Synthesis and biological activity of arylaliphatic <Emphasis Type="Italic">N</Emphasis>-(2-aminoethyl)-<Emphasis Type="Italic">N</Emphasis>-(2-hydroxy-2-phenylethyl)carboxamides

N-(2-Aminoethyl)-N-(2-hydroxy-2-phenylethyl)carboxamides were synthesized from styrene oxide by ring opening with N,N-disubstituted ethylenediamines followed by N-acylation. Synthesized compounds have pronounced antiarrhythmic activity and low toxicity.     

Oxidative trifluoroacetamidation of (1<Emphasis Type="Italic">E</Emphasis>,3<Emphasis Type="Italic">E</Emphasis>)-1,4-diphenylbuta-1,3-diene and 1,1,4,4-tetraphenylbuta-1,3-diene

Reactions of trifluoroacetamide with (1E,3E)-1,4-diphenylbuta-1,3-diene and 1,1,4,4-tetraphenylbuta-1,3-diene in the oxidative system t-BuOCl–NaI have been studied. The reaction with (1E,3E)-1,4-diphenylbuta-1,3-diene afforded three products, N,N′-(phenylmethylene)bis(trifluoroacetamide), 3-chloro-4-iodo- 2,5-diphenyl-1-(trifluoroacetyl)pyrrolidine, and trifluoro-N-[(3E)-2-hydroxy-1,4-diphenylbut-3-en-1-yl]acetamide, with a high overall yield. 1,1,4,4-Tetraphenylbuta-1,3-diene failed to react with trifluoroacetamide.     

Functionalized β-lactams based on (<Emphasis Type="Italic">E</Emphasis>)-1-(furan-2-yl)-<Emphasis Type="Italic">N</Emphasis>-[(4-methoxyphenyl)methyl]methanimine and its imine–imine rearrangement initiated by potassium hydride

Functionalized β-lactams were synthesized by reaction of (E)-1-(furan-2-yl)-N-[(4-methoxyphenyl)-methyl]methanimine with ketenes generated in situ from chloro- and dichloroacetic acids and 3-(methoxyimino) butanoic acid. (E)-1-(Furan-2-yl)-N-[(4-methoxyphenyl)methyl]methanimine underwent imine–imine rearrangement by the action of potassium hydride to give thermodynamically more stable (E)-N-[(furan-2-yl)-methyl]-1-(4-methoxyphenyl)methanimine.     

Alternative synthesis of alverine

An efficient synthesis of alverine via iron-catalyzed double cross-coupling of (2E)-3-chloro-N-[(2E)-3-chloroprop-2-en-1-yl]-N-ethylprop-2-en-1-amine with phenylmagnesium bromide is described.     

Enantioselective hydrogen transfer hydrogenation on rhodium colloid systems with optically active stabilizers

Hydrogen transfer hydrogenation of acetophenone and methyl benzoylformate with 2-propanol was studied on colloidal systems obtained by reduction of rhodium complexes in the presence of optically active compounds: chiral diamines, quaternary salt (4S,5S)-(–)-N¹,N⁴-dibenzylene-2,3-dihydroxy-N¹,N¹,N⁴,N⁴-tetramethylbutane-1,4-diammonium dichloride and (8S,9R)-(–)-cinchonidine. The increase in the molar ratio modifier/Rh leads to the increase in the enantioneric excess (ee) of the reaction products. The largest ee [43.8% of (R)-1-phenylethanol and 58.2% of methyl ester of (R)-mandelic acid] were achieved for the ratios (8S,9R)-(–)-cinchonadine: Rh = 9: 1 and 3: 1, respectively. The catalyst was characterized by the high-resolution transmission electron microscopy, X-ray diffraction analysis, and thermal analysis.     

Cobalt and manganese complexes with redox-active ligands in polymerization of acrylonitrile and methyl methacrylate

The influence of bis[4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-iminobenzosemiquinonato]cobalt(ii) and 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzosemiquinonato]-[4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolate]manganese(iii) on polymerization of methyl methacrylate and acrylonitrile in the presence of azobisisobutyronitrile (as a traditional radical initiator) and alkyl halides (used for initiation of controlled atom transfer radical polymerization process) was studied. The effect of the nature of the activating agents (amines) and the temperature conditions on the overall polymerization rate of the indicated monomers, as well as molecular weight characteristics of the synthesized polymers, were analyzed. The optimal conditions for the synthesis of polyacrylonitrile and poly(methyl methacrylate) with a relatively narrow molecular weight distribution were selected.     

New Quinoxaline-Containing Monomers for Narrow-Bandgap Polymers

Two new fused quinoxaline-containing monomers—2,3-bis(9-(2-decyltetradecyl)-9H-carbazol-3-yl)dithieno[3,2-f:2'3'-h]quinoxaline (М1) and 2,5-di(nonadecan-3-yl)bis[1,3]thiazolo[4,5-a:5',4'-c]bisthieno[3,2-h:2',3'-j]phenazine (М2)—have been synthesized in high yields of 88 and 83% as promising building blocks of D-A polymers for photovoltaic applications. The optical bandgaps, found from the absorption edge, are 2.79 and 2.88 eV, respectively. The HOMO/LUMO energies of М1 and М2 are–5.83/–2.96 and–5.83/–2.98 eV, respectively. Both monomers have low-lying HOMO levels, which is favorable for a high open-circuit voltage and a high stability in air in the development of PSCs. The E _g ^ec values of monomers М1 and М2 are 2.87 and 2.85 eV and are consistent well with the optical bandgap (2.79 and 2.88 eV, respectively).     

Glycosylation of panaxadiol

Glycosylation of 3β,12β-dihydroxy-20R,25-epoxydammarane (panaxadiol) (1) under Koenigs–Knorr, Helferich, and ortho-ester reaction conditions was studied. Condensation of panaxadiol and 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosylbromide (2) in the presence of silver oxide and 4-Å molecular sieves in dichloroethane gave a mixture of acetylated panaxadiol 3- and 12-O-β-D-glucopyranosides (3:1 ratio). Reaction of diol 1 and D-glucose tert-butylorthoacetate (3) in the presence of 2,4,6-collidinium perchlorate in chlorobenzene resulted in regioselective formation of panaxadiol 12-O-β-D-glucopyranoside tetraacetate. Reaction of equimolar amounts of 1 and glycosyl donor 2 in the presence of Hg(II) cyanide in nitromethane at 90°C was accompanied by opening of the tetrahydropyran ring and gave 3β,12β,25-trihydroxydammar20(22)E-ene 12-O-β-D-glucopyranoside tetraacetate. Panaxadiol 3- and 12-O-β-D-glucopyranosides and 3β,12β,25-trihydroxydammar-20(22)E-ene 12-O-β-D-glucopyranoside tetraacetate were synthesized for the first time.     

Copper,cobalt, and nickel complexes of azomethine compounds containing phenylazo group in the amine fragment: Syntheses,structures, and magnetic properties

The Cu, Ni, and Со complexes based on the following new azomethine compounds containing azobenzene groups in the ortho- or para-positions of the amine fragment are synthesized: 2-allyl-6-[(E)-[4-(E)-phenylazophenyl]iminomethyl]phenol (HL¹), 2-allyl-6-[(E)-[4-methyl-2-[(E)-phenylazo]-p-tolylazo] iminomethyl]phenol (HL²), 5-methoxy-2-[(E)-[4-[(E)-phenylazo]phenyl]iminoethyl]phenol (HL³), and 5-methoxy-2-[(E)-[4-methyl-2-[(E)-p-tolylazo]phenyl]iminomethyl]phenol (HL⁴). The structures of the complexes are determined by the data of IR and ¹Н NMR spectroscopy (for the azomethine compounds), X-ray absorption spectroscopy, and magnetochemistry. The coordination centers of all Cu complexes have a distorted square structure. A direct dependence of the geometry of the coordination polyhedron on the position of azobenzene groups in the amine fragments of the ligands is found for the Ni and Co complexes. The octahedral environment of the nickel and cobalt ions takes place in the case of the ortho-position of the amine fragment, whereas the square environment for the Ni complexes or the tetrahedral environment for the Co complexes is observed at the para-position. The molecular structures of two azomethines HL¹ and HL⁴ are determined by X-ray diffraction analysis (CIF files CCDC nos. 1552836 (HL¹) and 1552837 (HL⁴)).     

1,3-Dipolar cycloaddition of 3-phenylamino-5-phenylimino-1,2,4-dithiazole to 1-acyl-2-phenylacetylenes—A new route to functionalized 1,3-thiazole derivatives

3-Phenylamino-5-phenylimino-1,2,4-dithiazole reacted with 1-acyl-2-phenylacetylenes in ethanol or toluene on heating (78–80°C, 1 h) in chemo- and regioselective fashion to give previously unknown N-[5-acyl-3,4-diphenyl-1,3-thiazol-2(3H)-ylidene]-N′-phenylthioureas (yield 57–60%). The structure of N-[5-benzoyl-3,4-diphenyl-1,3-thiazol-2(3H)-ylidene]-N′-phenylthiourea was proved by X-ray analysis.     

Cycloaminomethylation of dihydric phenols catalyzed by <Emphasis Type="Italic">d</Emphasis>- and <Emphasis Type="Italic">f</Emphasis>-metal compounds

An efficient method has been developed for the synthesis of 7,16,25-triaryl-7,8,16,17,25,26-hexahydro-6H,15H,24H-tribenzo[f,m,t][1,5,8,12,15,19,3,10,17]hexaoxatriazacyclohenicosines, 3,8-diaryl-2,3,4,7,8,9-hexahydrobenzo[1,2-e:4,3-e′]bis[1,3]oxazines, 3,9-bis(chlorophenyl)-3,4,9,10-tetrahydro-2H,8H-benzo[1,2-e:3,4-e′]bis[1,3]oxazines, and 2,9-bis(chlorophenyl)-1,2,3,8,9,10-hexahydrobenzo[1,2-e:6,5-e′]bis-[1,3]oxazines via cycloaminomethylation of pyrocatechol, resorcinol, and hydroquinone with N,N-bis(methoxymethyl) anilines in the presence of samarium catalysts.     

Regio- and stereoselective <Emphasis Type="Italic">N</Emphasis><Superscript>2</Superscript>-functionalization with propanamide fragment of aromatic and heteroaromatic aldehydes thiosemicarbazones

Aiming at the synthesis of new potentially pharmacologically active compounds combining in the molecule structures of thiosemicarbazone and 3-hydrazinylpropionic acid, we performed a regio- and stereoselective N ²-functionalization of thiosemicarbazones of aromatic and heteroaromatic aldehydes by alkaline hydration of the corresponding (E)-N ²-cyanoethyl derivatives (propanenitriles) prepared by a regioand stereoselective cyanoethylation with acrylonitrile. The hydration proceeds with the retention of the Econfiguration of the initial propanenitriles.     

Reaction of aryl(diarylphosphoryl)methanols with alkyl propiolates. Regio- and stereoselective synthesis of functional vinyl ethers

Aryl(diarylphosphoryl)methanols reacted with alkyl propiolates under mild conditions (triethylamine, THF, 22?25°C), to give the corresponding anti-Markovnikov adducts, alkyl (E)-3-[aryl(diarylphosphoryl) methoxy]prop-2-enoates, with high yields (84–90%) and regio- and stereoselectivity.     

Bis[1,3]thiazolo[4,5-<Emphasis Type="Italic">f</Emphasis>:5',4'-<Emphasis Type="Italic">h</Emphasis>]thieno[3,4-<Emphasis Type="Italic">b</Emphasis>]quinoxaline Derivatives as New Building Blocks of Polymers for Organic Electronics

New derivatives of bis[1,3]thiazolo[4,5-f:5',4'-h]thieno[3,4-b]quinoxaline containing the fused thiadiazoloquinoxaline moiety have been prepared. Monomer M1 shows strong light absorption within 600–800 nm due to intramolecular charge transfer. The optical bandgap E _g ^opt determined from the absorption edge in a film is 1.44 eV. The HOMO and LUMO levels are–5.44 and–3.12 eV, respectively. The new structural fragment has a rather low frontier molecular orbital energies and a small bandgap; therefore, it is a promising building block for the synthesis of polymers for organic electronics.     

Dynamics of the photoinduced desorption of nitric oxide molecules from the surface of pure and modified platinum

The distribution of NO molecules desorbed from a Pt(111) surface due to valence electron excitation over rotational energy levels N(J) is analyzed using a simple impulse-induced model. A linear dependence is found between lnN(J) and (E_r)^1/2, where E_r is the rotational energy of the desorbed molecules. The lifetime of the excited state and the critical time of residence in the excited state estimated using this dependence are found to be close to one another (~10^?15 s). The frequency and amplitude of the tilting vibrations of the adsorbed molecules in the excited state are estimated.     

Solution Thermodynamics of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis><Superscript>/</Superscript>-Ethylenebis-(salicylideneiminato)-diaquochromium(III) Chloride in Aqueous Dimethylsulphoxide

The densities, viscosities and refractive indices of N,N ^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, [Cr(salen)(H₂O)₂]Cl, in aqueous dimethylsulfoxide (DMSO) with different mass fractions (w ₂ = 0.20, 0.40, 0.60, 0.80 and 1.00) of DMSO were determined at 298.15, 308.15 and 318.15 K under atmospheric pressure. From measured densities, viscosities and refractive indices the apparent molar volumes (V _φ ), standard partial molar volume (V _φ ⁰ ), the slope (S _V ^* ), standard isobaric partial molar expansibility (φ _E ⁰ ) and its temperature dependence (?φ _E ⁰ /?T) _p , the viscosity B-coefficient, its temperature dependence (?B/?T), solvation number (S _n ) and apparent molar refractivity (R _D ^φ ), etc., were calculated and discussed on the basis of ion–ion and ion–solvent interactions. These results revealed that the solutions are characterized by ion–solvent interactions rather than by ion–ion interactions and the complex behaves as a long range structure maker. Thermodynamics of viscous flow was discussed in terms of transition state theory.     

Rare-earth metal dichloride and bis(alkyl) complexes containing amidinate-amidopyridinate ligands: synthesis,structure, and reactivity

A reaction of anhydrous yttrium chloride with an equimolar amount of lithium amidinateamidopyridinate obtained in situ by metallation of N,N’-bis(2,6-dimethylphenyl)-N-{6-[(2,6-dimethylphenyl)amino]pyridin-2-yl}acetimidamide ((2,6-Me₂C₆H₃)NH(2,6-C₆H₃N)N(2,6-Me₂C₆H₃)C(Me)=N(2,6-Me₂C₆H₃), L¹H) (1) with n-butyllithium in THF at–70 °C was used to synthesize the yttrium dichloride complex (L¹)YCl₂(THF)₂ (2). The lutetium bis(alkyl) complex, namely, N’-(2,6-diisopropylphenyl)-N-(2,6-dimethylphenyl-N-{6-[(2,6-dimethylphenyl)amido]pyridin-2-yl}acetimidoamidinatebis(trimethylsilylmethyl)lutetium (4), was obtained by the reaction of N’-(2,6-diisopropylphenyl)-N-(2,6-dimethylphenyl)-N-(6-((2,6dimethylphenyl)amino)pyridin-2-yl)acetimidamide ((2,6-Me₂C₆H₃)NH(2,6-C₆H₃N)N-(2,6-Me₂C₆H₃)C(Me)=N(2,6-Pr ₂ ⁱ C₆H₃), L²H (3)) with an equimolar amount of Lu(CH₂SiMe₃)₃(THF)₂. Complex 4 was found to be very stable and did not show indications of C—H-activation and other kinds of disintegration in benzene or toluene solution even upon prolonged heating at 60 °C. The reaction of complex 4 with an equimolar amount of 2,6-diisopropylaniline in toluene solution at room temperature led to the formation of the lutetium alkyl-anilide complex (L²)Lu(CH₂SiMe₃)(NH-2,6-Pr ₂ ⁱ C₆H₃) (5). A three-component system 4—AlBu ₃ ⁱ —[X][B(C₆F₅)₄] ([X] = [Ph₃C], [PhNHMe₂], the molar ratio of 1: 10: 1) was found to catalyze polymerization of isoprene.     

Synthesis and redox characteristics of iron complexes with triphenylsubstituted corrols in the presence of argon and oxygen

para-Substituted iron meso-triphenylcorrole derivatives [Fe(ms-p-R-Ph)₃Cor] containing electron- donating (R = OMе) and electron-drawing (R = NO₂) groups in phenyl rings are synthesized and characterized by ¹H NMR, electronic absorption spectroscopy, and mass spectrometry. The effect of the nature of functional groups within iron complexes on the redox processes involving these complexes in water–alkaline solutions is analyzed. Electronic transitions in the ligand (E_red/ox = 0.820–0.850 V) and the metal (E_red/ox =–0.005 to–0.190 and–0.790 to–0.870 V for the Fe⁴⁺ ? Fe³⁺ and Fe³⁺ ? Fe²⁺ transitions, respectively) were found in the cyclic voltammograms. Iron in the synthesized complexes I–IV under the conditions under study exists in the +4 oxidation state. The activity of iron complexes in electroreduction of molecular oxygen significantly depends on the nature of a substituent, increases in the series: Fe(ms-p-NO₂Ph)₃Cor (II) < Fe(ms-p-MeOPh)₃Cor (I) < Fe(β-Br)₈(ms-Ph)₃Cor (IV) < Fe(ms-Ph)₃Cor (II) and is caused by the fact that low-energy redox electron transitions occur in the molecules. The electrocatalytic activity of iron corroles is much higher than that of metal porphyrins with a similar structure.     

Synthesis and properties of <Emphasis Type="Italic">N</Emphasis>-(alkenylidene)trifluoromethanesulfonamides

N-Alkenylidenetrifluoromethanesulfonamides TfN=CH–CR=C(Me)R′ (R, R′ = H, Me) have been synthesized by reaction of N-sulfinyltrifluoromethanesulfonamide TfNSO with (E)-but-2-enal, (E)-2-methylbut- 2-enal, and 3-methylbut-2-enal. Despite greater stability of N-alkenylidenetrifluoromethanesulfonamides relative to their propargyl isomers TfNHCH₂C≡CR, no rearrangement of the latter into the former occurs due to the presence of an acidic NH proton, which hampers formation of carbon-centered anion.     

β-Acetyl-β-nitrostyrenes: Structure and use for synthesis of heteryl-containing structures

¹H, IR, and electronic absorption spectroscopy and X-ray diffraction analysis were used to establish that 1-acetyl-1-nitro-2-phenyl-and 2-(p-methoxyphenyl)ethenes have Z configuration, and their 2-(p-N,Ndimethylaminophenyl)-substituted analog exists in chloroform-d ³ as a mixture of Z and E isomers. The reactions of gem-acetylnitroethenes with N-methylpyrrole were shown to involve alkylation at the C²-reaction center of the heterocycle. The reactions of these nitroalkenes with hydrazine form pyrazoles and azines, with acetylhydrazine, the corresponding hydrazones (via transalkenylation), and with sodium azide, acetylsubstituted 1,2,3-triazoles.