Triple co-oligomers of 4-isopropenylphenol, phenol and formaldehyde were synthesized and used for the first time as precursors in the structuring reaction in the presence of acrylonitrile and the initiator benzoyl peroxide. The yield of cross-linked copolymers is 84% (of theory). The use of hydrolyzed cross-linked copolymers is shown to be effective as sorbents for the extraction of UO 2 2+ ions from model aqueous systems under batch conditions, and the degree of their sorption significantly depends on the medium pH, the initial concentration of UO 2 2+ ions and the exposure time. The best results were achieved at pH 7 and 9, at which the degree of extraction of UO 2 2+ ions from an aqueous solution with their initial concentration of 134 ± 0.5 mg L –1 is ~93.5% (room temperature, 24 h), while the sorption capacity of the cross-linked copolymer is ~210 mg g –1 . The highest sorption capacity of the copolymer reaches 300 ± 30 mg g –1 . The possibility of regeneration of the sorbent with mineral acid (НNO 3 , HCl) was revealed; the maximum degree of desorption of UO 2 2+ ions is ~91%.

The reaction of methyl anthranilate with 2-methylphenyl- iso -selenocyanate in boiling absolute ethanol affords a new compound: 3-(2-methylphenyl)-2-selenoxo-2,3-dihydroquinazolin-4(1 Н )-one (HL). Free ligand HL, which is selone, is preliminarily transformed into the corresponding sodium selenolate [C 15 H 11 N 2 OSeNa] ( I) , which is then used without isolation in the reaction with cadmium chloride. This reaction leads to the formation of complex [Cd 2 (μ-L) 2 (L) 2 (C 2 H 5 OH) 2 ] ( II ). The structures of the compounds are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2142342 (НL) and 2246014 ( II )) and NMR spectroscopy ( 1 Н, 13 С, 15 N, and 77 Se). In the crystal, the molecules of HL form one-dimensional chains due to H…O and H…Se contacts and alternate in the syndiotactic order. Compound II is the centrosymmetric binuclear complex [C 64 H 56 Cd 2 N 8 O 6 Se 4 ]. The cadmium atoms in complex II are hexacoordinated by two chelate anionic ligands L – . According to the NMR data, in a DMSO-d 6 solution free ligand HL has the selone structure, whereas in cadmium complex II this ligand exists in the selenolate form, which is consistent with the XRD data on the crystal structures of the compounds.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

In the present paper, several computational binding analyses were performed on ethyl 3,3,5,5-tetracyano-2-hydroxy-2-methyl-4,6-diphenylcyclohexane-1-carboxylate which was newly synthesized by three-component condensation of benzaldehyde with ethyl acetoacetate and malononitrile in the presence of trichloroacetic acid, and the structure was finally proved by X-ray analysis. The visualization of molecular interaction was carried out through Hirshfeld surface analysis and ESP. The atomic charges, HOMO, LUMO, and electrostatic potential were also studied to explore the insight of the molecule deeper, and then, natural bonding orbitals (NBO) and non-linear optical properties (NLO) were calculated to reveal the interactions that happen to be between the filled and vacant orbitals. Afterwards, molecular docking studies predicted the compound binding mode fits in the minor groove of DNA and remained interacts via stable bonding as validated by molecular dynamics simulations. The binding energy estimation also affirmed domination van der Waals and electrostatic energies. Lastly, the compound was found as good drug-like molecule and had good pharmacokinetic profile with exception of toxic moieties.

This article presents the results of studies on the study of the reaction of triple alkaline polycondensation of 4-isopropenylphenol, formaldehyde and 4-(1-methyl-1-dimethoxyphosphorylethyl)phenol, as well as the structuring of the synthesized triple cooligomers in the presence of a cross-linking comonomer - acrylonitrile and an initiator of azo-bis-isobutyric acide dinitrile (ABD). It was found that the process of triple polycondensation of 4-isopropenylphenol, formaldehyde and 4-(1-methyl-1-dimethoxyphosphorylethyl)phenol proceeds well in the presence of a potassium hydroxide catalyst (0.5% per mixture of initial reagents) at a temperature of 60 degrees C for 3-4 h. The ratio of 4-isopropenylphenol, formaldehyde and 4-(1-methyl-1-dimethoxyphosphoryl-ethyl) phenol was 1:2:1 (mol), respectively. The yield of triple co-oligomers is 94%. The results of studies on the determination of the molecular weight of ternary cooligomers and their M-w obtained by the gel chromatographic method showed that the synthesized ternary cooligomers of 4-isopropenylphenol, formaldehyde, and 4-(1-methyl-1-dimethoxyphosphorylethyl)phenol are oligomeric compounds and they mainly represent are low molecular weight substances (Mw 2225, Mn 720, Mw/Mn 3.09). The content in them of relatively high molecular weight co-oligomers (Mw 7920, Mn 6450, Mw/Mn 1.23) does not exceed 15%. The main conditions for the process of structurization of the ternary co-oligomers are revealed. The ratio of co-oligomers: acrylonitrile is (2-3):1 mol. The structuring temperature is 75-80 degrees C, the amount of diniz initiator is 1% per mixture of reactants, the time is 5-8 h. The yield of the obtained cross-linked copolymers is 95-97%. The thermal properties of ternary cooligomers have also been studied. The structures of the ternary co-oligomers and the cross-linked copolymers obtained based on were confirmed by IR and NMR spectroscopy

Using radiothermoluminescence (RTL), the molecular mobility features in the temperature range of 77–300 K were studied for the polypropylene (PP)/ethylene propylene diene elastomer SKEPT-4044 with NiO, Cu2O, and Fe3O4 nanoparticles (NPs) based on ABS-acrylonitrile butadiene or SCS-divinyl styrene matrices. It has been shown that the introduction of nanofillers in PP significantly affects the nature and temperature of γ- and β-relaxation processes, while the region of manifestation of the β process noticeably shifts to the region of low temperatures. Composites with Cu2O NPs have a higher β-transition temperature Tβ than composites with other NPs. It has been found that PP/SKEPT-4044 composites with Cu2O NPs with a dispersion of 11–15 nm and acrylonitrile butadiene thermoplastics have optimal frost resistance compared to other compositions.

New complex compounds [Cd(μ-L1)2]n (I), [Cd(μ-L2)(μ-Cl)(μ-DMSO)]n (III), and [Cd2(μ-L2)(μ-Cl)3(μ-DMSO)DMSO/EtOH]n (IV) are synthesized by the reactions of 1-(4-methoxyphenyl)-1,4-dihydro-5H-tetrazole-5-thione (HL1) and 1-(2-methoxyphenyl)-1,4-dihydro-5H-tetrazole-5-thione (HL2) with cadmium chloride. The molecular and crystal structures of the complexes are determined by X-ray structure analysis (CIF files CCDC nos. 1993455 (I), 1869249 (III), and 1993497 (IV)). Complexes I, III, and IV have uniform polymeric structures. The О···Н, Cl···H, and C···S contacts are observed between 1D polymeric chains in the crystal cells of complexes I, III, and IV. Complexes III and IV contain DMSO molecules. Under other equivalent conditions, the reaction of HL1 or HL2 with cadmium chloride in ethanol affords complex I or II of different compositions. Complex II contains the chlorine atom as found by scanning electron microscopy, whereas no chlorine is observed in complex I according to the X-ray structure analysis data.

Composites based on a homogeneous mixture of low-density polyethylene (LDPE) with powdered natural zeolite (clinoptilolite and heulandite of Agdag deposits, Azerbaijan) in the form of films 140–200 μm thick and 20 mm in diameter have been obtained by hot pressing at a temperature of 403–413 K and pressure of 15 MPa, followed by quenching in a mixture of ice and water. The dielectric parameters (the real part of the dielectric constant (ε'), the tangent of the dielectric loss angle (tan δ), and the electrical conductivity (σ)) of the composite samples of 60 vol % LDPE/40 vol % zeolite and 40 vol % LDPE/60 vol % zeolite have been examined at frequencies of 25–106 Hz and in a temperature range of 293–403 K. On the basis of the temperature dependence of the electrophysical parameters of composite samples, it has been revealed that tanδ and σ increase with an increase in the filler content and this is associated with an increase in the concentration of charge carriers and their mobility. The study of the frequency dependences ε′ = f(log ν), tan δ = f(log ν), and log σ = f(log ν) has shown the presence of two linear regions of the frequency dependences of electrical conductivity, which change according to the law σac(ν) ∼ ν0.73, and this is more consistent with the hopping mechanism of electrical conductivity of LDPE/zeolite composites.

The article presents the results of studies on the synthesis of unsaturated ternary cooligomers of 4-isopropenylphenol, phenol and formaldehyde and their structuring with maleic anhydride. The indicated co-oligomers (molecular weight M-w=1300 and M-n=580) were obtained by polycondensation of 4-isopropenylphenol with phenol and formaldehyde in the presence of zinc acetate (5% mol). The ratio of the reagents is 1:1:2 (mol), the temperature is 90-95 degrees C, the reaction time is 3 h. The yield of co-oligomers is 96.5%. The process of structuring (hardening) of the synthesized co-oligomers with maleic anhydride in the presence of initiator azobisisobutironitrile and di-tertbutyl peroxide was studied, as well as thermally, and the optimal conditions for obtaining cross-linked copolymers were identified. These co-oligomers can be used as precursors for the synthesis of carboxyl sorbents. It was found that the cross-linking process of co-oligomers is influenced by various factors: the nature of the initiator, temperature, structuring time. So, in the presence of 0.5% di-tert-butyl peroxide at 120-140 degrees C for 5 h, the yield of cross-linked copolymers is 97-99%, while in the presence of a low temperature initiator azobisisobutironitrile, to achieve the maximum yield (96%), an increase in the amount of initiator is required to 1% (temperature 80 degrees C, time 5 h). When carrying out the reaction thermally at 120-140 degrees C, their maximum yield is 98% (5 h, 140 degrees C). The optimal conditions for the reaction were revealed: temperature 80 degrees C, time 5 h, initiator azobisisobutironitrile (1%). By derivatographic method was established that the structuring reaction proceeds exothermically due to the opening of multiple bonds of the isopropenyl fragment and maleic anhydride. It was also found that the synthesized cross-linked copolymer is stable up to a temperature of 380 degrees C. The structures of the synthesized cooligomers and their structured derivatives were confirmed IR and NMR spectroscopy data.

We studied the complexation of titanium(IV) with 2,2',3,4-tetrahydroxy-3'-nitro-5'-sulfoazobenzene (R) in the presence of cationic surfactants (CSs) cetylpyridinium chloride (CPCl), cetylpyridinium bromide (CPBr), and cetyltrimethylammonium bromide (CTMABr). In the presence of cationic surfactants, mixed-ligand complexes are formed with the ratio of components $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ : H4R– : CS = 1 : 2 : 2. The optimal pH values of the complex formation were found: 4.5 for ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2 and 3.5 for mixed-ligand complexes ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2(CPCl)2, ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2(CPBr)2, and ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2(CTMABr)2. We also investigated the effect of time, temperature, and concentrations of the reacting components on the formation of mixed-ligand complexes. The Beer law is observed in the concentration range of ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2, ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2(CPCl)2, ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2(CPBr)2, and ( $${\text{Ti}}({\text{OH}})_{{\text{2}}}^{{{\text{2}} + }}$$ (H3R2–)2(CTMABr)2 of 0.10–1.8, 0.10–1.92, 0.10–1.92, and 0.08–1.92, respectively. The effect of foreign ions and masking substances on the determination of titanium(IV) as mixed-ligand complexes was studied. We developed a procedure for the spectrophotometric determination of trace amounts of titanium in sea sand taken from the Caspian Sea coast near the Turkan village.

The sequential reaction of furfural with cyclic secondary amines and further with benzaldehyde and cyanoacetates affords new 2,4-dicyano-8-(R2N)-6-oxo-3-phenylbicyclo[3.2.1]-octane-2,4-dicarboxylates as rac-(1R,2R,3R,4S,5S,8R)-diastereomers. The structures of the reaction products were determined by X-ray diffraction.

Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this uncommon class of hindered triazoles will accelerate exploration of their therapeutic potential. The superior activity of copper(II) triflate in the formation of triazoles from sensitive alkyne substrates extends to simple terminal alkynes. Introduction 1,2,3-Triazoles demonstrate wide spread application in biological systems and drug development [1-12]. Copper-catalyzed azide–alkyne cycloadditions (CuAAC) regioselectively introduce a wide variety of substituents on 1,4-disubstituted 1,2,3triazoles from the organic azide or terminal alkyne starting materials [1,2]. These Huisgen reactions [13] facilitate rapid drug screening by allowing for tracking in biological systems and the exploration of structure-activity relationships [10,14-19]. Propargylamines are a popular choice for the terminal alkyne component and form highly selective inhibitors (Figure 1) [2]. Due to the difficulty of forming tetrasubstituted propargylamines, the incorporation of deprotectable variants into triazoles is extremely rare. The Ellman group demonstrates the power of their chiral sulfinylimine protocol to synthesize propargylamine-derived alpha-tetrasubstituted triazoles (tetrasubstituted carbon bearing amine highlighted in red, Figure 1). One such triazole is a cruzain inhibitor with activity against parasite Trypanosoma cruzi, which causes Chagas’ disease [6]. An alpha-tetrasubstituted triazole that inhibits cathepsin S can potentially treat ailments ranging from inflammation to autoimmune disorders [7,8]. Beilstein J. Org. Chem. 2015, 11, 1425–1433. 1426 Figure 1: A sampling of propargylamine-derived triazoles with therapeutic effects includes alpha-tetrasubstituted triazoles as cruzain and cathepsin inhibitors. Figure 2: A tetrasubstituted carbon bearing an amine (red) can provide 100-fold increase in activity compared to the trisubstituted carbon bearing an amine (blue). The core of the cathepsin S inhibitor is synthesized in six steps. Synthesis and isolation of an N-sulfinyl ketimine is followed by stoichiometric alkynylation with a trimethylsilyl-protected alkynyllithium reagent. Removal of the silyl and sulfinyl protecting groups allows for CuAAC with a resin-bound azide. Acylation of the amine followed by dehydration yields the active alpha-tetrasubstituted triazole [7]. The lengthy synthesis of tetrasubstituted propargylamine precursors limits the exploration of such alpha-tetrasubstitued triazoles. The vast majority of three-component couplings produce trisubstituted propargylamines. Copper remains the most popular catalyst for these multicomponent reactions, abbreviated as A3 reactions to indicate the Aldehyde, Amine, and Alkyne reaction partners [20,21]. Methods for the corresponding KA2, Ketone–Amine–Alkyne, three-component coupling reaction are rare due to the lower electrophilicity and greater steric hindrance of ketones [22-26]. Due to the release of torsional strain when the sp2 center in the six-membered ring is attacked, cyclohexanone represents a special case as this cyclic ketone is nearly as reactive as an aldehyde [24]. The resultant tetrasubstituted (red) cyclohexylamine is found in natural alkaloids such as (–)-lycodine (Figure 2), [27] and this motif is also critical to the activity of drugs like ketamine and phencyclidine (1-(1-phenylcyclohexyl)piperidine, PCP) [28]. Tetrasubstituted carbons bearing amines can provide much higher levels of activity than the corresponding trisubstituted center. For example, fentanyl is an anesthetic that is 100 times as powerful as morphine (Figure 2) [29]. By creating a tetrasubstituted variant, the activity is increased two orders of magnitude: carfentanil is over 10,000 times as active as morphine. Results and Discussion Reaction optimization The two-step/three-reaction sequence shown in Scheme 1 would streamline the synthesis of alpha-tetrasubstituted triazoles 6. In the first step, our solvent-free copper-catalyzed three-component coupling of cyclohexanone (1), amines 2, and alkynes 3 provides high yields of silyl-protected propargylic amines 4 [24,25]. Trimethylsilyl (TMS) acetylene was not stable in the presence of the copper(II) chloride catalyst, and triethylsilylacetylene did not convert cleanly to product. Triisopropylsilyl (TIPS) acetylene was found to be superior to tertbutyldimethylsilylacetylene as a source of silylated tetrasubstituted propargylic amines. Although TMS-protected alkynes have been converted to triazoles via a one-pot silyl deprotection CuAAC reaction [3033], TIPS-protected alkynes have not. As the triisopropylsilyl protecting group is more difficult to remove than the less Beilstein J. Org. Chem. 2015, 11, 1425–1433. 1427 Scheme 1: KA2 coupling followed by tandem silyl deprotection and triazole formation. Table 1: Optimization of silyl deprotection/cycloaddition. Entry Solventa Catalystb GC yield (%), 1 h GC yield (%), 18 h 1 t-BuOH/H2O (1:1 v/v) CuCl 21 2 2 DMSO/H2O (2:1 v/v) CuCl 0 0 3 DMF/H2O (1:2 v/v) CuCl 0 0 4 THF/MeOH (1:1 v/v) CuCl 4 34 5 t-BuOH CuCl 6 62 6 MeOH CuCl 13 65 7 MeOH CuBr 62 63 8 MeOH Cu Powder 24 24 9 MeOH CuCl2 72 90 10 MeOH CuBr2 65 86 11 MeOH CuF2·2H2O 69 88 12 MeOH CuSO4·5H2O 49 79 13 MeOH Cu(OAc)2·H2O 46 82 14 MeOH Cu(OTf)2 39 99 aEntries 7–14 were carried out under an atmosphere of argon. bEntries 9–14 with copper(II) sources include 5 mol % of sodium ascorbate reductant. hindered trimethylsilyl, conditions for TIPS deprotection include 1.5 equiv of AgF or Cu(OAc)2 combined with syringe pump addition of TBAF [34,35]. An additional difficulty is that Ellman’s alpha-tetrasubstituted triazoles are synthesized by CuAAC reaction with desilylated, purified tetrasubstituted propargylic amines [6-8]. Therefore, the goal was to develop the second portion of the sequence in Scheme 1: a tandem deprotection–cycloaddition of tetrasubstituted TIPS-protected propargylamines 4 that would allow them to react in situ with various azides 5 to give hindered triazoles 6. As a copper(I) catalyst is required for azide–alkyne cycloaddition, the development of a method for the one-pot deprotection/ CuAAC began with Cu(I) chloride and a survey of solvents reported [2] for triazole formation (Table 1). TIPS-protected propargylamine 4a and benzyl azide (5a) are heated in the presence of 1.5 equivalents of TBAF (tetrabutylammonium fluoride), 5 mol % CuCl, and the solvent(s) indicated (Table 1, entries 1–6). Aqueous solvent mixtures produce only trace amounts of product at 1 h and 18 h, but methanol and tertbutanol provide two-thirds conversion to triazole 6a after 18 h. To increase the rate of reaction and to induce complete conversion to 6a, copper(I) as well as copper(II) sources with an equal amount of sodium ascorbate as the reducing agent were tested in MeOH (Table 1, entries 6–14). All combinations of Beilstein J. Org. Chem. 2015, 11, 1425–1433. 1428 Table 2: Tetrasubstituted silylpropargylamines form hindered triazole products. Propargylic amine 4 Triazole product 6

Cascade reaction of 2 equiv. of furfural (or equimolar amounts of furfural and aromatic aldehyde) with secondary amines and ethyl cyanoacetate afforded diethyl esters of 8-(dialkylamino)-3-aryl-6-oxo-2,4-dicyanobicyclo[3.2.1]octane-2,4-dicarboxylic acids with yields of 37–54%. Antimicrobial activity of a number of obtained compounds in vitro was studied, and biological activity in silico was analyzed. The obtained bicyclo[3.2.1]octanes are inactive or exhibit weak fungicidal activity, but exhibit moderate bactericidal effect.

Изучена трехкомпонентная конденсация бензилиденацетона, ацетоуксусного эфира и малононитрила в мольном соотношении 1:1:1 соответственно, в присутствии эквимолекулярных количеств пиперидина и ледяной уксусной кислоты. В кристаллической структуре продукта этой реакции этил-2-дицианметилен-4-метил-6-фенил-3-циклогексен-1-карбоксилата, определенной РСА, с использованием метода атом-атомных потенциалов выявлены энергетические ловушки в виде двойных плоских и двойных двухсторонних захватов. За счет этих энергетических ловушек в кристалле формируются молекулярные агломераты в виде незначительно деформированных трансляционно идентичных гексагональных сеток.

В результате тройной конденсации малонодинитрила с бензальдегидом и этил 2-хлор-3-оксобутаноатом образуется соединение с 3-азабицикло[3.1.0]гексановым каркасом, кристаллическая структура которого определена методом РСА. В кристаллической структуре обнаружен слоистый характер молекулярной упаковки. Молекулы в слое объединены за счет Н-связей типа N—H…O=C и C—H…O=C, а также большого количества атом-атомных контактов, энергия которых соответствует потенциальным ямам.