[Z]-1-[2-(三芳基锡基)乙烯基]环辛醇的合成和性质

本文用三苯基氢化锡、三对甲苯基氢化锡作为锡氢化试剂与1-乙炔基环辛醇进行反应, 合成了两个有机锡化合物: [Z]-1-[2-(三苯基锡基)乙烯基]环辛醇(1)和[Z]-1-[2-(三对甲苯基锡基)乙烯基]环辛醇(2), 并测定了1的晶体结构。1和2分别与ICl, Br2, I~2反应, 得到六个有机锡一卤化物和三个有机锡二卤化物(3-11)。有机锡二卤化物6和一卤化物5与KOH乙醇溶液反应, 分别得到相应的锡氧化物和锡氢氧化物(12, 13)。有机锡二卤化物8分别与含氮双齿配体[2,2'-联吡啶(Bipy),5-硝基-1,10-邻菲罗啉(Nphen),8-羟基喹啉(Oxin)]反应, 得到三个相应的配合物(14-16)。十六个新化合物通过元素分析、锡含量测定、IR、^1H NMR测定对其结构进行了表征, 同时提出了1和2的生成反应历程。     

A gradient HPLC test procedure for the determination of impurities and the synthetic precursors in 2-[4-(1-hydroxy-4-[4-(hydroxydiphenylmethyl)-1-piperidinyl]-butyl)-phenyl]-2-methylpropionic acid

A gradient high-performance liquid chromatographic (HPLC) test procedure is developed and evaluated for its ability to establish the levels of impurities and remaining synthetic precursors in 2-[4-(1-hydroxy-4-[4-(hydroxydiphenylmethyl)-1-piperidinyl]-butyl)-phenyl]-2-methylpropionic acid. A gradient program with a mobile phase of 0.02 M sodium phosphate buffer and 0.004 M sodium perchlorate in acetonitrile-water (approximately pH 2.5) is used with a Spherisorb C6 column. The acetonitrile composition is increased linearly from 40% to 65% over a 45-min period and held at 65% for 20 min. UV detection at 210 nm is used to quantitate all components. The procedure is validated for accuracy using spiked levels (0.1% to 1.5%, w/w) with two suspected impurities, the synthetic precursors. A multiday repeatability study using two different Spherisorb C6 columns and HPLC systems shows consistent impurity quantitation results with one production lot of the bulk compound.     

(Z)-1[2-(苯基二溴化锡基)乙烯基]-1-环己醇的合成及晶体结构

报道了标题化合物〔C14H18Br2OSn〕的合成及晶体结构。该晶体属于单斜晶系，空间点群为P21/c，晶胞参数a=11.711(2)，b=9．114（2），c=16．864（3）A，β=102.94（1）°，V=1604.55（0）A3，Mr=480．78，Z=4，Dc=1．99g／cm3，u=65．20cm－1，F（000）=919，R=0．050，Rw=0．050．晶体结构由直接法解出。标题化合物分子中的锡原子被配体的2个碳、2个溴和1个氧原子配位，配位原子呈畸变的三角双锥构型，环已基为椅式构象，五员杂环为信封构象。     

（E）-1-[4-（2-hydroxy-5-methoxybenzylideneamino）-phenyl]ethanone and （E）-1-[4-（2-hydroxy-4-methoxybenzylideneamino） phenyl]ethanone：X-ray and DFT-calculated structures

The isomeric structures of(E)-1-[4-(2-hydroxy-5-methoxybenzylideneamino)-phenyl] ethanone(I) and(E)-1-[4-(2-hydroxy-4-methoxybenzylideneamino) phenyl]ethanone(Ⅱ) ,both C16H15NO3,have been determined using X-ray diffraction techniques and characterized by IR,and their molecular structures have also been optimized at the B3LYP/6-31G(d,p) level using density functional theory(DFT) . The energetic behaviors of the title compounds in solvent media have been examined using B3LYP method with the 6-31G(d,p) basis set by applying the polarizable continuum model(PCM) . The total energies of the title compounds decrease with the increasing polarity of the solvent. In addition,DFT calculations of the title compounds' molecular electrostatic potentials(MEP) were performed at the B3LYP/6-31G(d,p) level of theory. X-ray study shows that the title compounds both have strong intramolecular O-H…N hydrogen bonds. The molecules of Ⅰ are linked into a one-dimensional framework structure by C-H…π interactions,while in Ⅱ,intermolecular π···π interactions result in the formation of infinite chains running along the [010].     

Synthesis and spectral properties of 4-oxothiazolin-2-yl-[N-R1-2-(para-R2-phenyl)indol-3-yl] hydrazones

The preparation of several 4-oxothiazolin-2-yl-indol-3-yl hydrazones is described. The structure of all products was corroborated by ir, ¹H-nmr and mass spectrometry.     

Synthesis of (2S,3S)-[3-(2)H1]-4-methyleneglutamic acid and (2S,3R)-[2,3-(2)H2]-4-methyleneglutamic acid

(2S,3S)-[3-(2)H1]-4-Methyleneglutamic acid 1a and (2S,3R)-[2,3-(2)H2]-4-methyleneglutamic acid 1b have been synthesised for use in biosynthetic and metabolic studies.     

Evaluation and validation of an HPLC procedure for the determination of the positional isomeric impurity in 2-[4-(1-hydroxy-4-[4-(hydroxydiphenylmethyl)-1-piperidinyl]-butyl)-phenyl]-2-methylpropionic acid

A high-performance liquid chromatographic (HPLC) procedure was evaluated for the determination of a positional isomeric impurity in bulk 2-[4-(1-hydroxy-4-[4-(hydroxydiphenylmethyl)-1-piperidinyl]-butyl)-phenyl]-2-methylpropionic acid HCl drug substance. The use of a β-cyclodextrin bonded-phase column with a mobile phase of 20/80 (v/v) acetonitrile/water containing an ammonium acetate buffer at apparent pH 4.0 and a flow rate of 0.45 mL/min resulted in an excellent separation of the isomers. Ultraviolet detection was used at 220 nm. A recovery study of known spike levels (0.1 to 1.5% w/w) showed that the procedure was accurate. A two-day, two-column repeatability study showed consistent results with the test batch of the bulk compound. The level of impurity in the tested lot of the compound had a mean level of 0.32% (w/w) and a standard deviation of 0.038% (w/w, n = 5). The text was submitted by the author in English.     

Synthesis and Crystal Structure of (p-{2-[p-(5''''-Phenyl-1'''',3'''',4''''-oxadiazole-2''''-yl)-phenyl]- vinyl}-phenyl)-di-p-tolyl-amine

1 INTRODUCTION Triarylamines constitute a well known class of hole conducting material[1～4]. On the other hand , oxadiazole-based compounds as good electron- transporting materials[5,6] have played an important role in the fabrication of multiple-layer light- emitting diode devices. It is well known that, to achieve good performance in electroluminescence (EL) devices, the injection of electron and hole should be in balance[7]. The requirement might be met in a new compound containing …     

Synthesis,halogenation and structural characterization of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cyclododecanol

Synthesis and characterisation of (Z)-1-[2(triphenylstannyl)vinyl]-l-cyclododecanol, c-(CH₂)₁₁C(OH)CH=CHSnPh₃, are reported, together with its halogenation by I₂, Br₂ and ICI to yield derivatives of the types c-(CH₂)₁₁C(OH)CH=CHSnPhs_?nX_n (n=1, 2; X=I, Br, Cl, respectively). The molecular structures of two compounds have been determined by X-ray diffraction analysis. The tin atom exhibits a distorted tetrahedral geometry in the crystal of (Z)-l-[2–(triphenylstannyI)vinyl]-l-cyclododecanol, but a trigonal bipyramidal geometry in the monoiodo-derivative (Z)-l-[2]-(diphenyliodo-stannyl)vinyl)-1-cyclododecanol and other derivatives, in which significant intramolecular coordinative interaction HO→Sn ia observed. And the formation of a five-membered tin containing ring is significant for their antitumour activities.     

(Z)-1-[2-(二苯基碘化锡基)乙烯基]-1-环己醇的合成、晶体结构和性质

报道了标题化合物的合成、晶体结构及性质。该晶体属于单斜晶系，空间群为P2~1，晶胞参数a=0.9255(3)nm，b=1.0504(3)nm，c=1.0217(3)nm，β=100.99(2)°，V=0.9750nm^3，Z=2，D~c=1.790g/cm^3，R=0.025，晶体结构由直接法解出。标题化合物分子中的锡原子被配体的三个碳、一个碘和一个氧原子配位；配位原子是畸变的三角双锥构型；标题化合物具有与卤素发生取代反应而不发生加成反应的性质。     

Synthesis and Characterization of (Z)-1-[2-(Triarylstannyl)vinyl]-1-Cyclohexanols and their Arylhalostannyl Derivatives

1-Ethynyl-1-cyclohexanol reacts with a triaryltin hydride Ar₃SnH (Ar = phenyl, p-tolyl) and generates the corresponding (Z)-1-[2-(triarylstannyl)vinyl]-1-cyclohexanol. The product obtained reacts with one or two equivalents of halogen (ICl or I₂) to form the associated (Z)-1-[2-(diarylhalostannyl)-vinyl]-1-cyclohexanol or (Z)-1-[2-(aryldihalostannyl)vinyl]-1-cyclohexanol, respectively. All compounds were characterized by elemental analysis, ¹H, ¹³C, ¹¹⁹Sn NMR and Mössbauer spectroscopy.     

Synthesis,halogenation and structural characterization of (Z)-1-[2-(triphenylstannyl)vinyl]-l-cyclododecanol

Synthesis and characterization of (Z)-1-[2-(triphenylstannyl)vinylj-l-cyclododecanol,c-(CH2)11C(OH)CH=CHSnPh3,are reported,together with its halogenation by I2,Br2 and IC1 to yield derivatives of the types c-(CH2)11C(OH)CH=CHSnPh3_nXn (n=1,2; X=I,Br,Cl,respectively).The molecular structures of two compounds have been determined by X-ray diffraction analysis.The tin atom exhibits a distorted tetrahedral geometry in the crystal of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cyclododecanol,but a trigonal bipyramidal geometry in the monoiodo-derivative (Z)-1-[2-(diphenyliodo-stannyl)vinyl]-l-cyclododecanol and other derivatives,in which significant intramolecular coordinative interaction HO→Sn is observed.And the formation of a five-membered tin containing ring is significant for their antitumour activities.     

Crystal structure of 1-(4-chlorophenyl)-3-{4-[2-(5-ethyl-pyridin-2-yl)-ethoxy]-phenyl}-propenone

The title compound C₂₄H₂₂ClNO₂ belongs to the orthorhombic system, space group Pca2₁ with a = 12.1771(10) Å, b = 4.9305(4) Å, c = 34.419(3) Å, α = β = γ = 90°, V = 2066.5(3) ų, Z = 4, D_c = 1.260 g/cm³, F(000) = 824, R = 0.0402 and wR = 0.1144, S = 1.034, T = 293 K. The compound is a chalcone with 4-chlorophenyl and [(5-ethyl-pyridin-2-yl)-ethoxy]-phenyl substituents bonded at the opposite ends of a propenone group, the biologically active region. The propenone bridge makes dihedral angles of 10.61(23)° and 62.75(22)° respectively, with 4-chlorophenyl and the [(5-ethyl-pyridin-2-yl)-ethoxy]-phenyl group.     

Synthesis and in-vitro-antibacterial activity of [5-(furan-2-yl)-phenyl]-4,5-carbothioamide-pyrazolines

Cyclization of various different alkoxy [1-[2-(alkoxy)phenyl]-5-(furan-2-yl)-prop-2-en-1-one] chalcone with thiosemicarbazide in the presence of NaOH in ethanol afforded a series of novel 1-N-substituted cyclized pyrazoline analogues [5-(furan-2-yl)-3-[2-(alkoxy) phenyl]-4,5-dihydro-1H-pyrazole-1-carbothioamide 2a–2d. The structures of these compounds were elucidated by IR, ¹H NMR, ¹³C NMR, Fab mass spectrometry and their purities were confirmed by elemental analyses. In vitro antibacterial activity of these compounds were evaluated by the disk diffusion assay and then the minimum inhibitory concentration (MIC) strain of two Gram-positive and two Gram-negative bacteria like Aeromonas hydrophila, Yersinia enterocolitica, Listeria monocytogenes, and Staphylococcus aureus, among all the compounds, alkoxy [5-(furan-2-yl)-2-(benzyloxy)phenyl]-4,5-dihydro-1H-pyrazole-1-carbothioamide 2b and 5-(furan-2-yl)-1-[2-(naphthalen-2-ylmethoxy) phenyl]-4,5-dihydro-1H-pyrazole-1-carbothioamide 2d showed the most promising antibacterial agent when compared to gentamicin and tetracycline.     

Synthesis and Crystal Structure of N-[4-(4-Methyl-phenylsulfamoyl)-phenyl]-4-methyl-1,2,3-thiadiazole-5-carboxamide

The crystal structure of the title compound (C17H16N4O3S2, Mr = 388.46) has been determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 13.688(2), b = 16.704(3), c = 8.3308(12) , β = 99.474(6)o, V = 1878.8(5) 3, Mr = 388.46, Z = 4, Dc = 1.373 g/cm3, μ = 0.308 mm–1, F(000) = 808, R = 0.0389 and wR = 0.0917. X-ray analysis reveals that the crystal structure involves intermolecular N–H…O and N–H…N hydrogen bonds, which link the molecules into a layer parallel to the ac plane.     

Synthesis of 4-[3-(1H)-indolyl]-2-[N-guanidinomethyl]thiazole dihydrochloride

The title compound 3b was synthesized in three steps from acetaminothioacetamide ( 4b ) in 15% overall yield. This represents the first synthesis of a 2-guanidinomethylthiazole, which is a homolog of an important pharmacophore, 2-guanidinothiazole.     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

Synthesis of anacardic acids, 6-[8(Z),11(Z)-pentadecadienyl]salicylic acid and 6-[8(Z),11(Z),14-pentadecatrienyl]salicylic acid

11-Chloro-3-methoxy-2-undecenal was synthesized from 8-bromooctanol, and an annelation reaction with this aldehyde and ethyl acetoacetate proceeded to give the ethyl 6-(8-chlorooctyl)salicylate. Ethyl 6-(8-chlorooctyl)salicylate was converted to ethyl 6-(7-formylheptyl)-2-methoxybenzoate through the iodide after protection of the phenolic hydroxyl group. Finally, the Wittig reaction with the aldehyde and triphenylphosphonium iodides in the presence of BuLi gave the methoxybenzoates, and then treatments of these methoxybenzoates with BBr3 in CH2Cl2 and 10% NaOH in ethanol gave 6-18(Z),11(Z)-pentadecadienyllsalicylic acid (anacardic acid 3) and 6-[8(Z),11(Z),14-pentadecatrienyl]salicylic acid (anacardic acid 4) which were isolated from plants of the anacardiaceae.