About Ethers

The most common ether is diethyl ether. Diethyl ether is frequently used as a laboratory solvent because of its ability to dissolve many organic compounds and because of its low boiling point (34.6 °C). The low boiling point allows for easy removal of the solvent when necessary. Diethyl ether was also used as a general anesthetic for many years. When inhaled, diethyl etirer depresses the central nervous system, causing unconsciousness and insensitivity to pain. Its use as an anesthetic, however, has decreased in recent years because other compoimds have the same anesthetic effect with fewer side effects (such as nausea). 

Amines are most commonly known for their awful odors. When a living organism dies, the bacteria that feast on its proteins emit amines. For example, trimethylamine causes the smell of rotten fish, and cadaverine canses the smell of decaying animal flesh. 

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The Du Pont de Nemours company attempted to classify the risks of dangerous peroxidation of chemical compounds. This classification includes the hydrocarbons mentioned above. This list is to be found in the entry about ethers (see on p.261). 

In the paragraph about ethers, it has already been mentioned that epoxides are... 

From what has already been shown about ether, predict its approximate boiling point. 

Cautions About Ether. The vapor of ether is very infiammable, and when mixed with atmospheric air it forms a violently explosive mixture. The density of this vapor is 2.586, that of air being 1, hence it rapidly ain, and frequently accnmnlates in the lower parts of buil gs, e ecially cellars which are badly ventilated. Every crack, every joint in the floors of rooms, the space beneath doors, Ac, offer a road for the passage of this vapor, which, though invisible, as sorely runs out of every orifice, and finds its level, as a stream of water would do. The only remedy is thorough ventilation. Many serious accidents have arisen from, this cause a light carried where such vapor is present causes an explosion. 

See also A Word about Ether and Anesthesia in Chapter 8, page 243. 

The most important fact that needs to be conveyed about ether compounds has been raised numerous times already they form peroxides, which, at a high enough concentration, can detonate. A typical reaction scheme for peroxide formation is shown below for ethyl ether [799] ... 

In a conventional gasoline containing hydrocarbons or even ethers, the presence of water is not a problem in fact, water is totally soluble up to about 50 ppm at ambient temperature. Beyond this value water separates without affecting the hydrocarbon phase and the water leg can be withdrawn if necessary. On the other hand, in the presence of alcohols (ethanol and especially methanol), trace amounts of water can cause a separation of two phases one is a mixture of water and alcohol, the other of hydrocarbons (Cox, 1979). 

Now filter the ether through a fluted filter-paper directly into a 100 ml. distilling-flask, and then equip the latter with a 100° thermometer and a double-surface condenser to the end of the latter attach a receiver with a rubber delivery-tube precisely as before. Place the flask cautiously in a water-bath, the contents of which have previously been heated to about 60° at some distance from the apparatus arrange the depth of the flask in the water-bath so that the ether distils slowly over. Collect the fraction boiling between 34-39°. Yield, 25 g. (35 ml.). Not more than a verv small residue of etlianol should remain in the flask. 

After about 20 minutes, when the liquid should be dry, filter it through a small fluted filter-paper into a 100 ml. distilling-flask attached to a water-condenser. Add some fragments of unglazed porcelain to the ethyl acetate, fit a 100° thermometer to the flask, and place the latter on a cold water-bath, which is then brought to the boil. Some ether is always formed as a by-product with the ethyl acetate, and by these means is carefully distilled off as a... 

Add cautiously 15 ml. of concentrated sulphuric acid to 50 ml. of water in a 100 ml. distilling-flask, and then add 10 g. of pinacol hydrate. Distil the solution slowly. When about 40 ml. of distillate (consisting of pinacolone and water) have been collected, and no more pinacolone comes over, extract the distillate with ether. Dry the extract over sodium sulphate. Distil the dry filtered extract carefully, with the normal precautions for ether distillation (p. 164). When the ether has been removed, continue the distillation slowly, rejecting any fraction coming over below 100 . Collect the pinacolone, b.p. 106 , as a colourless liquid having a peppermint odour. Yield, 4 5-5 o g. A small quantity of higher-boiling material remains in the flask. 

Place the distillate in a separating-funnel and extract the benzonitrile twice, using about 30 ml. of ether for each extraction. Return the united ethereal extracts to the funnel and shake with 10% sodium hydroxide solution to eliminate traces of phenol formed by decomposition of the benzenediazonium chloride. Then run off the lower aqueous layer, and shake the ethereal solution with about an equal volume of dilute sulphuric acid to remove traces of foul-smelling phenyl isocyanide (CaHjNC) which are always present. Finally separate the sulphuric acid as completely as possible, and shake the ether with water to ensure absence of acid. Run off the water and dry the benzonitrile solution over granular calcium chloride for about 20 minutes. 

Now transfer the cold distillate to a separating-funnel, and shake vigorously with about 50-60 ml. of ether run oflF the lower aqueous layer and then decantf the ethereal solution through the mouth of the funnel into a 200 ml. conical flask. Replace the aqueous layer in the funnel, and extract similarly twice more with ether, combining the ethereal extracts in the conical flask. Add 3-4 g. of dry powdered potassium carbonate to the ethereal solution, securely cork the flask and shake the contents gently. The ethereal solution of the phenol... 

Toluene-/ sulplionamide is almost insolubb in cold water, but dissolves readily in sodium hydroxide solution (as the sodium derivative) aid is immediately reprecipitated on the addition of strong acids. To show the formation of the sodium derivative, dissolve about o-2 g. of metallic sodium in about 10 ml, of ethanol, cool the solution, and then add it to a solution of 1 g. of the sulphonamide in 20 ml. of cold edianol. On shaking the mixture, fine white crystals of the sodium derivative, CH,C,HjSO,NHNa, rapidly separate, and may be obtained pure by filtering at the pump, and washing firet with a few ml. of ethanol, and then with ether. 

Mix 6 2 ml. (6 4 g.) of pure ethyl acetoacetate and 5 ml. of pure phenylhydrazine in an evaporating-basin of about 75 ml. capacity, add 0 5 ml. of acetic acid and then heat the mixture on a briskly boiling water-bath (preferably in a fume-cupboard) for I hour, occasionally stirring the mixture with a short glass rod. Then allow the heavy yellow syrup to cool somewhat, add 30-40 ml. of ether, and stir the mixture vigorously the syrup may now dissolve and the solution shortly afterwards deposit the crystalline pyrazolone, or at lower temperatures the syrup may solidify directly. Note. If the laboratory has been inoculated by previous preparations, the syrup may solidify whilst still on the water-bath in this case the solid product when cold must be chipped out of the basin, and ground in a mortar with the ether.) Now filter the product at the pump, and wash the solid material thoroughly with ether. Recrystallise the product from a small quantity of a mixture of equal volumes of water and ethanol. The methyl-phenyl-pyrazolone is obtained... 

Now cork the flask securely, and shake it vigorously for about 5 minutes the solution should now have only a faint brown colour due to unchanged iodine. Cool the mixture in ice-water, pour it into a separating-funnel, and extract it twice with water to remove sodium iodide and most of the ethanol. Then shake the residual ethereal solution with a dilute aqueoussolution of sodium thiosulphate the excess of iodine is thus removed and the... 

Now remove the flask from the water-bath, and slowly add a solution of 5 ml. (5-2 g.) of dry ethyl benzoate in 15 ml. of anhydrous ether down the condenser in small quantities at a time, mixing the contents of the flask thoroughly between each addition. When the boiling of the ether again subsides, return the flask to the water-bath and reheat for a further 15 minutes. Then cool the mixture in ice-water, and carefully pour off the ethereal solution into a mixture of about 60 ml. of dilute sulphuric acid. and 100 g. of crushed ice contained in a flask of about 500 ml. capacity fitted for stearn-distillation, taking care to leave behind any unchanged magnesium. 

Fit securely to the lower end of the condenser (as a receiver) a Buchner flask, the side-tube carrying a piece of rubber tubing which falls well below the level of the bench. Steam-distil the ethereal mixture for about 30 minutes discard the distillate, which contains the ether, possibly a trace of unchanged ethyl benzoate, and also any biphenyl, CeHs CgHs, which has been formed. The residue in the flask contains the triphenyl carbinol, which solidifies when the liquid is cooled. Filter this residual product at the pump, wash the triphenyl-carbinol thoroughly with water, drain, and then dry by pressing between several layers of thick drying-paper. Yield of crude dry product, 8 g. The triphenyl-carbinol can be recrystallised from methylated spirit (yield, 6 g.), or, if quite dry, from benzene, and so obtained as colourless crystals, m.p. 162. ... 

A 1500 ml. flask is fitted (preferably by means of a three-necked adaptor) with a rubber-sleeved or mercury-sealed stirrer (Fig. 20, p. 39), a reflux water-condenser, and a dropping-funnel cf. Fig. 23(c), p. 45, in which only a two-necked adaptor is shown or Fig. 23(G)). The dried zinc powder (20 g.) is placed in the flask, and a solution of 28 ml. of ethyl bromoacetate and 32 ml. of benzaldehyde in 40 ml. of dry benzene containing 5 ml. of dry ether is placed in the dropping-funnel. Approximately 10 ml. of this solution is run on to the zinc powder, and the mixture allowed to remain unstirred until (usually within a few minutes) a vigorous reaction occurs. (If no reaction occurs, warm the mixture on the water-bath until the reaction starts.) The stirrer is now started, and the rest of the solution allowed to run in drop-wise over a period of about 30 minutes so that the initial reaction is steadily maintained. The flask is then heated on a water-bath for 30 minutes with continuous stirring, and is then cooled in an ice-water bath. The well-stirred product is then hydrolysed by the addition of 120 ml. of 10% sulphuric acid. The mixture is transferred to a separating-funnel, the lower aqueous layer discarded, and the upper benzene layer then... 

For dehydrogenation, add this ester to dilute nitric acid (20 ml. of the concentrated acid diluted with 40 ml. of water) and boil the mixture under reflux for about 5 minutes, during which the ester gently efferv esces and Anally gives a clear solution. Cool this solution in ice-w ater, make alkaline with aqueous sodium carbonate solution and extract tw ice with ether (50 ml. for each extraction). Dry the extract with sodium sulphate, filter, and then distil using a small distilling-flask... 

Collidine 2i5 d carboxylic acid. Boil a mixture of 5 g. of the ester (II) and 50 ml. of 15% ethanolic potash under reflux for 30 minutes. The dipotassium salt crystallises during the boiling and during the subsequent cooling. Filter off the potassium salt at the pump and wash it with a small quantity of ethanol. Dilute the filtrate with about an equal volume of ether to precipitate a further small crop of the salt. Yield of combined crops 4 5 g. from 5 g. of the estei (I). 

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