合成香料呋喃酮前体化合物α-甲基-缩二乙醇酸二乙酯的新方法

采用重氮乙酸乙酯(EDA)与乳酸乙酯在二水杨醛铜(Ⅱ)催化下进行O—H插入反应合成了香料呋喃酮前体化合物α-甲基-缩二乙醇酸二乙酯。讨论了催化剂、反应温度和物料比例对插入反应收率的影响,在优化反应条件下产率为69%。与原工艺采用的Williamson反应相比,反应收率提高10%,产品纯度大于98%,而反应条件更温和。

α-甲基-缩二乙醇酸二乙酯的合成研究

2,5-二甲基-4-羟基-3(2H)-呋喃酮是一种非常重要的原料,而α-甲基-缩二乙醇酸二乙酯是合成呋喃酮的重要中间体。本论文采用苯的同系物为溶剂,用金属钠和乳酸乙酯为原料制得乳酸乙酯钠盐,然后与氯乙酸乙酯制得该中间体。研究了加料顺序、反应温度、反应时间、物料摩尔比、溶剂效应对收率的影响,找到了最佳反应条件:采用正加的加料方式;反应温度90℃;反应时间3h;n(Ethyl chloracetate):n(Na)=1.2:1.0;所用溶剂为甲苯。在此条件下该中间体的总收率高达58.6%。

α-甲基-缩二乙醇酸二乙酯的合成研究

2,5-二甲基-4-羟基-3(2H)-呋喃酮是一种非常重要的原料,而α-甲基-缩二乙醇酸二乙酯是合成呋喃酮的重要中间体。本论文采用苯的同系物为溶剂,用金属钠和乳酸乙酯为原料制得乳酸乙酯钠盐,然后与氯乙酸乙酯制得该中间体。研究了加料顺序、反应温度、反应时间、物料摩尔比、溶剂效应对收率的影响,找到了最佳反应条件:采用正加的加料方式;反应温度90℃;反应时间3h;n(Ethyl chloracetate):n(Na)=1.2:1.0;所用溶剂为甲苯。在此条件下该中间体的总收率高达58.6%。

α-甲基-缩二乙醇酸二乙酯的合成

采用重氮乙酸乙酯(EDA)与乳酸乙酯在无水硫酸铜催化下进行O-H插入反应合成α-甲基-缩二乙醇酸二乙酯。讨论了反应时间,催化剂用量,反应温度和物料比例对插入反应收率的影响,在优化反应条件下产率为58.8%。产品纯度大于98%。

IN-SITU POLYMERIZED SYNTHESIS AND PROPERTIES OF NANO-ZnO/PEG/PET COMPOSITE

Nano-ZnO particle （nZnOp） reinforced polyethylene glycol （PEG）/polyethylene terephthalate （PET） （nZnOp/PEG/PET） copolymeric composites with different mass fractions and molecular weights of PEG are synthesized via in-situ polymerization. The dispersion of nZnOp in copolymer matrixes and the effects of PEG and nZnOp particles on the crystallization behavior of the composites are studied by TEM, differential scanning calorimetry（DSC）, XRD and Fourier thansform infrared spectroscopy （FTIR ）. The results reveal that nZnOp particles are dispersed in the matrixes with nano-scale, and the addition of PEG induces more homogeneous dispersion of nZnOp. Simultaneously, these nanoparticles become nucleating centers during the crystallization of the matrixes. PEG segments can improve the flexibility of the PET molecular chain, resulting in the drop of the cold crystallization temperature and the rise of the crystallization rate of the composites. Furthermore, PEG （4 000） with the mass fraction of 10% can promote the crystallization rate of the composites. The mechanical properties show that the nano-particles strengthen and toughen the PET matrix, whereas PEG weakens these improve- ments.

Identification of the toxic compounds produced by Sargassum thunbergii to red tide microalgae

The inhibitory effects of methanol extracts from the tissues of three macroalgal species on the growths of three marine red tide microalgae were assessed under laboratory conditions.Extracts of Sargassum thunbergii(Mertens ex Roth) Kuntz tissue had stronger inhibitory effects than those of either Sargassum pallidum(Turner) C.Agardh or Sargassum kjellmanianum Yendo on the growths of Heterosigma akashiwo(Hada) Hada,Skeletonema costatum(Grev.) Grev,and Prorocentrum micans Ehrenberg.Methanol extracts of S.thunbergii were further divided into petroleum ether,ethyl acetate,butanol,and distilled water phases by liquid-liquid fractionation.The petroleum ether and ethyl acetate fractions had strong algicidal effects on the microalgae.Gas chromatography-mass spectrometry analyses of these two phases identified nine fatty acids,most of which were unsaturated fatty acids.In addition,pure compounds of four of the nine unsaturated fatty acids had effective concentrations below 5 mg/L.Therefore,unsaturated fatty acids are a component of the allelochemicals in S.thunbergii tissue.

Optimization of Response Surface of Ultrasonic-assisted Extraction of Rizhao Black Tea

[ Objectivel The aim was to determine the optimal technology for ultrasonic-assisted extraction of black tea was determined. [ Methed] Taking Black Tea as materials, the Box-Behnken response surface design method of tea polyphenols ultrasonic-assisted extraction process optimi- zation was applied. The regression optimization model of the ethanol volume fraction, ultrasonic time, and ultrasonic temperature, ethyl acetate extract stalling time and tea polyphenols was established. [ Result] The influence of four factors on the black tea polyphenol solvents affecting size was as follows： ultrasonic time 〉 ethanol volume fraction 〉 stalling extraction time 〉 ultrasound temperature. The best extraction process was ultrasonic time 80 min, volume fraction of 88.99% ethanol, extraction time 89.97 min, ultrasonic temperature of 80℃. At the optimized technical parameters, the black tea phenolic extraction yield can be as high as 73.50%. [ Conclusion] The study provided theoretical basis for the development of tea leaves and black tea.

Preparation of Ethylene Glycol Monoethyl Ether Acetate Using a Tubular Reactor

Ethylene glycol monoethyl ether acetate (EGEA), an excellent solvent, is prepared with ethylene oxide (EO) and ethyl acetate (EA) in a tubular reactor under suitable reaction condition. The single circulation yield can reach 81%. This technology is not only safe but also makes it possible to continuously produce EGEA in industry,with low content of high boiling point by-products.

Kinetics of Glucose Ethanolysis Catalyzed by Extremely Low Sulfuric Acid in Ethanol Medium

The kinetics for production of ethyl levulinate from glucose in ethanol medium was investigated. The experiments were performed in various temperatures （433-473 K） and initial glucose concentrations （0.056-0.168 mol·L-1） with extremely low sulfuric acid as the catalyst. The results show that higher temperature can improve the conversion of glucose to ethyl levulinate, with higher yield of ethyl levulinate （44.79%, by mole） obtained at 473 K for 210 min. The kinetics follows a simplified first-order kinetic model. For the main and side reactions, the values of activation energy are 122.64 and 70.97 kJ·mo1-1, and the reaction orders are 0.985 and 0.998, respectively.

Excess Molar Volumes and Viscosities of Binary Mixture of Diethyl Carbonate+Ethanol at Different Temperatures

The purpose of this work was to report excess molar volumes and dynamic viscosities of the binary mixture of diethyl carbonate （DEC）+ethanol. Densities and viscosities of the binary mixture of DEC+ethanol at temperatures 293.15 K—343.15 K and atmospheric pressure were determined over the entire composition range. Densities of the binary mixture of DEC+ethanol were measured by using a vibrating U-shaped sample tube densimeter. Viscosities were determined by using Ubbelohde suspended-level viscometer. Densities are accurate to 1.0×10-5 g·cm-3, and viscosities are reproducible within ±0.003 mPa·s. From these data, excess molar volumes and deviations in viscosity were calculated. Positive excess molar volumes and negative deviations in viscosity for DEC+ethanol system are due to the strong specific interactions.All excess molar vo-（lumes） and deviations in viscosity fit to the Redlich-Kister polynomial equation.The fitting parameters were presented,and the average deviations and standard deviations were also calculated.The errors of correlation are very small.It proves that it is valuable for estimating densities and viscosities of the binary mixture by the correlated equation.

Biodegradation of DTP and PET Fiber by Microbe

The degradation of diethylene glycol terephthalate (DTP) and polyethylene terephthalate (PET) fiber by microbe was studied.The degree of DTP degradation was determined by High Performance Liquid Chromatography (HPLC) to be more than 90%.The products after degradation of DTP and PET fiber were various.The degradation of DTP can be described by the first-order reaction model.The degradation of PET fiber was found to be little,but surface erosion of PET fiber could be clearly seen from the SEM photographs indicating there occurred some traces of biodegradation on the PET fiber surface.

Flavonoid Content and Antioxidant Properties in Different Extracts of Calluna vulgaris （L,） Flowers

This study evaluated the effect of four different solvent, i.e., water, ethanol, water-ethanol mixture and ethyl acetate, on the antioxidant activities of wild and cultivated heather （Calluna vulgaris （L.） Hull） plant. The highest values for total flavonoid content were obtained for samples extracted using ethanol-water mixture and ethyl acetate. Cupric reducing antioxidant capacity （CUPRAC） method, scavenging ability on 1,1-diphenyl-2-pirylhydrazyl radicals （DPPH） radicals and chelating activity on Fe2~ ions have been used for evaluation of antioxidant activity of the extracts. Ethanolic fraction exhibited the lowest reducing capacity, despite a heather sample used. The extracts of cultivated heather exhibited significant scavenging effect on DPPH radicals, and ethanol and ethanol-water fractions were found to be the most effective. The metal-chelating effect of the extracts increased in the order： ethanol 〈 ethyl acetate 〈 ethanol-water 〈 water. The results may be helpful for better utilization of heather flowers extracts as potential pharmaceutical and nutraceutical ingredient.

Allelopathic Effects of Corrigiola Telephiifolia Root Extracts on Germination and Seedling Growth of Raphanus Sativus and Triticum Aestivum

The allelopathic potential of aqueous and organic solvent extacts from Corrigiola telephiifolia Pour which is an aromatic and medicinal plant in mediterranean regions, was investigated under laboratory conditions on two plant species： Raphanus sativus and Triticum aestivum. The aqueous extract of Corrigiola telephiifolia roots had an important inhibitory effect on the seed germination of the two tested plant species. The dichloromethane and the methanol extracts significantly reduced the growth of radish roots up to 84.44% and 68.85% respectively. The butanol, the dichloromethane and the ethyl acetate extracts had a high inhibitory effect on seed germination and roots growth of wheat. The presence of saponins in butanol extracts and tanins in dichlorometane and ethyl acetate extracts may be responsible of these allelopathic activities. These results suggest that Corrigiola telephiifolia Pour have allelopathic effects and contains potent allelochemicals which should be used for weeds management.