,b in a mixture of trifluoroacetic acid and organic anhydrides are accompanied by the acylation of the nitrogen atom adjacent to the reaction center and affords bis[(3-R-1-acyl-5-oxo-1,4,5,6-tetrahydro-1,2,4-triazin-6-yl)-2,6-dimethylphenoxy]-3-oxapentane or -3,6-dioxaoctane. The obtained adducts can smoothly be oxidized under mild conditions to form more stable products of nucleophilic hydrogen substitution in the triazine ring. The extraction and transport of Ca²⁺ and Mg²⁺ cations through an organic membrane by the compounds synthesized are discussed.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2210–2215, October, 2004.     

Starburst substituted hexaazatriphenylene compounds: synthesis, photophysical and electrochemical properties

Starburst-substituted hexaazatriphenylene compounds have been designed and synthesized by introducing various peripheral aryl substituents to the central heterocyclic core. The effects of various substituent groups on the photophysical and electrochemical properties of the substituted hexaazatriphenylene have been investigated. Significant red-shifts of the absorption peak (from 413 nm to 530 nm) and emission peak (from 432 nm to 700 nm) were observed when the electron-donating ability of the aryl substituents was increased, corresponding to a decrease in the band gap from 2.90 eV to 2.05 eV. Introducing bulky substituents with weak electron-donating ability enhances the fluorescence quantum yield from 23% to 87%. In contrast, incorporating aryl substituents with strong electron-donating ability decreases the fluorescence quantum yield. Also, due to the extended conjugation between the aryl substituents and the hexaazatriphenylene core, the reduction potentials of the compounds were reduced and the LUMO levels were thus increased.     

A novel entry into a new class of spiroheterocyclic framework: regioselective synthesis of dispiro[oxindole-cyclohexanone]pyrrolidines and dispiro[oxindole-hexahydroindazole]pyrrolidines

2,6-Bis(arylmethylidene)cyclohexanones undergo a regioselective 1,3-dipolar cycloaddition reaction with the azomethine ylide derived from isatin and sarcosine by a decarboxylative route affording a series of 1-N-methyl-spiro[2.3¹]oxindole-spiro[3.2¹¹]6¹¹-arylmethylidenecyclohexanone-4-aryl-pyrrolidines which were further annulated to give a series of novel 1-N-methyl-spiro[2.3¹]oxindole-spiro[3.7¹¹](3¹¹-aryl)Δ^111,711a-hexahydro-2H-indazole-4-aryl-pyrrolidines. The structures of which were established by spectroscopic techniques as well as single crystal X-ray analysis.     

Triphenylamine-based electroactive compounds: synthesis,properties and application to organic electronics

This review is devoted to low and high molecular mass electroactive materials containing triphenylamine (TPA) structural units. It is shown that by appropriate selection of C–C coupling methods, it is possible to obtain solution-processable, electroactive materials of tunable donor–acceptor properties, suitable for the use as active layers in p-channel or ambipolar field effect transistors, as hole-transporting layers and as electroluminophores in organic light-emitting diodes. Other applications involve their use as components of bulk heterojunctions in organic solar cells and dye-sensitized solar cells. Since TPA-based materials exhibit high electrochemical reversibility, they can also be technologically exploited as solution-processable electrochromic materials.     

Photooxidation of dispiro[2.0.2.4]deca-7,9-diene and its analogues: synthesis and properties of new nonenolizable cyclohex-2-ene-1,4-diones

Photooxidation of 1, 2, and 3 gave the corresponding 1,4-endoperoxides 4, 5. and 6, respectively, in good yields. Chemical transformations of these provided some new oxygen functionalized cyclohexane and cyclohexene derivatives. The interesting ene-1,4-diones 17 - 19 were prepared by base-catalyzed rearrangement of the endoperoxides and subsequent oxidation of the resulting hydroxyketones 14 – 16 with chromic acid. On the basis of the UV spectra of the diones 17 and 19, and their comparison with those of other model systems the extent of conjugation with the spirocyclopropane groups in 17 and 19 was established.     

New organophosphorus compounds containing nicotinamide: synthesis,structure and DFT calculations

Novel organophosphorus compounds, containing Nicotinamide, with formula C₅H₄NC(O)NHP(O)R₂, R=Cl (1), OH (2), N(C₂H₅)₂ (3), N(C₃H₇)₂ (4), N(n-C₄H₉)₂ (5), NHC₃H₅ (6), NHC₅H₉ (7), were synthesized and characterized by ¹H, ¹³C, ³¹P, NMR, IR, spectroscopy and elemental analysis. Single crystal structures of 3 7 were determined by X-ray crystallography. ¹HNMR spectra of compounds 2, 3, 6–8 demonstrated interesting long-range coupling constant, ⁿ J _P,H (n = 5 7). Crystallographic data revealed that in both molecules 3 and 7, the phosphoryl and the carbonyl groups have anti-configurations and the phosphorus atoms in these structures have distorted tetrahedral configuration. All the hydrogen bonds and electrostatic interactions make a three dimensional polymeric network for both 3 and 7. Interestingly, two independent conformers were detected in the unit cell of compound 7. The two conformers of the title compound can be observed in a solid phase but only one compound defined in a solution. These two conformers are connected to each other by a short contact, N (amine)···H–C (pyridine) with 2.626 Å distance. The molecular geometry of 7 was calculated by DFT/B3LYP (6–31+G**) quantum chemical calculations. The computational optimized geometric parameters and vibrational frequencies showed a good agreement with the experimental results, considering reasonable variations arising from the differences between solid and gaseous phases. Theoretical calculations revealed that the more stable conformer of the title compound is conformer 1 with the energy of ?1335.723996 a.u., which is about 1.17 kcal/mol lower than the energy of conformer 2.     

New star-like polydimethylsiloxanes: synthesis,properties, and application

Russian Chemical Bulletin - New star-like polydimethylsiloxanes with a cis-tetraphenylcyclotetrasilsesquioxane fragment as the core (branching center) were synthesized and characterized. The...     

New optoelectronic materials based on bitriazines: synthesis and properties

A series of bitriazine derivatives were synthesized for the first time by the self-coupling reactions of the monocholoro-triazines in the presence of nickel catalyst. Such bitriazines show excellent optoelectronic properties.     

New semi-interpenetrating network hydrogels: synthesis, characterization and properties

Amphiphilic hydrogels composed of aliphatic polyesters and poly(ethylene glycol) have potential applications in drug delivery, tissue engineering and other biomedical devices due to their advantageous biological properties, biocompatibility and biodegradability. However, they also exhibit some shortcomings in terms of their reactivity, swelling and mechanical properties. To address these limitations, new semi-interpenetrating network (semi-IPN) hydrogels based on poly(ethylene glycol)-co-poly(epsilon-caprolactone) (PEG-PCL) diacrylate macromer and hydroxypropyl guar gum (HPGG) were prepared by a low intensity ultraviolet (UV) light irradiation method, and characterized by FT-IR, DSC and WAXD analysis. Their properties were evaluated by investigating the swelling kinetics, dynamic mechanical rheology and the release behavior for bovine serum albumin (BSA). It was found that the introduction of the semi-IPN structure and HPGG decreased the crystallinity of PEG segments in the hydrogel, and improved the swelling and mechanical properties of the hydrogel, as well as lowered the release percentage of BSA from the hydrogel. Such hydrogel materials may have more advantages as a potentially interesting platform for the design of medical devices.The elastic modulus (G') and viscous modulus (G') as a function of frequency for various hydrogel samples.     

New polydimethylsiloxanes with bulky end groups: synthesis and properties

Russian Chemical Bulletin - New polydimethylsiloxanes (PDMS) containing bulky end groups were obtained. The structure of all obtained compounds was confirmed by a combination of physicochemical...     

Microwave synthesis,structure, and properties of molybdophosphate compounds

Two compounds of disphosphopentamolybdate(VI) with the formulae (C₄H₁₄N₂O)₃- [P₂Mo₅O₂₃]?·?3H₂O (1) and (C₄H₁₄N₂O)₅(NH₄)₂[P₂Mo₅O₂₃]₂?·?5H₂O (2) have been synthesized by a simple, fast and efficient microwave method, and their crystal structures and spectroscopic properties have been studied. The heteropoly anion [P₂Mo₅O₂₃]^6? has a known structure built of five MoO₆ octahedra and two PO₄ tetrahedra. The MoO₆ octahedra form a pentagonal ring by sharing four edges and one corner and the PO₄ tetrahedra are attached to one side of the ring by three oxygen atoms. The most interesting feature of compound 1 is its extensive framework based on a one-dimensional zigzag chain. In compound 2, a more extensive and complicated framework of hydrogen bonds joins the anions, organic cations and water molecules together.     

New proton-ionizable macrocyclic compounds containing one and two triazole subcyclic units — synthesis and complexation properties

A series of new macrocyclic compounds containing one and two proton-ionizable triazole subcyclic units have been prepared and characterized. These triazolo-crowns containing benzo, tert-butylbenzo or cyclohexano lipophilic groups show varying solubilities in chloroform. The bistriazolo-crowns dissolved in chloroform are highly effective for extraction of lead, mercury, and gold from aqueous solutions.     

New method for the synthesis of macrocyclic compounds

A mixture of isomers corresponding to closing of the ring at the 3 and 4 positions of the thiophene ring is formed during intramolecular acylation of 12-(5-methyl-2-thienyl)-lauryl chloride in a homogeneous medium; the reaction proceeds primarily to favor the formation of the isomer with the larger ring (80%). A method for the synthesis of macrocyclic -alkylcycloalkanones by reductive desulfurization of the corresponding bicyclic ketones, which contain thiophene rings, was developed.See Izv. Akad. Nauk SSSR, Ser. Khim., 2228 (1970) for Communication XI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1467–1472, November, 1970.     

New method for the synthesis of macrocyclic compounds

The intramolecular acylation of acid chlorides of ω-thienylalkanoic acids of various structures in the presence and absence of silica gel was investigated. The reaction of aluminum chloride etherate and the indicated acid chlorides with the surface groups of silica gel was studied by IR spectroscopy, and the role of the compounds formed on the surface in the reaction under consideration was discussed. A sequence of processes and a mechanism involving participation of the solid phase in the intramolecular acylation of acid chlorides of ω-thienylalkanoic acids are formulated.     

New method for the synthesis of macrocyclic compounds

The intramolecular acylation of acid chlorides of -(3-methyl-2-thienyl)- and -(4-methyl-2-thienyl)alkanoic acids proceeds at the free 5 position of the thiophene ring. A solid-phase effect (silica gel), which, under comparable conditions, leads to more than double the yields, is displayed during the cyclization of acid chlorides of the above acids. A modification was developed for the reductive desulfurization of cyclothienones with alkyl groups in the position of the thiophene ring; the modification includes the formation of unsaturated compounds and products of the reduction of the carbonyl group. A new route to the synthesis of - and -methylcycloalkanones, including DL-muscone, was developed.See [2] for communication XIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 170–176, February, 1972.