Radical cation salts of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and bis(methylenedithio)tetrathiafulvalene (BMDT-TTF) with the 8,8′-dichloro derivative of cobalt bis(1,2-dicarbollide) (BEDT-TTF) 2 [8,8′-Cl 2 -3,3′-Co(1,2-C 2 B 9 H 10 ) 2 ] ( 1 ) and (BMDT-TTF) 4 [8,8′-Cl 2 -3,3′-Co(1,2-C 2 B 9 H 10 ) 2 ] ( 2 ) were synthesized and their crystal structures and electrocon-ducting properties were determined. The synthesized radical cation salts are semiconductors with the conductivity σ 293 = 1.5 and 2.0 Ohm −1 cm −1 , respectively. A decrease in the size of the substituent in a series of (BEDT-TTF) 2 [8,8′-X 2 -3,3′-Co(1,2-C 2 B 9 H 10 ) 2 ] and (BMDT-TTF) 4 [8,8′-X 2 -3,3′-Co(1,2-C 2 B 9 H 10 ) 2 ] (X = I, Br, Cl) results in the compression of the anion sublattice of the crystal and compaction of the radical cation packing of the conducting layer, which, in turn, increases the conductivity of the crystals.

A technique is proposed for directed synthesis of 6,11-dichloro-9-dimethylthio-7,8-dicarba-nido-undecaborane [6,11-Cl2-9-SMe2-7,8-C2B9H9]. Single-crystal X-ray diffraction is used to identify the molecular and crystal structure of the compound.

2,3-Dihydrofuro[3,2-c]coumarin-3-one was synthesized in quantitative yield from 3-(ω-bromoacetyl)-4-hydroxycoumarin in the presence of nucleophiles (including solvents). This compound undergoes keto-enol tautomerization and easily reacts with aromatic and heteroaromatic aldehydes to form crotonization products having a Z configuration and exhibiting strong fluorescence.

The radical cation salts of tetrathiafulvalene (TTF) and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with iodo derivatives of cobalt bis(dicarbollide), (TTF)[9,9′,12,12′-I 4 -3,3′-Co(1,2-C 2 B 9 H 9 ) 2 ] and (BEDT-TTF)[9,9′(12′)-I 2 -3,3′-Co(1,2-C 2 B 9 H 10 ) 2 ], respectively, were synthesized and their crystal structures were determined. The introduction of iodine atoms into the lower rim of the dicarbollide ligands, unlike the substitution at the upper rim, leads to insignificant changes in the crystal structure and the conductivity of the radical cation salts compared to the analogous salts based on unsubstituted cobalt bis(dicarbollide).

Mechanisms of intramolecular transformations of carbanions generated from 2-aza-1,3,5-trienes by the action of potassium tert-butoxide, which could lead to homo- or heteroannular azacycloheptadienes, were studied by quantum-chemical methods in terms of the density functional theory. The corresponding gradient channels were localized for model 1-methylsulfanyl-1-(cyclopentylideneamino)- and 1-methylsulfanyl-1-(cyclohexylideneamino)buta-1,3-dien-2-ols. Analysis of the kinetic and thermodynamic parameters showed that carbanion generated from N-cyclopentylidenebuta-1,3-dien-1-amine undergoes rearrangement mainly into homoannular azacycloheptadiene and that analogous N-cyclohexylidene derivative gives rise to heteroannular isomer. The results of calculations were consistent with the experimental data.

Previously unknown bis[2-(4-tert-butyl)phen]ethylphosphine sulfide is obtained with a high yield from 4-tert-butyl styrene, red phosphorus, and elemental sulfur. Using single crystal XRD, multinuclear NMR, IR, and UV spectroscopy, it is found that the phosphorus atom is four-coordinated in the bis[2-(4-tert-butyl)phen]ethylphosphine sulfide molecule (regardless of the phase state of the compound: crystal, solution). By the example of phosphorylation of bis[2-(4-tert-butyl)phen]ethylphosphine sulfide acetylene in the KOH-DMSO system it is shown that the reaction proceeds by double addition with the participation of phosphorus-centered nucleophiles.

2,3-Dihydrofuro[3,2-c]coumarin-3-one reacts with aromatic amines in two pathways, depending on the solvent. The reactions in ethanol afford its enamines, while the use of acetic acid favors the formation of enamines of the 2,3-dihydrofuro[3,2-c]coumarin-3-one dimer. Electronic absorption spectroscopy in different solvents revealed that the enamines obtained can undergo tautomeric transformations. The product of a reaction of 2,3-dihydrofuro-[3,2-c]coumarin-3-one with 4-bromoaniline exists in the enamine form (X-ray diffraction data).

Steric structure of fluorinated 2-arylhydrazono-3-oxo esters was studied by 1 H, 19 F, and 13 C NMR spectroscopy and X-ray analysis. It was found that these compounds in the crystalline state and in solutions in acetone- d 6 , DMSO- d 6 , and CDCl 3 exist as Z isomers with the ester fragment involved in intramolecular hydrogen bond with the hydrazone NH proton. Exceptions are alkyl 2-arylhydrazono-4,4-difluoro-3-oxobutanoates which exist in acetone- d 6 as mixtures of Z and E isomers, the former prevailing. Unlike fluorinated analogs, ethyl 2-(4-methylphenyl)hydrazono-3-oxobutanoate in crystal has the structure of E isomer in which intramolecular hydrogen bond is formed between the NH proton and acetyl carbonyl group. The same compound in acetone- d 6 , DMSO- d 6 , and CDCl 3 gives rise to a mixture of Z and E isomers, the latter prevailing.

The reactions of 1-methylimidazoline-2-thione and its chemical oxidation product, viz., 2,2′-dithiobis(1-methylimidazolin-2-yl) diiodide, with molecular iodine were studied by UV-Vis spectroscopy. The crystal and molecular structure of the compound of composition [(C3H2N2)(HCH3)S]2(I3)2I2 was established by X-ray diffraction. In the crystal structure, the dications and the triiodide anions form mixed stacks, between which iodine molecules are located. The dications, anions, and iodine molecules are linked by numerous intermolecular interactions to form three-dimensional supramolecular associates.

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(3 H )-ylidene]- N ′-phenylthioureas (yield 57–60%). The structure of N -[5-benzoyl-3,4-diphenyl-1,3-thiazol-2(3 H )-ylidene]- N ′-phenylthiourea was proved by X-ray analysis.

Thiocarbonohydrazones derived from aromatic aldehydes reacted with 4-phenylbut-3-yn-2-one in aqueous acetic acid (20°C, 2 h) to produce previously unknown N″-[(E-s-cis)-arylmethylidene]-N″′-[(Z-s-trans)-1-methyl-3-phenylprop-2-yn-1-ylidene]thiocarbonohydrazides with high chemo-, regio-, and stereoselectivity. The steric structure of N″-[(E-s-cis)-benzylidene]-N″′-[(Z-s-trans)-1-methyl-3-phenylprop-2-yn-1-ylidene]thiocarbonohydrazide in crystal and in solution was studied by X-ray analysis and IR and NMR spectroscopy.

Condensation of ethyl 3-polyfluoroalkyl-3-oxopropionates with excess triethyl orthoformate gave ethyl 3-polyfluoroalkyl-2-ethoxymethylidene-3-oxopropionates which reacted with primary aliphatic, aromatic, and heterocyclic amines to form ethyl 2-alkyl(aryl, hetaryl)aminomethylidene-3-polyfluoroalkyl-3-oxopropionates. According to the X-ray diffraction and IR data, the latter exist in the crystalline state as the corresponding E isomers, while in solution (NMR data), as mixtures of Z and E isomers. Condensation of ethyl 2-ethoxymethylidene-3-oxopropionates with secondary heterocyclic amines (morpholine and pyrrolidine) led to the formation of 2-morpholino(pyrrolidin-1-yl)methylidene-3-fluoroalkyl-3-oxopropionates which were shown to exist as Z isomers both in the crystalline state and in solution.

Fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones react with methylamine in different ways, depending on the substrate structure. Arylhydrazones having a short fluoroalkyl substituent (RF = CF3, HCF2CF2) react at the carbonyl group adjacent to the nonfluorinated substituent to give 3-alkyl(aryl)-2-aryldiazenyl-3-methylamino-1-polyfluoroalkylprop-2-en-1-ones. Arylhydrazones with a long-chain fluoroalkyl group (RF = C3F7 and longer) and a bulky nonfluorinated group take up methylamine molecule at the carbonyl group linked to the fluorinated substituent, and the subsequent haloform reaction yields N-methyl-2-arylhydrazono-3-oxobutanamides. Both types of products are formed in reactions of methylamine with 1,2,3-triketone 2-arylhydrazones having a long fluoroalkyl group and methyl group at the other carbonyl group. Template condensation of fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones with methylamine over Ni(II) template gives bis[3-alkyl(aryl)-1-polyfluoroalkyl-3-methylamino-2-aryldiazenylprop-2-en-1-onato-N,N′]-nickel(II), regardless of the size of the fluoroalkyl substituent. The same complexes and their copper analogs can be obtained by treatment of 3-alkyl(aryl)-2-aryldiazenyl-3-methylamino-1-polyfluoroalkylprop-2-en-1-ones with the corresponding metal salts.

A new procedure was developed for the synthesis of 6-phenyltetrazolo[1,5-b]triazin-7-one. Aza analogs of uracil and isocytosine were prepared by the tetrazole ring cleavage. It was demonstrated that these transformations can be used in the synthesis of anomalous nucleosides.

1,2,4-Trimethylquinolinium triiodide ( I ) and 1-ethyl-2,4-dimethylquinolinium ( II ) triiodide are synthesized and studied by X-ray diffraction analysis. The layered structures of compounds I and II are formed by mixed stacks of cations and anions. Crystals of compound II consist of two types of anionic chains. The coordinating ability of the corresponding organic iodides toward molecular iodine in chloroform solutions is studied.

According to the 1 H, 13 C, and 19 F NMR data, fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones in CDCl 3 exist exclusively, while in (CD 3 ) 2 CO preferentially, as isomers in which the acyl or aroyl group is involved in intramolecular hydrogen bond. The isomer structure was assigned on the basis of the chemical shifts of the carbonyl carbon atoms and fluorine atoms and carbon-fluorine spin-spin coupling constants J C-F . X-Ray diffraction data showed that 1,2,3-trione 2-arylhydrazones in crystal have the same structure as in CDCl 3 solution. Quantum-chemical calculations were performed to rationalize predominant formation of 1,2,3-trione 2-arylhydrazone isomers with a free polyfluoroacyl group.

The crystal structures of the chelates NiIIL (L2− are the N,N′-(o-phenylene)-bis[4-(4-methylphenyl)hydrazono-3-oxo-1,1,2,2-tetrafluorononane-5-iminate], N,N′-ethylene-bis[3-(4-methylphenyl)hydrazono-4-oxo-5,5,6,6,7,7,8,8-octafluorooctane-2-iminate], or N,N′-ethylene-bis(4-hydroxy-5,5,6,6,7,7,8,8-octafluoro-3-octene-2-iminate) anions) were studied by X-ray diffraction. Magnetic measurements and ESR spectroscopic studies revealed the appearance of paramagnetism due to a tetrahedral distortion of the coordination unit and also the unusual behavior of the effective magnetic moment at low temperatures.

The structure of 2,3,4,6-tetra(O-vinyl) methyl-α-d-glucopyranoside, a new powerful carbohydrate synthon has been studied by 1H and 13C NMR, IR, MS and X-ray methods. The 13C–13C spin–spin coupling constants were measured to conclude that s-trans-conformation is preferable for the vinyloxy groups at C2, C3 and C4 atoms, while s-cis-conformation is inherent in the vinyloxy group at C6 atom. The data obtained are indicative of identical stereochemical structure of this compound both in crystals and in solution.