The ruthenium pyrazolonate complex Ru(PMIP)2(PPh3)2: Synthesis, structure, and some properties

The new ruthenium(II) complex Ru(PMIP)₂(PPh₃)₂ (HPMIP is 4-isobutyryl-3-methyl-1-phe-nylpyrazol-5-one) was obtained from RuCl₂(PPh₃)₃ and Na(PMIP)(DME) (DME is dimethoxyethane). The structures of the complex obtained and the starting sodium pyrazolonate were determined by X-ray diffraction. The ruthenium pyrazolonate complex initiates metathetical norbornene polymerization producing high-molecular-weight polynorbornene in low yield.     

Synthesis and properties of N-(2-chloro-5-fluoro-4-pyrimidyl)- and N-(2-ethylthio-5-fluoro-4-pyridmidyl)-substituted amino acids

Synthetic routes to and the properties of N-(2-chloro-5-fluoro-4-pyrimidyl)- and N-(2-ethylthio-5-fluoro-4-pyrimidyl)-substituted amino acids are shown.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 258–261, February, 1971.     

Synthesis and some reactions of 3-chloro-2-(cyanomethylene)-1,2-dihydroquinoxalines

2,3-Dichloroquinoxaline and some of its derivatives have been reacted with malononitrile and ethyl cyanoacetate to yield a variety of 3-chloro-2-(cyanomethylene)- 1,2-dihydroquinoxaline derivatives. The reaction of 3-chloro-2-(dicyanomethylene)-1,2- dihydroquinoxaline (2e) with pyridine and its methyl derivatives led to the zwitterionic structures 6a-6c. The structures of the newly synthesized compounds were assigned by spectroscopic data and elemental analyses.     

Synthesis,crystal structure and electronic properties of bis(N-2-bromophenyl-salicydenaminato)copper(II) complex

A new series of complexes of the type bis(N-substituted-salicydenaminato)copper(II) (1–9), have been synthesized and characterized by IR, UV–Vis and elemental analysis methods. The molecular structure of bis(N-2-bromophenyl-salicydenaminato)copper(II) (6), was determined using X-ray crystallography. There are two independent molecules in the structure. Each shows a neutral, mononuclear, four-coordinate, square-planar trans-Cu[N₂O₂] geometry and, in each, the Cu atom and the ligating atoms are coplanar. The chelating N–Cu–O angle is 91.39(11)° for molecule one and 91.20(11)° for molecule two, whereas the non-chelating N–Cu–O angles are 88.61(11) and 88.80(11)°, respectively. The trans-N–Cu–N and trans-O–Cu–O bond angles are 180°. The electronic absorption spectra of copper(II) complexes (1–9), indicate that the d–d band energy is dependent on the nature and position of substituent on phenyl ring of the salicyldenimine ligand. The UV–Vis spectra in various solvents were measured and a relationship between absorption spectra and dielectric constant of the solvents is reported.     

Synthesis and some transformations of N-cyclohexyl-3(4)-chloro-4(3)-methylthiobutyramides

Addition of methylsulfenyl chloride to N-cyclohexyl-3-butenamide yields N-cyclohexyl-4-chloro-3-methylthiobutyramide. Isomerization, oxidation of the latter, and β-elimination were studied.     

Synthesis,structures, and selected chemical properties of 2-chloro- and 2-bromo-1,1-diferrocenylcyclopropanes

2-Chloro- and 2-bromo-1,1-diferrocenylcyclopropanes were synthesized as Z- and E-isomers with respect to the ferrocenyl substituent having a bisector orientation. The structure of Z-2-chloro-1,1-diferrocenylcyclopropane was confirmed by X-ray diffraction analysis. Treatment of the resulting monohalides with potassium tert-butoxide in dimethyl sulfoxide afforded 3,3-diferrocenylcyclopropene in 20% yield. The small ring in halogen-substituted diferrocenylcyclopropanes and diferrocenylcyclopropene is readily cleaved to give predominantly 3-ferrocenyl-1H-cyclopentaferrocene.     

Preparation,structure, and some coordination properties of 2-chloro-3,3-diphenyl-3-thioxo-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene

A sterically encumbered 3-thioxo-1,3-diphosphapropene, bearing a P=C-P=S skeleton, was prepared, characterised, and allowed to react with a carbonyltungsten(0) reagent and iodine affording the corresponding chelate tungsten(0) complex and charge-transfer complex with iodine, respectively, which were analysed by the X-ray crystallography.     

Physical and chemical properties of N-(2-hydroxyethyl)alkylamines

Physical and chemical properties of N-(2-hydroxyethyl)alkylamines were studied, isotherms of a surface tension of homologous series of these compounds on a liquid-gas interface in water and hydrochloric acid were obtained.     

Synthesis and spectral properties of some N-(2-benzimidazoyl)-α-aminoesters and their N-oxides

A series of new N-(2-benzimidazol)(S)-α-aminoesters and the respective N-oxides have been prepared, and their spectral data discussed. The CD spectra of the aliphatic and aromatic amino ester derivatives of either series show sign reversal for the observed Cotton effect (CE) band. This chiroptical behaviour was rationalized as due to differences in conformational isomerism.     

Investigation of the decomposition of 1,3-diaryl-5-(3-chloro-2-quinoxalyl)-formazans by PMR and MASS spectrometry

In contrast to triarylformazans, 1,3-diaryl-5-(3-chloro-2-quinoxalyl)formazans are unstable in ordinary organic solvents. When they are heated in chloroform, they undergo acidic cleavage, which leads to the formation of 3-chloro-2-quinoxalylhydrazones of p-substituted benzaldehydes and arenediazonium cations. These compounds, as a result of a redox reaction with the participation of the solvent, are converted to 4-chloro-1-(4-Y-phenyl)-1,2,4-triazolo[4,3-a]quinoxalines, substituted benzenes, nitrogen, and hydrogen chloride. The formation of the latter transforms the entire decomposition process into an autocatalytic process. Effects of chemical polarization of the nuclei (CPN), which unambiguously indicate the intermediate formation of diazoaryl radicals during the process, are observed in the PMR spectra of the final products. Such CPN effects, which were also observed in dimethyl sulfoxide (DMSO) and glacial acetic acid, indicate a process involving the oxidative formation of annelated triazoles from -azahetarylhydrazones via a radical pathway within a solvent cage.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 413–420, March, 1985.     

Synthesis of n-(2-chloro-5-bromo-4-pyrimidyl)- and N-(2-chloro-5-iodo-4-pyrimidyl)amino acids

The previously unreported N-(2-chloro-5-bromo-4-pyrimidyl)- and N-(2-chloro-5-iodo-4-pyrimidyl) amino acids were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 527–529, April, 1971.     

Synthesis,structure, and optical properties of CsU2(PO4)3

CsU₂(PO₄)₃ was synthesized in highest yield by the reaction in a fused-silica tube of U, P, and Se in a CsCl flux at 1273 K. It crystallizes with four formula units in space group P2₁/n of the monoclinic system in a new structure type. The structure of CsU₂(PO₄)₃ is composed of U and Cs atoms coordinated by PO₄^3? units in distorted octahedral arrangements. Each U atom corner shares with six PO₄^3? units. Each Cs atom face shares with one, edge shares with two, and corner shares with three PO₄^3? units. The structure shares some features with the sodium zirconium phosphate structure type. X-ray powder diffraction results demonstrate that the present CsU₂(PO₄)₃ compound crystallizes in a structure different from the previously reported β′- and γ-CsU₂(PO₄)₃ compounds. CsU₂(PO₄)₃ is highly pleochroic, as demonstrated by single-crystal optical absorption measurements.     

Synthesis and chemical reactivity of the novel 3-chloro-3-(4-chlorocoumarin-3-yl)prop-2-enal

Vilsmeier-Haack formylation of 3-acetyl-4-hydroxycoumarin (1) afforded the unexpected 3-chloro-3-(4-chlorocoumarin-3-yl)prop-2-enal (3). Compound 3 reacted with p-toluidine and benzylamine producing Schiff base 4 and enamine 6, respectively. Treatment of compound 3 with hydrazine hydrate produced bis-coumarin 15 which upon treating with hydrazine hydrate afforded bis chromeno[4,3-c]pyrazole derivative 16. Compound 3 reacted with cyanoacetohydrazide under different conditions. Condensation of compound 3 with some heterocyclic amines and 1,2-N,N-binucleophiles was studied. Structures of the new synthesized products were deduced on the basis of their analytical and spectral data.     

3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮的合成与晶体结构

在THF溶液中合成了标题化合物3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮,并用FT-IR、UV-Vis、1HNMR、13C NMR、MS、元素分析和X-射线衍射等进行了表征。结果表明此化合物属正交晶系,空间群为Pbca,晶胞参数为:a=15.891(16),b=11.126(11),c=19.778(19),α=β=γ=90°,V=3497(6)3,Z=8,Dc=1.306Mg/m3,μ=0.234 mm-1,F(000)=1440。在化合物的分子结构中,两个苯环几乎垂直于呋喃酮平面,且它们与呋喃酮平面的两面角分别为89.38°和88.19°。     

Synthesis,Crystal structure and Fluorescence properties of a Binuclear Terbium(Iii) complex of N-(2-Pyridinyl)Ketoacetamide

A binuclear terbium(III) complex of N-(2-pyridinyl)ketoacetamide (HL) was synthesized and its crystal structure determined. Each terbium(III) binds to one N,O-bidentate HL, one O,O-bidentate L and two N,μ-O,O-tridentate bridging L ligands; the coordination polyhedron is a distorted square antiprism. The pyridine N and keto O atoms of the binucleating ligand are coordinated to each Tb with the amide O acting as a bridging atom. The adjacent [Tb₂(HL)₂L₄]²⁺ units are bridged by double C(R)NH…ONO₂…HN(R)C hydrogen bonds to form an infinite 1-D chain, and a 2-D layer structure results from a rare near face-to-face π,π-stacking interaction between the pyridine rings of the adjacent chains. The crystal structure analysis reveals that the ligands completely shield the Ln(III) ions. Excited by the absorption band at 370?nm, the Tb(III) complex displays characteristic metal-centered fluorescence while the ligand fluorescence is completely quenched, showing that efficient ligand-to-metal energy transfer (antenna effect) occurs.     

Synthesis, crystal structure and some physical properties of RuZn3

The crystal structure, phase relations and some physical properties of the binary zinc-rich phase RuZn3 are reported. The title compound is accessible via high-temperature reaction from the elements in the appropriate substance amount ratio. Its crystal structure was determined from a Rietveld profile fit to an X-ray diffractogram of pristine RuZn3 and confirmed by single-crystal X-ray structure analysis. The title compound adopts a tetragonal Al3Zr-type structure corresponding to an A2B2 anti-phase domain structure of the cubic AuCu3-type: a=376.82(3) pm, c=1554.78(13) pm, I4/mmm, Z=4, R(F)(all data)=0.0197, 153 unique reflections, 12 variables. The structure is discussed in the light of the Hume-Rothery concept. RuZn3 melts at 1373(2) K, is a moderate metallic conductor (rho(293 K)=6.2 mOmega cm) and exhibits basically temperature-independent paramagnetic properties. It coexists with Ru1-xZnx and RuZn6.