Epoxidation of natural propenylbenzenes catalyzed by [FeIII(Salen)Cl] and [FeIII(TPP)Cl]

Epoxidation of natural propenylbenzenes (safrol, isosafrol, anethol, eugenol and isoeugenol) was carried out using iron complexes as catalysts ([Fe^III(TPP)Cl] and [Fe^III(Salen)Cl] · H₂O, where TPP = 5, 10, 15, 20-meso-tetraphenylporphyrin and Salen = N,N′-(salicylaldehyde)ethylenediamine) in presence of hydrogen peroxide 30% and glacial acetic acid. Reaction products were identified by gas chromatography and satisfactory yields were obtained. Quantitative conversion of isosafrol to the corresponding epoxide was achieved in presence of [Fe^III(TPP)Cl] as catalyst.     

Meso-四甲基-meso-四对氨苯基杯[4]吡咯的合成及表征

以吡咯和对氨基苯乙酮为原料合成了meso-四甲基－meso-四对氨苯基杯[4]吡咯，研究了反应时间，温度、浓度等对收率的影响，其结构通过红外光谱，核磁共振，电喷雾质谱和元素分析进行了确证。     

Synthesis and characterization of strontium 1,3,5-benzenetricarboxylate, [Sr3(1,3,5-BTC)2(H2O)4]·H2O

A three-dimensional strontium-based metal-organic framework was constructed using 1,3,5-benzenetricarboxylic acid, [Sr₃((OOC)₃C₆H₃)₂(H₂O)₄]·H₂O. This new compound was synthesized hydrothermally and is a rare example of a strontium metal-organic network. The compound network contains three distinct Sr centers, one of which is seven-coordinate and the other two are nine-coordinate geometry. The benzene rings form a herring-bone type of arrangement down the a-axis. The material is thermally stable to ca. 230 °C and transforms to an unknown material before finally decomposing to phase-pure SrCO₃ at 650 °C. The synthesis, structure, morphology and materials properties are discussed.     

Synthesis of the [Ga]-MFI under atmospheric pressure

The crystallization of the [Ga]-MFI was investigated as a function of synthesis time under atmospheric pressure. The molar composition of the reactants was 100SiO₂-Ga₂O₃-llNa₂O-llTPABr-3500H₂O. The crystallinity of the [Ga]-MFT was examined by using several analytical instruments, such as XRD, XPS, XRF, FT-IR, solid-statemas-NMR, DTG/DTA, and SEM. The [Ga]-MFI was successfully synthesized under atmospheric pressure at 97 ‡C in 72 h. It was found that the nucleation of the [Ga]-MFI took a quite long time, but the crystallization took place very fast. It is supposed that nucleation is the rate-controlling step in the [Ga]-MFI synthesis under atmospheric pressure. Consequently, if the induction period of the nucleation can be shortened, it would be possible to synthesize the [Ga]-MFI commercially under atmospheric pressure.     

Synthesis and characterization of a Keggin-type V(V)-substituted isopolytungstate, (n-C3H7)5[H4VW11O40]

A new V(V)-substituted isopolytungstate, (n-C₃H₇)₅[H₄VW₁₁O₄₀], with Keggin structure was synthesized in an acidic aqueous–CH₃CN solution and characterized by elemental analysis, FT-IR, Raman, ¹H NMR, and cyclic voltammetry.     

Synthesis and characterization of poly[2-(10-undecenoyloxy)ethyl methacrylate]

Summary By Schotten-Baumann's esterification of poly(2-hydroxyethyl methacrylate) with 10-undecenoyl chloride a new multimonomer - poly[2-(10-undecenoyloxy)ethyl methacrylate] was prepared. Based on the results of elemental analysis, FTIR, ¹H-NMR and ¹³C-NMR spectra, the structure of the multimonomer was proposed. The thermal properties of the multimonomer were studied by DSC and TG. The rate of disappearance of double bonds in the multimonomer during UV irradiation was examined in the solid state to obtain a crosslinked product. Received: 17 September 2001/Revised version: 5 February 2002/ Accepted: 7 March 2002     

噁唑[4,5-b]吡啶-2(3H)酮的合成

以2-氨基-3-羟基吡啶为原料,固体光气为环化剂合成了甲基吡啶磷杀虫剂重要中间体噁唑[4,5-b]吡啶-2(3H)酮。考察了溶剂种类、溶剂用量、物料配比对反应的影响。优化的工艺条件为:33 g2-氨基-3-羟基吡啶,以70 mL吡啶为溶剂,n(光气)∶n(2-氨基-3-羟基吡啶)=1.1∶1,反应温度为60⁷0℃。优化条件下产品收率达84.31%。     

配合物[Cu（L）2]ECu’（L）2]·CH3OH·3H2O的合成和结构表征

以邻氯蜷苯磺酸与吡啶-2-甲醛进行缩合得到席夫碱配体（KL）,然后与Cu（AeO）2．H20进行配位反应,得到了席夫碱配合物[Cu（L）2][Cu’（L】2】’CH3OH·3H2O,用面素分析、FT—IR和X-射线单晶衍射进行r表征。结果表明t配合物属]i单斜晶系,P21／c空间群。配合物的一一个独立单元由置个品格水分子、一个晶格甲醇分子和两个不同的单核铜单元构成。有趣的是,这两个荤核铜单元的组成完全相同但配位模式不同,它们均由一个铜离子和两个脱质子的席夫碱配体组成,其中一个瞥核铜单元中的两个磺酸基均参与了配位,另一个则只有一个磺酸基配位。     

[1]-萘并[1,2-b]、[2,1-b]氧杂卓并[3,4-b]喹啉-15(8H)-酮的合成及量化计算

以邻硝基苯甲醛为起始原料,经还原、Friedlander缩合、溴化反应得到中间体2-溴甲基-3-喹啉酸乙酯,再将其分别与α-萘酚和β-萘酚一锅法高产率地合成2-(α-萘氧甲基)-3-喹啉酸和2-(β-萘氧甲基)-3-喹啉酸,然后分别通过Eaton’s Reagent环化,发生分子内Friedel-Crafts反应又得到2种新型闭环产物:[1]-萘并[1,2-b]氧杂卓并[3,4-b]喹啉-15(8H)-酮和[1]-萘并[2,1-b]氧杂卓并[3,4-b]喹啉-15(8H)-酮。合成产物经1H-NMR、MS和IR确认,并测定了在三氯甲烷中的紫外光谱和固体荧光光谱,并对其荧光光谱进行量子化学计算模拟。     

Synthesis,characterization, and evaluation of poly[n-alkyl(oxy)-n-hexyl acrylates]

Oxoalkyl acrylates of long-chain 7-oxo alcohols were synthesized as intermediate monomers for the preparation of poly[n-alkyl (oxy) -n-hexyl acrylates] for the first time. These polymers have wide applications as fluidity improvers (pour point depressants) for petroleum crude oils. Characterization of all the intermediate monomers was done by IR, ¹H-NMR, and MS, and that of polymers by IR, ¹H-NMR, and GPC. These polymers were systematically investigated for their efficacy as pour point depressants on three types of high waxy Bombay High (Indian) crudes. In addition to establishing the pour points, relevant rheological parameters of the untreated and the additive-treated crude oils were determined in the laboratory with a rotational viscometer. Results of the crude oils that were pre- and posttreated with these new polymers have shown enhanced activity of flow properties as compared to the crudes that were treated with poly(n-alkyl acrylate) flow improver.     

2，2-双[4-（3，4-二氨基苯氧基）苯基]六氟丙烷的合成及表征

以六氟双酚A与5-氯-2-硝基苯胺为原料,在N,N-二甲基甲酰胺中发生缩合反应,再经Pd/C催化剂还原合成了一种新型的六氟四胺,其结构分别用元素分析、IR和 1HNMR进行了表征.这种新型四胺由于引入了六氟丙基和氧原子,可以用于合成溶解性能良好的聚苯并咪唑.     

[68Ga]Ga-DFO-c(RGDyK): Synthesis and Evaluation of Its Potential for Tumor Imaging in Mice

Angiogenesis has a pivotal role in tumor growth and the metastatic process. Molecular imaging was shown to be useful for imaging of tumor-induced angiogenesis. A great variety of radiolabeled peptides have been developed to target αvβ3 integrin, a target structure involved in the tumor-induced angiogenic process. The presented study aimed to synthesize deferoxamine (DFO)-based c(RGD) peptide conjugate for radiolabeling with gallium-68 and perform its basic preclinical characterization including testing of its tumor-imaging potential. DFO-c(RGDyK) was labeled with gallium-68 with high radiochemical purity. In vitro characterization including stability, partition coefficient, protein binding determination, tumor cell uptake assays, and ex vivo biodistribution as well as PET/CT imaging was performed. [⁶⁸Ga]Ga-DFO-c(RGDyK) showed hydrophilic properties, high stability in PBS and human serum, and specific uptake in U-87 MG and M21 tumor cell lines in vitro and in vivo. We have shown here that [⁶⁸Ga]Ga-DFO-c(RGDyK) can be used for αvβ3 integrin targeting, allowing imaging of tumor-induced angiogenesis by positron emission tomography.     

三唑酮的合成工艺

以2-氯吡啶为原料经水合肼取代,再和尿素环化合成标题化合物,条件温和,操作简单,收率较高.在取代过程中未反应完的原料可循环套用,适合工业化生产.     

稀土配合物[Ln2(sba)3(phen)2(H2O)2](Ln=Eu,Tb)合成、表征和性质研究

在乙醇和水的混合溶剂中,利用辛二酸[Suberic acid=H2sba]、邻菲罗啉(Phen)合成了标题化合物,通过化学分析、元素分析、红外光谱、热分解等方法对配合物组成进行了分析和表征,并研究了两种配合物的荧光性质。     

2-氟-9,10-亚甲二氧基-6[H]-[1]苯并吡喃并[4,3-b]喹啉的合成与表征

以6-氟-色满酮-4为原料，与6-氨基胡椒醛发生Friedǎnder合反应而得到新的喹啉衍生物2-氟-9，10-亚甲二氧基-6[H]-[1]苯并吡喃并〔4，3-b]喹啉，其结构经IR、^1HNMR、MS和元素分析确证。     

1，4-双[β-（p-氨基苯基）乙基]苯的合成与表征

以1,4-二乙炔基苯与1-溴-4-硝基苯为原料,通过Sonogashina反应和Pd/C水合肼还原反应生成标题化合物.用元素分析、IR和1HNMR等手段对产物的组成和结构进行了表征,并讨论了芳卤试剂、催化剂、缚酸剂、溶剂和反应温度等因素对反应产率的影响.     

三维网状化合物[(H2DABCO)CaCl4(H2O)2]的合成、结构及性能

将1,4-二氮杂二环[2,2,2]辛烷(DABCO)、氯化钙、盐酸以一定比例溶入甲醇溶液,通过自然蒸发方式获得一种具有三维网状结构的新颖有机-无机杂化化合物[(H2 DABCO)CaCl4(H2 O)2],以红外光谱(IR)、元素分析、单晶X衍射、X-射线粉末衍射、热重分析(TG)、变温-变频介电等测试,确定化合物的结...     

Two types of tetrasubstitution in [H4Ru4(CO)12]: spectroscopic characterization and crystal structure determination of [H4Ru4(CO)8(PMe2Ph)4] and [H2Ru4(CO)9(PMe2Ph)4]

Two tetrasubstituted tetranuclear ruthenium clusters containing dimethylphenylphosphine [H₄Ru₄(CO)₈(PMe₂Ph)₄] and [H₂Ru₄(CO)₉(PMe₂Ph)₄] were prepared and characterized spectroscopically as well as by X-ray crystallography. Both compounds show a structure based on the usual 60-electron tetrahedral framework with each ruthenium atom being bonded to one phosphine ligand. In the case of the nonacarbonyl derivative, one of the ruthenium atoms has one terminal carbonyl group and is also bonded to two semibridging carbonyl groups; two other metal–metal bonds are bridged by the hydride groups. In the case of the octacarbonyl compound all the ruthenium atoms are bonded to two terminal carbonyls and to two bridging hydrides. NMR spectroscopical information of [H₄Ru₄(CO)₈(PMe₂Ph)₄] suggests the presence of two isomers in solution which we propose to have D_2d and C_s symmetries. The observation of the NMR properties gives some observations about conditions that favour coupling between substituents in different ruthenium atoms.     

[Nd(6-OHnicH)3(H2O)6]n配合物的合成和晶体结构研究

在水热反应条件下,采用6-羟基吡啶-3-甲酸(6-OHnicH)与稀土金属离子钕合成了标题化合物。运用元素分析、红外光谱、X-射线衍射等进行了表征。X-射线衍射结果表明:该配合物属于三斜晶系,空间群是P-1,晶胞参数为:a=7.1693(8),b=10.3227(12),c=16.7831(19),α=73.3000(10)°,β=88.0070(10)°,γ=88.2180(10)°,Z=2。该配合物最终通过分子间氢键作用堆积为三维网状结构。     

微波催化合成四苯基卟啉

在有机溶剂体系中,利用微波催化苯甲醛、吡咯合成四苯基卟啉。最佳反应条件为:二甲苯溶剂100ml,对硝基苯甲酸催化剂1.8g,苯甲醛0.02mol、吡咯0.02mol,微波功率210W,辐射时间15min,产率达到52 9%,经重结晶,双组分紫外光谱法测定四苯基卟啉纯度达96%。