The Structure of Di-Substituted Derivatives of Phenyl Sulfone

Citation

Bowman, Robert Barkley (1926) The Structure of Di-Substituted Derivatives of Phenyl Sulfone. Bachelor's thesis, California Institute of Technology. doi:10.7907/FGVN-P306. https://resolver.caltech.edu/CaltechETD:etd-11292004-135829

Abstract

Phenyl sulfone may be considered a dephenyl derivative of sulfuric acid, in which two of the DH groups of the acid are replaced by phenyl groups. It is also called dephenyl sulfone, and in German "sulfobenzid," but in this paper it will always be referred to as phenyl sulfone. It is formed in appreciable quantities as a by-product in the sulfonation of benzene, especially when very concentrated acid is used. Perhaps the best method of preparing it for laboratory use is by the Friedel-Crafts synthesis, in which the chloride of benzene sulfonic acid and benzene condense in the presence of aluminum chloride.

Substituted phenyl sulfones are produced either by the direct substitution of the hydrogen atoms in the benzene rings, or through the action of sulfuric anhydride on substituted benzenes. Thus phenol and sulfur trioxide yield dihydroxy phenyl sulfone; brombenzine and sulfur trioxide yield dibrom phenyl sulfone, etc. Chlorine may be directly substituted under certain conditions, and the nitro and sulfonic acid derivatives may be directly produced by the action of a mixture of fuming nitric and fuming sulfuric acids, and of chlorsulfonic acid, respectively.

After the war considerable quantities of phenyl sulfone were left over from the various industrial processes, and the problem of its use became of importance. This need for a use to which the excess product could be put led M. E. Granmougin to prepare a great many derivatives of the substance with the hope of being able to apply some of them in the dye industry. He based his structures on an assumption, which although it may be correct, cannot be said to absolutely justified. Several other investigators had worked with the directly substituted derivatives of phenyl sulfone, but in no case had the structure of the disubstituted products been unquestionably determined by actually splitting apart the two rings and determining the structure of the resulting products.

It has always been assumed that these products have a symmetrical constitution. This assumption seems to be justified in that both the phenyl groups are equivalent, and should be subject to the same directing influence of the SO2 group. It has also been assumed that all of the products formed with the aid of substituted benzenes conform to that constitution which the directing influence of the substituted benzene group would call for.

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