2- -ethyl iodide

Preparation of Ethyl Iodide from Ethyl Alcohol and Hydriodic Acid.—Place 60 grams of a strong solution of hydriodic acid and water (the constant-boiling mixture, which contains 57 per cent hydrogen iodide, and has the specific gravity 1.7) in a 

Ethyl iodide boils at 72.3°, and has the specific gravity 1.944 (14°). The yield in this preparation is about 90 per cent of the theory, calculated from alcohol a slight excess of the hydriodic acid is used. 

---

ETHYL IODIDE 253-333 1.4679E40I -3 77I1E403 1.1605E-02 -1 1006E400 -1 3066E-05... 

This is a modification of Method 5, iodine being added to a mixture of red phosphorus and ethanol phosphorus tri- iodide is thus formed m situ, and readily reacts with the ethanol, giving ethyl iodide and phosphorous acid (p. 96). 

Fit the flask with a 100° thermometer and a water-condenser, and distil the ethyl iodide carefully from a water-bath, collecting the fraction which distils between 68° and 73°. Yield, about 24 g. 

Ethyl iodide is a heavy liquid, of b.p. 72° and of d, 1 94 insoluble in water, When freshly distilled it is colourless, but on prolonged exposure to light it darkens in colour owing to the liberation of free iodine. Its chemical properties are almost identical with those of ethyl bromide given on pp. 102 and 103. 

Since aliphatic hydrocarbons (unlike aromatic hydrocarbons, p. 155) can be directly nitrated only under very special conditions, indirect methods are usually employed for the preparation of compounds such as nitroethane, CjHsNO. When ethyl iodide is heated with silver nitrite, two isomeric compounds are formed, and can be easily separated by fractional distillation. The first is the true ester, ethyl nitrite, C,HiONO, of b.p. 17° its identity is shown by the action of hot sodium hydroxide solution, which hydrolyses it, giving ethanol and... 

In the reaction described below triethyl phosphite (p. 308) is heated with ethyl iodide to give diethyl ethylphosphonate. Although theoretically a very small amount of ethyl iodide would suffice, it is advantageous to use more than the minimum amount so as to reduce the temperature of the boiling reaction-mixture. 

Methyl iodide ethyl bromide ethyl iodide, higher alkyl halides, chloroform, iodoform, carbon tetrachloride, chlorobenzene, bromobenzene, iodobenzene, benzyl chloride (and nuclear substituted derivatives)... 

Physical Properties. All heavier than, and insoluble in water. All liquids, except iodoform, CHI3, which is a yellow crystalline solid with a characteristic odour. The remainder are colourless liquids when pure ethyl iodide, CjHjI, and iodobenzene, CjHgl, are, however, usually yellow or even brown in colour. Methyl iodide, CH3I, ethyl bromide, CgH Br, ethyl iodide, chloroform, CHCI3, and carbon tetrachloride, CCI4, have sweetish odours, that of chloroform being particularly characteristic. 

Ethyl bromide and ethyl iodide behave similarly. Benzyl chloride gives a faint precipitate in the cold, but the precipitation is complete on gentle warming. 

Similar results are obtained with methyl iodide, ethyl bromide, ethyl iodide, iodoform, carbon tetrachloride, and benzyl chloride. 

Methyl iodide, ethyl bromide and ethyl iodide also evolve small amounts of ethylene when treated as above. If this is suspected, a small quantity of the substance should be heated with alcoholic NaOH solution in a small flask, fitted with a knee delivery-tube. Pass the gas evolved through a very dilute solution of KMn04 which has been made alkaline with aqueous NagCOj solution. If ethylene has been formed, a brown precipitate of MnOj will be produced (a transient green colour may appear). 

The reaction with ethyl iodide is less rapid and it is necessary to warm the mixture gently until cloudy. On cooling, crystals of the ethiodide are formed, and after recrystallisation from methylated spirit have m.p. 84 . 

Let us suppose it is desired to calculate the theoretical yield of ethyl maleate when 33 g. of silver maleate, suspended m dry ether, are treated with the calculated quantity of ethyl iodide (31-2 g.). 

From the equation representing the chemical reaction involved, it is evident that 330 g. of silver maleate will theoretically react with 312 g. of ethyl iodide in ethereal solution to produce 172 g. of ethyl maleate. It follows, therefore, that 33 g. (0 1 mol) of silver maleate will react with 31-2 g. (0 2 mol) of ethyl iodide to give a theoretical yield of 17 2 g. (0-1 mol) of ethyl maleate. In practice, the actual yield found for these quantities is of the order of 16 0 g. the percentage yield is therefore (16 0/17-2) X 100 = 93 per cent. 

Three reactants. Ethyl iodide may be prepared by the interaction between iodine, ethyl alcohol and red phosphorus. The quantities employed and the yield obtained in a particular experiment are given below the equation. 

To decide which component should be employed for the calculation of the yield of ethyl iodide, the weights of the reactants are first divided by the appropriate atomic or molecular weight in order to obtain the number of gram atoms or gram mols actually used. The equation shows that the alcohol and iodine react in the ratio of 5 5 or 1 1. Inspection of the results clearly shows that the alcohol is present in about 20 per... 

Add 4 0 g. (4 0 ml.) of pure anihne dropwise to a cold solution of ethyl magnesium bromide (or iodide) prepared from 1 Og. of magnesium, 5 0 g. (3-5 ml.) of ethyl bromide (or the equivalent quantity of ethyl iodide), and 30 ml. of pure, sodium-dried ether. When the vigorous evolution of ethane has ceased, introduce 0 02 mol of the ester in 10 ml. of anhydrous ether, and warm the mixture on a water bath for 10 minutes cool. Add dilute hydrochloric acid to dissolve the magnesium compounds and excess of aniline. Separate the ethereal layer, dry it with anhydrous magnesium sulphate and evaporate the ether. Recrystallise the residual anihde, which is obtained in almost quantitative yield, from dilute alcohol or other suitable solvent. 

Place 32 g. of potassium ethyl xanthate (Section 111,166) and 50 ml. of absolute ethyl alcohol in a 500 ml. round-bottomed flask provided with a double surface condenser. Add 32 g. (16-5 ml.) of ethyl iodide. No reaction appears to take place in the cold. Heat on a water bath for 3 hours a reaction sets in within 15 minutes and the yellow reaction mixture becomes white owing to the separation of potassium iodide. Add about 150 ml. of water, separate the lower layer, and wash it with water. Dry it with anhydrous calcium chloride or anhydrous calcium sulphate and distil from a 50 ml. Claisen flask. Collect the ethyl S-ethyl xanthate at 196-198°. The yield is 23 g. 

The ethiodide is prepared similarly, using ethyl iodide. 

Keep a coil of copper wire (prepared by winding copper wire round a glass tube) or a little silver powder in the bottle, which should be of brown or amber glass the methyl iodide will remain colourless indefinitely. Ethyl iodide may sometimes give more satis factory results. 

It is of interest to note that by substituting alkyl bromides for cyciohexyl bromide the corresponding a-phenyl-a-alkyl-acetonitriles are obtained, which may be hydrolysed to the a-phenylaliphatic acids thus with ethyl iodide a-phenyl-lwt3Tonitrile is produced, hydrolysed by ethanoUo potassium hydroxide to a-phenylbutyric acid. 

Place 1 55 g. of clean sodium in a 250 ml. round-bottomed flask equipped with a reflux condenser. Add 40 ml. of absolute alcohol (or rectified spirit). If all the sodium has not disappeared after the vigorous reaction has subsided, warm the flask on a water bath until solution is complete. Cool the mixture and add 10 g. of p-acetylaminophenol. Introduce 15 g. (8 ml.) of ethyl iodide slowly through the condenser and reflux the mixture for 45-60 minutes. Pour 100 ml. of water through the condenser at such a rate that the crystalline product does not separate if crystals do separate, reflux the mixture until they dissolve. Then cool the flask in an ice bath collect the crude phenacetin with suction and wash with a little cold water. Dissolve the crude product in 80 ml. of rectified spirit if the solution is coloured, add 2 g. of decolourising carbon and filter. Treat the clear solution with 125 ml. of hot water and allow to cool. Collect the pure phenacetin at the pump and dry in the air. The yield is 9-5 g., m.p. 137°. 

The condensation of 1 mol of ethyl malonate with two mols of ethyl iodide in the presence of two mols of sodium ethoxide gives a good yield of ethyl diethylraalonate. Upon allowing the latter to react with the theoretical quantity of urea in the presence of an alcoholic solution of sodium ethoxide, veronal (diethylbarbituric acid or diethylmalonylurea) is produced. 

Ethyl phenylethylmalonate. In a dry 500 ml. round-bottomed flask, fitted with a reflux condenser and guard tube, prepare a solution of sodium ethoxide from 7 0 g. of clean sodium and 150 ml. of super dry ethyl alcohol in the usual manner add 1 5 ml. of pure ethyl acetate (dried over anhydrous calcium sulphate) to the solution at 60° and maintain this temperature for 30 minutes. Meanwhile equip a 1 litre threenecked flask with a dropping funnel, a mercury-sealed mechanical stirrer and a double surface reflux condenser the apparatus must be perfectly dry and guard tubes should be inserted in the funnel and condenser respectively. Place a mixture of 74 g. of ethyl phenylmalonate and 60 g. of ethyl iodide in the flask. Heat the apparatus in a bath at 80° and add the sodium ethoxide solution, with stirring, at such a rate that a drop of the reaction mixture when mixed with a drop of phenolphthalein indieator is never more than faintly pink. The addition occupies 2-2 -5 hoius continue the stirring for a fiuther 1 hour at 80°. Allow the flask to cool, equip it for distillation under reduced pressure (water pump) and distil off the alcohol. Add 100 ml. of water to the residue in the flask and extract the ester with three 100 ml. portions of benzene. Dry the combined extracts with anhydrous magnesium sulphate, distil off the benzene at atmospheric pressure and the residue under diminished pressure. C ollect the ethyl phenylethylmalonate at 159-160°/8 mm. The yield is 72 g. 

Thioethers usually yield sulphonium salts when warmed with ethyl iodide and allowed to cool. The physical properties (b.p., density and refractive index) are useful for identification purposes. 

See the same reference in Pihkal for details on how to use ethyl iodide instead of diethyl sulfate. 

Strike couldn t find any decent nitroethane synths except for a couple of Chemical Abstract articles. One suggestion is to treat 1.5 moles of Na2C02 with 1 mole of sodium ethylsulfite and 0.0645 moles of K2CO3 at 125-130°C. Another route would be to use silver nitrate and ethyl iodide [8 p119]. This type of reaction has been used to nitrate other paraffins and would probably work. 

---