Synthesis,Structure, and Reactivity of Naphtho-Fused 2-(Furan-2-yl)-1,3-thiazole

The condensation of naphthalen-2-amine with furan-2-carbonyl chloride in propan-2-ol gave N-(naphthalen-2-yl)furan-2-carboxamide which was treated with excess P₂S₅ in anhydrous toluene to obtain the corresponding thioamide. The oxidation of the latter with potassium hexacyanoferrate(III) in alkaline medium afforded 2-(furan-2-yl)naphtho[2,1-d][1,3]thiazole. A probable mechanism of its formation was proposed, and the ring closure involving C¹ of the naphthalene fragment was substantiated by quantum chemical calculations. Electrophilic substitution reactions of 2-(furan-2-yl)naphtho[2,1-d][1,3]thiazole (nitration, bromination, formylation, and acylation) involved exclusively the 5-position of the furan ring.     

Variations in functional substitution of the macroheterocycle and structure of stable rhenium(V) porphyrins

Rhenium(V) porphyrin complexes with different natures of substituents and substitution patterns in the organic fragment (5,10,15,20-tetraphenylporphyrin, 2,3,7,8,12,13,17,18-octaethylporphyrin, 2,3,7,8,12,13,17,18-octaethyl-5-phenylporphyrin, and 2,3,7,8,12,13,17,18-octaethyl-5,15-diphenylporphyrin dianions) and different axial ligands {phenoxide and chloride ions, 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-3-ylmethyl)pyrrolidino[3′,4′: 1,9](C₆₀-I _h)[5,6]fullerene} have been synthesized, and their principal properties (spectral parameters and reactivity toward fullerene-containing base) have been studied.     

New derivatives of 4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrazole, 4,5-dihydro-1,2-oxazole,and pyrimidine prepared proceeding from (<Emphasis Type="Italic">E</Emphasis>)-3-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-1-ferrocenylprop-2-en-1-one

Condensation of acetylferrocene with 5-phenyl(4-methylphenyl)-1,2-oxazole-3-carbaldehydes afforded (Е)-3-[5-phenyl(4-methylphenyl)-1,2-oxazol-3-yl]-1-ferrocenylprop-2-en-1-ones. Reactions of (Е)-3-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-1-ferrocenylprop-2-en-1-one with semicarbazide, thiosemicarbazide, and hydroxylamine led to the formation of 5-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-3-ferrocenyl-4,5-dihydro-1H-pyrazole- 1-carboxamide, 5-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-3-ferrocenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide, and 5-(4-methylphenyl)-3'-ferrocenyl-4',5'-dihydro-3,5'-bi-1,2-oxazole respectively. Reactions of (Е)-3-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-1-ferrocenylprop-2-en-1-one with guanidine and thiourea result in 4-[5-(4-methyl-phenyl)-1,2-oxazol-3-yl]-6-ferrocenylpyrimidin-2-amine and -2-thione respectively.     

Nanoparticles and nanocrystals of a new bidentate nickel(II) complex of N-[ethyl(propan-2-yl)carbamothioyl]-4-nitrobenzamide: synthesis,characterization, and crystal structures

The nickel(II) complex of N-[ethyl(propan-2-yl)carbamothioyl]-4-nitrobenzamide has been synthesized and characterized by Fourier transform-infrared spectroscopy, elemental analysis, nuclear magnetic resonance spectroscopy, and mass spectrometry (atmospheric pressure chemical ionization mass spectrometry). The single-crystal X-ray structures of N-[ethyl(propan-2-yl)carbamothioyl]-4-nitrobenzamide (1) and bis[N-[ethyl(propan-2-yl)carbamothioyl]-4-nitrobenzamide]nickel(II) (2) have been determined from single-crystal X-ray diffraction data. Loss of the N–H proton resonance and the N–H stretching vibration and the shift of the ν_C=O and ν_C=S stretching vibrations confirm formation of the metal complex. These studies show that the metal complex is neutral in cis-configuration. The complex has been used as a single-source precursor for the deposition of nickel sulfide nanocrystals by thermolysis. The nickel sulfide nanocrystals were characterized by X-ray powder diffraction and transmission electron microscopy.     

Catalytic alkylation of cycloalkaneindoles and tetrahydro-γ-carboline with 9-oxiranylmethylcarbazole

Catalytic alkylation of substituted indoles such as cycloalkaneindoles and tetrahydro-γ-carboline using 9-oxiranylmethylcarbazole leads to the formation of 1-(carbazol-9-yl)-3-{dihydrocycloalkane[b]indol-4(1H)-yl}propan-2-ols and 1-(carbazol-9-yl)-3-{2,8-dimethyl-3,4-dihydro-1H-pyrido[4,3-b]indol-5(2H)-yl}propan-2-ol, conjugates containing 2-hydroxypropylene spacer.     

Determination of saterinone enantiomers in plasma samples with an internal standard using a Chiralcel OD column, fractionation and reversed-phase chromatography

A specific and validated high-performance liquid chromatographic method was developed for the determination of the S-(-) and R-(+) enantiomers of saterinone. 1-[(4-cyano-1,2-dihydro-6-methyl-2-oxopyridin-5-yl)phenoxyl] -3-[4-(2- methoxyphenyl)piperazin-1-yl]propan-2-ol, in plasma at the low ng/ml level. The enantiomers of saterinone and an internal standard, 1-[(4-cyano-1,2-dihydro-6-methyl-2-oxo-pyridin-5-yl)phenoxy]-3-[4-(2- ethoxyphenyl)piperazin-1-yl]propan-2-ol, were chromatographed on a chiral Chiralcel OD stationary phase. However, the S-(-) enantiomers of saterinone and the internal standard were unresolved, as were the R-(+) enantiomers of both substances. Therefore, the two fractions were collected and each was separately resolved on an achiral Polyencap A reversed-phase column and quantified. The detection limit was 0.5 ng/ml of enantiomer, allowing the determination of plasma levels up to 36 h after oral administration of 90, 150 and 180 mg of saterinone to twelve subjects.     

Synthesis and properties of 2-(furan-2-yl)thiazolo[5,4-<Emphasis Type="Italic">f</Emphasis>]quinoline

N-(Quinolin-6-yl)furan-2-carboxamide was prepared by the coupling of quinoline-6-amine with furan-2-carbonyl chloride in propan-2-ol. Treatment of the product with excess Р2S₅ in anhydrous pyridine gave N-(quinolin-6-yl)furan-2-carbothioamide which was oxidized with potassium ferricyanide in an alkaline medium by the Jakobson procedure to obtain 2-(furan-2-yl)thiazolo[5,4-f]quinoline. The latter was subjected to electrophilic substitution reactions (nitration, bromination, formylation, and acylation), as well as characteristic nucleophilic substitution involving the quinoline ring and quaternization with methyl iodide in benzene.     

Formation mechanism and conformational structure of 2,3,4-trimethyl-1,5-di(thiophen-2-yl)pentane-1,5-dione: quantum chemical study

The mechanism of formation of 1,5-diketone, a key intermediate in the stereoselective assembly of 2,3,4-trimethyl-7-methylidene-1,5-di(thiophen-2-yl)-6,8-dioxabicyclo[3.2.1]octane, and the conformational structures of the reagents and products were studied by quantum chemical calculations at the MP2/6-311++G**//B3LYP/6-31G* level of theory with solvent effects treated within the polarizable continuum model. The activation barrier for the addition of the 1-oxo-1-(thiophen-2-yl)propan-2-ide ion (1), which is generated from 1-(thiophen-2-yl)propan-1-one, to acetylene is 15.2 kcal mol^–1. The reaction affords β,γ-unsaturated ketone. The subsequent addition of carbanion 1 to the C=C double bond of the resulting β,γ-unsaturated ketons yields 1,5-diketone and occurs with insignificant (less than 1 kcal mol^–1) activation barrier.     

Synthesis and Characterization of Zn(II) Complexes of 2-(7-Bromo-2-oxo-5-phenyl-2,3-dihydro-1<Emphasis Type="Italic">H</Emphasis>-1,4-benzodiazepin-1-yl)acetohydrazide and Its Condensation Products with Pyruvic Acid and Isatin

The systems ZnCl₂–2-(7-bromo-2-oxo-5-phenyl-2,3-dihydro-1H-1,4-benzodiazepin-1-yl)acetohydrazide (Hydr)–propan-2-ol, ZnCl₂–Hydr–pyruvic acid (HPv), and Zn(CH₃COO)₂–Hydr–isatin(HIz)–propan-2-ol were studied. Optimal synthesis conditions were determined, and the complexes [Zn(Hydr)₂Cl₂], [Zn(HydrHPv)₂Cl₂], and [Zn(HydrIz)₂] were isolated. The complexes were characterized by elemental analysis, thermogravimetry, IR spectroscopy, and mass spectrometry. The electrical conductivities of the complexes were measured. The local environment of the central atom in the coordination entity was determined by X-ray absorption spectroscopy.     

Reaction of 1,3,4,6-tetraketones with <Emphasis Type="Italic">p</Emphasis>-toluidine and benzaldehyde

Reactions of 1,6-diphenylhexane-1,3,4,6-tetraone, octane-2,4,5,7-tetra-one, and decane-3,5,6,8-tetraone with a mixture of p-toluidine and benzaldehyde afforded, respectively, 2-[4-benzoyl-3-hydroxy-1-(4-methylphenyl)-5-phenyl-1H-pyrrol-2-yl]-1-phenylethanone, (1E)-1-[4-acetyl-3-hydroxy-1-(4-methylphenyl)-5-phenyl-1,5-dihydro-2H-pyrrol-2-ylidene]propan-2-one, and 2-hydroxy-1-(4-methylphenyl)-2-(2-oxobutyl)-4-propanoyl-5-phenyl-1,2-dihydro-3H-pyrrol-3-one.     

Nickel(II) complexes prepared from NNN type ligands and pseudohalogens

Six nickel(II) complexes, using azide and thiocyanate ions, have been synthesized from bis-2,6(pyrazol-1-yl)pyridine (pp) and some methyl derivatives, 2-(3,5-dimethyl(pyrazol-1-yl)-6-(pyrazol-1-yl)pyridine (app) and bis-2,6(3,5-dimethyl(pyrazol-1-yl) pyridine (dmpp) in non-aqueous media. The complex structures were analyzed using elemental analysis, IR spectroscopy and thermogravimetry. Appropriate crystals of complex, containing azide [Nipp(N₃)₂]·MeOH (I) and thiocyanate [Nidmpp(SCN)₂·MeOH] (VI) were prepared and the molecular structures determined using X-ray diffraction. Complex I was seen to be dinuclear as stated in literature, space group P2₁/n, monoclinic, a=10.503, b=10.681, c=13.291 Å, β=106.56° and Z=2 whereas complex VI was found to be mononuclear, space group P2₁/n, monoclinic, a=8.646, b=12.614, c=20.697 Å, β=97.18° and Z=2. The Ni(II) coordination in both complexes were octahedral. Thermogravimetric studies showed azide containing structures to resemble the characteristics of explosive materials. Coordinative MeOH were seen to leave the structure in thiocyanate containing complexes, followed by irregular degradation above 300°C.     

Reaction of perfluorinated 1-ethyl-, 1,1-diethyl-, and 1,2-diethylcyclobutabenzenes with pentafluorobenzene in SbF<Subscript>5</Subscript>

Perfluoro(1-ethyl-1,2-dihydrocyclobutabenzene) reacts with pentafluorobenzene in SbF5 to give perfluoro(1-ethyl-2-phenyl-1,2-dihydrocyclobutabenzene). Analogous reaction of a mixture of perfluoro(1,1-diethyl-1,2-dihydrocyclobutabenzene) and perfluoro(1,2-diethyl-1,2-dihydrocyclobutabenzene) leads to the formation (after hydrolysis of the reaction mixture) of perfluorinated 7-phenyl-8,8-diethylbicyclo[4.2.0]octa-1,4,6-trien-3-one, 1,1-diethyl-2-(4-oxocyclohexa-2,5-dienylidene)-1,2-dihydrocyclobutabenzene, and 2-(pent-2-en-3-yl)benzophenone (from the 1,1-isomer) and perfluorinated (E)-1,2-diethyl-1-phenyl-1,2-dihydrocyclobutabenzene, 7,8-diethyl-8-phenylbicyclo[4.2.0]octa-1,4,6-trien-3-one, and 1-[2-(1-phenylprop-1-en-1-yl)-phenyl]propan-1-one (from the 1,2-isomer).     

5-phenyl-2H-tetrazol-2-ylmethyl ketones in the synthesis of tetrazolylalkanols and tetrazolyl(hydroxy)alkylphosphonates

The reduction of 1-(5-phenyl-2H-tetrazol-2-yl)propan-2-one and 1-phenyl-2-(5-phenyl-2H-tetrazol-2-yl)ethanone with sodium tetrahydridoborate gave 1-(5-phenyl-2H-tetrazol-2-yl)propan-1-ol and 1-phenyl-2-(5-phenyl-2H-tetrazol-2-yl)ethanol, respectively. Only 1-(5-phenyl-2H-tetrazol-2-yl)propan-2-one was reduced with baker’s yeast with an appreciable yield. 1-(5-Phenyl-2H-tetrazol-2-yl)propan-2-one and 1-phenyl-2-(5-phenyl-2H-tetrazol-2-yl)ethanone reacted with diethyl phosphonate in the presence of potassium fluoride to produce the corresponding diethyl [hydroxy(5-phenyl-2H-tetrazol-2-yl)alkyl]phosphonates.     

Sequential ortho effects: characterization of novel [M - 35]+ fragment ions in the mass spectra of 2-alkyl-4, 6-dinitrophenols

High-resolution mass spectrometry (HRMS), hybrid tandem mass spectrometry (MS/MS) (EBqQ), and photoelectron-photoion coincidence (PEPICO) experiments were conducted to examine a possible ortho-ortho effect resulting in a novel [M - 35]⁺ fragment ion in 2-alkyl-4, 6-dinitrophenols. For compounds having ethyl or larger alkyl substituents, [M35]⁺ was observed only when [M - 18]⁺ ions were present, with the ortho nitro group being involved in the reaction to [M- 35]⁺. For [M - 18]⁺ and [M - 35]⁺, HRMS results were consistent with losses of H₂O and H₂O + OH, respectively, whereas MS/MS results indicated a sequential reaction due to metastable dissociations. The appearance energy determined by PEPICO for [M - 35]⁺ was found to be greater than the appearance energy for [M - 18]⁺, thus supporting a sequential reaction. 69–75).     

Synthesis,structures, sorption and magnetic properties of coordination polymers based on 3d metal pivalates and polydentate pyridine-type ligands

The reactions of 3d metal pivalates with pyridine-containing ligands of different structures afforded the 1D coordination polymers [Co₂(Piv)₄(dpe)₂] _n , [Ni(Piv)₂(dpe)(EtOH)₂] _n , [Cu₂(Piv)₄(dpe)] _n , [Cu(Piv)₂(dpe)] _n , [Ni(Piv)₂(4-ptz)(EtOH)₂] _n , and [Cu₂(Piv)₄(4-ptz)· ·mSolv] _n (Solv is EtOH, m = 2; Solv is C₆H₆, m = 1; Piv^? is pivalate, dpe is trans-1,2-bis(4-pyridyl)ethylene, 4-ptz is 2,4,6-tris(4-pyridyl)-1,3,5-triazine), as well as the 3D coordination polymer [{Cu₂(Piv)₄}₃(3-ptz)₂] _n (3-ptz is 2,4,6-tris(3-pyridyl)-1,3,5-triazine). The sorption and magnetic properties of a series of the synthesized compounds and magnetic properties of the earlier characterized coordination polymer [Mn₂(O₂CC₆H₅)₄(dpe)₂·dpe] _n were studied. It was shown that the desolvation of the complexes [Ni(Piv)₂(4-ptz)(EtOH)₂] _n and [Cu₂(Piv)₄-(4-ptz)·2EtOH] _n resulted in the formation of the crystal structures, in which the pores are accessible to nitrogen and hydrogen at 78 K (S _BET are up to 92 m² g^?1). The temperature dependences of the molar magnetic susceptibility for [Co₂(Piv)₄(dpe)₂] _n , [Mn₂(O₂CC₆H₅)₄-(dpe)₂·dpe] _n , [Ni(Piv)₂(dpe)(EtOH)₂] _n , [Ni(Piv)₂(4-ptz)(EtOH)₂] _n , and [Cu₂(Piv)₄-(4-ptz)·2EtOH] _n are described in terms of models taking into account the zero-field splitting and exchange interactions or isotropic exchange Hamiltonians.     

The formation of 'classical' and 'half unit' Schiff-base ligands from their components on a molybdenum(IV) centre

The in situ synthesis of the complex, (PPh₄)[Mo(CN)₃O(aceen)] (aceen = N-[1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine), with a 'half unit' Schiff base ligand (with a free amino group) is described and compared with that of [Mo(CN)₂O(diaceen)]·H₂O (diaceen = N,N-bis[1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine) in which a 'classical', tetradentate Schiff base ligand is formed. The mechanism of the 'half unit' and 'classical' template Schiff bases ligand formation is discussed.     

Synthesis of Dicarboxylic Acid Amides and Diamides on the Basis of [4-(4-Methoxyphenyl)tetrahydro-2<Emphasis Type="Italic">H</Emphasis>-pyran-4-yl]methanamine

The condensation of various nonaromatic amines with ethyl N-{[4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methyl}oxamate prepared from [4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methanamine and diethyl oxalate afforded the corresponding N,N'-disubstituted oxamides. N-Aryloxamides were synthesized by the reaction of [4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methanamine with ethyl N-aryloxamates. The condensation of N-{[4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methyl}succinamic acid with primary amines gave N,N'-disubstituted siccinamides.     

Dynamic in situ solvothermal reactions between ZnX<Subscript>2</Subscript> (X = Cl,ClO<Subscript>4</Subscript>) and a heterocyclic disulfide

Solvothermal reactions of 2-ppds (2-ppds = di[4-(pyridin-2-yl)pyrimidinyl]disulfide) with ZnX₂ (X = Cl, ClO₄) in mixed CH₃OH–CH₂Cl₂ solvent have been investigated. To better understand these reactions, solution analysis was conducted in parallel with single-crystal X-ray diffraction analysis of the in situ generated coordination complexes. At 120 °C, solvothermal reaction of 2-ppds with ZnCl₂ resulted in a discrete mononuclear coordination complex formulated as [ZnCl₂(L1)] (1), in which the zwitterion L1 (1-methyl-4-(pyridin-2-yl)pyrimidin-1-ium-2-olate) was formed in situ from 2-ppds, and solution analyses based on TLC and ESI–MS further showed that the reaction solution also contains in situ transformed products of L2 (bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane) and L3 (2-methoxy-4-(pyridin-2-yl)pyrimidine). At 90 °C, solvothermal reaction between 2-ppds and Zn(ClO₄)₂ led to a discrete mononuclear coordination complex formulated as [Zn(SH)(L2)]ClO₄ (2) that features a terminally bound –SH group, while the reaction solution was also found to contain a library of in situ reaction products of 2-ppds including L1, L2, L3 and L4 ((4-(pyridin-2-yl)pyrimidin-2-yl) 4-(pyridin-2-yl)pyrimidine-2-sulfonothioate). Thus, the heterocyclic disulfide 2-ppds is transformed in situ into various organic products in a series of reactions involving C–S/S–S bond cleavage.     

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).