Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

Hydrothermal Synthesis and Structure of a Novel Coordination Polymer Co_3(tma)(pda)_2(H_2O)_3]n·nH_2O

1INTRODUCTION Recently,the design and preparation of coordina-tion polymers with new porous frameworks are of great interest due to their potential functionalities such as catalysis,gas absorption,separation and molecu-lar recognition.In designing1-D,2-D and3-D porous coordination polymers,the selection of appropriate ligands is crucial for determining the structure.The mixed-linker systems of both carboxylates and pyri-dyls have proved to be effective for the preparation of novel coordi…     

高相对分子质量8-羟基喹啉锂聚合物的制备和性能

高分子电致发光显示器(PLED)是近几年来国际、国内的研究热点,取得了很大的进展,其中高分子化金属配合物是一类很有价值的功能材料。通过甲基丙烯酸甲酯(MMA)、苯乙烯(S)和含有8-羟基喹啉的单体共聚合成模板聚合物,再与氢氧化锂作用,实现了8-羟基喹啉锂配合物的高分子化,获得了一种能够溶解在普通的溶剂中的高相对分子质量的含喹啉锂配合物的发光聚合物,并利用元素分析、¹H-NMR、FTIR、UV、PL光谱、DSC、TGA、GPC等方法对其结构和性能作了表征。紫外吸收和光致发光(PL)光谱说明合成共聚物的发光来自于Liq基团,引入的可聚合的链段以及共聚物中的甲基丙烯酸甲酯或苯乙烯链段,并没有影响发光波长的改变。亲核溶剂改变8-羟基喹啉金属配合物分子结构,使共聚物光谱明显红移20nm左右。     

HgCl2/I2复合催化剂协同催化合成异丙醇钇的研究

以金属钇和异丙醇为原料，以HgCl2/I2为复合催化剂，通过对金属钇的机械加工以增加其比表面，并将异丙醇脱水使其含水量降低至0．05％，体系在82℃回流5h，经过滤、减压蒸馏，得到了白色海绵状异丙醇钇，其产率高达83％，合成时间比文献报道的缩短了19h，产率提高了8％。文章确定了催化剂的最佳用量为20gY加入60mg HgCl2/I2，研究了合成产率与HgCl2/I2催化剂和HgCl2催化剂的依赖关系及异丙醇中含水量对合成产率的影响，并对HgCl2/I2的催化作用机理进行了初步探讨。     

Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.     

A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.     

2-芳基-3-N-丙酰基-5-(4-溴苯基)-1,3,4-噁唑啉类化合物的合成

噁唑啉类化合物是重要的杂环族化合物,在农药化学和医药化学中应用及其广泛。在现有的文献中已报道的大多是3-N乙-酰基-1,3,4噁-唑啉类化合物的合成[1-6],而3-N乙-酰基-1,3,4噁-唑啉类化合物的合成却很少见。为了深入研究同一分子中聚集不同骨架杂环化合物的合成以及开发新型高     

A convenient semicarbazide resin for the solid-phase synthesis of peptide ketones and aldehydes

Use of a semicarbazide resin for the solid-phase preparation of peptide ketones and aldehyde led to optimal results in terms of both purity of the final product and overall yield. This resin was prepared without complication by activation of the commercial available aminomethyl polystyrene with CDI at room temperature, followed by treatment with tert-butyl carbazate. Furthermore, the TNBSA colorimetric assay has been adapted for checking the incorporation of the carbonyl moiety onto hydrazine-based resins.     

A Facile Synthesis of α-Phenylthio-α,β-Unsatuated Esters

α-phenylthio-α，β-unsaturated esters 6 were synthesized by Witting reaction of 3.which were prepared by a phenylsulfenyllation-trans-ylidation reaction.