新型含硫化合物的合成及其晶体结构研究

通过简单的一步亲核取代反应合成了一新型含硫化合物(4-羧基甲硫醇基-2,3,5,6-四氯-苯硫醇基)乙酸(1),产物经乙酸乙酯重结晶分离纯化,并在适当的条件下培养得到单晶,测定了该化合物的晶体结构,以及其DMSO加合物的晶体结构.其中该化合物晶体属于单斜晶系,空间群为P21/c,a=0.508 93(4)nm,b=0.969 81(7)nm,c=1.439 1(1)nm,β=91.036(4)°,V=0.710 20(9)nm3,Z=2,Dc=1.843 g/cm3,F(000)=392,μ=1.133,R1[I2σ(I)]=0.097 3,wR2[I2σ(I)]=0.193 1.其DMSO加合物的晶体结构属于正交晶系,空间群为Pnma,a=1.372 48(2)nm,b=2.883 6(4)nm,c=0.461 48(6)nm,V=1.826 4(4)nm3,Z=4,Dc=1.703 g/cm3,F(000)=936,μ=1.010,R1[I2σ(I)]=0.088 8,wR2[I2σ(I)]=0.203 9.晶体结构分析表明,分子间氢键是这一化合物的一大特点.     

含吡唑啉酮酰肼类衍生物的合成与结构

报道了PMBP-NTH(NTH为烟酰肼)与PMBP-PAH(PAH为对甲氧基苯甲酰肼)的合成、表征和晶体结构分析,PMBP-NTH晶体属三斜晶系,具有P1空间群,a=0.9024(2)nm,b=1.0953(2)nm,c=1.1635(2)nm,α67.070(10)°,β=68.220(10)°,γ=84.770(10)°,V=0.9816(3)nm^3,Z=2,Dc=1.345g/cm^3,μ=0.090mm^-1,F(000)=416,R=0.0363,ωR=0.0870.PMBP-PAH属单斜晶系,具有P21/c空间群,a=1.2715(4)nm,b=0.91710(10)nm,c=1.8979(3)nm,β=106.890(10)°,V=2.1177(8)nm^3,Z=4,Dc=1.338g/cm^3,μ=0.090mm^-1,F(000)=896,R=0.0414,ωR=0.0972.这两个化合物在分子内都形成了大的共轭体系,由于分子间氢键力的作用,又使它们在晶体中以二聚体形式存在.     

Synthesis and spectroscopic characterization of cobalt(II) thiosemicarbazone complexes

Thiosemicarbazone derivatives are formed on reaction between acetophenone, salicylaldehyde, benzophenone and/or 2-hydroxy-4-methoxybenzophenone and thiosemicarbazide or its N⁴H substituents (ethyl-, phenyl-, and p-chlorophenyl-). The ligands were investigated by elemental analysis and spectral (IR, ¹H?NMR and MS) studies. The formulas of the prepared complexes have been suggested by elemental analyses and confirmed by mass spectra. The coordination sites of each ligand were elucidated using IR spectra revealing bidentate and tridentate coordination. Different geometries for the complexes were proposed on the basis of electronic spectra and magnetic measurements. The complexes have been analyzed thermally (TG and DTG) and the kinetic parameters for some of their degradation steps were calculated.     

Synthesis, spectroscopic characterization and vulcanization activity of a new compound containing the anion bis(4-methylphenylsulfonyldithiocarbimato)zincate(II)

A new compound of the formula: (Bu₄N)₂[Zn(4-CH₃C₆H₄SO₂NCS₂)₂] (Bu₄N = tetrabutylammonium cation) was obtained by the reaction of CH₃C₆H₄SO₂NCS₂K₂ · 2H₂O with zinc(II) acetate dihydrate and tetrabutylammonium bromide in dimethylformamide. The elemental analyses of C, H, N and Zn are consistent with the proposed formula. The IR data point to the formation of a zinc(II)-bis(dithiocarbimato) complex. The ¹H NMR and ¹³C NMR spectra showed the expected signals for the tetrabutylammonium cation and the dithiocarbimato moiety. This compound was evaluated as for the vulcanization activity and compared to the commercial accelerators CBS, MBTS and TMTD. These studies showed that the zinc(II)-ditiocarbimates are a new class of rubber vulcanization accelerators, worth of further investigation.     

Synthesis and spectroscopic properties of new water-soluble phthalocyanines containing pyridinium hydrochloride fragments

New 2,9,16,23-tetra[o-(hydroxymethyl)benzyloxy]-substituted phthalocyanines were synthesized. Their reaction with 4-bromopyridine afforded 2,9,16,23-tetra[o-(4-pyridyloxymethyl)benzyloxy]-substituted analogs, treatment of which with HCl led to water-soluble pyridinium salts. Spectroscopic properties of the phthalocyanines obtained were studied and a hypsochromic shift of the Q-band of the hydrochloride as compared with the corresponding pyridinium analogs was observed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2350–2354, December, 2007.     

Synthesis and photochromism of a new binuclear porphyrazinato magnesium(II)

The synthesis, characterization and photochromism of a new coplanar binuclear porphyrazine bearing six bis-(trimethylthiophenyl) photochromic functionalities at the periphery are described. The synthetic route is concise and the near-infrared luminescence changes of this binuclear porphyrazine can be regulated in a reversible manner by the photoisomerization of the bisthienylethene moiety.     

Synthesis,structure and spectroscopic properties of some thiosemicarbazone complexes of platinum

Reaction of salicyldehyde thosemicarbazone (H₂L¹), 2-hydroxyacetophenone thiosemicarbazone (H₂L²) and 2-hydroxynapthaldehyde thiosemicarbazone (H₂L³) (general abbreviation H₂L, where H₂ stands for the two dissociable protons, one phenolic proton and one hydrazinic proton) with K₂[PtCl₄] afforded a family of polymeric complexes of type [{Pt(L)}_n]. Reaction of the polymeric species with two monodentate ligands (D), viz. triphenylphosphine (PPh₃) and 4-picoline (pic), yielded complexes of the type [Pt(L)(D)]. These mixed-ligand complexes were also obtained from the reaction of the thiosemicarbazones with [Pt(PPh₃)₂Cl₂] and [Pt(pic)₂Cl₂]. The crystal structure of [Pt(PPh₃)(L²)] has been determined. The thiosemicarbazone ligands are coordinated, via dissociation of the two protons, as dianionic tridentate O,N,S-donors. The [Pt(L)(D)] complexes show characteristic ¹H NMR spectra and intense absorptions in the visible and ultraviolet region. They also fluoresce in the visible region at ambient temperature.     

含吡唑基的苯骈咪唑的合成与光谱性能(英文)

在乙醇溶剂中,于温和条件下以邻苯二胺和1-苯基吡唑-4-醛为原料合成了一种结构新颖的含吡唑取代基的苯骈咪唑杂环化合物,通过元素分析,MS,1H NMR对所合成的苯骈咪唑化合物的组成与结构进行了表征,同时对该化合物的紫外-可见光谱和荧光光谱进行了研究.     

几种新的4-酰基吡唑酮类螯合剂的合成

Eight new 1-phenyl-3-methyl-4-acyl-pyrazolones (1a-f, 2a, b) have been synthesized in good yield by reacting the corresponding acid halide with 1-phenyl-3-methyl-pyrazolone in dioxane in the presence of suspended Ca(OH)2 or Ba(OH)2, the products were identified by elemental analyses, IR, UV and 1H NMR spectra. Preliminary experiments indicate that all of their extraction efficiency for (UO2)2+ in chloroform-water are better than that of PMBP. The relative efficiency is found to be of the following order: 1b, 1d, 1f>1a, 1e>1c, 2a>2b>PMBP.     

Synthesis of new spiropyranes and study of the effect of the nature of substituents on their photochromism and complexation

A series of new hydrazones based on 3,3-dimethyl-7-hydroxy-8-formyl-[2H]-1-benzopyran-2,1-[2]-oxaindane] with the substituents of different nature in the hydrazone moiety was synthesized. A comparative study of photochromism and complexation of the synthesized spiropyrans with a number of metal cations was carried out. Spectral and kinetic differences in photochromism and complexation of these compounds were revealed.     

New chelating sorbents based on pyrazolone containing amines immobilized on styrene-divinylbenzene copolymer-I Synthesis and analytical characterization

A series of new cheating sorbents has been prepared by modification of styrene-divinylbenzene copolymer with different pyrazolone-containing amines. The substances were characterized by elemental analysis and infared spectroscopy. The complexation ability of the sorbents towards alkali, alkaline-earth, transition and precious metals has been studied. The new sorbents may successfully be applied to the simultaneous preconcentration of alkaline-earth and transition elements in neutral medium and to the selective separation of precious metals in acidic medium.     

Synthesis,DNA binding,and antimicrobial studies of novel metal complexes containing a pyrazolone derivative Schiff base

A novel series of Co(II), Ni(II), Cu(II), Zn(II), and VO(IV) complexes has been synthesized from the Schiff base derived from 4-[(3,4-dimethoxybenzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one and 1,2-diaminobenzene. Structural features were determined by analytical and spectral techniques. Binding of synthesized complexes with calf thymus DNA (CT DNA) was studied by spectroscopic methods and viscosity measurements. Experimental results indicate that the complexes are able to form adducts with DNA and to distort the double helix by changing the base stacking. Lower DNA affinity of the VO(IV) complex is caused by the change of coordination geometry by the vanadyl ion resulting in a somewhat unfavorable configuration for the DNA binding. Oxidative DNA cleavage activities of the complexes were studied with supercoiled (SC) pUC19 DNA using gel electrophoresis; the mechanism studies revealed that the hydroxyl radical is likely to be the reactive species responsible for the cleavage of pUC19 DNA by the synthesized complexes. The in vitro antimicrobial screening effects of the investigated compounds were monitored by the disc diffusion method. The synthesized Schiff base complexes exhibit higher antimicrobial activity than the respective free Schiff base.     

Synthesis and spectroscopic characterization of new Schiff bases containing the benzo-15-crown-5 moiety

New crown ether Schiff base derivatives were prepared by the condensation of 4'-formylbenzo-15-crown-5 or 4'-formyl-5'-hydroxybenzo-15-crown-5 with 1,2-bis(2-aminophenoxy)ethane. The structures of these new compounds were confirmed on the basis of elemental analysis, IR, (1)H- and (13)C-NMR, UV-Vis and mass spectroscopic data.     

Synthesis,photochromism, and complexing ability of new derivatives of N-aminofulgimide

On the basis of N-aminofulgimide two new photochromic compounds of the fulgimide class were synthesized. The performed spectral-kinetic studies have shown that the obtained fulgimide derivatives suffer thermally irreversible transformation similar to those observed for the starting N-aminofulgimide except for the absorption bands of the corresponding cyclic forms to undergo red shift. One of the obtained compounds is capable to form complexes with rare-earth metal ions.     

Synthesis and vibrational spectroscopic characterisation of nickel containing aurichalcite

Raman spectroscopy complimented with supplementary infrared spectroscopy has been used to characterise a synthetic nickel substituted aurichalcite a zinc/nickel hydroxy carbonate, (Zn²⁺, Cu²⁺, Ni²⁺)₅(CO₃)₂(OH)₆. XRD patterns show high orientation and indicate the presence of some minor impurities. The diffraction patterns for the Ni-aurichalcite are well correlated with the standard reference patterns. EDAX analyses indicate variations in chemical composition of Zn/Ni ratios of ∼20:1. The symmetry of the carbonate anion in aurichalcite is C_s and is composition dependent. This symmetry reduction results in multiple bands in both the symmetric stretching and bending regions. The intense band for the Ni-aurichalcite at 1070 cm⁻¹ is assigned to the ν₁(CO₃)²⁻ symmetric stretching mode. Three Raman bands assigned to the ν₃(CO₃)²⁻ antisymmetric stretching modes are observed for Ni-aurichalcite at 1372, 1480 and 1543 cm⁻¹. Multiple Raman bands are observed in the regions from 800 to 850 cm⁻¹ and 720 to 750 cm⁻¹, and are attributed to ν₂ and ν₄ bending modes confirming the reduction of the carbonate anion symmetry in the aurichalcite structure. This research proves that nickel containing aurichalcites can be synthesised in the laboratory thus mimicing the natural nickel containing aurichalcites.     

Synthesis and photochromism of 3-indylfulgides

Six fulgides of indole series are prepared. Three of them are photochromic. The others in which R¹ is hydrogen atom do not show photochromism. Only Z-E isomerizations occur on irradiation at 365 nm. The effects of molecular structural modifications on photochromic properties are also discussed.     

Synthesis and spectroscopic properties of new bis-tetrazoles

Syntheses of N,N′-phenyltetrazole podands link with aliphatic chains containing oxygen, nitrogen and sulphur atoms, are described. The complexing properties of these compounds towards metal cations (Fe²⁺, Cu²⁺, Zn²⁺, Co²⁺, Ni²⁺) were investigated by absorption and infrared spectroscopy. The UV–Vis titrations were performed to estimate the stability constant values of the respective complexes with Cu²⁺ ion. Changes in UV–Vis absorption spectra and IR spectra of compound 6 under various concentrations of Cu²⁺ ion in methanol suggest formation of very unstable complex. The structure of ligand 2 has been deduced by X-ray crystallography.     

Synthesis of a new macrocyclic compound and its self-assembly

A new macrocyclic compound has been synthesized by condensation of pyridine-1-oxide-2,6-dialdehyde with diethylenetria-mine. The self-assemly behaviours were studied by X-ray diffraction. The results show that the self-assembly were controlled by intermolecular hydrogen bonds and π-π stacking effects.