亚砜类化合物的合成及其萃取稀土的结构-性能研究

本文报道具不同结构辛烷基的三种类型亚砜的合成并研究了它们的化学结构与萃取稀土性能的关系.辛烷基的支链化程度对化合物的脂溶性有显著影响.具有两个亚砜基化合物萃取稀土的分配比较高,尤以其间有两个次甲基相隔者更显著.对硝酸及水分子的萃取和稀释剂影响也作了讨论.不同类型的亚砜与硝酸稀土形成不同组成的络合物,连续变法、固体络合物元素分析与差热分析结果均一致.红外光谱研究说明,亚砜基氧原子均参加配位,NO_3呈及配体,镧的配位数可达10。     

STRUCTURE-REACTIVITY STUDIES ON THE EXTRACTION OF RARE EARTHS BY DIALKYL ISOPROPYLPHOSPHONATES

Dialkyl isopropylphosphonates with various alkyl groups are synthesized for the structure-reactivity studies on the extraction of rare earths. Steric effect of ligands on the extrac-tion behaviour of rare earth is well demonstrated due to the lanthanide contraction. Thethermodynamic functions of the extraction reaction are estimated and the influence of chem-ical structure of extractants is discussed. By the method of continuous variation as well asthe elementary analysis, the composition of the extracted species is deduced as Ln(NO_3)_3·3L.The structure of the coordination compound is further elucidated by IR and NMR spectra.The magnetic property and the differential thermal analysis of the complexes are also studied.     

有机磷化合物的研究ⅪⅩ.亚磷酸二烷基酯钠的相转移催化P-烷基化反应

碳-磷键的形成反应在有机磷合成中占有重要地位,烷基磷酸二烷基酯是一类具有实用价值的有机磷化合物,因此其合成方法受到人们重视。Michaelis-Becker反应是合成这类化合物的重要方法之一,但由于反应条件剧烈,常有副反应产生,其一是亚磷酸二烷基酯与其钠盐易发生岐化反应,另一是反应中所形成的卤化盐促进产物烷基膦酸酯与烷基卤的酯交换反应,从而影响了产物纯度与产率,烷基氯或具空间位阻的烷基溴与亚磷酸二烷基酯钠的反     

有机磷化合物的研究——氧化膦酰化反应—合成二烃基膦酸及其衍生物的新方法

本文报道了一个基于二烃基亚膦酸在碱及四氯化碳存在下与亲核试剂反应制备二烃基膦酸及其衍生物的新法,研究了反应条件与亲核剂的结构对氧化膦酰化反应得率的影响,讨论了反应机理。     

EXTRACTION CHEMISTRY OF RARE EARTHS BY MONO-ALKYL ISOPROPYLPHOSPHONATES

The influence of chemical structure of ester alkyl group of mono-alkyl isopropylphosphonates on the extraction behaviours of rare earth has been studied. The mono-alkyl isopropylphosphonate bearing β-substituted ester alkyl group shows high K_(ex) value, which is evidently depressed, usually in two orders of magnitude, by introducing a branch chain on the α-position of the ester alkyl group. The steric effect of ligand is usually enhanced due to the characteristic lanthanide contraction.z2The extraction chemistry of rare earths by mono-amylnonyl isopropylphosphonates (MANPP) was studied in detail The thermodynamic function was estimated and the "tetrad effect" between K_(ex) value or △G value and atomic number was observed. In addition, the composition and structure of the coordinated compound was studied. As demonstrated by the experimental data, the extractive separation of Sm and Nd by MANPP in chloride solution was better than that in nitrate system.     

辛基膦酸单丁酯萃取钴(Ⅱ)、镍(Ⅰ)的结构-性能关系

在钴、在钻、镍的湿法冶炼工艺中,溶剂萃取技术己获得了广泛的应用.自1968年Ritcey等首次提出采用二(2一乙基己基)磷酸(DEHPA)作为硫酸盐介质中分离钻、镍的萃取剂以来,又先后出现了2一乙基己基麟酸单2一乙基己基醋(EHEHPA)     

Regio-and Stereo-selective Bioreduction of Diketo-n-butylphosphonate by Baker''''s Yeast

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｂａｋｅｒ’ｓｙｅａｓｔ (Ｓａｃｃｈａｒｏｍｙｃｅｓｃｅｒｅｖｉｓｉａｅ)ｉｓｗｅｌｌｒｅｃｏｇｎｉｚｅｄａｓａｖａｌｕａｂｌｅｓｔｅｒｅｏｓｅｌｅｃｔｉｖｅｒｅａｇｅｎｔｉｎｂｉｏ ｔｒａｎｓｆｏｒｍａｔｉｏｎｓｏｆｏｒｇａｎｉｃｍｏｌｅｃｕｌｅｓ .Ｔｈｅａｓｙｍｍｅｔｒｉｃｒｅ ｄｕｃｔｉｏｎｏｆｃａｒｂｏｎｙｌｇｒｏｕｐｓｗｉｔｈｔｈｉｓｍｉｃｒｏｂｅｈａｓｂｅｅｎｓｔｕｄｉｅｄｅｘｔｅｎｓｉｖｅｌｙ .Ｍｏｒｅｏｖｅｒ,ｉｎｔｈｅｃｏｕｒｓｅｏｆｒｅｄｕｃｔｉｏｎｏ…     

7-取代-8-羟基喹啉的合成

由2-氯辛烷与8-羟基喹啉钠反应制得7-(1′-甲基庚基)-8-羟基喹啉.用长碳链脂肪醛在碱性介质中与8-羟基喹啉反应,合成了一系列7-烯基-8-羟基喹啉(1);对不同结构长碳链脂肪醛合成作了研究.     

纸上反相分配层析与液液萃取分离2-乙基己基膦酸单(2-乙基已基)酯对镧系元素反相分配层析研究

Cerrai^[1,2]等曾研究了二(2-乙基己基)磷酸(HDEHP)对稀土元素的反相层析,并用斜率法测定了萃合物组成.Cvjelicanin^[3]用反相层析研究了二丁基磷酸对铍、镧及铈的萃取机理和平衡常数.我们以往的研究结果说明,配位体结构的极性效应和空间效应对分离金属离子的反相层析行为与液液萃取极相似^[4,5].     

有机磷化合物的研究 Ⅶ.二丁基膦酸酯的合成及其碱性水解反应

提供一个由氧化二丁基膦在四氯化碳存在下与碱、醇或酚反应,合成二丁基瞵酸及其酯的方法。研究二丁基瞵酸对位取代苯酯的取代基性质与超加折射值、纸上层析比移值与紫外光谱的关系。取代基团的σ值与红外光谱特征频率及Lewis碱性参数间均有良好的线性关系。应用电导法测得二丁基瞵酸对位取代苯酯的等浓度碱性水解速度常数,计算了相应的活化能。这些常数与取代基的σ值均存在线性关系,并在此基础上讨论了碱性水解反应机理。为探讨磷-氧键的dπ-pπ键特性,比较了相应羧酸的水解行为。