Part 2

Am. Chem. Journ. XVII, 311.

Ibid XVII, 230.

Ibid XVII, 354.

Ibid XVIII, 794.

In 1895, Gray isolated the two corresponding isomeric chlorides of paranitroorthosulphobenzoic acid, the lower melting chloride being obtained in small quantity only. The succeeding year Hollis made a more careful study of this lower melting chloride, and prepared it in considerable quantity.

From evidence drawn from the action of ammonia upon these chlorides, taken in connection with a number of other facts, the higher melting chloride is identified as the one possessing a symmetrical structure, while the lower melting chloride possesses an unsymmetrical structure. The first one, when treated with ammonia is slowly transformed into the ammonium salt of paranitrobenzoic sulphinide:

Inaug. Diss. J. H. Univ. 1895.

Inaug. Diss. J. H. Univ. 1896.

CO / \ COCl / N.NH₄ / / / C₆H₃——SO₂Cl + 4NH₃ = C₆H₃——SO₂ + 2NH₄Cl. \ \ NO₂ NO₂

while the lower melting chloride is quickly transformed into the ammonium salt of paranitroorthocyanbenzenesulphonic acid:

CCl₂ / \ / O CN / / / C₆H₃——SO₂ + 4NH₃ = C₆H₃——SO₂ONH₄ + 2NH₄Cl. \ \ NO₂ NO₂

Gray’s study of the symmetrical chloride was confined for the most part to the preparation of a series of salts of this latter acid, and to an investigation of the action of aniline upon the chloride itself. It was thought to be of interest to extend this study to a wider range of reactions, as well as to improve, if possible, the method of preparing the chloride in pure condition. At the suggestion of Prof. Remsen this work was accordingly undertaken.

II. Preparation of Material.

The method employed in the preparation of paranitroorthosulphobenzoic acid was essentially that described by Hart, Kastle, Gray and Hollis. The details of it are repeated here for the purpose of calling attention to certain facts that came under the author’s notice.

Am. Chem. Journ. I, 350.

Ibid XI, 177.

Inaug. Diss. J. H. Univ. 1845.

Inaug. Diss. J. H. Univ. 1896.

100 grams of paranitrotoluene are added to 400 grams of fuming sulfuric acid, and the mixture heated in a balloon flask at 100° on a water bath. The heating is continued until a few drops of the mixture, added to cold water, dissolves completely to a clear solution. The time required for this operation varies much with the conditions. Continued stirring very considerably hastens the reaction, as paranitrotoluene forms a layer on the acid, which presents a small surface to its action. With constant stirring the reaction is complete in a few hours, whereas if no stirring is resorted to, as much as several days may be required, especially when large quantities are employed at one time.

When the reaction is complete, the mixture is poured into a large volume of water, and neutralized with calcium carbonate. In the filtrate from calcium sulphate, the calcium salt of paranitroorthotoluene sulphonic acid is found, and this is converted into the potassium salt in the usual way.

The oxidation of the potassium salt is effected as follows. 50 grams of the salt are dissolved in 2½ litres of water, and to this is added a solution of 15 grams of potassium hydroxide. The mixture is heated to 100° on a water-bath, and when this temperature is reached, 110 grams of potassium permanganate are added. Heating is continued until the solution is decolorized, care being taken to prevent the evolution of free oxygen.

The oxides of manganese are then filtered off, the filtrate neutralized with hydrochloric acid, and evaporated to about one fifth of its original volume. Strong hydrochloric acid is them added in excess, and on cooling the acid potassium salt of paranitroorthosulphobenzoic acid separates in very slender colorless needles completely filling the liquid.

For the success of this operation it is important that the potassium salt of paranitroorthotoluenesulphonic acid and the potassium hydroxide should both be perfectly dissolved before they are heated together. If the two substances lie together in solid form at the bottom of the flask, a very slight elevation of temperature leads to the formation of an extremely troublesome red substance, which is very difficult to remove. It is almost impossible to remove it from the oxidation product by recrystallization, since any considerable amount of it has a marked influence on the solubility of the salt, rendering it much more soluble. It persists throughout all subsequent transformations of paranitroorthosulphobenzoic acid, and should therefore be carefully avoided.

Otto Fischer has shown that in concentrated solution, potassium hydroxide acts on nitro derivatives of toluene, with the formation of various colored substances derived from stilbene. In the case of paranitroorthotoluenesulphonic acid, he describes the substance formed as possessing a cherry red color. The reactions involved in its formation are:

CH₃ HC ============ CH / / \ 2C₆H₃——SO₂OK = C₆H₃——SO₂OK KO.O₂S——C₆H₃ + 2H₂O \ \ / NO₂ \ / \ /-- O --\ / N N \-- O --/

By oxidation this passes to a nitro compound of the composition

HC============ CH / \ C₆H₃——SO₂OK KOO₂S——C₆H₃ \ / NO₂ O₂N

It was no doubt the formation of substances of this nature that occasioned the color observed in some of the oxidations.