123 g of nitrobenzene are added into 375 g of oleum (25 % free sulfur

trioxide) at 70 C. The mixture warms up rapidly to 100-110 C, but must not

be allowed to rise any higher. When all nitrobenzene has been added,
the mixture is heated at 110-115 C until a test portion poured into water no
longer gives any odor of nitrobenzene. If complete sulfonation has not
occurred within half an hour, then insufficient amount of oleum has been
used. In this case 50 g more oleum are added drop by drop, and if necessary
a further quantity after half an hour more. The reaction mixture is then
allowed to cool, and is poured on to 500 g ice with good mechanical stirring.
The nitrobenzene sulfonic acid goes completely into solution with the
exception of a small proportion of side product bis(3-nitrophenyl)
sulfone. 200 g of sodium chloride, in small quantities at a time, are
added with continuous stirring. The sodium salt of 3-nitrobenzenesulfonic
acid separates out as a thick paste, and stirring must be continued for some
time, until the mass again liquefies. After about 10 hours the solid is filtered
yielding the crude sodium 3-nitrobenzenesulfonate, which may be obtained
purified by recrystallization from water. 3-nitrobenzenesulfonic acid is
obtained by neutralizing sodium 3-nitrobenzenesulfonate with stereochemical
amount of dilute sulfuric acid.