二茂铁及其衍生物的合成与色谱分离课件.ppt

实验一,(Experiment 1),二茂铁及其衍生物,的合成与色谱分离,(Synthesis and chromatographical separation of ferrocene and its derivatives,),Structure of,Ferrocene,二茂铁,(Fe(C,5,H,5,),2,ferrocene),是一个典型的金属有机化合物,夹心型结构,(Sandwich,structure,）,G Wilkinson,和,Woodward,在,1952,年确定了它的结构。,促进了化学键理论的发展，扩大,了配合物的研究领域,简介,(introduction),二茂铁分子的轨道形成情况（定性）,(Orbitals formation of ferrocene(arbitrary),熔点：,172173，400,不分解，但在,100,开始升华。能溶于乙醚、石油醚等非极性溶剂，不溶于水。,(mp:172173;sublime:100.Soluble in diethyl ether,petroleum ether and other unpolar solvents.,insoluble in water),对碱和非氧化性酸稳定。具有芳香性，在环上能进行酰化反应，烷基化反应等芳香环所具有的反应特性。特别是它的带有手性的衍生物，可以作为手性配体，用于手性化合物催化合成的辅助配体。,化学性质(Chemical properties),物理性质(Physical properties),二茂铁的性质(Properties of ferrocene),Ferrocene is stable to bases and non-oxidizing acids.It is of,aromaticity and thereby undergoes a few characteristic,reactions of aromatic rings such as acylation,alkylation,etc.,Particularly,its chiral derivatives are usually employed as,auxiliary ligands for asymmetric synthesis of chiral compounds.,可以作为汽油的抗震剂，紫外线的吸收剂，火箭燃料的添加剂等,used as anti-shock additives in gasolines;as UV adsorbents,as a component in rocket fuels.,用途(Application),二茂铁的合成方法很多，一般都是用绿化亚铁和环戊二烯,的盐在碱的作用下得到的。例如：,制备(Preparation),注意事项,(Attention),1,环戊二烯有毒，需在通风厨中小心取用，尽量不要洒在实验,台上,.,Cyclopentadiene is toxic and therefore should be dealed in,a hood.,环戊二烯解聚,(depolymerization of dicyclopentadiene),实验步骤(experimental),2,液体不要加热过快，以免蒸馏速度太快，导致少量环戊二烯二聚体混入单体中,.,the boiling liquid should not be overheated(a student should be responsible for the distillation),otherwise this will result in dicyclopentadiene being distilled over.,3,解聚后的单体应尽快使用，因为即使保存在冰箱中也会慢慢重新聚合。,The newly distillated cyclopentadiene monomer should be used as quickly as possible,since it will repolymerized gradually during conservation,even in refrigerator,.,氯化亚铁,(FeCl,2,4H,2,O),的制备（,preparation of ferrous chloride),注意事项,(Attention),1,使用浓盐酸过程中，需小心仔细,.,must be carful when dealing with conc.HCl,2,铁钉除锈后，要用蒸馏水冲洗干净,.,please wash the nails after derusting,3,滤液浓缩时，温度不可太高。,dont overheated during concentration of the solution,二茂铁的合成（Synthesis of Ferrocene),To a 250ml three-neck round flask,equipped with a mechanical stirrer and a pressure equalizing funnel,was added 17g KOH and 40ml anhydrous diethyl ether.Stirring for 10 min,4ml cyclopentadiene monomer was added and stirred for further 20min.5g FeCl,2,4H,2,O dissolved in 17ml DMSO and 2ml diethyl ether was,then,added dropwise through the funnel.After further stirred for 1h,the ether phase was separated and the aqueous phase was extracted with ether(2 x 10ml)and combined the ether phase,which was washed with 2mol/L HCl(2 x 10ml)and then with water(2 x 10ml).The ether solution was dried with anhydrous Na,2,SO,4,.,注意事项,(Attention),1,搅拌器的搅拌头要尽可能接近瓶底，但不要直接接触,.,The stirrer head should be near the bottom of the flask.,2,搅拌过程中，要塞紧瓶塞，但要不时放气，防止乙醚,气体冲掉瓶塞,.,The flask should be stoppered and leaked at intervals,avoiding the damage of the stopper,3,搅拌速度应高些，加速二茂铁的生成,The stirring rate should be higher in order to increase the comeout of ferrocene,4,第一次分离水相和有机相时，不要晃动分液漏斗，漏斗中两相界面不清楚时，可通过观察漏斗出口液体颜色来分液。,dont shake the separatory funnel during seperation of ether,and aqueous phases in the first time.Please observe the,colour change at the outlet of the funnel to separate the ether,phase.,乙酰二茂铁的制备,(Preparation of acetyl ferrocene),3,中和用碳酸氢钠要适量，每次加入量也不能太多否则会起,泡沫溢出烧杯，造成不必要的损失。,sodium hydrogen carbonate should be added in portions and,carefully,preventing overflow of the products from the beaker.,注意事项,(Attention),1,药品加入顺序为二茂铁、乙酐、磷酸,.,The order of adding the chemical reagents is:ferrocene,acetic,anhydride and finally phosphoric acid.,2,乙酰二茂铁在水中有一定的溶解度，用冰量不可太多，,洗涤时最好用冰水，洗涤次数也切忌过多,Acetyl ferrocene is marginally soluble in water and therefore,ice should not be over-added and washing times not to be more.,注意事项,(Attention),1,棉花装的松紧程度应合适,.,The tightness of the cotton at the throat of the column should be appropriate,2,柱体中不可以出现大的气泡。如出现,气泡应赶掉,(No big air bubbles are,permitted in the column and should be removed if existed,.,3,装石英砂时应慢慢加入，不可一次加入而造成柱层破坏,.,sand should be added carefully,otherwise the silica gel layer will be destructed.,柱色谱分离,(column chromatographical separation),1,制二茂铁时为什么要在,FeCl,2,4H,2,O,的二甲亚砜溶液,上面加乙醚,？,why was diethyl ether layered on the DMSO solution of,FeCl,2,4H,2,O during preparation of ferrocene?,2,合成乙酰二茂铁过程中为什么在反应瓶上要加干燥管？,why was a drying tube charged on the reaction bottle for synthesis of acetyl ferocene?,思考题,(problems),