二茂铁及其衍生物的合成与色谱分离

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滤液(filte)
15ml conc.HCl + 15ml H2O heated to 70℃
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。 don’t overheated during concentration of the solution
FeCl2 +C5H6
N(C2H5)3
Fe(C5H5)2 Fe(C5H5)2 Fe(C5H5)2
FeCl2 + MC5H5(M=Na, K) FeCl2 + C5H5MgBr
实验目的(Aim)
1 掌握无水操作的一般方法 Learn the general method of moisture-free operation techniques. 2 熟悉柱色谱分离技术的技术要点 Familiar with the column chromatographic techniques. 3 了解二茂铁及其衍生物的结构，图谱特征及性质等。 Understanding the structures of ferrocene and its derivatives, their properties and spectroscopic characteristics.
实验步骤(experimental)
环戊二烯解聚(depolymerization of dicyclopentadiene)
环戊二烯二聚体 解聚 环戊二烯单体（41～44℃馏分）
cyclopentadiene dimer
depolymerization
cyclopentadiene monomer
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
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.
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.
二茂铁的合成（Synthesis of Ferrocene)
4ml环戊 二烯单体
5gFeCl2 4H2O +17mlDMSO 缓慢加入
继续搅拌1小时
萃取，洗涤
17gKOH+ 40ml无水乙醚 二茂铁纯品
干 躁 升华 二茂铁粗品
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 FeCl2· 2O 4H 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 Na2SO4.
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.
柱色谱分离( column chromatographical separation) 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
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.
colour change at the outlet of the funnel to separate the ether
phase.
Fra Baidu bibliotek
乙酰二茂铁的制备(Preparation of acetyl ferrocene)
干燥管
15min 二茂铁 乙酐 磷酸 水浴
水解，中和 粗品 冷却，过滤 冰
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，
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
Fe
Structure of Ferrocene
二茂铁分子的轨道形成 情况（定性） (Orbitals formation of ferrocene (arbitrary))
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.
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
二茂铁的性质(Properties of ferrocene)
物理性质(Physical properties) 熔点：172～173℃，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:172~173℃; sublime:100 ℃. Soluble in diethyl ether, petroleum ether and other unpolar solvents., insoluble in water)
氯化亚铁(FeCl2· 2O)的制备（preparation of ferrous chloride) 4H
4g reduced Fe powder 4g还原铁粉
iron nail
铁钉
conc. cryst. filted
过滤
filted
15ml浓盐酸＋15ml水 ，加热至70℃
浓缩，结晶，抽滤
FeCl2 4H2O
制备(Preparation)
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：
三乙胺 Fe(C5H5)2 Fe(C5H5)2 Fe(C5H5)2
FeCl2 +C5H6
FeCl2 + MC5H5(M=Na, K) FeCl2 + C5H5MgBr
A number of synthetic methods of ferrocene are known. But a generally method is the reaction of ferrous chloride(FeCl2) with cyclopentadienyl anion in the presence of base such as KOH, NaOH, N(C2H5)3. For example:
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。
don’t shake the separatory funnel during seperation of ether and aqueous phases in the first time. Please observe the
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)
简介(introduction)
二茂铁(Fe(C5H5)2, ferrocene)
auxiliary ligands for asymmetric synthesis of chiral compounds. 用途(Application) 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.
化学性质(Chemical properties)
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。
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