树脂催化法合成糖醇酯的研究

利用大孔阳离子交换树脂为催化剂，催化合成乙酸糖醇酯，丙酸糠醇酯，丁酸糠醇酯，乙酸四氢糠醇酯，丙酸四氢糠醇酯，丁酸四氢糠醇酯，对影响反应的诸因素进行了讨论。     

高分子固载化螯合钛酸酯的合成及酯化催化性能研究

将高分子载体聚苯乙烯二乙醇胺树脂与乙二胺钛酸二丁酯反应，制得高分子固载化螯合钛酸酯催化剂，并对其在高沸点酯的合成反应中的催化性能进行了研究，结果表明它具有良好的催化活性，易与产品酯分离，可以回收及重复使用。     

氢醌单丙酸酯的改进合成

氢醌单丙酸酯的改进合成马美玲（西安地质学院应用化学系，西安７１００５４）邓月松谢明贵（四川大学化学系，成都６１００６４）关键词除色素剂氢醌单羧酸酯氢醌单丙酸酯中图分类号Ｏ６２５．３２３氢醌单脂肪酸酯是一类很好的皮肤去色素剂，其中尤以氢醌单丙酸酯为最佳...     

树枝状十二酯的合成

以乙二胺和丙烯酸十二酯为原料，甲醇为溶剂，采用迈克尔加成反应合成了低代的树枝状十二酯。探讨了反应条件对树枝状十二酯收率的影响。乙二胺2mL(30mmol)，n(乙二胺)：n(丙烯酸十二酯)=1：6，甲醇占反应液总体积的50％，反应温度40℃，反应时间48h，产率54．9％。     

有机相中脂肪酶催化糖酯合成的研究

研究了有机相中脂肪酶催化以单糖和乙酸乙烯酯或乙酸酐为底物的糖脂合成反应。建立了定性、定量检测糖酯的方法，考察了７种脂肪酶催化糖酯合成的活力，发现来自假单孢菌属的ＰＳＬ１的活力最高。研究了ＰＳＬ１对不同单糖底物的选择性，发现对甘露醇的选择性最好，转化率可达９５％。研究了反应体系中的含水量对糖酯合成的影响，探讨了酶浓度和温度对反应的影响。     

钌系双组分催化剂上α,ω—二元羧酸单酯加氢合成ω—羟基羧酸酯的研究

在小型高压反应釜中，研究了钌系双组分催化剂对α，ω－二元羧酸单酯加氢生成ω－羟基羧酸酯的催化性能，结果表明，Ｒｕ－Ｒｅ及Ｒｕ－Ｍｏ双组分催化具有良好的催 氢性能，α，ω十五一酸单甲酯在Ｒｕ－Ｒｅ以及Ｒｕ－Ｍｏ双组分催化剂另氢，生成ω－羟基十五烷酸甲酯的收率分别为８９．０％和７１．０％，反应温度对α，ω二元羧酸单酯加氢生成ω－羟基羧酸酯的收率有较大的影响。     

胆红素单二元醇酯的合成及其在溶液中的结构

利用二元醇的单甲苯磺酸酯同胆红素的四丁基氢氧化铵盐反应，合成出胆红素单葡萄醛酸酯的模型化合物－２个胆红素单乙二醇酯和２个胆红素单丙二醇酯，通过＾１Ｈ ＮＭＲ对它们在溶液中的结构进行了研究。     

疏水缔合型增稠剂聚(丙烯酰胺-丙烯酸高级酯)的合成及增稠性能研究

采用沉淀聚合法合成了聚（丙烯酰胺－丙烯酸十四酯），聚（丙烯酰胺－丙烯酸十六酯）和聚（丙烯酰胺－丙烯酸十八酯），重点讨论了共聚物中疏水基团数量及疏水基团链长对增稠性能的影响。采用凯达尔定氮法和动态热分析（DMTA）测定了共聚物的组成及玻璃化温度。     

甲基丙烯酸甲酯和联苯酯的基团转移共聚

甲基丙烯酸甲酯和联苯酯的基团转移共聚邹友思，林国良，姚青青，潘容华（厦门大学化学系，厦门，３６１００５）关键词基团转移共聚，竞聚率，甲基丙烯酸甲酯，甲基丙烯酸联苯酯前文［１］报道了基团转移嵌段共聚的结果，用混合投料的方法进行了基团转移无规共聚并研究了...     

高效液相色谱法测定尿液中的异硫氰酸酯

 省去合成1,3 苯二硫杂环五烯 2 硫酮这一步骤，直接用异硫氰酸丙基酯与1,2 苯二硫酚反应作标准，建立了尿液中异硫氰酸酯的反相高效液相色谱(HPLC)测定方法。异硫氰酸丙基酯的标准曲线回归方程 y =0.418 2x + 2.821 ( r2 = 0.999 3 )与异硫氰酸甲基酯的回归方程 y = 0.412 2x + 2.442 3 ( r 2= 0.996 6 )基本拟合。检出限(以信噪比为2.5计)为0.08 μ mol/L 。日内重现性( n =21)以相对标准偏差(RSD)表     

己二酸二酯原位功能化SiO2稳定Pickering乳液的相反转研究

研究了原位改性SiO₂稳定的己二酸二酯-水体系的乳液相反转特性, 探究了不同己二酸二酯分子对SiO₂的功能化改性能力. 研究发现, 己二酸二酯的烷基链长对乳化行为有重要影响, 长分子链二酯倾向于形成O/W乳液, 而短分子链二酯则倾向于形成W/O型乳液. 结果表明, 短分子链的己二酸二酯对SiO₂粒子的原位功能化改性效果更好, 其原因在于短分子链的己二酸二酯空间位阻较小, 酯基与Si—OH形成氢键能力较强. 改性SiO₂的红外光谱证明了SiO₂表面不同己二酸二酯的数量变化. 碱性条件下乳液稳定特性再次证实了所提出的机理.     

Simultaneous determination of phthalates and adipates in human serum using gas chromatography–mass spectrometry with solid‐phase extraction

A gas chromatography–mass spectrometry assay was developed and validated for the simultaneous determination of phthalates and adipates in human serum. The phthalates and adipates studied were dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzylbutyl phthalate, di‐2‐ethylhexyl phthalate, di‐n‐octyl phthalate, diethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2‐butoxyethyl) adipate and di‐2‐ethylhexyl adipate, with diisooctyl phthalate as internal standard. The extraction and cleaning up procedure was carried out with solid‐phase extraction cartridges containing dimethyl butylamine groups, which showed extraction efficiencies over 88% for each analyte and the internal standard. The calibration curves obtained were linear with correlation coefficients greater than 0.98. For all analytes, the assay gave CV% values for intra‐day precision from 4.9 to 13.3% and mean accuracy values from 91.4 to 108.4%, while inter‐day precision was 5.2–13.4% and mean accuracy 91.0–110.2%. The limits of detection for the assay of phthalates and adipates were in the range 0.7–4.5 ng/mL. The method is simple, sensitive and accurate, and allows for simultaneous determination of nanogram levels of phthalates and adipates in human serum. It was successfully applied to an investigation on the level of phthalates and adipates in a non‐occupationally exposed population.     

A thermogravimetric study of the adipates and sebacates of praseodymium and neodymium

A study of the thermal decomposition, in air, of praseodymium and neodymium adipate and sebacate has suggested the decomposition pattern which follows (An represents either adipate or sebacate). The compounds were prepared by homogeneous precipitation.For the adipates formed at pH greater than 5 as well as for the sebacates precipitated at any pH:

The sebacates were precipitated quantitatively at pH greater than about 5.1; precipitation of the adipates was incomplete even at values of pH as high as 8.8. The adipates were thermally stable up to 180°C whereas the sebacates underwent slow decomposition at temperatures close to 100°C.     

Organosilicon compounds XVII. Introduction of the dialkyl phosphonate and dialkyl thiophosphonate moieties on an organosilicon substituted heterocyclic system

A number of new dialkyl 2-(5-trisubstitutedsilyl)thienylphosphonates and thiophosphonates as well as dialkyl 2-(5-trisubstitutedsilyl)furylphosphonates and thiophosphonates were prepared via reaction of the 5-(trisubstitutedsilyl)-2-lithiothiophenes and furans with dialkyl chloro-phosphate and dialkyl chlorothiophosphate. Moreover, some diethyl 2-[5-(trisubstitutedsiIyl)-2-thienyl] ethyl thiophosphates are reported.     

Synthesis of dialkyl esters of arylamino(2-pyridyl)methyl-phosphonic acids

Crystalline dialkyl esters of arylamino(2-pyridyl)methylphosphonic acids have been synthesized by the reaction of 1-pyridylazomethines with dialkyl phosphites in the presence of sodium alkoxides. When -pyridinealdehyde was condensed with dialkyl phosphites in the presence of sodium alkoxides, dialkyl esters of hydroxy(2-pyridyl) methylphosphonic acids were obtained in the form of viscous liquids. These compounds were identified in the form of the crystalline methiodides.     

Ligand Exchange Gas Chromatography on PTFE Open Tubular Columns

Two kinds of capillary columns were prepared and tested as the stationary phases of ligand exchange gas chromatographic separation of dialkyl sulfides. The PTFE column wall-coated with silane-DTC-Cu but without the addition of silicone exhibits significantly better selectivity towards dialkyl sulfides than a column wall-coated with 10% silane-DTC-Cu in silicone. With the first column connected to a microsample injection valve and a microsample loop, the quantitative determination of dialkyl sulfides can be performed. The column also shows great promise for the separation of dialkyl sulfide-hydrocarbon mixtures.     

Microwave Irradiation Technique for Synthesis of Dialkyl Dithiophosphoric Acids

Microwave heating technique was applied to the preparation of dialkyl dithiophosphoric acids from the reaction of alcohol with phosphorus pentasulphide. A microwave oven (CEM-MDS 2000) was utilized to determine the preparation conditions for the best yield of dialkyl dithiophosphoric acids under atmospheric pressure at various times and power. Six different (C 4 -C 9 ) chain-length of dialkyl dithiophosphoric acids were studied. All experiments were performed in an open Teflon (poly-tetrafluoroethylene) vessel. The results obtained showed that the reaction of dialkyl dithiophosphoric acids can be achieved more rapidly using microwave heating than using conventional procedures.     

Studies on the Selective Syntheses of Sodium Ditelluride and Dialkyl Ditellurides

Studies on the selective synthetic method for dialkyl ditellurides 1, a representative class of organyl tellurium compounds, were presented. Considering the difficulty in conducting previous harsh reactions and in suppressing the formation of dialkyl tellurides 2 as side products, we optimized reaction conditions for selective syntheses of sodium ditelluride and the corresponding dialkyl ditellurides 1. We reduced tellurium to sodium ditelluride by using NaBH₄ and subsequently, treated the obtained sodium ditelluride with alkyl halides (RX) to give the target compounds 1. Consequently, by applying various alkyl halides (RX) we achieved the selective syntheses of dialkyl ditellurides 1 (13 examples with 4 new compounds) in modest to good yields. We also suggested the mechanistic pathways to dialkyl ditellurides 1.     

A Three‐Component One‐Pot Synthesis of Functionalized 5,5‐Dicyanocyclopenta‐1,3‐dienes from Arylidene­malononitriles,Activated Acetylenes,and KCN or KSCN

The reaction of dialkyl acetylenedicarboxylates with arylidenemalononitriles in the presence of KSCN in MeCN led to a mixture of dialkyl (3E)‐4‐aryl‐3‐(arylideneamino)‐5,5‐dicyanocyclopenta‐1,3‐diene‐1,2‐dicarboxylates and dialkyl 4‐aryl‐5‐cyanothiophene‐2,3‐dicarboxylates. When these reactions were performed in the presence of KCN, only the functionalized 5,5‐dicyanocyclopenta‐1,3‐dienes were obtained.     

THE REACTION OF ACETYLACETONE WITH DIALKYLPHOSPHITES: Synthesis of Dialkyl 1-methyl-3-oxo-1-butenyl-phosphonates

Abstract

Acetylacetone and its related compounds were transformed into the dialkyl 1-methyl-1-trimethylsiloxyl-3-oxo-butylphosphonates, which after treatment with trifluoroacetic acid were converted into the dialkyl 1-methyl-3-oxo-1-butenylphosphonates.