Tertiary alcohols, R1 R2 R3.COH, may be synthesised by

Action of the Grignard reagent upon diethyl carbonate

UREA
Wohler’s classical synthesis of urea from ammonium cyanate may be carried
out by evaporating solutions of sodium cyanate and ammonium sulphate

Pseudo-saccharin ethers.

Pseudo-saccharin chloride reacts with alcohols to give ethers (0-alkyl derivatives of
saccharin) :

Heat a little pseudo-saccharin chloride with excess of the anhydrous alcohol in a test-tube until hydrogen chloride is no longer evolved. Recrystallise from alcohol or other organic solvent. With the lower primary alcohols, heating at 100° for 10 minutes uffices: for higher alcohols, a temperature of 125° is preferable. Secondary alcohols
require longer heating at 125°. A large excess of alcohol should be used when dentifying the lower alcohols and the excess removed by evaporation ; for the higher alcohols, it is better to employ an excess of pseudo-saccharin chloride and the product washed free from the reagent with dilute aqueous alkali erivatives of selected alcohols

Treat 1 ml. of the alcohols enumerated
in (iv) cautiously with 0-5-0-7 ml. of acetyl chloride. Observe the
reaction which occurs. After 2-3 minutes, pour the contents of the
various test-tubes into 3 ml. portions of water, neutralise the aqueous
layer with solid sodium bicarbonate, and examine the residual liquids
for odour and density (relative to water).

Treat 2 ml. of absolute methyl alcohol with a small thin slice of dry, freshly-cut sodium Observe the result. Cool the solution when all the sodium has reacted. Add a little water and test the solution with litmus paper. Obtain five small dry test-tubes and introduce 1 ml. of the following alcohols into each : ethyl alcohol, n-butyl alcohol, sec.-butyl alcohol, q/c/ohexanol and tert.-butyl alcohol. Add a minute fragment of sodium to each and observe the rate of reaction. Arrange the alcohols in the order of decreasing reactivity towards sodium. The reaction with sodium is by no means an infallible practical test for alcohols since, strictly speaking, it is applicable only to pure anhydrous liquids. Traces of water, present as impurities, would give an initial evolution of hydrogen, but reaction would stop after a time if an alcohol is absent: furthermore, certain esters and ketones also evolve hydrogen when treated with sodium. It may, however, be assumed that if no hydrogen is evolved in the test, the substance is not an alcohol.

Carry out the following simple experiments ; these have been selected to illustrate some of the general properties of alcohols.
(i) Miscibility with water. Measure out 3-1 ml. (2-5 g.) of n-butyl alcohol into a dry 100 ml. conical or flat-bottomed flask provided with a well-fitting stopper. From a burette add distilled water to the alcohol, a few drops at a time and shake vigorously after each addition, until a slight but permanent turbidity is produced. Note the volume of water added and calculate the solubility of water in n-butyl alcohol at the temperature of the laboratory. Continue the addition of water, 2-3 ml. at a time and with vigorous shaking, until the contents of the flask are just homogeneous : near the point of homogeneity the additions should be reduced to portions of 1 ml. Note the total volume of water which has been added from the burette, and calculate the solubility of n-butanol
in water at the temperature of the laboratory.
The student will doubtless be aware of the fact that methyl, ethyl, n-propyl and tso-propyl alcohols are completely miscible with water. The solubilities of the higher alcohols decrease progressively as the carbon content increases. The solubilities of all types of alcohols with five carbon atoms or more are quite smal miscible.
Divide the saturated solution of n-butyl alcohol in water into three approximately equal parts. Treat these respectively with about 2*5 g. of sodium chloride, potassium carbonate and sodium hydroxide, and shake each until the solids have dissolved. Observe the effect of these compounds upon the solubility of n-butanol in water. These results illustrate the phenomenon of salting out of organic compounds, i.e., the decrease of solubility of organic compounds in water when the solution is saturated with an inorganic compound. The alcohol layer which separates is actually a saturated solution of water in n-butyl alcohol.

JPV