Synthesis and crystal structure of 2-isocyano-4-methylphenyl diphenylacetate: a rare case of an easily accessible odourless isocyanide.

Acidic hydrogen containing 2-isocyano-4-methylphenyl diphenylacetate, C22H17NO2, (I), was synthesized by the base-promoted reaction between 5-methylbenzoxazole and diphenylacetyl chloride. Achiral (I) crystallizes in the chiral P212121 space group. The C[triple-bond]N bond length is 1.

Acid-promoted transformations of 1-(diphenylphosphoryl)allenes: synthesis of novel 1,4-dihydrophosphinoline 1-oxides.

1-(Diphenylphosphoryl)alka-1,2-dienes (phosphonoallenes) in Brønsted (super)acids (TfOH, FSO3H, and H2SO4) at -70 to 120 °C for 30 min to 4 h gave, at first, (3-hydroxyalk-1-en-1-yl)diphenylphosphine oxides, as kinetically favorable reaction products, that are further converted into 1-phenyl-1,4-dihydrophosphinoline 1-oxides as thermodynamically stable compounds. The latter compounds are formed from phosphonoallenes under the action of a strong Lewis acid AlCl3 at room temperature for 10-120 min. This is a novel, simple and efficient (short reaction time, high yields) method for synthesis of such 1,4-dihydrophosphinoline 1-oxides.

Novel (cyanamide)Zn(II) complexes and zinc(ii)-mediated hydration of the cyanamide ligands.

The cyanamides NCNR2 (R2 = Me2, Ph2, C5H10) react with ZnX2 (X = Cl, Br, I) in a 2 : 1 molar ratio at RT, giving a family of zinc(ii) complexes [ZnX2(NCNR2)2] (R2 = Me2, X = Cl , X = Br , X = I ; R2 = C5H10, X = Cl , X = Br ; X = I ; R2 = Ph2, X = Cl , X = Br , X = I ; 75-92% yields). Complexes and undergo ligand redistribution in wet CH2Cl2 solutions giving the [Zn(NCNPh2)4(H2O)2][Zn2(μ-X)2X4] (X = Cl , Br ) species that were characterized by (1)H NMR, HRESI-MS, and X-ray diffraction. Halide abstraction from by the action of AgCF3SO3 or treatment of Zn(CF3SO3)2 with NCNR2 (R2 = Me2, C5H10) leads to labile complexes [Zn(CF3SO3)2(NCNR2)3] (R2 = Me2, ; C5H10, ).

Zinc(II)-mediated nitrile-amidoxime coupling gives new insights into H⁺-assisted generation of 1,2,4-oxadiazoles.

The cyanamides Me2NCN (1a), OC4H8NCN (1b), and PhC(═O)N(H)CN (1c) and the conventional nitriles PhCN (1d) and EtCN (1e) react with 1 equiv of each of the amidoximes R'C(═NOH)NH2 (R' = Me (2a), Ph (2b)) in the presence of 1 equiv of ZnCl2 producing the complexes [ZnCl2{HN═C(R)ON═C(R')NH2}] (R/R' = NMe2/Me (3a), NMe2/Ph (3b), NC4H8O/Me (3c), NC4H8O/Ph (3d), N(H)C(═O)Ph/Me (3e), N(H)C(═O)Ph/Ph (3f), Ph/Me (3g), Ph/Ph (3h), Et/Ph (3j)) with the chelate ligands originating from the previously unreported zinc(II)-mediated nitrile-amidoxime coupling. Addition of 1 equiv of p-TolSO3H to any of one 3a-h, 3j results in the ligand liberation and formation of the iminium salts [H2N═C(R)ON═C(R')NH2](p-TolSO3) ([4a-j](p-TolSO3)), which then at 20-65 °C spontaneously transform to 1,2,4-oxadiazoles (5a-j). As a side reaction, cyanamide derived species [4a-f](p-TolSO3) undergo Tiemann rearrangement to produce the substituted ureas R'NHC(═O)NH2 (R' = Me (6a), Ph (6b)) and RC(═O)NH2 (R = NMe2 (6c), NC4H8O (6d), N(H)C(═O)Ph (6e)), whereas phenyl and ethyl cyanide derivatives besides their transformation to the oxadiazoles undergo hydrolysis to the parent amidoxime R'C(═NOH)NH2 (R' = Me (2a), Ph (2b)) and the carboxamides RC(═O)NH2 (R = Ph (6f), Et (6g)).

2-[(Pyridin-2-yl)amino]-pyridinium 2,4,6-tri-nitro-phenolate.

In the cation of the title salt, C10H10N3 (+)·C6H2N3O7 (-), the pyridine and pyridinium rings are linked by an intra-molecular N-H⋯N hydrogen bond and are approximately coplanar, with a dihedral angle between their planes of 4.24 (6)°. In the crystal, the cations and anions are linked through N-H⋯O hydrogen bonds, forming supra-molecular chains propagating along the c-axis direction.

Surface dilational rheological properties in the nonlinear domain.

The interfacial tension response to dilational deformation of interfacial area exhibits a (more or less) nonlinear behavior, depending on the amplitude of the deformation. Studies of such observable interfacial properties in the nonlinear domain suggest valuable information about the two-dimensional microstructure of the interfacial layer, as well as about the structure time-evolution. In this article, the emphasis is centered on the available mathematical methods for quantitatively analyzing and describing the magnitude and the characteristics of the nonlinear interfacial viscoelastic properties.

Dilational surface elasticity of spread monolayers of polystyrene microparticles.

The dependence of the dilational surface elasticity on the surface pressure of the spread monolayers of polystyrene microparticles is studied at the water-air interface. The surface rheological measurements together with the data from optical methods allow the division of the whole range of surface pressures into three zones characterized by different monolayer structures. The extremely high surface elasticity (∼500 mN m(-1)) at surface pressures close to 30 mN m(-1) is similar to the results for the adsorption layer of the complexes formed between silica particles and surfactant molecules and is probably caused by strong hydrophobic attraction between the particles.

Synthesis and investigation of biological properties of modified 6-oxa-estra-1,3,5(10),8(9)-tetraenes.

To investigate the relationship between structure and biological activity of analogues of steroid estrogens we have developed the synthesis of 7α-methyl-6-oxa-estra-1,3,5(10),8(9)-tetraenes with cis- and trans-junction of C and D rings. We found that such compounds have stronger osteoprotective, cholesterol-lowering and antioxidant properties in comparison with uterotrophic activity; that is the advantage in comparison with clinically used 17α-ethynylestradiol.

Eucken correction in high-temperature gases with electronic excitation.

In the present paper, thermal conductivity coefficient of high-temperature molecular and atomic gases with excited electronic states is studied using both the kinetic theory algorithm developed by authors earlier and the well known simple expression for the thermal conductivity coefficient proposed by Eucken and generalized by Hirschfelder. The influence of large collision diameters of excited states on the thermal conductivity is discussed. The limit of validity of the Eucken correction is evaluated on the basis of the kinetic theory calculations; an improved model suitable for air species under high-temperature conditions is proposed.

Di-chlorido-[N-(N,N-di-methyl-carbamimido-yl)-N',N',4-tri-methyl-benzohydrazonamide]-platinum(II) nitro-methane hemisolvate.

In the title compound, [PtCl2(C13H21N5)]·0.5CH3NO2, the Pt(II) atom is coordinated in a slightly distorted square-planar geometry by two Cl atoms and two N atoms of the bidentate ligand. The (1,3,5-tri-aza-penta-diene)Pt(II) metalla ring is slightly bent and does not conjugate with the aromatic ring.

2,3-Di-phenyl-male-imide 1-methyl-pyrrol-idin-2-one monosolvate.

In the title compound, C16H11NO2·C5H9NO, the dihedral angles between the male-imide and phenyl rings are 34.7 (2) and 64.8 (2)°.

5-Imino-3,4-diphenyl-1H-pyrrol-2-one.

The title compound, C16H12N2O, exists in the crystalline state as the 5-imino-3,4-di-phenyl--1H-pyrrol-2-one tautomer. The dihedral angles between the pyrrole and phenyl rings are 35.3 (2) and 55.

Tetra-kis[bis-(pyridin-2-yl)amine-κN (2)](nitrato-κO)silver(I).

In the title complex, [Ag(NO3)(C10H9N3)4], the nitrate ligand is found to be disordered over two sets of positions, with occupancy factors of 0.473 (5) and 0.527 (5).

Bis(hy-droxy-ammonium) hexa-chlorido-platinate(IV)-18-crown-6 (1/2).

In the title complex, (NH3OH)2[PtCl6]·2C12H24O6, the Pt(IV) atom is coordinated by six chloride anions in a slightly distorted octa-hedral geometry. The Pt-Cl bond lengths are comparable to those reported for other hexa-chlorido-platinate(IV) species. The hy-droxy-ammonium groups act as linkers between the [PtCl6](2-) anion and the crown ether mol-ecules.

Effect of tetracaine on DMPC and DMPC+cholesterol biomembrane models: liposomes and monolayers.

Different types of lipid bilayers/monolayers have been used to simulate the cellular membranes in the investigation of the interactions between drugs and cells. However, to our knowledge, very few studies focused on the influence of the chosen membrane model upon the obtained results. The main objective of this work is to understand how do the nature and immobilization state of the biomembrane models influence the action of the local anaesthetic tetracaine (TTC) upon the lipid membranes.

Compositional surface-layered sorbents for pre-concentration of organic substances in the air analysis.

We juxtapose methods of synthesis of non-polar surface-layered sorbents on the platform of a carrier, which combines macro-porous coarse-dispersed polytetrafluoroethylene with micro-dispersed activated carbon. Further, we present data about the sorption properties of the said materials alongside perspectives of their analytical applications. Our study established that with respect to efficacy of dynamic sorption from gaseous phases these sorbents outperform bulk-porous analogues in their normal, granular form.

Protein conformational transitions at the liquid-gas interface as studied by dilational surface rheology.

Experimental results on the dynamic dilational surface elasticity of protein solutions are analyzed and compared. Short reviews of the protein behavior at the liquid-gas interface and the dilational surface rheology precede the main sections of this work. The kinetic dependencies of the surface elasticity differ strongly for the solutions of globular and non-globular proteins.

Dichloridobis[3-(4-chloro-phen-yl)-2,N,N-trimethyl-2,3-di-hydro-1,2,4-oxa-diazole-5-amine-κN (4)]platinum(II)-4-chloro-benzaldehyde (1/1).

In the title 1:1 co-crystal, [PtCl2(C11H14ClN3O)2]·C7H5ClO, the coordination polyhedron of the Pt(II) atom is slightly distorted square-planar with the chloride and 2,3-di-hydro-1,2,4-oxa-diazole ligands mutually trans, as the Pt atom lies on an inversion center. The 4-chloro-benzaldehyde mol-ecules are statistically disordered about an inversion centre with equal occupancies for the two positions. The Pt(II) complex forms a three-dimensional structure through C-H⋯Cl and weaker C-H⋯O inter-actions with the 4-chloro-benzaldehyde mol-ecule.

Dichloridobis[3-(4-meth-oxy-phen-yl)-2-methyl-5-(piperidin-1-yl)-2,3-di-hydro-1,2,4-oxa-diazole-κN (4)]platinum(II).

In title compound, [PtCl2(C15H21N3O2)2], the Pt(II) cation, located on an inversion center, is coordinated by two Cl(-) anions and two 3-(4-meth-oxy-phen-yl)-2-methyl-5-(piperidin-1-yl)-2,3-di-hydro-1,2,4-oxa-diazole ligands in a distorted Cl2N2 square-planar geometry. The di-hydro-oxa-diazole and piperidine rings display envelope (with the non-coordinating N atom as the flap atom) and chair conformations, respectively. In the crystal, weak C-H⋯Cl hydrogen bonds link the mol-ecules into supra-molecular chains running along the b axis.

Alternate stresses and temperature variation as factors of influence of ultrasonic vibration on mechanical and functional properties of shape memory alloys.

It is known that the main factors in a variation in the shape memory alloy properties under insonation are heating of the material and alternate stresses action. In the present work the experimental study of the mechanical behaviour and functional properties of shape memory alloy under the action of alternate stresses and varying temperature was carried out. The data obtained had demonstrated that an increase in temperature of the sample resulted in a decrease or increase in deformation stress depending on the structural state of the TiNi sample.

Dialkylcyanamides are more reactive substrates toward metal-mediated nucleophilic addition than alkylcyanides.

The dialkylcyanamide complexes Q[PtCl3(NCNR2)] (Q = Ph3PCH2Ph, R2 = Me21, Et22, C5H103, C4H8O 4; Q = NMe4, R2 = Me25; Q = NEt4, R2 = Me26) were synthesized either by dissolving Q2[Pt2(μ-Cl)2Cl4] in neat NCNR2 (1-4) or by substitution of a NCNR2 ligand with Cl(-) in [PtCl2(NCNR2)2] by its treatment with QCl (5, 6). Nucleophilic addition of dibenzylhydroxylamine, HON(CH2Ph)2, to 1-6 results in the formation of the complexes Q[PtCl3{NHC(NR2)ON(CH2Ph)2}] (Q = Ph3PCH2Ph, R2 = Me2, 7; Et2, 8; C5H10, 9; C4H8O, 10; Q = Me4N, R2 = Me211; Q = Et4N, R2 = Me2, 12) that further convert at room temperature in the solid state (1-24 h) or in a solution (0.5-2 h) to the imine complexes Q[PtCl3{N(CH2Ph)=C(H)Ph}] (Q = Ph3PCH2Ph, 13; Me4N, 14; Et4N, 15) and the corresponding dialkylureas H2NC(=O)NR2.

Amidrazone complexes from a cascade platinum(II)-mediated reaction between amidoximes and dialkylcyanamides.

The aryl amidoximes R'C6H4C(NH2)═NOH (R' = Me, 2a; H, 2b; CN, 2c; NO2, 2d) react with the dialkylcyanamide platinum(II) complexes trans-[PtCl2(NCNAlk2)2] (Alk2 = Me2, 1a; C5H10, 1b) in a 1:1 molar ratio in CHCl3 to form chelated mono-addition products [3a-h]Cl, viz. [PtCl(NCNAlk2){NH═C(NR2)ON═C(C6H4R')NH2}]Cl (Alk2 = Me2; R' = Me, a; H, b; CN, c; NO2, d; Alk2 = C5H10; R' = Me, e; H, f; CN, g; NO2, h). In the solution, these species spontaneously transform to the amidrazone complexes [PtCl2{NH═C(NR2)NC(C6H4R')NNH2}] (7a-h; 36-47%); this conversion proceeds more selectively (49-60% after column chromatography) in the presence of the base (PhCH2)3N.

Tetra-butyl-ammonium 2-[2,5-dimethyl-3-(4-nitro-phen-yl)-2,3-dihydro-1,2,4-oxadiazo-lium-4-yl]nona-hydro-closo-deca-borate.

The title ionic compound, C16H36N(+)·C10H20B10N3O3(-), consists of a tetra-butyl-ammonium cation and a closo-deca-borate cluster anion, which is bound to the substituted 2,3-dihydro-1,2,4-oxadiazole ring through a B-N bond [1.540 (2) Å]. The distances between connected B atoms in the deca-borate cluster range from 1.

cis-Dichloridobis(2-isocyano-phenyl 4-meth-oxy-benzoate)palladium(II) chloro-form monosolvate.

In the title compound, [PdCl2(C15H11NO3)2]·CHCl3, the Pd(II) atom adopts a slightly distorted square-planar coordination geometry composed of two Cl atoms in cis positions and two C atoms from isocyano-phenyl ligands. The mol-ecular conformation is stabilized by π-π stacking inter-actions [shortest centroid-centroid distance = 3.600 (1) Å] between substituted benzene rings of different ligands.