含甲氧基偶氮苯基元的苯甲酸衍生物的合成与液晶性研究

合成和表征了新型的含有甲氧基偶氮苯液晶基元的3,4,5-三取代苯甲酸衍生物Dn, 研究了结构对其相行为的影响. 结果表明, 在Dn中, 羰基(C=O)和羟基(OH)之间的氢键相互作用存在于结晶态、液晶态和各向同性状态, 在各向同性态时氢键较弱. 通过对其分子结构的调控, 有效地抑制了微相分离和强的分子间的相互作用, 得到了具有单向向列型液晶行为的3,4,5-三取代的苯甲酸衍生物.     

Hetero type III-B rotaxane dendrimers

Type III-B rotaxane dendrimer is a member of the rotaxane dendrimer family, but it is defined as dendritic polyrotaxane, branched through rings. Such rotaxane dendrimers have been synthesized through versatile copper-catalyzed azide-alkyne cycloaddition reactions. In order to incorporate more functionalities into type III-B rotaxane dendrimers, three different potential functionalities—azobenzene toward light switch, daisy chain toward higher degree of contraction, and extension and cyclobis (paraquat-p-phenylene) (CBPQT) toward redox chemistry—were combined into the original design of type III-B rotaxane dendrimers. Two azo-based G1/G2 and four new G1 and G2 hetero type III-B rotaxane dendrimers were synthesized and characterized by ¹H NMR spectroscopy and electrospray ionization mass spectrometry.     

1,6‐Dinitroperylene Bisimide Dyes: Synthesis,Characterization and Photophysical Properties

1,6‐ and 1,7‐regioisomers of dinitro‐substituted perylene bisimides ( 1a — 1b and 2a — 2b ) were synthesized under mild condition in high yields. The 1,6‐ and 1,7‐regioisomers were successfully isolated from the regioisomeric mixture using conventional methods of separation and subsequently characterized by 500 MHz ¹H NMR spectroscopy. This is the first time when 1,6‐dinitroperylene bisimides ( 1a — 1b ) are obtained in pure form. Furthermore, the photophysical and electrochemical properties of 1 and 2 were found to be almost the same. The nitro functionalities provide stability of n‐type charge carriers by lowering the LUMO to resist ambient oxidation, which may offer potential applications in air‐stable n‐type organic semiconductors.     

Convenient Syntheses of Some Analogs of the Sex Pheromone of Citrus Mealybug,Planococcus citri (Risso)

A series of structural analogs(4a—h) of(+)-cis-(1R)-3—isopropenyl—2, 2—dimethylcyclobutanemethanol acetate, the sex pheromone of citrus mealybug, Planococcus citri (Risso), was synthesized from (+)—α—pinene(l) via intermediate, (+)—cis—(lR)—2, 2—dimethyl—3—acetylcyclobutaneethanol(2).     

含4-噻唑啉酮环的新烟碱类化合物的合成及生物活性

根据生物等排原理和新烟碱类化合物与乙酰胆碱酯酶的作用机理, 以4-噻唑啉酮(4)为中间体设计合成了2-取代-3-(2-氯-5-吡啶亚甲基)-4-氰基亚胺基-1,3-噻唑烷(8a~8c)和5-芳基次甲基-2-芳基-3-(2-氯-5-吡啶亚甲基)-4-噻唑啉酮(5a~5e)两类化合物. 中间体(4)由醛、胺和巯基乙酸缩合得到. 所有化合物的结构均经元素分析和1H NMR确证. 初步生物活性试验结果表明, 部分化合物具有一定的杀菌活性和促进黄瓜子叶生根活性, 化合物8b显示出很好的抗HIV-1蛋白酶活性.     

Syntheses and some spectroscopic properties of polyanions with pendant merocyanine dyes

Polymers tagged with a local pH reporter were synthesized. A methacrylate-type monomer containing a merocyanine dye residue as a reporter dye—1-(2-methacryloyloxyethyl)-4-(2-(4-hydroxyphenyl)-ethenyl)quinolinium bromide—was synthesized. Its homopolymer and copolymers with sodium 2-acrylamido-2-methylpropanesulfonate were prepared by free radical polymerization. These polymers showed a characteristic color change in aqueous solutions from yellow to red with increasing pH from acidic to basic conditions according to the acid-base equilibria of the merocyanine dye residues. Since the electrostatic potential and polarity of media have a strong effect on the acid–base equilibria, the pendant merocyanine residues are expected to serve as a reporter to provide information on the local environments around the polymer chain at which the dye molecules are incorporated.     

Steroid Total Synthesis,Part II; (−)-17β-Hydroxy-des-A-androst-9-en-5-one

Based on the results obtained in the racemic series (part I), (—)-17β-hydroxy-des-A-androst-9-en-5-one has been synthesized, starting with (S)-(—)-5-heptanolide. The key step, viz. the condensation of (S)-(—)-7-hydroxy-1-nonen-3-one (or its amine adduct) with 2-methyl-cyclopentane-1, 3-dione involves an asymmetric induction. Model experiments with (R)-(+)-5-decanolide leading to the enantiomeric homolog of the BCD-tricyclic compound are also described.     

噻吩和吡啶取代三芳基三唑的两个铜配合物的合成与晶体结构

分别以3-(2-吡啶基)-4-苯基-5-(2-噻吩基)-1,2,4-三氮唑(L1)和3-(2-吡啶基)-4-(4-氯苯基)-5-(2-噻吩基)-1,2,4-三氮唑(L²)作为配体,合成了2个新的单核铜配合物:trans-[Cu(L1)2(Me OH)2](Cl O4)2(1)和trans-[Cu(L2)2(Cl O4)2]·2Me CN(2),并对其进行了红外、元素分析、单晶结构和粉末X射线衍射表征。2个配合物都属于单斜晶系,P21/c空间群。单晶结构分析表明,配合物1和2中的铜离子均处于一个扭曲的八面体配位环境[Cu N₄O₂],其中1的轴向由2个甲醇分子配位,而2的轴向由2个高氯酸根配位。处于赤道面的配体的吡啶N原子和三氮唑的一个N原子采用螯合双齿模式参与配位,而噻吩不配位。配合物2含2个乙腈客体分子,乙腈与三氮唑环之间存在π…π堆积作用。配合物1和2中存在O—H…O、C—H…O、C—H…N氢键和C—H…π相互作用,从而连接单核配合物形成三维网络。     

Mixed Chloro Bis[Alkylenedithiophosphato] Antimony(III) and Their Heterobinuclear Derivatives with Boron Tetraisopropoxide: Synthesis and Characterization

Chloro bis(alkylenedithiophosphato)antimony(III) complexes of the type [OGOP(S)S]₂SbCl (1–5) [where G = —C(Me)₂—CH₂—CH(Me)—1 —C(Me)₂—C(Me)₂—2, —CH₂—C(Me)₂—CH₂—3, —CH(Me)—CH(Me)—4 and –CH(Me)—CH₂—CH₂—5] have been synthesized by the reaction of SbCl₃ with sodium salts of alkylenedithiophosphoric acids in a 1:2 molar ratio in refluxing benzene. Reactions of chloro bis(alkylenedithiophosphato) antimony(III) compounds, [OGOP(S)S]₂SbCl with sodium tetraisopropoxoborate, NaB(OPrⁱ)₄, in a 1:1 molar ratio in refluxing benzene yielded some new heterobinuclear derivatives of antimony(III) and boron(III) of the type[OGOP(S)S]₂Sb(μ—OPrⁱ)₂B(OPrⁱ)₂. These newly synthesized complexes have been characterized by elemental analysis and molecular weight measurement, and their plausible structures have been proposed on the basis of IR, NMR (¹H, ¹³C,³¹P,¹¹B), and FAB-mass spectral studies. On the basis of the spectroscopic evidence, a pseudo octahedral geometry around antimony and tetrahedral geometry around boron atom has been proposed. Cyclic O,O′-alkylenedithiophosphate ligands and their corresponding chloro bis(alkylenedithiophosphato)antimony(III) compounds have been screened for microbial activities. These compounds showed significant antifungal activity against Fusarium and Trichoderma and antibacterial activity against E. Coli and Pseudomonas.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

1-甲基-3-(2-甲基丙烯酰乙基)-咪唑氯离子液体/ 苯乙烯无规共聚物及其CdTe量子点复合物的合成

以偶氮二异丁腈(AIBN)为引发剂, 通过自由基聚合制备了1-甲基-3-(2-甲基丙烯酰乙基)-咪唑氯离子液体和苯乙烯的无规共聚物P(MMEIM⁺Cl^--co-St). 用红外光谱、核磁共振氢谱和凝胶渗透色谱表征了共聚物的结构. 共聚物的氯仿溶液与巯基乙酸稳定的CdTe量子点水溶液混合, 通过静电相互作用复合组装, 得到澄清透明且稳定的CdTe/P(MMEIM⁺Cl^--co-St)纳米复合物的氯仿溶液. 复合物的紫外吸收光谱、荧光发射光谱和透射电子显微镜的表征结果表明, 量子点均匀分散于共聚物中, 无团聚, 且保持了量子点的荧光性能.     

新型4-(5-N-取代-1,3,4-噻二唑-2-巯基)-苯并[4,5]呋喃[3,2-d]嘧啶类衍生物的合成及其抗癌活性

将5-取代胺基-2-巯基-1,3,4-噻二唑引入苯并[4,5]呋喃[3,2-d]嘧啶中,设计并合成了10个新型的4-(5-N-取代-1,3,4-噻二唑-2-巯基)-苯并[4,5]呋喃[3,2-d]嘧啶类衍生物(3a～3j),其结构经1H NMR,13C NMR,IR和MS确认。用MTT法测定了3a～3j对人胃腺癌细胞体(MGC)的体外增殖活性。结果表明,3a～3j均具有不同程度的抑制MGC的活性,其中4-(5-N-2’-甲氧基苯基-1,3,4-噻二唑-2-巯基)-苯并[4,5]呋喃[3,2-d]嘧啶(3j)在10μmol·L-1的浓度下对MGC的抑制率为86.4%。     

Chemical Bonding Analysis as a Guide for the Preparation of New Compounds: The Case of VIrGe and HfPtGe

The chemical bonding of transition metal compounds with a MgAgAs‐type of crystal structure is analyzed with quantum chemical position‐space techniques. The observed trends in QTAIM Madelung energy and nearest neighbor electron sharing explain the occurrence of recently synthesized MgAgAs‐type compounds, TiPtGe and TaIrGe, at the boundary to the TiNiSi‐type crystal structure. These bonding indicators are used to identify favorable element combinations for new MgAgAs‐type compounds. The new phases—the high‐temperature VIrGe and the low‐temperature HfPtGe—showing this type of crystal structure are prepared and characterized by powder X‐ray diffraction and differential thermal analysis.     

Functional derivatives of thiophene

A method is proposed for the synthesis of isatin analogs — 4,5-dioxothieno[2,3-b] pyrroles and 5,6-dioxothieno[3,2-b]pyrroles — by reaction of oxalyl chloride with amino-substituted α-amino- and Β-aminothiophene. The thiosemicarbazones of 4-ary1-5,6-dioxothieno[3,2-b]pyrroles were synthesized. n]mis|See [1] for communication X.     

Studies on the identification and synthesis of insect pheromone: XVI. Synthesis of the optically active sex pheromone of gypsy moth and its three other optical isomers

The sex pheromone of gypsy moth (+)-(7R, 8S)-7,8-epoxy-2-methyl-octadecane (la) and its three other optical isomers lb—d were synthesized stereoselectively from (+)-(R)-glyceraldehyde acetonide (2), obtained from (+)-mannitol, in 9—10 steps in an overall yield of 20—30%.     

Pheromone synthesis—63 Synthesis of both the enantiomers of 2,3-dihydro-2- isopropyl-2,5-dimethylfuran,a sex specific compound in females of the beetle hylecoetus dermestoidesL

Both the enantiomers of 2,3-dihydro-2-isopropyl-2,5-dimethylfuran were synthesized employing the Sharpless asymmetric epoxidation reaction. The (R)-(—)-enantiomer of this cyclic enol ether was also synthesized starting from (R)-(—)-linalool.     

Adamantane acid esters with alkoxyaryl alcohols: Synthesis,antiproliferative activity,and influence on microtubule network of tumor cells

Adamantaneacetic and adamantanecarboxylic acid esters containing 3-hydroxy-4-methoxybenzyl, 3,4,5-trimethoxybenzyl, or 5-(hydroxymethyl)-2-methoxyphenyl groups were synthesized as unusual analogs of natural antitumor and anti-tubulin agents combretastatin A-4 and 2-methoxyestradiol. The compounds were found to possess noticeable cytotoxicity to epithelial human carcinoma cell line A549 (EC₅₀ = 4.3—81 μmol L^–1). An ability to cause complete depolymerization of microtubule network of A549 cells was demonstrated for 5-(hydroxymethyl)-2-methoxyphenyl adamantan-1-ylacetate (6a) at a concentration of 100 μmol L^–1. Ester 6a belongs to a new structural type, which is unusual for the ligands of the tubulin colchicine domain, and is an interesting lead compound for further structural optimization.     

氨甲酰基硅烷与硝酮的反应及产物的互变异构

氨甲酰基硅烷可以与硝酮反应, 合成α-(N′-甲基-Ｎ′-三甲基硅氧基)氨基-N,N-二甲基苯乙酰胺(5). 经研究发现, 该产物具有互变异构现象, 提出了这一互变异构体的结构, 并通过1H NMR谱在不同温度(55～－30 ℃)下的数据, 证实了指定结构的存在: 在55 ℃时, 呈现结构(5)的形式; 而在－30 ℃时, 呈现结构(8)的形式, 它们互变的中间体结构则在55～－30 ℃之间随温度的变化而变化.     

Synthesis and pharmacological activity of a silicon—zinc—boron-containing glycerohydrogel

Russian Chemical Bulletin - A new pharmacologically active nanostructured silicon—zinc—boron-containing glycerohydrogel was synthesized by the sol—gel method using silicon, zinc,...     

Supramolecular hexagonal network based on a tritopic amine hydrochloride and a cucurbit[5]uril analogue

Research on Chemical Intermediates - A planar tritopic 120° ammonium salt—1,3,5-tri(4-aminophenyl)benzene hydrochloride—was synthesized. Each of the three protonated amine moieties...     

Crystal structure and quantum chemical investigation of 4-(3,4-dichlorphenyl)-1,2,4-triazole

1,2,4-Triazole derivative substituted in the 4th position — 4-(3,4-dichlorphenyl)-1,2,4-tirazole — has been synthesized. Crystal and molecular structure of the compound were determined by single crystal X-ray diffraction. Molecular geometry optimization and effective charge calculations were performed by DFT methods.