- General procedures for the purification of Ethers
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The purification of diethyl ether is typical of liquid ethers. The most common contaminants are the alcohols or hydroxy compounds from which the ethers are prepared, their oxidation products (e.g. aldehydes), peroxides and water. Peroxides, aldehydes and alcohols can be removed by shaking with alkaline potassium for several hours, followed by washing with water, concentrated sulfuric acid [CARE], then water. After drying with calcium chloride, the ether is distilled. It is then dried with sodium or with lithium aluminium hydride, redistilled and given a final fractional distillation. The drying process should be repeated if necessary.
Alternatively, methods for removing peroxides include leaving the ether to stand in contact with iron filings or copper powder, shaking with a solution of ferrous sulfate acidified with N sulfuric acid, shaking with a copperzinc couple, passage through a column of activated alumina, and refluxing with phenothiazine. (Ⅲ) hydroxide has also been used.
A simple test for ether peroxides is to add 10mL of the ether to a stoppered cylinder containing 1mL of freshly prepared 10% solution of potassium iodide containing a drop of starch indicator. No colour should develop during one minute if free from peroxides. Alternatively, a 1% solution of ferrous ammonium sulfate, 0.1M in sulfuric acid and 0.01M in potassium thiocyanate should not increase appreciably in red colour when shaken with two volumes of the ether.
As a safety precaution against explosion (in case the purification has been insufficiently thorough) at least a quarter of the total volume of ether should remain in the distilling flask when the distillation is discontinued as peroxides are generally higher boiling. To minimize peroxide formation, ethers should be stored in dark bottles and, if they are liquids, they should be left in contact with type 4A Linde molecular sieves, in a cold place, over sodium amalgam. The rate of formation of peroxides depends on storage conditions and is accelerated by heat, light, air and moisture. The formation of peroxides is inhibited in the presence of diphenylamine, di-tert-butylphenol, or other antioxidants as stabiliser.
Ethers that are solids (e.g. phenyl ethers) can be steam distilled from an alkaline solution which will hold back any phenolic impurity. After the distillate is made alkaline with sodium carbonate, the insoluble ether is collected either by extraction (e.g. with chloroform, diethyl ether or toluene) or by filtration. It is then crystallised from alcohols, alcohol/petroleum ether, petroleum ether, toluene or mixtures of these solvents, sublimed in a vacuum and recrystallised if necessary.
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