96 



REPORTS ON THE STATE OF SCIENCE. 



formed in the chlorination of acylanilides. The results so far obtained 

 are shown in the table. The acyl group is found to have a very- 

 powerful influence. Other circumstances, media, temperature, and 

 concentration, have little effect on the proportion, but the production of 

 a dichloro-derivative is more pronounced in other media than dilute 

 acetic acid. 



The numbers represent the percentage of the anilide chlorinated, 

 found in the product in one or other form. 



Obviously the chlorination of acetanilide is the best method of pre- 

 paring o-chloroaniline. 



An Application oj the Reaction between Chloroamines and Hydrogen 

 Chloride as a method of Chlorinating Anilines and Phenols.* 

 (With Harold King.) 



The fact that chloroamines and hydrogen chloride react quantitatively 

 in glacial acetic acid producing anilide and chlorine, gives a very effec- 

 tive method of chlorinating such anilides and phenols as are particularly 

 susceptible of oxidation, or by the usual methods yield di- or poly- 

 chloro-derivatives. 



Molecular proportions of the substance to be chlorinated and a 

 chloroamine, for example, that derived from 2 : 4-dichloroacetanilide or 

 p-nitroacetanihde, are mixed in glacial acetic acid solution, and some 

 small proportion of hydrogen chloride, one-hundredth to one-twentieth 

 gram irolecular proportion, added. From the reaction between the 

 chloroamine and the hydrogen chloride, chlorine is formed in amount 

 molecularly equivalent to the hydrogen chloride used. The chlorine 

 in its turn attacks the substance to be chlorinated, forming at the same 

 time an equivalent of hydrogen chloride. Chlorine is again regenerated, 

 and hence is thus maintained at a constant low concentration, fixed by 

 the amount of hydrogen chloride originally introduced, through the 

 greater part of the reaction. 



In this way 5-chloro-m-xylidine, 6-chloro- i^-cumidine, 5-chloro-o- 

 anisidine, 5-chloro-p-anisidine, 5-chloro-o-phenetidine and 5-chloro- 

 m-xylenol have been for the first time prepared. Further, Mr. King 

 has been able to chlorinate a-naphthol directly without any oxidation. 

 Owing to the fact, however, that the speeds of interaction of a-naphthol 

 and 4-chloro-a-naphthol and chlorine are of similar magnitude, much 



4 Trans. Chan. Soc, 1911, 99, 1185. 



