Meyer (Ber., 18 94, 2 7, p. 510 et seq.) showed that in benzenoid compounds ortho-substituents exert a great hindering effect on the esterification of alcohols by acids in the presence of hydrochloric acid, this hindering being particularly marked when two substituents are present in the ortho positions to the carboxyl group. In such a case the ester is best prepared by the action of an alkyl halide on the silver salt of the acid, and when once prepared, can only be hydrolysed with great difficulty.
The mixed secondary amines are prepared by the action of alkyl iodides on the primary amines, or by heating salts of the primary amine with alcohols under pressure.
The genesis and formulation of these types may be readily understood by considering the relation which exists between the alcohols and the parent hydrocarbon.
These changes can be followed out by determinations of the vapour density, and so provide a method for characterizing alcohols (see Compt.
Alcohols may be readily prepared from the corresponding alkyl haloid by the action of moist silver oxide (which behaves as silver hydroxide); by the saponification of their esters; or b the reduction of of h dric alcohols by P Y Y with hydriodic acid, and the subsequent conversion of the resulting alkyl iodide into the alcohol by moist silver oxide.
An important class of compounds, termed amines (q.v.), results from the condensation of alcohols with ammonia, water being eliminated between the alcoholic hydroxyl group and a hydrogen atom of the ammonia.
Now in oxidizing, or introducing more oxygen, for instance, by means of a mixture of sulphuric acid and potassium bichromate, and admitting that oxygen acts on both compounds in analogous ways, the two alcohols may give (as they lose two atoms of hydrogen) CH 3 CH 2 COH and CH 3 C0 CH 3.
On treatment with the Grignard reagent, in absolute ether solution, they yield addition products which are decomposed by water with production of tertiary alcohols (V.
The haloid esters of the paraffin alcohols formed by heating the alcohols with the halogen acids are the monohaloid derivatives of the paraffins, and are more conveniently prepared by the action of the phosphorous haloid on the alcohol.
Nitric acid and chromic acid oxidize them in such a manner that they yield the same products as the alcohols from which they are derived.