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Pd-catalyzed arylation of grosshemin by iodoarenes synthesized products with an exocyclic C-11,13 double bond in the (E)- and (Z)-configurations. The structures of four compounds were established by X-ray crystal structure analyses. The antibacterial activity and cytotoxicity of the new compounds were assessed.

The dammarane triterpenoid hollongdione was modified at the C3 and C20 positions to obtain 3β,20α-dihydroxy and (3E,20ZE)-3,20-dihydroxyimino derivatives whose structure was confirmed by X-ray analysis.

For the first time we synthesized a hydrazone derivative of harmine, namely (Z)-8-(1-hydrazonoethyl)-7-methoxy-1-methyl-9H-pyrido[3,4-b]indole based on indole alkaloid harmine. The structure of the synthesized compound is confirmed by NMR, mass spectroscopy, and single crystal X-ray diffraction data.

New tripodal ligand, tris(2-carbamoylmethoxyphenyl)phosphine oxide, has been synthesized via the alkylation of tris(2-hydroxyphenyl)phosphine oxide with chloroacetamide. The ligand structure has been studied by means of IR and NMR (1H, 31P) spectroscopy as well as X-ray diffraction.

Diethylaminovinyl derivatives of halogenated 1,4-quinones (enaminoquinones) are produced by the interaction of halogenated 1,4-quinones with N,N-diethyl-N-vinylamine obtained in situ from Et2NH and MeCHO. Molecular and crystal structures of enaminoquinones halogenated in the quinone fragment are determined. It is shown that in the solid phase, atoms of the entire push-pull system of enaminoquinones lie practically in one plane.

A reaction of a [1,4-C6H4(CH2PPy3)2]Cl2 cationic ligand with CuI (MeCN, r.t.) produces an ionic [C6H4(CH2PPy3)2][C6H4(CH2PPy3Cu3I5)2] complex containing structurally unprecedented [Cu3I5]2– inorganic module in the anionic part. The title complex in the solid manifests a weak deep-red luminescence with λmax = 680 nm and lifetimes of 14 μs and 17 μs at 300 K and 77 K, respectively.

1-D chain coordination polymer (CP) of [Cu2I2(PymPPh2)]n type has been synthesized reacting CuI with 2-(diphenylphosphino)pyrimidine (PymPPh2) under mild conditions (MeCN, r.t.). The structure of the CP is imagined by double-stranded (Cu2I2)n ribbons, the Cu atoms of which are bridged by the PymPPh2 ligands in a 1,3-N,P fashion. At ambient temperature the solid-state CP manifests broad-band photoluminescence (λmax = 530 nm) with the average lifetime of 1.2 µs and quantum efficiency being 15%.

Reaction of 2-(methylthio)pyrazine (L) with CuI (MeCN, r.t.) results in formation of iodide-bridged complex [Cu2(μ2-I)2L4], wherein Cu⋯Cu contact of 2.6351(4) A is observed. The each metal atom of the [Cu2(μ2-I)2] core is coordinated by the two ligands via 4-pyrazyl nitrogen atoms. In the solid state at room temperature, the complex obtained emits an orange photoluminescence (λmax = 600 nm) with the average lifetime of 1.66 μs and quantum yield of 17%.

The synthesis and properties of tricyclic diterpenoids containing a C-4 functionalized oxazole ring are reported. The reaction of 4-[5-(bromomethyl)oxazol-2-yl]-18-norisopimarane with sodium azide in the presence of hydrated copper sulfate and sodium ascorbate in DMF gave the corresponding azide, from which new diterpenoid derivatives containing a 1H-substituted 1,2,3-triazol-4-yl substituent were synthesized. Reduction of the azide produced the terpenoid 5-aminomethyloxazole. Reaction of 4-[5-(bromomethyl)oxazol-2-yl]-18-norisopimarane with methyl esters of amino acids in DMF in the presence of potash synthesized compounds with oxazole C-5 amino-acid substituents. Cytotoxicity of the new isopimaric acid derivatives gainst CEM-13, MT-4, U-937, MCF-7, and MDA-MB-231 human tumor cells was studied.

It has been established that ethyl iodoacelate and 1,4-diiodobutane alkylate triarylantimony Ar3Sb with the formation of [Ar3SbCH2C(O)OEt]+I− and [Ar3Sb(CH2)4I]+I−, \({[{\rm{A}}{{\rm{r}}_3}{\rm{Sb}}{({\rm{C}}{{\rm{H}}_2})_4}{\rm{I}}]^ + }{{\rm{I}}^ - },\;{[{\rm{A}}{{\rm{r}}_3}{\rm{Sb}}{({\rm{C}}{{\rm{H}}_2})_4}{\rm{SbA}}{{\rm{r}}_3}]^ {2+} }{\rm{I}}_2^ - \), where Ar = 2,6-(OMe)2C6H3. The complexes \([{\rm{A}}{{\rm{r}}_3}{\rm{SbC}}{{\rm{H}}_2}{\rm{C}}({\rm{O}}){\rm{OEt}}]_2^ + \;{[{\rm{H}}{{\rm{g}}_2}{{\rm{I}}_6}]^{2 - }}\) and \([{\rm{A}}{{\rm{r}}_3}{\rm{SbMe}}]_2^ + \;{[{\rm{Hg}}{{\rm{I}}_4}]^{2 - }}\) · DMSO have been synthesized by the reaction of [Ar3SbCH2C(O)OEt]+I− and [Ar3SbMe]+I− with mercury diiodide and studied by X-ray diffraction. The antimony and iodine atoms have a distorted tetrahedral coordination. The CSbC and IHgI angles are ranged within 103.28(14)°–116.68(14)°, 103.7(4)°–115.5(4)° and 98.122(9)°–125.590(12)°, 102.66(2)°–115.64(2)°, respectively.

A new series of push–pull azo-dyes containing tricyanodiphenyl electron-withdrowing block, namely (4-N,N-dialkylaminophenyl)azobiphenyl-2,3’,4’-tricarbonitriles, was proposed and synthesized. The azo-dyes possess high temperature stability and are prone to form polymorph modifications. DSC measurements indicated solid-phase transitions of these polymorphs. X-ray diffraction (XRD) analysis revealed that in all solved structures, there is a network of short intermolecular contacts between HArom atoms and N atoms of cyano groups. The supramolecular structure of these contacts depends on the alkyl chain length in the aniline moiety, and changes after temperature induced phase transitions.

Tri-p-tolylbismuth perchlorate (1) and μ-oxo-bis[(perchlorato)tri-p-tolylbismuth] (2) have been synthesized by the reaction between tri-p-tolylbismuth dibromide and silver perchlorate and its hydrate. The complexes have been studied by chemical analysis, IR spectroscopy, and X-ray diffraction. Complex 1 is triclinic, space group Pī, Z = 4, a =10.7271(9) A, b = 13.5585(11) A, c = 18.1592(13) A, α = 110.867(3)°, β = 94.944(3)°, γ = 96.888(3)°, V = 2426.3(3) A3, ρcalcd = 1.865 g/cm3; complex 2 crystallizes in trigonal symmetry, space group R $$\bar 3$$ , a = 13.1157(2) A, c = 22.1959(2) A, γ = 120°, V = 3306.64(8) A3, ρcalcd = 1.777 g/cm3. The bismuth atoms in the molecular structure of complex 1 have a distorted trigonal bipyramidal coordination to the apically arranged oxygen atoms of perchlorate ions (Bi–C, 2.180(5)–2.201(5) A; Bi–O, 2.324(4)–2.355(4) A; OBiO axial angles, 170.1(1)°, 174.5(1)°). The structure of complex 2 contains binuclear [p-Tol3Bi(ClO4)]2O molecules (Bi–O, 2.371(15), 1.9107(7) A; OBiO axial angle, 180.0°).

A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with 2-methoxypentafluoro-1,4-naphthoquinone to form a product of addition at the carbonyl function: radical 2-(3,5,6,7,8-pentafluoro-1-hydroxy-2-methoxy-4-oxo-1,4-dihydronaphthalen-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl. The yield of the addition product increased with temperature and reached 84% at 0 °C. The reaction of the lithium derivative with hexafluoro-1,4-naphthoquinone gave rise to a product of addition at both carbonyl groups, namely, nitronyl nitroxide diradical 2,3,5,6,7,8-hexafluoro-1,4-bis(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazole-2-yl)-1,4-dihydronaphthalene-1,4-diol in a 16% yield. The structures of both mono- and diradical were solved by X-ray diffraction analysis, which revealed formation of an intramolecular H-bond between the OH group and nitroxide oxygen. According to electron paramagnetic resonance (EPR) spectroscopy, the obtained mono- and dinitroxide are prone to spontaneous deoxygenation in a toluene solution to give corresponding iminonitroxides. In water, they are much more stable.

Tris(2,6-dimethoxyphenyl)antimony diazide has been synthesized and characterized by X-ray diffraction. The antimony atoms in four crystallographically independent molecules have a distorted trigonal pyramidal coordination. Axial angles range within 174.57°–178.95°.

Double ionic complexes [M(C5H5NCOO)3(H2O)2][Cr(NCS)6] · nH2O, where M = Eu (I), n = 1.15; Dy (II), Er (III), n = 1.5; M = Yb (IV), n = 2, have been synthesized by the reaction between M(NO3)3, M = Eu, Dy, Er, Yb, K3[Cr(NCS)6], and nicotinic acid (C5H5NCOO) in an aqueous solution and studied by chemical analysis, IR spectroscopy, and X-ray diffraction. Crystals of complexes I–IV are monoclinic, space group P21/n, Z = 4; a = 9.5358(2) A, b = 25.4871(5) A, c = 15.4303(4) A, β = 105.513(1)°, V = 3613.6(1) A3, ρcalcd = 1.799 g/cm3 for I, a = 9.5901(5) A, b = 25.8599(15) A, c = 15.6316(9) A, β = 106.829(2)°, V = 3710.6(4) A3, ρcalcd = 1.782 g/cm3 for II, a = 9.5640(3) A, b = 25.8936(11) A, c = 15.6498(7) A, β = 106.895(2)°, V = 3708.3(3) A3, ρcalcd = 1.791 g/cm3 for III, and a = 9.5049(2) A, b = 25.6378(4) A, c = 15.5120(3) A, β = 106.934(1)°, V = 3616.1(1) A3, ρcalcd = 1.864 g/cm3 for IV.

By cross-coupling of 2-iodo-polyfluoroanilines with a [AuPPh3NN] complex (where NN is 4,4,5,5- tetramethyl-3-oxide-1-oxyl-2-imidazolin-2-ide) in the presence of [Pd(PPh3)4], nitroxide radicals (2-aminopolyfluorophenyl- 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyls) are synthesized. Their molecular and crystal structures are determined by the X-ray crystallographic analysis. It is shown that in the solid phase there are both intra- and intermolecular hydrogen bonds between NH2 groups and O atoms of paramagnetic fragments, which link the molecules into chains or dimers.

Reactions of hexafluoro-1,4-naphthoquinone with phosphorus-centered bis-phenylphosphanes with structure Ph2P(CH2)nPPh2 (where n = 1–5) and Et2P(CH2)2PEt2 in various solvents (anhydrous C6H6, aq. C6H6, aq. dioxane, aq. DMSO, or MeOH) were investigated. It was shown that the use of aqueous dioxane and DMSO leads to target products of phosphanodefluorination (i.e., phosphorus-containing betaines and bis-betaines) with high yields. We found that the betaines upon purification by thin-layer chromatography underwent various transformations such as a ring contraction (thus yielding novel polyfluorinated indenones) or addition of an acetone molecule at the C O bond of the fluorinated 1,4-naphthoquinone. According to X-ray diffraction analysis, there were intermolecular F⋯π interactions in the crystal packing of all the obtained betaines. The interactions are characterized by short distances F⋯Cg from 3.151(5) to 3.831(2) A (where Cg is a centroid of π-system).

(4-(Diphenylphosphino)pyrimidin-2-yl)diphenylphosphine oxide is unexpectedly formed in 24% yield in the reaction of 2,4-dichloropyrimidine with 2 equiv. of Ph2PLi in THF solution. It was demonstrated that title compound reacts with AgNO3 forming 1D polymer [Ag(L)NO3], wherein P,N,O-bringing coordination of the ligand is observed. At 300 K, both free ligand and the 1D polymer exhibit solid-state photoluminescence maximized at 480 and 538 nm with 3.2 ns and 2.95 µs afterglow times, respectively.

New double complexes [Co(DMSO)6][SiF6] ⋅ 2H2O (I) and [Co(DMF)3(H2O)3][SiF6] ⋅ DMF (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction. Crystals of complex I belong to the tetragonal symmetry system, space group R3, Z = 3, a = 11.8232(3) A, c = 18.4699(5) A, V = 2235.97(10) A3, ρcalc = 1.573 g/cm3. Crystals of complex II are triclinic, space group P1, Z = 2, a = 8.6264(4) A, b = 10.1419(4) A, c = 13.9657(6) A, α = 100.847(2)°, β = 98.549(2)°, γ = 93.479(2)°, V = 1181.71(9) A3, ρcalc = 1.539 g/cm3.

[Mn2(C11H13N3O)6(H2O)2][Cr(NH3)2(NCS)4]4 (I) has been synthesized by the reaction between MnCl2 · H2O, NH4[Cr(NH3)2(NCS)4] · 0.5H2O and 4-aminoantipyrine (C11H13N3O) in an aqueous solution, and its structure has been determined by IR spectroscopy and X-ray diffraction. Crystals of complex I are triclinic, space group \(P\bar 1\) , Z = 1, a = 13.2378(5) A, b = 15.7796(5) A, c = 16.7703(6) A, α = 83.194(2)°, β = 75.874(2)°, γ = 66.529(1)°, V = 3115.2(2) A3, and ρcalcd = 1.407 g/cm3.

The conditions of synthesis of a new binary complex salt [Co(Cpl)6][Hg2I6] (Cpl is e-caprolactam e-C6H11NO) have been developed, and its structure has been characterized. The salt crystallizes in triclinic system, space group \(P\bar 1\) , a = 10.1078(4) A, b = 12.2680(5) A, c = 13.0782(5) A, α = 62.872(2)°, β = 72.394(2)°, γ = 76.834(2)°, V = 1367.98(9) A3, Z = 1, and ρcalc = 2.297 g/cm3. The structure is insular and consists of isolated ions.

An improved procedure was developed for the synthesis of 3,3,3-trifluoro-1-nitropropene, and a new representative of gem-bromonitroalkenes, 1-bromo-3,3,3-trifluoro-1-nitropropene, was synthesized therefrom. Its reaction with phenyl azide gave a mixture of two regioisomeric 1,2,3-triazoles, from which pure 5-nitro-1-phenyl-4-(trifluoromethyl)-1H-1,2,3-triazole was isolated.

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.

Phase transitions in a glassy film of 4-((4-(dibutylamino)phenyl)diazenyl)-biphenyl-2,3′,4′-tricarbonitrile was initiated by a monochromatic X-ray microbeam with λ = 0.71 A (MoKα). At the site of the film that was directly impacted by irradiation noticeable morphological changes immediately occurred with subsequent crystal formation. From the site of irradiation, the front of transition of the glassy film into a liquid crystal phase propagated isotropically in all directions. This phenomenon is reproducible and clearly observed in the film prepared by heating the azo compound until melting and cooling it down to room temperature. These results highlight the fact that X-rays can be used as a tool to stimulate phase transitions in glassy azo compounds, which could also give birth to new and unexpected discoveries.

The reaction of 2-X-trifluoro-1,4-benzoquinones (X = F, Cl, Me, OMe) with triphenylphosphane in various solvents (C6H6, Et2O, THF, dioxane, MeOH, aq. dioxane and Me2SO) has been investigated. It was shown that: (1) the quinones react with PPh3 at an oxygen atom and at a carbon atom with formation of products of reduction and of triphenylphosphanodefluorination, accordingly; (2) the use of more polar solvents, such as MeOH, aq. dioxane and Me2SO, leads to an increase in products of phosphanodefluorination; (3) triphenylphosphanodefluorination of 2-X-trifluoro-1,4-benzoquinones (X = Cl, Me, OMe) takes place at positions 5 and 6 to X in ratios depending on the nature of the substituent X. Possible reasons for obtained results are discussed in detail. The entry of solvent molecule into products of phosphanodefluorination of fluoranil was observed in MeOH. The triphenyl(3,4,6,6-tetrafluoro-2-oxido-5-oxocyclohexa-1,3-dien-1-yl)phosphanium and its analogs serves as starting material for a new type of nitrogen-containing phosphorus compounds. The structures of isolated betaines were proved by the XRD and the 19F, 31P{1H} and 13C{1H} NMR data.

Trimethylsilylphosphines PhRPSiMe3 (1 R = Me, 2 R = Ph) have been shown to phosphinodefluorinate 1,2,3- (3), 1,3,5- (4) and 1,2,4-trifluorobenzene (5) in benzene solution or without solvent at 150–200 °C to form the respective (difluorophenyl)methylphenyl- and -diphenylphosphines in high NMR yields under harder conditions compared to the previously reported reactions of Me2PSiMe3 with the same substrates. Hexafluorobenzene (6), pentafluorobenzene (7) (at 150 °C), octafluorotoluene (8) and pentafluoropyridine (9) (at 20 °C) react with phosphine 2 without a solvent almost quantitatively under fluorine 1,4-disubstitution (for 6) or monosubstitution (for 7–9) by the Ph2P group to give the corresponding (polyfluoroaryl)diphenylphosphines in 50–60% (for 6–8) and 95% (for 9) isolated yields. The regio and substrate selectivities exhibited by 3–5 in the reactions of the single substrates and in competitive reactions of 3 vs. 4 with 1 or 2 and 4 vs. 5 with 2 indicate relative fluorine substituent rate factors fo-F > fm-F consistent with the concerted ANDN mechanism which is supported by high level quantum chemical DFT-studies for the reactions of the substrates 3 and 4 with 1, 2 and 10 as well as for 6 with 2.

The reaction of 4-hydroxycoumarin with 2-acetyloxiranes in dimethylformamide in the presence of triethylamine gave 2,3-dihydro-4H-furo[3,2-c]chromen-4-ones which were converted into 4H-furo[3,2-c]-chromen-4-one derivatives as a result of dehydration or fragmentation.

The reaction of heptafluoro-1-naphthol with N,N-dialkyl-p-nitrosoanilines or N,N-dialkyl-p-phenylenediamines in the presence of HIO3 gave the corresponding polyfluorinated N-aryl-1,4-naphthoquinone 4-imine derivatives which exist in solution as equilibrium mixtures of Z and E isomers. 2,3,5,6,7,8-Hexafluoro-N-(4-dimethylaminophenyl)-1,4-naphthoquinone 4-imine in crystal has exclusively the Z-isomer structure.

Peucedanin reacted with methylideneiminium salt generated in situ from N,N,N′,N′-tetramethylmethanediamine and acetyl chloride to give 2-(dimethylaminomethyl)oreoselone. Reactions of peucedanin with aminomethylating agents generated in situ from formaldehyde and dimethylamine, N-methylpiperazine, or N-Boc-piperazine in boiling methanol smoothly afforded the corresponding 9-aminomethyl derivatives whose hydrolysis produced 9-aminomethyl-substituted oreoselones. 2,3,9-Trisubstituted linearly fused furocoumarins were synthesized by reactions of 9-substituted oreoselone trifluoromethanesulfonates with arylboronic acids.

Fluorinated benzo-fused 1,3-diazoles, 1,2,3-triazoles, 1,2,5-thia/selenadiazoles and 1,4-diazines were synthesized and tried for cytotoxicity towards the Hep2 (laryngeal epidermoid carcinoma) cells. The diazoles, triazoles and selenadiazoles were cytotoxic with IC50 = 2.2–26.4 µM and induced the cells apoptosis at concentrations C = 1–25 µM. At the same time, they were nontoxic towards normal cells. Due to this, these scaffolds were used in the computer-aided molecular design of new antitumor agents. Particularly, novel 1,2,3-triazole and 1,3-diazole derivatives for the binding site of the PAS domain of the transcription factor HIF were designed and some of them synthesized for further study. Overall, new anticancer agents featuring apoptotic activity are suggested.

N-(2-Vinyloxyethyl)phosphinothioamides and -phosphinoselenoamides prepared by oxidative cross-coupling of 2-vinyloxyethylamine with secondary phosphine chalcogenides undergo thermal (75–100 °C) cyclization into the corresponding 3-(diorganylchalcogenophosphoryl)-2-methyl-1,3-oxazolidines in 80–90% yields.

16-Propargylaminomethyl substituted and 16-propargyloxymethyl substituted furanolabdanoids were synthesized, which under the action of AuCl3 in acetonitrile underwent cycloisomerization forming 7-hydroxyisoindolines or 7-hydroxydihydroisobenzofurans substituted by a terpenoid fragment.

It was shown that plants of the genus Ferulopsis are valuable sources of coumarins. Nine angular 8-substituted and 8,9-disubstituted 8,9-dihydrofurocoumarins were isolated. The cytotoxicity of these compounds was studied on models of human CEM-13, MT-4, and U-937 tumor cells. X-ray structure data were obtained for peucenidin.

Allylic oxidation of phlomisoic acid and its methyl ester by selenium dioxide occurred stereoselectively to form 7α-hydroxy derivatives of labdanoids, which were oxidized by active manganese dioxide to 7-ketofuranolabdanoids. Oximation of the last by hydroxylamine hydrochloride in MeOH in the presence of NaOAc gave pure (E)-ketooximes. Beckmann rearrangement of 7-ketooximes of phlomisoic acid and its methyl ester occurred with formation of the corresponding octahydro-1 H-benzoazepines.

Thermal transformations of 2H-benzimidazole 1,3-dioxides represented by spiro[2H-benz-imidazole-2,1′-cyclohexane] 1,3-dioxide and its 5-nitro derivative were studied. Their heating resulted in reversible isomerization to spiro[3H-[2,1,4]benzoxadiazine-3,1′-cyclohexane] 4-oxides. More prolonged heating of 2H-benzimidazole 1,3-dioxides caused sequential elimination of the first and then (at higher temperature) the second N-oxide oxygen atom to form 2H-benzimidazole derivatives, which upon further heating were transformed to 7,8,9,10-tetrahydro-6H-azepino[1,2-a]benzimidazoles. A scheme of the process was suggested, which described the experimental data obtained. Spiro[3H-[2,1,4]benzoxadiazine-3,1′-cyclohexane] 4-oxides on exposure to the sunlight were quantitatively transformed to 2H-benzimidazole 1,3-dioxides.

Palladium-catalyzed Heck reaction of oreoselone trifluoromethanesulfonate with various terminal alkenes (methyl acrylate, styrene, vinylpyridines, N-vinylpyrrole, and N-vinyl-1,2,4-triazole) led to the formation of the corresponding (E)-3-vinyl-7H-furo[3,2-g]chromen-7-ones. The yield was found to depend on the catalytic system and initial olefin structure.

By Heck reaction of isoalantolactone with aryl bromides or aryl iodides (3aR,4aS, 8aR,9aR,E)-3-arylmethylidene-8a-methyl-5-methylidenedecahydronaphtho[2,3-b]furan-2(3H)-ones and (4aS,8aR,9aS)-3-arylmethyl-8a-methyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-2(4H)-ones, products of the double bond shift, were synthesized. The yields of the arylation products depend on the nature of the catalytic system and on the structure of the aryl halide. The structures of (3aR,4aS,8aR,9aR,E)-3-(3,4-dimethoxybenzylidene)-8amethyl-5-methylidenedecahydronaphtho[2,3-b]furan-2(3H)-one and (4aS,8aR,9aS)-3-(2-methylsulfanylbenzyl)-8amethyl-5-methylidene-4a,5,6,7,8,8a,9,9a-octahydronaphtho[2,3-b]furan-2(4H)-one were proved by XRD analysis.

Reactions of 16-cyanomethyllambertianate with organozinc reagents obtained from ethyl esters of α-bromoacetic, α-bromopropionic, and α-bromobutyric acids gave the corresponding enaminoesters, β-ketoesters, and β-hydroxyesters of labdanoids whose yield depended on the reaction conditions and the structure of the α-bromoester. By Reformatsky reaction of 16-formylmethyllambertianate with α-bromoesters of carboxylic acids stereoisomeric β-hydroxyesters of labdanoids were synthesized.

Slow evaporation in air of the solution of trimeric perfluoro-ortho-phenylene mercury (1) and 2,1,3-benzothiadiazole (2) in THF affords a complex l.2 2·H2O0.59 (3). A complex of 1 with di(tetrahydrofur-2-yl) ether (4; probably, a THF oxidation product) with a composition of 1.4 2 (5) is detected as a minor admixture to 3. The structure of complexes 3 and 5 is determined by single crystal XRD. In complex 3, a molecule of 1 participates in Hg…N and πF…H—C interactions with one molecule of 2 and in the πF…πH stacking interaction with another. Complex 5 is formed by Hg…O interactions with the participation of both heterocycles of a molecule of 4.

Reduction of anti-1-benzoylanthraquinone oxime gave 2-phenylanthra[9,1-bc]pyrrol-6-one whose structure was determined by X-ray analysis. The molecule of 2-phenylanthra[9,1-bc]pyrrol-6-one is almost planar, and its crystalline structure is characterized by head-to-tail chains formed via intermolecular hydrogen bonds N-H ... O.

By reactions of 4-amino-2,6-dihalonitrosobenzenes with sodium azide and 4,6-dihalo-2,1,3-benzoxadiazoles with amines a group of 2,1,3-benzoxadiazole aminoderivatives was prepared.

A method for preparing 15,16-epoxylabda-8(9),13(16),14-trien-18-oic (phlomisoic) acid was proposed. Its structure was confirmed by an XSA. N-containing derivatives of phlomisoic acid that contained amines, hydrazides, and methyl esters of amino acids on the C-18 atom in addition to (2-oxo-2-aminoacetyl)-substituted derivatives of the C-16 methyl ester of phlomisoic acid were prepared.

Rods (1D assemblies) formed by alternate crown ether and arylenediamine molecules are the motif of the supramolecular architecture of crystals of molecular associates of 18-crown-6 with tetrafluoro-1,4- and -1,3-phenylenediamines, hexafluoro-2,6- and -2,7-naphthylenediamines. Molecules in the assemblies are arranged via H-bond predominantly between the crown ether oxygen atoms and the polyfluoroarene amino group hydrogen atoms. Influence of the amino groups mutual arrangement and the aromatic framework size on the crystal supramolecular architecture is characterized. Specific melting heats of the crystalline 1D assemblies of para- and pseudo-para-arylenediamines are higher than those of meta- and pseudo-meta-analogs; the associates having higher melting heats selectively crystallize from solutions of isomeric phenylene- or naphthylenediamine mixtures.

Intermolecular interactions in crystals of various azachalcagenenes with aromatic substituents, including polyfluorinated derivatives, are first analyzed and systematized. A topological analysis of crystal packing is carried out, and main supramolecular motifs are identified.