No abstract

Since the foregoing procedure has given rather low yields (about 22%), an effort will be made in subsequent work to ascertain the conditions for the optimum results. The use of a larger quantity of the dihalogen derivative would doubtless be of great importance. Summary A method has been described for the synthesis of the -methyl-, -ethyl-, -w-propyl-and a-nbutyl -a-phenylychlorobutyronitriles. These compounds are being used in the synthesis of 1pyrrolines and other derivatives. Troy, N. Y.

The addition of sulfuric acid during the nitration of some aromatic compounds is known to influence the ratio of meta to ortho-para substitution. This is especially true of aromatic amines such as aniline, of which the ortho-para directing NH2 group is converted, by salt formation, into the meta directing NHs group. An explanation has been advanced3 for this behavior on two grounds, viz., (1) the addition of the proton to the lone electron pair of the nitrogen atom greatly increases the electron attraction of the entire group, and (2) the blocking off of the lone pair prevents any possibility of addition formation at this point with the reagent and therefore of subsequent rearrangement to ortho and para positions on the ring.According to Vorlander, Robinson, Ingold and others4 the most strongly meta-directing groups are the positive poles directly attached to the benzene ring. Thus phenyltrimethylammonium nitrate is nitrated exclusively in the meta positions and many other compounds of similar type yield meta derivatives almost exclusively on nitration; among these may be mentioned diphenyl iodonium nitrate," triphenylantimony dinitrate,' triphenylbismuth dinitrates and diphenyllead dir~itrate.~The change in the ortho-para directive influence of the NH2 group to the meta orienting influence of the NHIX group through salt formation has been ascribed to the ionization of the salt to give a positive ion in which substituents take the meta position because of the positive charge carried by the NH3+ group. Fliirscheim and Holmes4d found that the addition of ammonium sulfate to the nitrating mixture of nitric and sulfuric acid decreased the yield of the meta isomeride formed during the nitration of benzyldiethylamine while Pollard and Robinson*o observed similar effects in the nitration of benzylpiperidine. In these cases the added salts depress the ionization of the salt undergoing nitration and thus cause a decrease in the meta directive power of the positive pole.Since the oxygen atom resembles the nitrogen atom in the formation of (1) Paper presented a t the Denver