I.Introduction.[Page 1]
II.Preparation of the Acid Potassium Salt
of Paranitroorthosulphobenzoic Acid.[ 6]
III.Preparation of the Symmetrical Chloride
of Paranitroorthosulphobenzoic Acid.[12]
IV.Properties of the Symmetrical Chloride
of Paranitroorthosulphobenzoic Acid.[19]
V.The Action of Benzene and Aluminium
Chloride on the Symmetrical Chloride
of Paranitroorthosulphobenzoic Acid.[22]
The Barium Salts of
Paranitroorthobenzoybbenzenesulphonic Acid.[24]
VI.The Action of Alcohols on the Symmetrical Chloride
of Paranitroorthosulphobenzoic Acid.[30]
1. Methyl Alcohol.[31]
2. Ethyl Alcohol.[32]
Action of Ethyl Alcohol on the Unsymmetrical
 Chloride.[36]
VII.The Action of Phenols on the Symmetrical Chloride
of Paranitroorthosulphobenzoic Acid.[38]
1. Phenol.[40]
2. Orthocresol.[48]
3. Paracresol.[51]
4. Hydroquinone.[53]
5. Resorcin.[56]
6. Pyrogallol.[59]
7. β-naphthol.[61]
VIII.The Action of Aniline on the Symmetrical Chloride
of Paranitroorthosulphobenzoic Acid.[62]
IX.The Action of Phosphorus Oxychloride on the Fusible
Anilid of Paranitroorthosulphobenzoic Acid.[71]
X.The Action of Reagents on the Dianil of
Paranitroorthosulphobenzoic Acid.[77]
1. Of Hydrochloric Acid.[77]
2. Of Alcoholic Potash.[78]
3. Of Glacial Acetic Acid.[79]
XI.Conclusions.[82]
Biographical.[85]

I. Introduction.

The sulphobenzoic acids have been the subject of investigation in this laboratory for a number of years past. Among the many interesting facts that have been brought to light in the course of this study, perhaps no others have been attended with more interest than the discovery of well characterized isomerism in the case of the chlorides of orthosulphobenzoic acid, and its paranitro derivative; together with the preparation of a series of isomeric derivatives of these substances. The chlorides themselves have been isolated in the crystalline condition, and have been found to differ markedly, not only in chemical, but in physical properties as well.

The first evidence that such isomerism existed, was obtained by Remsen and Coates[1] who, in the course of an investigation of the action of aniline upon the chloride of orthosulphobenzoic acid, obtained two isomeric anilids quite different in properties, which they designated as fusible and infusible respectively. The following year, Remsen and Kohler[2] obtained one of the chlorides in crystalline form, together with an oil which they did not succeed in crystallizing.

This however was accomplished the succeeding year by Remsen and Saunders[3], and a still more satisfactory result was obtained by Remsen and McKee[4] in 1895. The chloride melting at 79° was found to yield only the fusible anilid, together with an anil, while from the lower melting chloride, in addition to these, the infusible anilid was also formed.

In 1895, Gray[5] isolated the two corresponding isomeric chlorides of paranitroorthosulphobenzoic acid, the lower melting chloride being obtained in small quantity only. The succeeding year Hollis[6] 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:

CO
/\
COCl /N.NH₄
///
C₆H₃—SO₂Cl + 4NH₃ = C₆H₃—SO₂ + 2NH₄Cl.
\\
NO₂NO₂

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

CCl₂
/   \
/OCN
///
C₆H₃—SO₂ + 4NH₃ = C₆H₃—SO₂ONH₄ + 2NH₄Cl.
\\
NO₂NO₂