Benzenesulfonic Acids and Their Derivatives: 1. General Aspects

Benzenesulfonic Acids and Their Derivatives 1
Benzenesulfonic Acids and Their Derivatives

For nitrobenzenesulfonic acids, see → Nitro Compounds, Aromatic; sulfobenzoic acids are treated under
→ Benzoic Acid; alkylbenzenesulfonic acids with aliphatic side chains longer than ethyl are treated under
→ Surfactants
Otto Lindner, Bayer AG, Leverkusen, Federal Republic of Germany

Lars Rodefeld, Bayer AG, Leverkusen, Federal Republic of Germany
1. General Aspects . . . . . . . . . . . . . 1 2.1. Benzenesulfonic Acid . . . . . . . . . 11

1.1. Physical Properties . . . . . . . . . . . 1 2.2. 1,3-Benzenedisulfonic Acid . . . . . . 14
1.2. Chemical Properties . . . . . . . . . . 2 2.3. Alkylbenzenesulfonic Acids . . . . . 15
1.3. Production . . . . . . . . . . . . . . . . 3 2.4. Formylbenzenesulfonic Acids . . . . 20
1.3.1. Direct Sulfonation . . . . . . . . . . . . 3 2.5. Chlorobenzenesulfonic Acids . . . . 20
1.3.2. Oxidation of Sulfur Compounds . . . 5 2.6. Aminobenzenesulfonic Acids . . . . 22
1.3.3. Diazo Reaction . . . . . . . . . . . . . . 5 2.7. Hydroxybenzenesulfonic Acids . . . 25
1.3.4. Sulfite Reaction . . . . . . . . . . . . . . 6
2.8. Chloro-alkylbenzenesulfonic Acids 27
1.4. Uses . . . . . . . . . . . . . . . . . . . . . 6
2.9. Amino-alkylbenzenesulfonic Acids . 29
1.5. Analysis . . . . . . . . . . . . . . . . . . 6
2.10. Amino- and Hydroxycarboxyben-
1.6. Environmental Aspects . . . . . . . . 7
zenesulfonic Acids . . . . . . . . . . . 29
1.7. Economic Aspects . . . . . . . . . . . . 8
1.8. Toxicology and Ecotoxicology . . . . 8 2.11. Chloro-hydroxybenzenesulfonic
1.9. General Characteristics of Benzene- Acids . . . . . . . . . . . . . . . . . . . . 30
sulfonic Acid Derivatives . . . . . . . 8 2.12. Aminohydroxybenzenesulfonic
1.9.1. Benzenesulfonyl Chlorides . . . . . . . 8 Acids and Aminochlorohydroxyben-
1.9.2. Benzenesulfonamides . . . . . . . . . . 10 zenesulfonic Acids . . . . . . . . . . . 31
1.9.3. Benzenesulfonohydrazides . . . . . . . 11 2.13. Amino-chlorobenzenesulfonic Acids 33
1.9.4. Benzenesulfonic Esters . . . . . . . . . 11 2.14. Amino-chloro-alkylbenzenesulfonic
2. Individual Benzenesulfonic Acids Acids . . . . . . . . . . . . . . . . . . . . 34
and Derivatives . . . . . . . . . . . . . 11 3. References . . . . . . . . . . . . . . . . . 35
1. General Aspects Aminobenzenesulfonic acids are weak acids;

they form zwitterions, which are poorly soluble
1.1. Physical Properties in water, but their alkali salts are water-soluble.
Unlike the free acids, the metal salts of the ben-
The benzenesulfonic acids, with the exception zenesulfonic acids, particularly the alkali salts,
of the aminobenzenesulfonic acids, are strong are stable at temperatures up to and exceeding
acids, which are almost entirely dissociated in 300 ◦ C. Most of them can be precipitated by
aqueous solution. Some of them, including ben- adding an excess of salt to their aqueous solu-
zenesulfonic acid, can be distilled in a high vac- tion. The calcium salts are more freely soluble
uum without decomposition. They have a ten- in water than calcium sulfate. This is exploited
dency to form hydrates, which are very stable industrially in the “liming” of the sulfonation
in some cases and can be isolated from aque- mixture (see Section 2.2). In contrast to these
ous hydrochloric acid and dried at tempera- metal salts certain organic salts are poorly sol-
tures up to 100 ◦ C without the water being lost. uble in water; for example, the salts with ary-
However, azeotropic distillation with benzene or lamines and S-benzylisothiourea have definite
chlorobenzene (depending on the heat stability melting points and are therefore suitable deriva-
of the hydrate) gives the anhydrous sulfonic acid. tives for the identification of benzenesulfonic
acids. For the physical properties of individual
c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a03 507
2 Benzenesulfonic Acids and Their Derivatives
compounds, see Section 1.9 and Chap. 2 of this and permits the selective introduction of fur-
article. ther substituents, e.g., in the manufacture of o-
chlorotoluene:
1.2. Chemical Properties
Desulfonation. The sulfonation of aromatic

compounds to form arylsulfonic acids is a re-
versible reaction. It proceeds through various
activated complexes and intermediates; Figure 1
2,6-Dichlorophenol and 6-halogeno-2-
shows a schematic plot of the enthalpy along the
methylphenol can be produced analogously. In
reaction coordinate. The ease with which sul-
a similar manner 2,6- and 2,5-dichlorotoluene
fonation and desulfonation occur (kinetic con-
and 2,3,6-trichlorotoluene are obtained
trol) and the position of the equilibrium (thermo-
from toluenesulfonic anhydride by chlori-
dynamic control) are dependent on the relative
nation and subsequent desulfonation [24].
height of these enthalpies [8]. They are largely
Sulfonation – desulfonation is also important
affected by other substituents present in the ben-
in the production of 1,4-benzenedisulfonic acid
zene nucleus. This is reflected by the various
(Section 2.2).
temperatures at which acidic desulfonation oc-
Alkali Fusion. Alkaline cleavage of benzene-
curs [13]:
sulfonic acids leads to phenols according to the
benzenesulfonic acid 227 ◦ C following equation:
2-methylbenzenesulfonic acid 188 ◦ C
3,4-dimethylbenzenesulfonic acid 176 ◦ C ArSO3 Na + 2 NaOH −→ ArONa + Na2 SO3 + H2 O
2,4-dimethylbenzenesulfonic acid 137 ◦ C In former times this was the method of choice
2,4,6-trimethylbenzenesulfonic acid 100 ◦ C
to produce phenol on an industrial scale; how-
ever, this process has mostly been replaced by
the Hock process (→ Acetone, Chap. 4.1.).
Figure 1 also explains the general rule accord-
Sulfone Formation. Benzenesulfonic acids
ing to which acidic desulfonation of benzenesul-
react with aromatic compounds to form sul-
fonic acids occurs the more easily the easier it
fones. This reaction is an undesired side reac-
is to introduce the sulfonic acid group (higher
tion in industrial sulfonation (see Section 2.1);
sulfonation rate). This is often exploited indus-
it is promoted by Friedel – Crafts reagents and
trially in the separation and purification of aro-
inhibited by alkali metal ions [25].
matic compounds as described in the next para-
Reaction with Halogenides. The reaction
graph.
with phosphorus halogenides (PCl5 , PBr5 ),
Pure p-xylene can be obtained from a
chlorosulfuric acid, thionyl chloride, or phos-
mixture of o- and p-xylene by sulfonation
gene leads to sulfonyl halogenides:
and subsequent removal of water-soluble o-
xylenesulfonic acid [14]. The same principle can
C6 H5 SO2 OH + PCl5 −→ C6 H5 SO2 Cl + POCl3 + HCl
be used to separate m-xylene from p-xylene [15],
[16] and from ethylbenzene [17], or 1-ethyl-3,5- If benzenesulfonic acid reacts with an excess of
dimethylbenzene from other ethylxylenes [18], PCl5 , chlorobenzene is formed according to
or 4-chloro-1,3-xylene from its isomers [19]. In
the manufacture of DDT excess chlorobenzene C6 H5 SO2 Cl + PCl5 −→ C6 H5 Cl + SOCl2 + POCl3
was recovered by sulfonation, removal of the
sulfonic acid, and subsequent desulfonation at Sulfonyl fluorides are obtained by the reaction
190 ◦ C [20]. m-Dichlorobenzene can be sepa- of sulfonyl chlorides with KF in the presence of
rated as a sulfonic acid derivative from a mix- phase-transfer catalysts in sulfolane.
ture of isomeric dichlorobenzenes and obtained Anhydride Formation. Sulfonic anhydrides
by subsequent desulfonation [21], [22]. The sul- are made by the reaction of P2 O5 , SOCl2 , or
fonic acid group also serves as a protective group SO3 with benzenesulfonic acids [26]. They are
Figure 1. Sulfonation and desulfonation of benzene (E+ = SO3 or HSO+

3 ), ∆H R = reaction enthalpy
also formed through side reactions in the prepa- Sulfonation with sulfuric acid is a reversible
ration of benzenesulfonic acids or benzene- reaction (see also Figure 1):
sulfonyl chlorides; in this case, however, they are
frequently not observed because they are rapidly ArH + H2 SO4 ArSO3 H + H2 O
hydrolyzed in aqueous acid.
Esterification. Benzenesulfonic esters are It can be shifted optimally to the right if the
formed in the reaction of the sulfonic acids or water of the reaction is bound or removed by
sulfonyl chlorides with alcohols or ethers (see distillation. Higher temperatures usually shift
Section 1.9.4). the equilibrium towards the right [28]. However,
both methods increase sulfone formation.
The water of the reaction can also be bound
1.3. Production by adding thionyl chloride:
1.3.1. Direct Sulfonation C6 H6 + H2 SO4 + SOCl2 −→ C6 H5 SO3 H + SO2 + 2 HCl
The direct introduction of the sulfonic acid For example, the sulfonation of benzene with
group is one of the most important reactions in sulfuric acid and thionyl chloride gives a mix-
industrial organic chemistry. Together with ni- ture consisting of 96.3 % benzenesulfonic acid,
tration and chlorination, it belongs to the im- 2.7 % sulfuric acid, and 1.6 % diphenyl sulfone
portant group of electrophilic aromatic substi- [29]. Similar yields are obtained when sulfonat-
tution reactions. It gives high yields under rel- ing toluene or chlorobenzene in this way.
atively mild conditions and usually results in No reaction water is formed in sulfona-
well-defined benzene derivatives. tions using chlorosulfuric acid or sulfur trioxide.
Aqueous sulfuric acid, at various concentra- However, increased sulfone formation occurs.
tions from about 76 % up to 100 %, is frequently As a sulfonating agent pure sulfur trioxide gen-
used as the sulfonating agent. In industry 100 % erally reacts too violently and leads to extensive
sulfuric acid is often called monohydrate. Oleum side reactions including oxidation and sulfone
is a solution of sulfur trioxide in sulfuric acid; formation. Hence it is used in complexed form,
for sulfonation it is generally used at SO3 con- e.g., with pyridine, dioxane, trimethylamine, or
centrations of 20 or 65 wt % because the solid- dimethylformamide [30]. Many industrial pro-
ification points at these two concentrations are cesses use sulfur trioxide gas as the sulfonating
minimal (0 and 2 ◦ C, respectively). Other con- agent, normally mixed with an inert gas such as
centrations are less favorable with regard to stor- air, nitrogen, or carbon dioxide [31–33]. Thus,
age and transportation because the solidification the sulfonating agent is diluted or evenly dis-
points are higher (for example, 45 % oleum so- tributed so that the heat of the reaction is quickly
lidifies already at 35 ◦ C) [27]. dissipated [34] (see also → Surfactants). In the
liquid phase, sulfur dioxide or dichloromethane

is suitable as diluent. However, dichloromethane
reacts with sulfur trioxide at temperatures above
0 ◦ C, and highly poisonous decomposition prod-
ucts are formed, such as bis(chloromethyl) ether.
1,1-Dichloroethane also reacts with sulfur triox-
ide at 80 ◦ C; the decomposition products include
phosgene. Orientation Rules. The sulfonation of ben-
In stoichiometric amounts, chlorosulfuric zene derivatives C6 H5 Y is facilitated over that
acid serves as a sulfonating agent according to of benzene if the substituent Y supplies electron
density to the aromatic ring. Examples are:
ArH + ClSO3 H −→ ArSO3 H + HCl
Substituent Y Electronic effect
When using an excess of chlorosulfuric acid, Alkyl +I
OR, NR2 +M>−I
sulfonyl chlorides are formed, see Section O− + M; + I
1.9.1. The chlorosulfonation of toluene, for ex-
where I = inductive effect and M = mesomeric effect
ample, with chlorosulfuric acid at low temper-
ature yields predominantly o-toluenesulfonyl
chloride. This is the first step in the in- Benzene derivatives are sulfonated with
dustrially important synthesis of saccharin greater difficulty than benzene if the substituent
(→ Sweeteners). Y withdraws electron density from the aromatic
ring. Examples are:
Reaction Mechanism. The basic reaction Substituent Y Electronic effect
mechanism of aromatic sulfonation is described COR, COOR, CN, NO2 , N+
2 , SO3 H −M; −I
in Figure 1. The nature of the electrophilic agent Cl, Br −I > + M
NR+ −I
E+ , however, varies according to the sulfonating 3
agent used and the solvent. where I = inductive effect and M = mesomeric effect
In monohydrate (100 %) or only slightly di-
luted (92 – 99 %) sulfuric acid, sulfur trioxide The electron-releasing substituents and the
is the electrophilic agent [35], [36]. The rate- halogens direct the SO3 H group predominantly
determining step in this reaction is the elimina- into the o- and p-positions (first-order sub-
tion of the proton. stituents). On the other hand, the electron-
withdrawing substituents (except for the halo-
gens) generally direct the SO3 H group into
the m-position (second-order substituents). The
seemingly exceptional role of the halogens is
explained by the electronic stabilization of the
various reaction intermediates (π complexes, σ
complex); this is discussed extensively in text-
books on organic chemistry.
This fundamental rule of aromatic substi-
In sulfonation with disulfuric acid and with
tution is valid particularly at low temperature.
chlorosulfuric acid the SO3 H+ cation (sulfate
Raising the temperature may change the iso-
cation) is assumed to be the sulfonating agent
mer distribution in the product mixture due to
[37]:
the transition from kinetic to thermodynamic
control. For example, sulfonation of benzene
with sulfuric acid at about 80 ◦ C yields predom-
inantly 1,3-benzenedisulfonic acid (see Sec-
tion 2.2); however, by raising the temperature to
The SO3 H+ cation is also formed as an in- 250 ◦ C an isomer mixture consisting of 67 %
termediate when sulfur trioxide is used as the 1,3-disulfonic acid and 33 % 1,4-disulfonic
sulfonating agent [38–40] acid is formed. When sulfonating first-order-
substituted benzene derivatives, the ratio of the is re-used. Sulfonates practically free from inor-
ortho and para isomer formed is also shifted in ganic salts are obtained in this way [41], [42].
favor of the para isomer if the temperature is Special sulfonation and processing methods
raised. have been developed for compounds that with-
stand high temperatures and therefore allow the
Technology of Sulfonation. Sulfonation is excess sulfuric acid to be distilled off in vacuo
carried out in cast-steel or enameled steel ves- (see Hooker process for the production of ben-
sels; in continuous processes, the vessels are ar- zenedisulfonic acid, see page 15). This gives sul-
ranged in cascades. In the batchwise mode the fonic acids almost free from sulfuric acid, which,
sulfonating agent is introduced into the vessel, with skillful mixing, can be neutralized and sub-
the aromatic compound is subsequently added, jected to alkali fusion in a single step [43].
and the reaction is controlled by means of tem- Aromatic amines may be sulfonated by a spe-
perature profiles or metering. In continuously cial solid-state process, called baking: the am-
run cascades the sulfonating agent is often intro- monium hydrogensulfate that is first formed in
duced into two or three vessels simultaneously. the reaction between the amine and sulfuric acid
On completion of the reaction the batch is is dewatered and simultaneously rearranged to
forced into water, which causes unconverted aro- aminobenzenesulfonic acid at 150 – 300 ◦ C. The
matic compounds to be expelled. The dilute sul- reaction product is solid, which requires the re-
fonation mass is then cooled, and the free acid action to be carried out on trays in an oven.
separated by filtration. If the free acid is too solu- The solids can also be suspended in an or-
ble, sodium sulfate or sodium chloride is added, ganic liquid such as diphenyl sulfone [44] or o-
after which the acid is separated as the sodium dichlorobenzene [45]; in this way the mass can
salt (salting out). Often it is also possible to neu- be stirred during the entire reaction. This gives
tralize a concentrated solution with sodium hy- final products of higher quality because local
droxide and then remove the precipitated sodium overheating cannot occur (see also manufacture
sulfate at 70 – 90 ◦ C. The filtrate then contains of p-sulfanilic acid, see page 23).
the sodium salt of the arylsulfonic acid almost
free from inorganic salt. It can be dried in drum
or spray dryers. 1.3.2. Oxidation of Sulfur Compounds
If isolation is not possible in this way, the ex-
cess sulfuric acid can be neutralized by adding Such sulfur compounds as thiophenols and di-
calcium carbonate. This leads to a large amount aryl disulfides can be oxidized with chlorine so-
of gypsum, which is removed in the hot state lution, permanganate, or nitric acid to form sul-
(“liming” or “chalking”). The dissolved calcium fonic acids. The process is industrially important
arylsulfonate is then treated with soda and the wherever it is difficult or impossible to introduce
precipitated calcium carbonate is removed by the sulfonic acid group directly and the starting
filtration. The filtrate contains the sodium aryl- compounds are easily produced. An example of
sulfonate. Today, in large-scale manufacture the the use of halogens as oxidizing agents is given
economical removal of byproduct gypsum is, es- in [46].
pecially in Europe, very difficult, and other iso-
lation techniques such as temperature-controlled
crystallization or reactive extraction have be- 1.3.3. Diazo Reaction
come more favorable.
In the reactive extraction process the uncon- Aryldiazonium halides are converted to aro-
verted sulfuric acid is recovered by converting matic sulfonic acids in glacial acetic acid con-
the sulfonic acid into its ammonium salt with taining SO2 in the presence of copper(I) chloride
a long-chain aliphatic amine. This salt is sepa- [47].
rated from the sulfuric acid as a liquid phase and This reaction, which was first observed by
then converted with sodium hydroxide solution L. Landsberg, permits the production of, for
into sodium sulfonate solution and the amine; example, 1,2-benzenedisulfonic acid from or-
the latter can be separated as a liquid phase and thoanilic acid with a yield of 68 % [48].
Hydrogensulfite addition, followed by the

formation of a benzenesulfonic acid, gives sat-
isfactory yields in special cases only and has
therefore acquired little industrial importance so
far.
1.4. Uses
Benzenesulfonic acids are used chiefly as in-
termediates. They are employed in the manu-
facture of sulfonic acid amides, hydrazides, and
esters; of sulfinic acids, sulfones, phenols, and
thiophenols; and of other compounds. Sulfonic
acids that are substituted with OH and/or NH2
1.3.4. Sulfite Reaction groups serve as intermediates in the manufacture
of finishing agents, optical brighteners, pick-
Aromatic halogen compounds can react with ling agents, dyes, tanning agents, water-soluble
sulfite to form sulfonic acids if the halogen sub- resins, insecticides, ion-exchange resins, wet-
stituent is activated by nitro groups. For exam- ting agents, pharmaceuticals, polymeric thick-
ple, 1-chloro-2,4-dinitrobenzene reacts with sul- eners, plasticizers, etc. Benzenesulfonic acids
fite to give 1,3-dinitro-4-benzenesulfonic acid. are also used as such as acidic catalysts and stan-
The reaction is catalyzed by copper ions. 2- dardizing agents in dye manufacture.
Formylbenzenesulfonic acid and 2-sulfobenzoic
acid are obtained similarly from the correspond-
ing chlorine compounds. 1.5. Analysis
The addition of hydrogensulfite to aromatic
systems succeeds when their aromatic charac- Today benzenesulfonic acids and most of their
ter is disturbed by the presence of certain sub- derivatives are analyzed by HPLC with high ac-
stituents. The formation of 3-hydroxybenzene- curacy and efficiency [52]. By this method it
sulfonic acid from resorcinol [49] and the sul- is possible, both in the laboratory and in in-
fitation of m-dinitrobenzene with simultaneous dustry, to analyze the exact composition of sul-
reduction of a nitro group [50] (Piria reaction) fonation mixtures, which frequently consist of
are examples: many components, and to observe how the com-
position is affected by the reaction parameters.
Gas chromatography (GC) is used less often, but
can be as effective, for example, after derivati-
zation of reactive functional groups. GC meth-
ods have been reported for the analysis of o-
aminobenzenesulfonic acids via their sulfonyl
chlorides [51]. Benzenemonosulfonic and ben-
zenedisulfonic acid mixtures can also be sepa-
rated and analyzed quantitatively by GC analysis
of their sulfofluorides [53].
In particular cases, benzenesulfonic acids are
determined quantitatively in the presence of sul-
furic acid and sulfones by titrating the total acid
with alkali potentiometrically and then deter-
mining the sulfuric acid content gravimetrically
with barium chloride. The difference gives the
content of sulfonic acid. In general, in the case
of the analysis of isolated salts of sulfonic acids,
the content should usually be referred to the free 3) Precipitation of the final product from the
acid. sulfuric acid solution without adding salt,
Older laboratory methods are the follow- e.g., by cooling (see isolation of p-toluene-
ing: Aminobenzenesulfonic acids can be ren- sulfonic acid, see page 17).
dered distinctly visible on a paper chromatogram 4) Distillative separation of the sulfuric acid
by diazotization and subsequent azo dye for- (see manufacture of benzenedisulfonic acid,
mation. Hydroxybenzenesulfonic acids can be see page 15).
stained well on the paper by coupling with a 5) Formation of a separate liquid phase consist-
diazonium salt. Most other sulfonic acids can ing of an ammonium sulfonate. After phase
be recognized clearly from their fluorescence- separation, the sulfuric acid phase is returned
extinguishing effects on chromatography paper to the sulfonation reactor.
previously sprayed with Pinakryptol Yellow and 6) Precipitation of the excess sulfuric acid as
thus rendered fluorescent in UV light [54]. sodium sulfate if sodium sulfate is less solu-
ble than the sodium sulfonate.
7) Precipitation of the excess sulfuric acid as
1.6. Environmental Aspects calcium sulfate. The gypsum thus obtained
is either dumped or used, depending on its
Organic Compounds in Wastewater. Ben- quality.
zenesulfonic acid is biologically degradable. 8) Removal of the excess sulfuric acid by treat-
However, the direct biological degradation of ing it with additional aromatic compounds
many substituted benzenesulfonic acids is diffi- that are more reactive than that used for the
cult or impossible; these compounds are there- desired reaction. The resulting mixture could
fore not suitable for treatment in biological be subjected to alkali fusion to form phenols,
wastewater purification plants without oxida- which can be separated by distillation.
tive pretreatment.
If the desired benzenesulfonic acid can be Waste Gas. The main organic constituents
precipitated from sulfuric acid solution without of waste air from benzenesulfonic acid produc-
salt being added, the spent acid can be upgraded tion plants are unconverted portions of such
in a sulfuric acid recovery plant. If the waste- starting materials as benzene, toluene, or halo-
water contains salts and nondegradable sulfonic genated benzene derivatives. They are usually
acids, low-pressure wet oxidation is a possible removed in a sulfuric acid scrubber with a down-
method of treatment that subsequently allows stream thermal waste-gas remover. The waste
effective degradation in wastewater treatment sulfuric acid obtained in the scrubber can be re-
works. cycled as a sulfonating agent. Because benzene
is carcinogenic (Group C 1, MAK commission)
Inorganic Compounds in Wastewater. In the benzene emissions of newly built plants for
the operation of large plants the treatment of the production of benzenesulfonic acid must be
such inorganic constituents as acids and salts in accordance with the accepted lowest techni-
is becoming an increasingly important cost fac- cally feasible levels.
tor in addition to the treatment of the organic Sulfur trioxide in waste gas forms aerosols
constituents. that can only be removed effectively with spe-
The following methods are available to de- cially designed scrubbers loaded with concen-
crease the acid or salt content of the wastewater. trated sulfuric acid. In most sulfonations the ox-
idative effects of sulfuric acid or sulfur trioxide
1) Azeotropic distillation of the reaction water lead to the formation of sulfur dioxide, which
with a solvent. This improves the utilization can suitably be removed from the waste gas by
of the sulfuric acid. alkali scrubbing.
2) Use of oleum, sulfur trioxide, or chlorosul- In the production of benzenesulfonyl chlo-
furic acid in place of sulfuric acid. The re- rides the main impurity of the waste gas is hy-
sulting increase in sulfone formation can be drogen chloride. It can be used to produce hy-
counteracted, though not eliminated, with drochloric acid or chlorosulfuric acid, provided
the aid of additives. that organic matter has been removed from it by
2-Amino-5-chloro-4-methylbenzene- Lake Red C
sulfuric acid scrubbing. Phosgene in the waste sulfonic
gas is hydrolyzed with water on activated carbon acid
to form carbon dioxide and hydrogen chloride. 2-Formylbenzenesulfonic acid triphenylmethane
dyes, optical
brightener
2-Methylbenzenesulfonyl chloride saccharin
4-Methylsulfonamide plasticizer
1.7. Economic Aspects
Most benzenesulfonic acids, chlorides, and

amides are used as intermediates in the man- 1.8. Toxicology and Ecotoxicology
ufacture of dyes, crop protection agents, and
pharmaceuticals. Because of the large number In general, benzenesulfonic acids, chlorides, and
of producers and uses, little is known about ex- amides are not very toxic. Nevertheless, ben-
act market volumes. Especially in Asia and India zenesulfonic acids and chlorides are strong skin
the number of producers has increased, making irritants. Amino substitution does increase their
the business for European suppliers increasingly pK a values, but aminobenzenesulfonic acids and
difficult. -chlorides are still moderately irritant. In ad-
Table 1 lists some estimated production data dition, benzenesulfonyl chloride can act as a
for some benzenesulfonic acids, chlorides, and skin sensitizer [55]. Benzenesulfonyl hydrazide
amides. is suspected to be mutagenic in vitro [56].
Table 1. Estimated production data for some benzenesulfonic acids, Concerning ecotoxicology, except for benzene-
chlorides, and amides sulfonyl chloride, none of the compounds listed
Production, Year in Table 2 represent a potential major hazard for
103 t/a aquatic ecosystems.
p-Toluenesulfonic acid
W. Europe 65.5 1990
World 115 1990 1.9. General Characteristics of
4-Aminobenzenesulfonic acid
W Europe 11.5 1994 Benzenesulfonic Acid Derivatives
World 25 1994
m-Aminosulfonic acid 1.9.1. Benzenesulfonyl Chlorides
W. Europe 2.3 1994
China 5.0 1994
India 9.4 1994 Properties. The chlorides of benzenesul-
Japan 1.0 1994 fonic acids are crystalline substances with def-
World 17.7 1994
2-Amino-1,4-benzenedisulfonic acid inite melting points. They decompose with for-
World 2.0 1995 mation of sulfur dioxide at temperatures bet-
2-Amino-5-chloro-4-methylbenzene-
sulfonic
ween 100 and 200 ◦ C, depending on their struc-
acid ture. They undergo hydrolysis, which in some
World 9.9 1990 cases is very slow. Hydrolysis is accelerated by
2-Formylbenzenesulfonic acid
World 4.0 1996 hydrogen ions; this explains why the decompo-
2-Methylbenzenesulfonyl chloride sition of moist pastes may not occur until a con-
World 11.2 1995
4-Methylsulfonamide
siderable time has expired after their production,
World 10 – 15 1994 and why it may then take place exothermally
and very rapidly, with the result that dangerous
Some use of selected benzenesulfonic acids, local overheating occurs. The chlorides of the
chlorides, and amides follow: benzenesulfonic acids react with amines to form
sulfonamides and with alcohols to form esters.
p-Toluenesulfonic acid resins, p-cresol,
C-Acid, acid catalyst
4-Aminobenzenesulfonic acid dyes, optical Production. The most convenient method
brightener for the production of benzenesulfonyl chlorides
m-Aminosulfonic acid dyes
2-Amino-1,4-benzenedisulfonic acid dyes, optical is the chlorosulfonation reaction of benzene or
brightener substituted benzene with chlorosulfuric acid.
Sulfonation and formation of the sulfonyl chlo-
ride take place in one reaction sequence:
Table 2. Toxicological and ecotoxicological data for benzenesulfonic acids and their derivatives
Compound LD50 (rat, oral), Aquatic toxicity Degradation

mg/kg
species LC0 , LC50 , Test method %
mg/L mg/L
Benzenesulfonic acid 1170 Zahn – Wellens [57] 90

4-Methylbenzenesulfonic acid 2480 Leuciscus idus >500 Zahn – Wellens 100
2-Aminobenzenesulfonic acid 2700 Leuciscus idus 1000 closed bottle 90
4-Aminobenzenesulfonic acid 12 300 Leuciscus idus 1000 OECD screening [58] 90
4,6-Diamino-1,3-benzenesulfonic acids 2990 Brachydanio rerio 100 closed bottle 0
3-Amino-4-methylbenzenesulfonic acid 8480 Brachydanio rerio 500 0
4-Amino-3-methylbenzenesulfonic acid Salmo gairdneri 133 dissolved organic 24
carbon
2-Amino-5-methylbenzenesulfonic acid 11 700
3-Amino-4-methoxybenzenesulfonic acid > 5000 Brachydanio rerio 100 closed bottle 0
3-Amino-4-chlorobenzenesulfonic acid > 5000 Brachydanio rerio 100 closed bottle 0
2-Amino-4,5-chlorobenzenesulfonic acid > 5000
3-Amino-5-chloro-2-hydroxybenzenesul- > 5000 Brachydanio rerio 100 closed bottle 3
fonic
acid
2,5-Dichlorobenzenesulfonic acid 1170
Benzenesulfonyl chloride 1960 Salmo trutta 3 closed bottle 65
4-Methylbenzenesulfonyl chloride 4680 Brachydanio rerio >1000
Benzenesulfonamide 960 Leuciscus idus 200 closed bottle 0
N-(Butyl)benzenesulfonamide 1725 – 2050
4-Methylbenzenesulfonamide 2330 (BSB5 :CSB) × 100 13
4-Aminobenzenesulfonamide >5000 Leuciscus idus 1000 Closed bottle 0
4-Chlorobenzenesulfonamide 515 Brachydanio rerio 100 198 Zahn – Wellens 6
3-Amino-4-hydroxybenzenesulfonamide 2160 (BSB5 :CSB) × 100 1 – 10
enameled steel vessel and 10 – 25 mol % of the

aromatic compound is stirred in at 25 – 30 ◦ C,
Ar−H + Cl−SO3 H −→ ArSO3 H + HCl
whereupon sulfonation of the aromatic com-
pound and HCl formation occur. The formation
ArSO3 H + Cl−SO3 H ArSO2 Cl + H2 SO4
of sulfonyl chloride is initiated by heating the
Sulfone is formed in a side reaction of the reactants to 50 – 80 ◦ C. The reaction is exother-
chlorosulfonation (up to 7 % of sulfone is formed mic. The temperature must be controlled accu-
when benzene is used as raw material and up rately to ensure uniform release of the HCl gas.
to 35 % when chlorobenzene is used). It is at- Restarting of the agitator after an interruption
tributed to the reaction of the initially formed of the electricity supply is hazardous and may
sulfonic acid with unconverted aromatic com- cause the contents of the vessel to foam over.
pound: The sulfonyl chloride is isolated by draining the
reaction mass onto water and simultaneous cool-
ArSO3 H + ArH −→ ArSO2 Ar + H2 O ing. Excess chlorosulfuric acid is decomposed,
and the sulfonyl chloride either precipitates or
H2 O + ClSO3 H −→ H2 SO4 + HCl separates as an organic liquid phase. The qual-
ity of the chlorosulfuric acid affects the yield.
In this reaction the chlorosulfuric acid serves as In the case of aromatic compounds that
a condensation agent. easily take up two sulfochloride groups, e.g.,
The amount of sulfone formation can be re- anisole, monochlorosulfonation is carried out
duced by diluting with a solvent, by using a with only a little more than the calculated
large excess of chlorosulfuric acid, or by adding amount of chlorosulfuric acid at a low tempera-
sulfone-inhibiting substances, e.g., alkali metal ture (0 ◦ C) and in the presence of a diluent such
and ammonium salts, acetic acid, phosphoric as dichloromethane. The reaction of benzenesul-
acid, dimethylformamide, or amidosulfuric acid fonic acids with chlorosulfuric acid is an equi-
[59]. librium reaction. Therefore, the yield can be in-
For industrial chlorosulfonation the chloro-
sulfuric acid is introduced into a cast-steel or
creased by using an excess of chlorosulfuric acid chlorosulfonation and subsequent dechlorosul-

[60]. fonation at 200 ◦ C and passing chlorine gas
Other chlorinating agents, such as phosgene, through the reaction mixture [66].
thionyl chloride, sulfuryl chloride, or phos-
phorus pentachloride, can be used instead of
chlorosulfuric acid. When thionyl chloride is
used the sulfonyl chloride is obtained from the
sulfonic acid in high yield and without formation
of sulfuric acid:
ArSO3 H + SOCl2 −→ ArSO2 Cl + SO2 + HCl Due to their poor storage properties, many
benzenesulfonic acids are reduced to the cor-
A one-pot procedure is described in [61]. Ac- responding benzenesulfinic acids at 60 ◦ C and
cording to [62] the highest degree of conver- pH 6 – 9.
sion is obtained in the presence of at least 5 %
of a sulfonating agent, e.g., sulfur trioxide, or ArSO2 Cl + NaHSO3 + 3 NaOH
an excess of chlorosulfuric acid. If phosgene is −→ ArSO2 Na + NaCl + Na2 SO4 + 2 H2 O
used as a chlorinating agent, the reaction can
be accelerated by adding dimethylformamide Sulfinates are often converted with ethylene
[62] or the less problematic dibutylacetamide oxide into β-hydroxyethylsulfones.
for dimethylcarbamoyl chloride as byproduct is
avoided. The crude sulfonyl chlorides can be pu- Uses. Benzenesulfonyl chlorides are impor-
rified either by fractional distillation or by crys- tant as intermediates. They are used to pro-
tallization from an anhydrous solvent. duce sulfonic acids, sulfonyl fluorides, sul-
In a diazo reaction, an NH2 group can be fonamides, sulfonohydrazides, sulfonic esters,
ultimately replaced by the SO2 Cl group; this re- sulfinic acids, sulfones, and thiophenols.
action is suitable for the preparation of special
sulfonyl chlorides whose SO2 Cl group must be
in a specific position [63]. A hydrochloric acid 1.9.2. Benzenesulfonamides
solution of the diazonium salt, whose concen-
tration must be as high as possible, is allowed to Properties. Benzenesulfonamides are read-
flow into a CuCl2 -containing 30 % solution of ily crystallizing, colorless compounds with de-
sulfur dioxide in glacial acetic acid [64]. A sim- fined melting points and poor solubility in water.
ilar procedure using thionyl chloride was also They are therefore suitable for the characteriza-
described [65]. Diazonium chlorides with sub- tion of sulfonic acids (via the sulfonyl chlorides)
stituents having a strong negative inductive ef- and of primary and secondary amines and for the
fect (NO2 , SO3 H) give the best results. Poor separation of amine mixtures (Hinsberg method)
yields can be improved by adding magnesium [67], [68].
chloride or a water-immiscible solvent having a Benzenesulfonamides are weak acids and
low dielectric constant. Disulfides can be con- form salts with bases. They are thermally stable
verted into sulfonyl chlorides with chlorine in and very difficult to hydrolyze with alkali; how-
aqueous suspension. The reaction is also appli- ever, they are more easily hydrolyzed with min-
cable to thiophenols. eral acids. In concentrated sulfuric acid sodium
nitrite splits them into sulfonic acids and nitro-
(C6 H5 )2 S2 + 5 Cl2 + 4 H2 O −→ 2 C6 H5 SO2 Cl + 8 HCl gen. The hydrogen atoms bound to the nitrogen
can be substituted.
The dechlorosulfonation of benzenesulfonyl Dibenzenesulfonylamines are acids similar
chlorides offers the possibility to selec- in strength to the mineral acids [69]; they react
tively introduce chlorine into aromatics. 1,2,4- with amines to form salts with definite melting
Trichlorobenzene can be produced from 1,2- points [70].
dichlorobenzene without formation of undesir-
able tetra- or higher chlorinated products via
Production. Sulfonamides are produced by

treating the sulfochlorides with ammonia, pri- ArSO2 NHNH2 + HNO2 −→ RSO2 N3 + 2 H2 O
mary, or secondary amines in water. Alterna-
tively they are produced in the presence of a
base such as sodium hydroxide solution, sodium
hydrogencarbonate, calcium carbonate, sodium
sulfite, a second equivalent of amine or pyridine, 1.9.4. Benzenesulfonic Esters
or sodium acetate in glacial acetic acid; in this
case, the reaction proceeds in an inert solvent, Esters of benzenesulfonic acid are liquids or
e.g., toluene or acetone. low-melting crystalline substances. They have
Dibenzenesulfonylamines are obtained anal- relatively high thermal stability and can be puri-
ogously according to the following reaction fied by vacuum distillation. In general, they can
[71]: be hydrolyzed with alkali at elevated tempera-
tures only. The esters of benzenesulfonic acid
2 ArSO2 Cl + NH3 −→ ArSO2 NHSO2 Ar + 2 HCl are produced by treating benzenesulfonic acid
halides with alcohols in the presence of a base
Unsymmetrical disulfonylamines are produced [76], [77] or by treating benzenesulfonic acids
from sulfonamides and sulfochlorides in the ab- with ethers [78]. These compounds are used as
sence of water [72] or in sodium hydroxide so- alkylating agents and plasticizers.
lution [73], [70].
Uses. Benzenesulfonamides serve as inter- 2. Individual Benzenesulfonic Acids

mediates in the production of polysulfonamides, and Derivatives
which are used as tanning agents and plas-
tics. N-Alkylamides of the benzenesulfonic and 2.1. Benzenesulfonic Acid
toluenesulfonic acids can be used as plasticiz-
ers. Aminobenzenesulfonamides and diaryld- Benzenesulfonic acid [98-11-3], C6 H5 SO3 H,
isulfonylamines with amino groups serve as in- M r 158.17, was first obtained, together with
termediates in the production of azo dyes. diphenyl sulfone, by E. Mitscherlich in 1834
Sulfonamides, especially those derived from by heating benzene with fuming sulfuric acid.
p-sulfanilic acid, sulfonyl ureas and sulfonyl The industrially important reaction of benzene-
guanidines are important in medicine as antibi- sulfonic acid with alkali hydroxide to form phe-
otics, antidiabetics, diuretics, and anthelmintics nol (alkali fusion) was developed by A. Wurtz
[74], [75]. and A. Kekulé in 1867 and by P. O. Degener
in 1878. Until the early 1960s benzenesulfonic
acid was used chiefly in the manufacture of phe-
1.9.3. Benzenesulfonohydrazides nol. Other phenol syntheses are preferred now
(→ Phenol).
Properties. Benzenesulfonohydrazides, un-
like the benzenesulfonamides, are thermally un- Properties. Benzenesulfonic acid crystal-
stable. They decompose, when heated in water lizes from aqueous solution as a hydrate with
in some cases, to form sulfides, thiosulfonates, 1.5 H2 O in the form of deliquescent needles;
and nitrogen; for this reason they are used as its melting point is 43 – 44 ◦ C. The monohy-
blowing agents in the production of foams. drate melts at 45 – 46 ◦ C. The anhydrous acid,
which can be distilled without decomposition at
Production. Benzenesulfonohydrazides are 171 – 172 ◦ C (0.13 mbar), melts at 65 – 66 ◦ C.
produced by treating benzenesulfonyl chlorides It is very easily soluble in water and alcohol,
with hydrazine in dioxane, alcohol, or water and poorly soluble in benzene, and insoluble in di-
in the presence of a second equivalent of hy- ethyl ether and carbon disulfide. Its dielectric
drazine or another base. They react with nitrous constant in aqueous solution is 0.2. For the den-
acid to form benzenesulfonyl azides according sity and refractive indices of aqueous solutions,
to the following equation: see [79].
Sodium benzenesulfonate decomposes at to a greater or lesser extent. The following meth-

about 450 ◦ C. It is soluble in 1.75 parts of wa- ods have been used industrially:
ter at 30 ◦ C and in 0.8 part of boiling water, and 1) Use of oleum or sulfur trioxide instead of
crystallizes from aqueous solutions with 1 mol sulfuric acid
of water of crystallization. The calcium and bar- 2) Extraction of the benzenesulfonic acid from
ium salts are also soluble in water. the reaction mixture with benzene
Benzenesulfonic acid has the characteris- 3) Azeotropic removal of the reaction water
tic reactions of a strong aromatic sulfonic with benzene
acid. Acid hydrolysis at 175 ◦ C splits it into
benzene and sulfuric acid. Additional sul- Classical Process. The sulfonation by the
fonation with fuming sulfuric acid gives 1,3- classical process [81] is now of historical inter-
benzenedisulfonic acid, which reacts further to est only, because it is coupled with the synthesis
1,3,5-benzenetrisulfonic acid, and also diphenyl of phenol (use of sulfite from phenol production
sulfone disulfonic acid (see Section 2.2). to neutralize the benzenesulfonic acid). Details
Benzenesulfonic acid reacts with benzene of the process can be found in [82].
to form diphenyl sulfone according to a Continuous Sulfonation with Oleum (Mon-
Friedel – Crafts-type reaction: santo process) [83]. Benzene and oleum are
pumped simultaneously into the first of six sul-
fonation vessels forming a cascade. The vessels,
which have propeller stirrers, are connected to
one another by overflow pipes so that the re-
action mixture can flow from one vessel to the
Benzenesulfonic acid reacts with alkali metal next.
hydroxide at 320 – 350 ◦ C to form sodium phe- The first two vessels are cooled, whereas the
nolate according to others are heated. If optimal temperature con-
ditions are provided, the reaction is complete
C6 H5 SO3 Na + 2 NaOH −→ C6 H5 ONa + Na2 SO3 + H2 O
when the sulfonation mixture leaves the last ves-
This reaction was used in the first industrial syn- sel. The excess sulfuric acid is removed by neu-
thesis of phenol. tralizing the reaction mixture with sodium sul-
fite or sodium hydroxide solution. Sodium sul-
Production. Benzenesulfonic acid is formed fate precipitates and is separated in a number of
from benzene and sulfuric acid in an exothermic centrifuges. The solution of sodium benzenesul-
reaction according to fonate is concentrated in an evaporator, which
causes more sodium sulfate to precipitate. Af-
C6 H6 + H2 SO4 −→ C6 H5 SO3 H + H2 O ter centrifuging, the benzenesulfonic acid can be
converted directly to phenol or dried. Accord-
Crooks and White investigated the effects of ing to Carswell oleum containing 35.6 % of
temperature and of the composition of the sul- sulfur trioxide is used and the temperatures of
fonation mixture on the reaction rate and de- the first and last sulfonation vessels are held at
veloped a formula for calculating this rate [80]. 70 – 80 ◦ C and 110 ◦ C, respectively. About 1 %
The reaction stops at a particular sulfuric acid of the benzene is converted to diphenyl sulfone.
concentration between 74 and 78 %, which de- Continuous Extraction Process. Under vig-
pends on the temperature and the amount of wa- orous stirring excess benzene and sulfur triox-
ter formed. A proportion of the sulfuric acid ide are introduced into a vessel through separate
(45 % in the classical process) is not utilized, pipes leading into the bottom of the vessel [84].
but serves as a solvent and diluent and ensures A benzene layer saturated with benzenesulfonic
that byproducts, particularly diphenyl sulfone, acid collects in the upper part of the vessel and
are formed in low yield only. In industry the ex- passes through an overflow pipe into a second
cess acid is removed by adding calcium carbon- agitator vessel. In this vessel the benzenesul-
ate. fonic acid is removed from the benzene extract
Any method that serves to reduce the excess by continuous washing with water or sodium hy-
of sulfuric acid increases the sulfone formation droxide solution. The benzene is separated from
the aqueous benzenesulfonic acid solution in a The sulfuric acid formed simultaneously in-
separator. After being dried it is returned to the hibits the reaction. Therefore the yield of sul-
reaction vessel. The sulfuric acid consumption fonyl chloride is about 75 %, based on benzene.
is 1260 kg for 1000 kg of converted benzene. Benzenesulfonic acid and diphenyl sulfone are
Diphenyl sulfone formation is below 2 % [85]. formed as byproducts in yields of approximately
Azeotropic Removal of Reaction Water [86], 18 % and 5 – 7 %, respectively.
[87]. Sulfuric acid with a concentration of, for The yield can be raised by partly replacing the
example, 79 % is heated to 170 ◦ C in a cast-iron chlorosulfuric acid with thionyl chloride. If this
or enamelled steel sulfonation vessel and finely is done, the raw material and wastewater treat-
divided benzene vapor is introduced through a ment costs are reduced, but the flue gas contains
perforated plate situated in the lower part of the sulfur dioxide in addition to hydrogen chloride.
vessel. A portion of the benzene vapor, of which Absorption of the gases in water recovers impure
an excess is used, is sulfonated, whereas the un- hydrochloric acid. The sulfur dioxide leaves the
converted portion continuously removes the wa- top of the hydrochloric acid recovery plant and
ter from the reaction mixture as it is formed. The can be used further in a sulfuric acid plant.
mixture of benzene and water vapor leaving the At the end of the reaction the products are
vessel is condensed; after phase separation the cooled and simultaneously forced into a vessel
benzene is returned to the evaporator. containing water. The benzenesulfonyl chloride
Continuous operation of this process gives a separates from the aqueous phase as a liquid or-
final product containing 80.2 % of benzenesul- ganic phase. It is then washed twice with water
fonic acid and 14.3 % of sulfuric acid; in batch and distilled; before that, the residual water is
operation the final product contains 93.1 % of removed in vacuo. The main bottom product of
sulfonic acid and 4.8 % of sulfuric acid. When the distillation column is diphenyl sulfone. The
adding sodium benzenesulfonate to the sulfona- reaction can be carried out in vessels of cast iron
tion mixture the sulfone formation can be kept or enameled steel.
below 2 % [88]. Uses. Benzenesulfonyl chloride is produced
Analysis. A sample is taken from the sul- on an industrial scale in Europe, the United
fonation reactor and is diluted with water. Un- States, and Japan. It is used as an intermedi-
converted benzene is determined by gas chro- ate for dyes and in the manufacture of benzene-
matography, benzenesulfonic acid and diphenyl sulfinic acid, sulfonamides, and sulfonic esters.
sulfone by high performance liquid chro- Benzenesulfonohydrazide serves as a blowing
matography. The sulfate concentration is de- agent in the production of foams (trade name:
termined at pH 2 – 3 by photometric titration Porofor BSH, Bayer).
with lead nitrate solution and dithizone (1,5-
diphenylthiocarbazone) indicator in aqueous Methyl Benzenesulfonate [80-18-2],
acetone solution [89]. C7 H8 O3 S, M r 172.20, bp20 mbar 150 ◦ C, d 17
4
Quality. Benzenesulfonic acid generally is 1.2730, is produced by treating benzenesulfonyl
sold as the sodium salt. This is almost colorless chloride with methanol in the presence of
and without substantial impurities except for a sodium carbonate [91] and is used as an alkyl-
small percentage of sodium sulfate. ation agent. Yield: 87 %.
Uses. Benzenesulfonic acid is used as an acid
catalyst. The sodium salt is used to standardize Ethyl Benzenesulfonate [515-46-8],
dyes. C8 H10 O3 S, M r 186.23, bp20 mbar 156 ◦ C, d 17
4
1.2192. Its manufacture and use are analogous
Benzenesulfonyl Chloride [98-09-9], to those of the methyl ester.
C6 H5 SO2 Cl, M r 176.62, bp1013 mbar 251.5 ◦ C,
bp13.3 mbar 120 ◦ C, mp 14.5 ◦ C, d 15 15 2-Chloroethyl Benzenesulfonate [27887-43-0],
1.3842. Benzenesulfonyl chloride is made by C8 H9 ClO3 S, M r 220.67, bp12 mbar 184 ◦ C, d 15
4
treating benzene with chlorosulfuric acid at 1.353, is produced by treating 2-chloroetha-
30 – 35 ◦ C [90]: nol and benzenesulfonyl chloride at 12 – 15 ◦ C
(at most 25 ◦ C) and adding sodium carbonate.
C6 H6 + 2 ClSO3 H −→ C6 H5 SO2 Cl + HCl + H2 SO4
The reaction product is diluted with water and

rendered alkaline by adding sodium carbonate.
The organic lower layer is removed and dis-
tilled in vacuo [92]. Yield: 87.8 %, calculated
on benzenesulfonyl chloride.
p-Chlorophenyl Benzenesulfonate and 2,4-

Dichlorophenyl Benzenesulfonate are impor-
tant as acaricides.
1
Benzenesulfonamide [98-10-2],
C6 H5 SO2 NH2 , M r 157.19, needles from water, N-(4-Aminophenyl)benzenesulfonamide
flakes from alcohol, mp 156 ◦ C. Obtainable from [5466-91-1], C12 H12 N2 O2 S, M r 248.3, mp
benzenesulfonyl chloride and ammonia. Used to 171 – 172 ◦ C. Made from the 4 -acetylami-
manufacture chloramine B and dichloramine B noanilide by splitting off the acetyl group in
(→ Chloroamines). an alkaline medium. Used as an intermediate
for dyes.
N-(Methyl)benzenesulfonamide [5183-78-8],
C7 H9 NO2 S, M r 171.22, bp22.5 mbar 202 ◦ C, mp N-(Phenylsulfonyl)benzenesulfonamide
30 ◦ C, freely soluble in dilute alkaline solutions. [2618-96-4], C12 H11 NO4 S2 , M r 297.35, mp
Produced in the same way as the amide. Used 157 – 158 ◦ C, poorly soluble in water and al-
as a plasticizer. cohol, insoluble in ether, slightly soluble in
acetone. Sodium salt: mp 314 – 316 ◦ C; anilin-
N-(Ethyl)benzenesulfonamide [5339-67-3], ium salt: mp 176 ◦ C. Manufactured by treating
◦
C8 H11 NO2 S, M r 185.25, mp 57 – 58 C. Ob- benzenesulfonamide in 5 % sodium hydrox-
tained as crystals from alcohol. Soluble in ex- ide solution with benzenesulfonyl chloride at
cess alkaline solution. Produced from benzene- 50 – 55 ◦ C (1 – 2 h). During the reaction the pH
sulfonyl chloride with ethylamine and sodium value must be kept at 7.2 by adding 5 % sodium
carbonate. Yield: 98.7 % [93]. hydroxide solution. At the end of the reaction the
disulfonylamine is precipitated from the clear
N-(Butyl)benzenesulfonamide [3622-84-2], solution by adding hydrochloric acid. Yield:
C10 H15 NO2 S, M r 213.23, oil. Used as a plasti- 70 – 98 % [95]. Additive for electroplating baths
cizer. [96].
Benzenesulfonohydrazide [80-17-1],
C6 H8 N2 O2 S, M r 172.21, mp 101 – 103 ◦ C, 2.2. 1,3-Benzenedisulfonic Acid
white powder, 1.48 g/cm3 , is used as a blow-
ing agent in foam manufacture (Porofor BSH, 1,3-Benzenedisulfonic acid [98-48-6] (1),
Bayer). C6 H6 O6 S2 , M r 238.24, is a hygroscopic sub-
stance with a solidification point of 137 ◦ C.
4-[N-(Phenylsulfonyl)amino]acetanilide
[565-20-8], C14 H14 N2 O3 S, M r 290.34, mp
157 ◦ C, crystallized from alcohol. Manufactured
by treating 4-(amino)acetanilide with benzene-
sulfonyl chloride in water at 65 ◦ C to which lime
is added [94]. The compound is used to manufac- 1
ture N-(4-aminophenyl)benzenesulfonamide. It is formed as the main product in
the sulfonation of benzene or benzenesul-
fonic acid with excess oleum at tempera-
tures of 80 – 250 ◦ C. In proportion to the
oleum concentration and reaction temperature
1 – 29 % of diphenyl sulfone disulfonic acid is vapor, a mixture of monosulfonic and disulfonic

formed as an undesired byproduct [97]. 1,4- acid is obtained which can be used directly to
Benzenedisulfonic acid is formed also, espe- produce phenol and resorcinol in the ratio 8 : 1
cially at high temperature, through rearrange- [99].
ment; mercury accelerates this process. At tem- Particularly pure 1,3-benzenedisulfonic acid
peratures of 240 – 250 ◦ C an equilibrium exists is obtained according to the process of Hooker
at a ratio of the p-acid to the m-acid of 1 : 2. Chemical Corp. [102]. Benzene is sulfonated
The disodium salt of 1,3-benzenedisulfonic with 96 % sulfuric acid at a molar ratio of the
acid is soluble in water at 27.5 ◦ C to the extent reactants of 1 : 3.4. The temperature is initially
of 41 %. With potassium or sodium hydroxide in 65 ◦ C, but is then raised to 80 ◦ C. The water of
aqueous solution under pressure it forms 3-hy- the reaction is then removed by evaporation at
droxybenzenesulfonic acid at 180 – 200 ◦ C. At 33 mbar and 200 ◦ C. Finally, during disulfona-
higher temperature resorcinol is formed. tion at 1.3 mbar and 210 – 235 ◦ C, sulfuric acid
and reaction water are distilled. The reaction
Industrial Production [98]. Benzene is in- product has a purity of 98.7 % and a solidifi-
troduced into a cast-steel agitator vessel contain- cation point of 136 ◦ C. The process also can be
ing 100 % sulfuric acid. The contents of the reac- operated continuously.
tor are heated to 100 ◦ C and kept at this temper- In a patent Koppers Co. [103] proposes that
ature for one hour. The products of the reaction the disulfonation and simultaneous removal of
(monosulfonation) are transferred to an agitator water and excess sulfuric acid be carried out
vessel containing 65 % oleum. in a thin-film evaporator at a film thickness of
The temperature rises from 30 to 80 ◦ C and is 0.5 – 3 mm and a residence time of one minute.
maintained at this level for another 1 – 2 h. The A vacuum of 13 mbar is claimed to be sufficient.
sulfonation mass is freed from sulfate ions in
the normal way by adding calcium hydroxide or Uses. 1,3-Benzenedisulfonic acid is used to
calcium carbonate and then removing the gyp- produce resorcinol and 3-hydroxybenzenesulfo-
sum. It is then converted with sodium carbonate nic acid.
into the disodium salt, which is dried on a drum
dryer. The yield is 93 % and the product has a 1,3-Benzenedisulfonyl Chloride [585-47-7],
purity of 96 %. C6 H4 Cl2 O4 S2 , M r 275.13, prisms from
In a process patented by Farbwerke Hoechst ether, mp 63 ◦ C, bp1.3 mbar 145 ◦ C,
◦
[25] benzenesulfonic acid is mixed simultane- bp27 mbar 210.7 C. Manufactured from m-
ously with benzene and sulfur trioxide at temper- benzenedisulfonic acid and phosphorus pen-
atures above 120 – 140 ◦ C. Sulfone formation is tachloride or from benzenesulfochloride and
prevented by adding 3 – 15 % of the disodium chlorosulfuric acid. The compound is used to
salt of benzenedisulfonic acid. The excess of produce 1,3-benzenedisulfonohydrazide.
sulfur trioxide is about 0.2 mol per mole of ben-
zene. The process can be operated continuously 1,3-Benzenedisulfonamide [3701-01-7],
or discontinuously. After being neutralized with C6 H8 N2 O4 S, M r 236.27, obtained as needles
sodium hydroxide solution the final product can from water, mp 229 ◦ C. Manufactured from m-
be melted to resorcinol directly. There is no ne- benzenedisulfochloride and aqueous ammonia.
cessity to remove sulfate ions. Excess sulfonat-
1,3-Benzenedisulfonohydrazide [4547-70-
ing agent can be removed by subsequent reac-
0], C6 H10 N4 O4 S2 , M r 266.31, white powder,
tion with benzene, toluene, or xylene. A mix-
mp 163 ◦ C (decomp.), 1.24 g/cm3 , is suit-
ture of resorcinol and phenol, cresol, or xylenol,
able as a blowing agent for foams (Porofor
is then formed by alkali fusion; the components
B 13 CP 50, Bayer).
of this mixture can be separated by distillation
[99–101].
If benzene is sulfonated with 30 % oleum at 2.3. Alkylbenzenesulfonic Acids
120 ◦ C in the presence of sodium sulfate and the
excess sulfuric acid is then converted into ben- This group of compounds comprises methyl-
zenemonosulfonic acid by introducing benzene benzenesulfonic acids (toluenesulfonic acids),
[25231-46-3], C7 H8 O3 S, M r 172.20, methyl- They are used as intermediates in the production

benzenedisulfonic acids (toluenedisulfonic of cresols and sulfobenzoic acids.
acids) C7 H8 O6 S2 , M r 252.26, dimethyl-
benzenesulfonic acids (xylenesulfonic acids) 2-Methylbenzenesulfonic Acid [88-20-0]
[58723-02-7], C8 H10 O3 S, M r 186.23, and their (2), o-toluenesulfonic acid, C7 H8 O3 S, M r
derivatives. 172.20, flaky crystals (dihydrate), mp 62.1 ◦ C.
Production. The sulfonation of toluene is

accomplished more easily than that of ben-
zene and is accompanied by less sulfone for-
mation. Low temperatures favor o-substitution;
m-substitution occurs only to the extent of about (2)
2 – 3 %. At temperatures around 100 ◦ C the ra- Produced together with 4-methylbenzene-
tio of o- to p-substitution is about 3 : 7. The sul- sulfonic acid by sulfonation of toluene with 96 %
furic acid concentration has a strong influence sulfuric acid at 40 ◦ C, or preferably with 1 mol
on the isomer ratio [104]. Surprisingly, almost of chlorosulfuric acid at 0 to −10 ◦ C. Used to
100 % p-substitution is obtained at −10 ◦ C if produce o-sulfobenzoic acid.
sulfur dioxide is used as the solvent [105].
At a sulfonation temperature of 100 ◦ C and 2-Methylbenzenesulfonyl Chloride
a sulfuric acid concentration of 97.4 %, 31 % [133-59-5], C7 H7 ClO2 S, M r 190.65, bp13 mbar
m-substitution is achieved [106]. Through re- 126 ◦ C, mp 15.5 ◦ C. Manufactured by treating
arrangement at 140 – 200 ◦ C the concentration toluene with chlorosulfuric acid at temperatures
of m-toluenesulfonic acid rises to about 46 % not exceeding 3 ◦ C, forcing the reaction mixture
[107], [108]. If this is followed by hydrolysis into ice, siphoning off the water, and centrifug-
with steam at 170 – 200 ◦ C, the concentration of ing 4-methylbenzenesulfonyl chloride. Used in
m-isomer rises to more than 90 % [109]. the production of toluenesulfonamide.
Isolation from the Mixture. p-Toluene- 2-Methylbenzenesulfonamide [88-19-7],
sulfonic acid can be crystallized from 66 – 71 % C7 H9 NO2 S, M r 171.22, mp 156.5 ◦ C, is ob-
sulfuric acid, or from concentrated hydrochloric tained by treating 2-methylbenzenesulfonyl
acid at temperatures below 0 ◦ C [110]. Then, chloride with aqueous ammonia (d 0.910). Pu-
according to the reaction conditions of the pre- rified by fractional precipitation: hydrochloric
ceding sulfonation, the o- or m-toluenesulfonic acid is added to a solution which has been ren-
acid can be obtained from the mother liquor. dered alkaline with sodium hydroxide; the im-
If the compounds are required to be very pure, purities are precipitated first. Used in the manu-
the route via the toluidines (diazotization and facture of saccharin (→ Sweeteners, Chap. 6.4.).
reaction with sulfur dioxide) is preferred [47].
2,6-Toluenedisulfonic acid can be obtained 3-Methylbenzenesulfonic Acid [617-97-0]
by adding 65 % oleum to the sulfonation re- (3), m-toluenesulfonic acid, C7 H8 O3 S, M r
action mixture while the temperature is be- 172.20. The pure acid can be obtained from
low 100 ◦ C and then raising the temperature to m-toluidine. Isomer mixtures with m-isomer
125 ◦ C. In 90 % sulfuric acid at 190 ◦ C, 64 % of concentrations of more than 50 % are obtained
the 2,4-toluenedisulfonic acid rearranges to 3,5- from toluene sulfonation mixtures by bubbling
toluenedisulfonic acid. The 3,5-isomer is iso- in toluene vapor at 180 – 205 ◦ C [113], see also
lated from hydrochloric acid solution at −15 ◦ C [109]. Used to manufacture m-cresol (→ Cresols
[111]. and Xylenols).
Uses. Toluenesulfonic acids are used as iso-
mer mixtures, or as mixtures with xylenesul-
fonic acids; they serve as solubilizers, as acidic
catalysts, and as additives for detergents [112].
(3)
3-Methylbenzenesulfonyl Chloride 190.65, bp25 mbar 138 – 139 ◦ C, mp 69 ◦ C.

[1899-93-0], C7 H7 ClO2 S, M r 190.65, bp29 mbar Formed as a byproduct in the manufacture of
146 ◦ C, mp 11.7 ◦ C. Obtained from m-toluidine 2-methylbenzenesulfonyl chloride, from which
according to [33]. Yield: 71.2 %. it can be separated by remelting several times
under water.
3-Methylbenzenesulfonamide [1899-94-1], This compound is used in the produc-
C7 H9 NO2 S, M r 171.22, mp 103 ◦ C. tion of sulfonamides, arylides, nuclear-
substituted toluenesulfonyl chlorides, 4-
4-Methylbenzenesulfonic Acid [104-15-4] (chloromethyl)benzenesulfonyl chloride, and
(4), p-toluenesulfonic acid, C7 H8 O3 S, M r p-toluenesulfinic acid. The tosylation of hy-
172.20, mp 38 ◦ C, monohydrate mp 106 ◦ C, droxyl groups, i.e., their esterification with p-
trihydrate mp 93 ◦ C, bp26.3 mbar 140 ◦ C. toluenesulfonyl chloride, serves to protect these
groups; this method is employed particularly
often in the chemistry of natural substances
[117].
4-Methylbenzenesulfonamide [70-55-3],
C7 H9 NO2 S, M r 171.22, mp 137 ◦ C, dihydrate
(4) mp 105 ◦ C, weak acid, soluble in aqueous al-
kali. Produced from the sulfonyl chloride with
Production. According to the process of Al- aqueous ammonia. Used in the production of
lied Chemical and Dye Corp. [114], boiling chloroamines, e.g., chloramine T and dichlo-
toluene is sulfonated with 90 – 95 % sulfuric ramine T (→ Chloroamines).
acid. Evaporating toluene is condensed, sepa-
rated from water, dried, and recycled. A mix- Methyl 4-Methylbenzenesulfonate
ture with a p-isomer content of 75 – 85 %, an [80-48-8], C8 H10 O3 S, M r 186.23, bp17 mbar
o-isomer content of 10 – 20 %, a m-isomer con- 168 – 170 ◦ C, mp 28 ◦ C, is obtained from the
tent of 2 – 5 %, and less than 1 % of sulfuric chloride of the acid by reaction with methanol;
acid is present at the end of the reaction. There important alkylating agent.
is very little sulfone formation. The process can
also be performed continuously in a vertical re- Ethyl 4-Methylbenzenesulfonate [80-40-0],
actor [116]. C9 H12 O3 S, M r 200.26, bp0.4 mbar 137 – 139 ◦ C,
The reaction of toluene in a continuous pro- bp12 mbar 165 – 166 ◦ C, mp 34 ◦ C, is obtained
cess with sulfur trioxide as sulfonating agent al- from the sulfonyl chloride and ethyl alcohol at
lows toluenesulfonic acid to be generated with −5 to 0 ◦ C after addition of 45 – 50 % sodium
high para selectivity and with the advantage of hydroxide solution [118]. Used as an alkylating
few byproducts and low waste-gas emissions agent and as a plasticizer.
[115].
For some purposes, for example, for use as 4-(Chloromethyl)benzenesulfonic Acid
an acidic catalyst or in cresol manufacture, the [46062-27-5], C7 H7 ClO3 S, M r 206.65, hy-
crude toluenesulfonic acid obtained according groscopic crystals, is obtained at a yield of
to the above processes does not have to be pu- 90 % through the action of chlorine on sodium
rified. Purification is possible by crystallization 4-methylbenzenesulfonate in the presence of
from 66 % sulfuric acid or via the barium salt. dichlorobenzene [119]. Used in the manufac-
Uses. The applications of 4-methylbenzene- ture of surfactants.
sulfonic acid include the manufacture of
4-formylbenzenesulfonic acid, p-sulfobenzoic 4-(Chloromethyl)benzenesulfonyl Chlo-
acid, 2-chlorotoluene-4-sulfonic acid, and 4- ride [2389-73-3], C7 H6 Cl2 O2 S, M r 225.09,
(chloromethyl)phenylmethanesulfonic acid. mp 64 – 65 ◦ C, bp20 mbar 183 – 195 ◦ C, is ob-
tained by treating 4-methylbenzenesulfonyl
4-Methylbenzenesulfonyl Chloride chloride with chlorine in the presence of PCl5
[98-59-9], tosyl chloride, C7 H7 ClO2 S, M r at 120 – 140 ◦ C.
Methyl 4-(Chloromethyl)benzenesulfonate 4-Methyl-1,3-benzenedisulfonyl Chloride

[89981-68-0], C8 H9 ClO3 S, M r 219.67, is used [2767-77-3], C7 H6 Cl2 O4 S2 , M r 289.16, mp
as a quaternizing agent. Reactions with tertiary 56 ◦ C, is produced from toluene and chlorosul-
amines, e.g., trimethylamine, give sulfobetaines furic acid at 120 ◦ C [122]. Addition of phos-
with fungistatic properties [120]. phorus pentoxide raises the yield [123].
4-Methyl-1,3-benzenedisulfonamide
[717-44-2], C7 H10 N2 O4 S2 , M r 250.30, mp
190 – 191 ◦ C.
2,4-Dimethylbenzenesulfonic Acid
[88-61-9] (7), m-xylenesulfonic acid,
C8 H10 O3 S, M r 186.23, dihydrate: mp 57 ◦ C,
4-(Acetylaminomethyl)benzenesulfonyl prisms or flakes. Produced by sulfonating m-
Chloride [39169-92-1] (5), C9 H10 ClNO3 S, xylene with concentrated sulfuric acid; the acid
M r 247.70, mp 95 – 97 ◦ C, is obtained from is precipitated by dilution with water. Of the
N-acetylbenzylamine and chlorosulfuric acid three isomeric xylenes, m-xylene is the one
[121]. most easily sulfonated. The ease of sulfonation
decreases in the order m>p>o, whereas the ease
of hydrolysis increases in the order o<m<p. m-
Xylenesulfonic acid is hydrolyzed at 180 ◦ C.
Used in the production of nitroxylenesulfonic
acid, chloroxylenes, and chloroxylenesulfonic
acids.
(5)
4-(Acetylaminomethyl)benzenesulfon-
amide [2015-14-7], C9 H12 N2 O3 S, M r 228.27,
mp 177 ◦ C (from water or aqueous alcohol), is (7)
produced from the sulfonyl chloride with aque-
ous ammonia at 15 and 70 ◦ C; yield 80 %. It is
an important intermediate in the manufacture of 2,4-Dimethylbenzenesulfonyl Chloride
4-(aminomethyl)benzenesulfonamide. [609-60-9], C8 H9 ClO2 S, M r 204.68, mp 34 ◦ C.
4-Methyl-1,3-benzenedisulfonic Acid 2,4-Dimethylbenzenesulfonamide [7467-

[121-04-0] (6), C7 H8 O6 S2 , M r 252.26, is a 12-1], C8 H11 NO2 S, M r 185.25, mp 138 ◦ C.
viscous oil. Obtained by additional sulfonation
2,5-Dimethylbenzenesulfonic Acid
of the o- and p-toluenesulfonic acid mixture
[609-54-1] (8), C8 H10 O3 S, M r 186.23, mp
with 66 % oleum at 125 ◦ C. Used in the manu-
48 ◦ C, bp 149 ◦ C (cathode vacuum), is solu-
facture of 4-formyl-1,3-benzenedisulfonic acid,
ble in chloroform. The dihydrate, mp 95 ◦ C, is
4-carboxy-1,3-benzenedisulfonic acid, and 4-
obtained by sulfonating p-xylene with 93 % sul-
methylresorcinol.
furic acid and removing the water by distillation
[124]. Used in the production of 2,5-xylenol.
(6)
(8)
2,5-Dimethylbenzenesulfonyl Chloride
[19040-62-1], C8 H9 ClO2 S, M r 204.68, mp
25.5 ◦ C, bp29 mbar 152 – 153 ◦ C.
2,5-Dimethylbenzenesulfonamide [6292-
58-6], C8 H11 NO2 S, M r 185.25, mp 148 ◦ C.
(10)
4-Ethylbenzenesulfonic Acid [98-69-1],
C8 H10 O3 S, M r 186.21, is produced by sul- 4-Vinylbenzenesulfonic acid has been pro-
fonating ethylbenzene with sulfuric acid. It is posed for copolymerization with acrylonitrile to
separated from the isomers via the aniline salt improve the dyeing properties of the fibers [134]
[125]. Used in the production of p-ethylphenol. and as a starting product in the manufacture of
polymeric styrenesulfonic acid [131], [132].
4-(2-Bromoethyl)benzenesulfonic Acid
[54322-31-5] (9), C8 H9 BrO3 S, M r 265.13; 4-Vinylbenzenesulfonamide [2633-64-9],
S-benzylisothiuronium salt, mp 149 – 150 ◦ C. C8 H9 NO2 S, M r 183.23, mp 138 – 139 ◦ C [135].
The acid is obtained by sulfonating 1 mol of
(bromoethyl)benzene with 1.1 mol of SO3 in 4-tert-Butyl-2,6-dimethylbenzenesulfonic
methylene chloride [126], see also [127], [128]. Acid [28188-48-9] (11), C12 H18 O3 S, M r
The potassium salt is obtained by treating the 242.31, is prepared from 1-tert-butyl-3,5-di-
sulfonyl chloride with potassium carbonate in methylbenzene with 5 % oleum at 20 – 45 ◦ C.
water [129]. Used in the manufacture of 4-tert-butyl-2,6-di-
methylphenol and 2,6-xylenol [136].
(9)
(11)
4-(2-Bromoethyl)benzenesulfonyl Chlo-
ride [64062-91-5], C8 H8 BrClO2 S, M r 283.58,
is produced from 2-(bromoethyl)benzene and 2,3-Dihydro-1H-indene-5-sulfonic acid
chlorosulfuric acid at temperatures not exceed- [40117-41-7] (12), C9 H10 O3 S, M r 198.24, is
ing 25 ◦ C [130]. Used in the production of 4- obtained by precipitation as a sodium salt, after
vinylbenzenesulfonic acid. 2,3-dihydro-1H-indene and concentrated sulfu-
ric acid have been reacted at 150 ◦ C [137]. At
4-(2-Bromoethyl)benzenesulfonamide low temperatures mainly 1H-indene-4-sulfonic
[5378-84-7], C8 H10 BrNO2 S, M r 264.15, mp acid is formed. 1H-Indene-5-sulfonic acid has
185.5 – 186 ◦ C. been proposed as a starting material for the man-
ufacture of sulfonylureas with hypoglycemic
4-Vinylbenzenesulfonic Acid [98-70-4] effects [138].
(10), C8 H8 O3 S, M r 184.21; p-toluidine
salt, mp 182 – 183 ◦ C, is obtained in
the form of the potassium salt from 4-
(2-bromoethyl)benzenesulfonic acid with (12)
methanolic KOH [131] or from 4-(2-
bromoethyl)benzenesulfonyl chloride with al-
coholic KOH [132]. The monomer can be sta- 2,3-Dihydro-1H-indene-5-sulfonyl Chlo-
bilized by adding 0.5 – 5 % of sodium nitrite ride [52205-85-3], C9 H9 ClO2 S, M r 216.69, mp
[133]. 49 ◦ C, bp21 mbar 180 ◦ C, is obtained by treating
the sodium salt of 1H-indene-5-sulfonic acid carbazone decomposes at 230 ◦ C. 4-

with PCl5 , or by the reaction of 2,3-dihydro- Formylbenzenesulfonic acid is produced by
1H-indene and chlorosulfuric acid at 0 – 15 ◦ C, oxidation of p-toluenesulfonic acid with man-
pouring onto ice, and extracting with chloroform ganese dioxide in 25 % oleum or by oxidation
[139]. of p-toluenesulfonyl chloride in glacial acetic
acid – acetic anhydride with chromium trioxide
2,3-Dihydro-1H-indene-5-sulfonamide and concentrated sulfuric acid at 0 ◦ C and hy-
[35203-93-1], C9 H11 NO2 S, M r 197.26, mp drolysis of the sulfonyl chloride of the aldehyde-
135 ◦ C. hydrate diacetate with dilute hydrochloric acid
[142].
2.4. Formylbenzenesulfonic Acids
2-Formylbenzenesulfonic Acid [91-25-8]

(13), C7 H6 O4 S, M r 186.18, is obtained as a
thick syrup by treatment of its barium salt with
sulfuric acid. Acquires a deep reddish-violet (14)
color if Schiff’s reagent is added. In contrast to
the poorly soluble barium salt, the sodium salt 4-Formyl-1,3-benzenedisulfonic Acid
is freely soluble in water; it is also freely soluble [88-39-1] (15), C7 H6 O7 S2 , M r 266.25, is freely
in hot, but not in cold, ethyl alcohol. soluble in water. The sodium salt crystallizes
with 2 mol of H2 O and is freely soluble in wa-
ter and poorly soluble in ethyl alcohol. It is
made by reaction of 2,4-dichlorobenzaldehyde
with sodium hydrogensulfite liquor or oxidation
of 2,4-toluenedisulfonic acid with manganese
(13)
dioxide in sulfuric acid. The acid is used in
Production. The starting material is o- the production of triphenylmethane dyes and
chlorobenzaldehyde, which is heated with wetting agents.
sodium hydrogensulfite solution in an auto-
clave to 190 – 200 ◦ C, with the result that its
chloro substituent is replaced by the sulfonic
acid group. The batch is allowed to cool, sulfuric
acid is added, and excess sulfur dioxide and un-
converted chlorobenzaldehyde are driven off by
boiling. The resulting solution is used directly (15)
in the manufacture of dyes. The acid can also
be produced by oxidation of o-toluenesulfonic
acid with oxygen in the presence of bromine and
cobalt as catalysts [140]. 2.5. Chlorobenzenesulfonic Acids
Uses. 2-Formylbenzenesulfonic acid is an
intermediate in the manufacture of optical 4-Chlorobenzenesulfonic Acid [98-66-8]
brighteners [141], trade names including Uvi- (16), C6 H5 ClO3 S, M r 192.62, mp 68 ◦ C, deli-
tex NFW (for textiles) and Tinopal CBS (for quescent needles, is soluble in water and ethanol.
detergents). Triphenylmethane dyes are pro- Prepared by sulfonation of chlorobenzene with
duced by condensation of the acid with various sulfuric acid; the water formed in the reaction is
N,N-dialkylanilines, N,N-dialkyl-m-aminophe- removed continuously. It can be hydrolyzed to
nols, and their sulfonic acids. chlorobenzene with steam at 190 ◦ C [143] and
is used in the manufacture of 4-chloro-3-nitro-
benzenesulfonic acid.
4-Formylbenzenesulfonic Acid [5363-54-2]
(14), C7 H6 O4 S, M r 186.18. The thiosemi-
3,4-Dichlorobenzenesulfonic Acid
[939-95-7] (18), C6 H4 Cl2 O3 S, M r 227.06,
is poorly soluble in water; the calcium salt
is freely soluble, barium and lead salts are
slightly soluble. Manufactured by sulfonating
o-dichlorobenzene with oleum [151].
(16)
4-Chlorobenzenesulfonyl Chloride
[98-60-2], C6 H4 Cl2 O2 S, M r 211.01, bp16 mbar
140 ◦ C, mp 55 ◦ C, is manufactured by mixing 4-
chlorobenzene and chlorosulfuric acid at 35 ◦ C,
heating for two hours at 80 ◦ C, and discharging (18)
the contents of the reactor into ice water; yield
81 % of theory, together with a small amount of 3,4-Dichlorobenzenesulfonyl Chloride
bis(4-chlorophenyl) sulfone [145], [146]. Used [98-31-7], C6 H3 Cl3 O2 S, M r 245.51, fp 22.4 ◦ C,
in the manufacture of chlorobenzenesulfinic is manufactured from o-dichlorobenzene and
acid and sulfimides; three-step reaction to the chlorosulfuric acid; used as an inexpensive acy-
sulfone in a single reactor is possible without lating agent.
intermediate isolation [147].
4-Chlorobenzenesulfonamide [98-64-6], 3,4-Dichlorobenzenesulfonamide [23815-

C6 H6 ClNO2 S, M r 191.63, mp 146 ◦ C, is freely 28-3], C6 H5 Cl2 NO2 S, M r 226.08, mp 140 ◦ C.
soluble in ethyl alcohol, ether, and hot water.
2,4,5-Trichlorobenzenesulfonic Acid
4-Chloro-N-[ (4-chlorophenyl)sulfonyl]- [6378-25-2] (19), C6 H3 Cl3 O3 S, M r 261.51,
benzenesulfonamide [2725-55-5], is obtained in the form of the sodium salt by
C12 H9 Cl2 NO4 S2 , M r 366.24, mp 298 ◦ C (from sulfonating 1,2,4-trichlorobenzene with 25 %
water), is prepared by treating the corresponding oleum and pouring the clear sulfonation mix-
sulfonyl chloride with 0.45 mol of ammonium ture into a solution of sodium chloride in water;
chloride at 0 – 3 ◦ C, with dropwise addition of yield 94 – 95 %.
sodium hydroxide solution at pH 8; yield 91 %
[148]. Used as a reagent for identifying amines.
2,5-Dichlorobenzenesulfonic Acid
[88-42-6] (17), C6 H4 Cl2 O3 S, M r 227.06, crys-
tals, freely soluble in water. Obtained by sul-
fonating 1,4-dichlorobenzene with oleum. (19)
2,4,5-Trichlorobenzenesulfonyl Chloride
[15945-07-0], C6 H2 Cl4 O2 S, M r 279.96, mp
65 – 67 ◦ C (from petroleum ether), bp0.6 mbar
(17) 138 ◦ C, is obtained from trichlorobenzene by
chlorosulfonation with chlorosulfuric acid at
90 ◦ C and pouring the reaction mass into water
2,5-Dichlorobenzenesulfonyl Chloride [152–154].
[5402-73-3], C6 H3 Cl3 O2 S, M r 245.51, mp Esters and amides of several chlorobenzene-
39 ◦ C, needles (from ethyl alcohol), is made sulfonic acids (particularly 4-chlorobenzenesul-
by treating 1,4-dichlorobenzene with chlorosul- fonic acid, 2,5-dichlorobenzenesulfonic acid,
furic acid at 150 ◦ C and stirring into ice water;
yield 85 % [149]. It has been described as a
modifier for Nylon 6 [150].
and 2,4,5-trichlorobenzenesulfonic acid) have reduced to 2,2 -diaminodiphenyl disulfide and

acquired some importance as crop protection then oxidized with hydrogen peroxide in aque-
products and agents for the control of fiber pests. ous sulfuric acid to 2-aminobenzenesulfonic
acid [161], [162].
2,2 -Diamino-diphenyldisulfide can also be
2.6. Aminobenzenesulfonic Acids arrived at by alkaline hydrolysis of benzothia-
zole or mercaptobenzothiazole, followed by ox-
The rearrangement of the N-phenylsulfamic idation with hydrogen peroxide. The additional
acid initially formed in the sulfonation of aniline oxidation leading to 2-aminobenzenesulfonic
is dependent on temperature. At elevated tem- acid can be performed in alkaline solution. Thus
peratures it gives 4-aminobenzenesulfonic acid the synthesis starting from benzothiazole can be
almost quantitatively. carried out exclusively in alkaline solution in a
Even at low temperatures, the two other single reactor [163]. Yield: 70 %, based on ben-
isomers are formed in only relatively small zothiazole.
amounts. They are therefore manufactured in-
dustrially in other ways (see below). 2-Aminobenzenesulfonamide [3306-62-5],
For identification, aromatic aminosulfonic C6 H8 N2 O2 S, M r 172.21, mp 153 ◦ C, crystals
acids cannot be converted into amides via (from water), is freely soluble in water, glacial
the sulfonyl chlorides; they must first be con- acetic acid, ethyl alcohol, acetone, and metha-
verted to the corresponding chlorobenzenesul- nol; insoluble in benzene.
fonic acids by Sandmeyer’s reaction [155], and
then derivatized. Today, identification is by 2-Amino-N-methylbenzenesulfonamide
HPLC. [16288-77-0], C7 H10 N2 O2 S, M r 186.23, is ob-
tained by treating 2-nitrobenzenesulfonyl chlo-
2-Aminobenzenesulfonic Acid [88-21-1], ride with methylamine and subsequent reduc-
C6 H7 NO3 S, M r 173.19, is obtained as a tion. Used as a dye component [164].
byproduct in the manufacture of 3-ami- The amides of 2-aminobenzenesulfonic acid
nobenzenesulfonic acid by nitration of benzene- can be treated with aldehydes or orthoformic
sulfonic acid at 100 ◦ C, separation of the result- acid esters to give 1,2,4-benzothiadiazine 1,1-
ing nitrobenzenesulfonic acids via the magne- dioxides or their dihydro compounds; these sub-
sium salts, and reduction with iron turnings. stances have been proposed as diuretics [165].
In the reaction between amidosulfuric (sul-
famic) acid and excess aniline at temperatures 2-Amino-N-(phenylsulfonyl) benzene-
up to 160 ◦ C, 2-aminobenzenesulfonic acid and sulfonamide, C12 H12 N2 O4 S2 , M r 312.37, mp
4- aminobenzenesulfonic acid are obtained in a 193 – 194 ◦ C, is obtained by treating 2-nitroben-
ratio of 3 : 2 [156]. The two isomers are sepa- zenesulfonyl chloride with benzenesulfonamide
rated by means of their different solubilities in at 70 ◦ C in the presence of aqueous sodium hy-
aqueous KOH [157]. droxide solution and subsequent reduction of
2-Aminobenzenesulfonic acid is obtained the nitro group [87]. Used as a component of
from 2-nitrothiophenol by boiling in a mixture azo dyes.
of dioxane and water (ratio 20 : 1) for seven Phenyl 2-Aminobenzenesulfonate [68227-
hours; the yield is 86.7 % of theory [158]. 69-0], C12 H11 NO3 S, M r 249.29, mp 70 ◦ C,
The acid can also be produced as follows: is obtained by treating 2-nitrobenzenesulfonyl
2-chloronitrobenzene is reacted with sodium chloride with sodium phenolate and subsequent
disulfide in aqueous alcoholic solution to form reduction of the nitro group. Used as an azo dye
2,2 -dinitrodiphenyldisulfide. After having been component.
dissolved in a mixture of hydrochloric acid and
nitric acid this is oxidized with chlorine to form 3-Aminobenzenesulfonic Acid (metanilic
2-nitrobenzenesulfonyl chloride [159], which acid) [121-47-1], C6 H7 NO3 S, M r 173.19, can
is then hydrolyzed with soda solution and fi- be obtained by sulfonation of aniline sulfate
nally reduced with iron turnings [160]. Alterna- with oleum and boric acid at 20 – 50 ◦ C. The
tively 2,2 -dinitrodiphenyl disulfide can first be yield is 98 % [166].
Production. For industrial production, how- actor. The reaction mass is spread on trays and
ever, nitrobenzene is sulfonated to m-nitroben- baked in an oven at 190 – 220 ◦ C, the water of
zenesulfonic acid, which is then reduced either the reaction being removed continuously. The
with iron [167], [168] or catalytically with hy- process is complete if a sample dissolves clearly
drogen [169]. in a dilute alkaline solution and has practically
Crude 3-aminobenzenesulfonic acid can be no smell of aniline. The crude product is dis-
used directly, either as a solution or dried, to ob- solved as a sodium salt in water that has been
tain 3-aminophenol by alkali fusion. It is not suf- rendered alkaline with sodium carbonate solu-
ficiently pure for use in dye manufacture, how- tion; traces of aniline are removed by blowing
ever. Therefore the crude solution is acidified; with steam. The solution is clarified by filtration
after filtration the product thus obtained is of and can then be processed further immediately.
satisfactory purity. The baking operation can be carried out in vacuo,
3-Aminobenzenesulfonic acid is used in the which facilitates the removal of the water of the
manufacture of dyes and optical brighteners reaction.
[170]. It is also used to manufacture 3-hydroxy- In industrial manufacture the aniline hydro-
benzenesulfonic acid and 3-aminophenol. The gensulfate is placed on trays in trolleys and
latter is an important intermediate in the man- these are passed at constant speed through a
ufacture of 4-amino-2-hydroxybenzoic acid (p- tunnel-shaped oven against an air current at
aminosalicylic acid) used to fight tuberculosis. 260 – 280 ◦ C. The aniline hydrogensulfate is
thus brought to the baking temperature very
3-Aminobenzenesulfonamide [98-18-0], gradually. It leaves the oven after 12.5 h [173].
C6 H8 N2 O2 S, M r 172.21, mp 142 ◦ C, is poorly According to [174] the reaction can be carried
soluble in cold water. out in a fluidized bed consisting of sulfanilic
acid.
3-Amino-N-(phenylsulfonyl)benzenesul- The baking process can also be carried out in
fonamide, C12 H12 N2 O4 S2 , M r 312.37, is ob- a multiphase reactor, with a resultant shortening
tained by treating 3-nitrobenzenesulfonyl chlo- of reaction time and improvement in quality of
ride with benzenesulfonamide and subsequent the end product [175]. The baking process can be
reduction of the nitro group. It is used as a dye simplified if the formation of the aniline salt and
component [171]. The use of the N-acrylsulfon- subsequent rearrangement are carried out suc-
amide in the polymerization of acrylonitrile has cessively or simultaneously in a solvent, e.g.,
been proposed to improve the dyeing properties diphenyl sulfone [67] or 1,2-dichlorobenzene
of the fibers [172]. [176]; this enables the reaction mass to be stirred
throughout the production process [177]. Partic-
4-Aminobenzenesulfonic Acid (sulfanilic ularly high yield and end product purity can be
acid) [121-57-3], C6 H7 NO3 S, M r 173.19, is achieved if the reactants are used in a molar ratio
made by the reaction of aniline with sulfuric of 1 : 1; the rearrangement is carried out under
acid at temperatures above 190 ◦ C: a slight positive pressure (1 – 3 bar) and at 200 –
240 ◦ C; water vapor is expelled from the reactor
simultaneously [178]. The reaction time is three
hours.
Analysis. The assay is carried out by diazoti-
zation. Impurities (aniline, 2,4-disulfanilic acid,
2- and 3-aminobenzenesulfonic acid) are deter-
mined by HPLC.
Uses. 4-Aminobenzenesulfonic acid is an
important intermediate in the production of
dyes, pesticides, pharmaceuticals, etc.
4-Aminobenzenesulfonamide [63-74-1],
Production. Equimolar amounts of aniline C6 H8 N2 O2 S, M r 172.21, forms the basis for
and sulfuric acid are reacted in a lead-lined re- chemotherapeutical sulfonamides.
4-(Acetylamino)benzenesulfonic Acid
[121-62-0], C8 H9 NO4 S, M r 215.23, is pro-
duced by dissolving aminobenzenesulfonic acid
in water, adding sodium carbonate, acetylating
with acetic anhydride at 45 – 50 ◦ C, and salt-
ing out with sodium chloride; the yield is 82 % (20)
[179].
4-(Acetylamino)benzenesulfonyl Chloride 5-Amino-1,3-benzenedisulfonyl Chloride,

[121-60-8], C8 H8 ClNO3 S, M r 233.67, mp C6 H5 Cl2 NO4 S2 , M r 290.14, is obtained from
149 ◦ C (from benzene), is relatively stable to the sodium salt or free acid with chlorosulfuric
water; therefore it can be precipitated from al- acid at 100 – 160 ◦ C [182].
coholic solutions with water. It is freely soluble
in diethyl ether and ethyl acetate; obtainable as 5-Amino-N,N-bis(2-chloroethyl)-1,3-
an anhydrous product from the aqueous paste if benzene-disulfonamide [22480-69-9],
this is subjected to azeotropic distillation with a C10 H15 Cl2 N3 O4 S2 , Mr 376.28, mp
water-immiscible solvent at a low temperature. 126 – 128 ◦ C, is formed by treating the dichlo-
Production (see also [180] ). Acetanilide is ride with 2-chloroethylamine [183], [184].
introduced into stirred chlorosulfuric acid so-
lution at 20 ◦ C. The solution is then heated to 4-Amino-1,3-benzenedisulfonic Acid
55 ◦ C and kept at this temperature for 1.5 h. The [137-51-9] (21), C6 H7 NO6 S2 , M r 253.25, crys-
solution is cooled to 20 ◦ C and introduced as a tallizes with two moles of H2 O. The com-
thin jet into water, the temperature of which is pound is freely soluble in water and ethyl
kept at 0 – 5 ◦ C by external cooling. The pre- alcohol. It is prepared by sulfonating 4-ami-
cipitated sulfochloride is filtered and washed nobenzenesulfonic acid with oleum at 20 ◦ C
with cold water until neutral to Congo Red. and 130 ◦ C (4 – 6.5 h), draining the sulfonation
Yield is 80 – 82 %. The crude product contains mixture into water under pressure, adding lime
about 60 % water; the dried product melts at at 70 – 75 ◦ C, separating the resulting gypsum,
144 – 147 ◦ C. About 1 – 2 % of bis(acetylami- precipitating the calcium ions with soda, remov-
nophenyl) sulfone is obtained as a byproduct. ing the calcium carbonate formed, and concen-
If thionyl chloride is added, less chlorosul- trating the sodium salt solution by evaporation.
furic acid is needed because it can be replaced Yield 90 – 91 % [185].
partly by oleum. The product is stable for sev-
eral days if kept in a cool place. It is generally
used directly in the moist state. 4-(Acetylami-
no)benzenesulfonyl chloride is an important in-
termediate in the manufacture of sulfonamides
and in the synthesis of parabase ester [181].
(21)
4-(Acetylamino)benzenesulfonamide
[121−61−9], C8 H10 N2 O3 S, M r 214.24, 4-Amino-1,3-benzenedisulfonamide
mp 219 ◦ C, is obtained from 4-acetylami- [40642−90−8], C6 H9 N3 O4 S2 , M r 251.28, mp
nobenzenesulfonyl chloride and aqueous am- 235 ◦ C, crystals (from water). The compound is
monia at temperatures not exceeding 30 ◦ C. used as a dye intermediate.
Uses include the manufacture of sulfanilamide.
2-Amino-1,4-benzenedisulfonic Acid
5-Amino-1,3-benzenedisulfonic Acid [98-44-2] (22), C6 H7 NO6 S2 , M r 253.25, is ob-
[5294-05-3] (20), C6 H7 NO6 S2 , M r 253.25, tained by sulfonating metanilic acid in 100 %
is obtained by reduction of 5-nitro-1,3- sulfuric acid with 50 % oleum at 160 ◦ C (5 – 6 h);
benzenedisulfonic acid. the sulfonation mixture is diluted with water,
lime is added, and the resulting calcium sulfate
is removed; the product is then precipitated with 4,6-Diamino-1,3-benzenedisulfonic Acid

excess concentrated hydrochloric acid in hot [137-50-8] (24), C6 H8 N2 O6 S2 , M r 268.27, is
solution; yield 90 – 91 % [186]. obtained from m-phenylenediamine by sulfona-
tion with excess oleum at 70 – 130 ◦ C. Used as
an intermediate for dyes [193], [194].
(22)
The trisulfonic and tetrasulfonic acids formed (24)

in this sulfonation process are unstable in hot
aqueous solution. When water is added to the
sulfonation mass they eliminate sulfonic acid 2,5-Diamino-1,4-benzenedisulfonic Acid
groups, thus forming the end product; see also [7139-89-1] (25), C6 H8 N2 O6 S2 , M r 268.27,
[187]. It is also possible to start from 4-chloro- is obtained from p-phenylenediamine and
3-nitrobenzenesulfonic acid, in which case sul- 25 % oleum at 140 ◦ C [195] or by heat-
fite is used to replace the chlorine by the sul- ing p-phenylenediamine sulfate and 98 %
fonic acid group and the resulting 2-nitro-1,4- sodium hydrogen sulfate in a mixture of 1,2,4-
benzenedisulfonic acid is then reduced [188]. trichlorobenzene and 1-chloronaphthalene to the
Compound 22 is used as an intermediate boiling point of the solvent mixture (215 ◦ C), re-
for dyes; for example, see [189]. 2-Amino-1,4- moving the solid product, dissolving it in water,
benzenedisulfonic acid is converted to triazine neutralizing it with sodium hydroxide solution
derivatives, which are intermediates in the man- to pH 7.5 – 8, and clarifying the solution with
ufacture of dyes and optical brighteners [190], kieselguhr. The product contains 5 % of mono-
[191]. sulfonic acid, but only a small amount of the
isomeric 2,6-disulfonic acid; yield 90 % [196].
2,4-Diaminobenzenesulfonic Acid [88-63-1] The compound is used as an intermediate for
(23), C6 H8 N2 O3 S, M r 188.2, monoclinic plates dyes.
or triclinic prisms, poorly soluble in cold wa-
ter, is obtained by sulfonating a solution of m-
phenylenediamine in 100 % sulfuric acid with
oleum at 155 ◦ C, adding water to the sulfonation
mixture, desulfonating the resulting disulfonic
acids at 140 ◦ C, and isolating the free acid at
10 ◦ C; yield 93 % [192]. Another process starts (25)
from 1-chloro-2,4-dinitrobenzene, which, as an
alcoholic solution, is reacted with sodium sul-
fite solution to form 2,4-dinitrobenzenesulfonic 2.7. Hydroxybenzenesulfonic Acids
acid [89-02-1], from which the end product is
obtained by reduction with iron according to The chemical properties of the phenolsulfonic
Béchamp [188, pp. 99, 100]. acids are characterized by the reactive aromatic
hydroxyl group. The reactions of these acids
therefore include azo coupling reactions with
diazonium salts to form azo dyes. Hydroxyben-
zenesulfonic acids with more than one hydroxyl
group on the benzene nucleus form complexes
with metal ions.
(23)
2-Hydroxybenzenesulfonic Acid [609-46-1]
(26), C6 H6 O4 S, M r 174.17, mp 145 ◦ C (mono-
hydrate); aniline salt mp 165 ◦ C; potassium salt Production: phenol (25 kg) and 96 % sulfu-
(dihydrate) mp 235 – 240 ◦ C. If phenol is sul- ric acid (28 kg) are heated to 50 ◦ C; then 1.25 kg
fonated with an equal amount of 100 % sulfuric additional sulfuric acid is added and the reaction
acid under mild conditions, a mixture consist- mixture is heated at 110 ◦ C for 5 – 6 h. Reaction
ing of 2-hydroxy- and 4-hydroxybenzenesulfo- water, together with about 5 % of the phenol, is
nic acid in a ratio of roughly 2 : 3 is obtained. distilled off during this period. Yield 95 % [200].
The 2-hydroxybenzenesulfonic acid can be iso- Crude 4-hydroxybenzenesulfonic acid ob-
lated from this mixture via the monobarium salt tained by hot sulfonation, i.e., mixed with 2-
[197]. The pure compound is obtained by diazo- hydroxybenzenesulfonic acid, is used as such
tizing 2-aminobenzenesulfonic acid and boiling in the manufacture of synthetic tanning agents.
it under acid conditions. Condensation products of phenolsulfonic acid
mixtures with formaldehyde improve the dye-
ing properties of polyamide fibers [201].
4-Hydroxybenzenesulfonic acid and 2-
halogenomalonic esters form the corresponding
ethers, which are used in the manufacture of
(26)
polyesters with improved affinity for basic dyes
[202].
3-Hydroxybenzenesulfonic Acid [585-38-6] If a mixture of hydroxybenzenesulfonic acids
(27), C6 H6 O4 S, M r 174.17; potassium salt and bis(hydroxyphenyl) sulfone is condensed
(monohydrate) mp 200 – 210 ◦ C; sodium salt with formaldehyde, and hydrogensulfite is sub-
(from ethyl alcohol) mp 314 ◦ C, is synthesized sequently added, substances with good dispers-
by the reaction of 1,3-benzenedisulfonic acid ing effects on dyes are obtained. They also are
and sodium hydroxide in water in an autoclave used as thinning agents for cement [203], [204].
for 30 h at 250 ◦ C. The reaction mass is neutral- Most of the 4-hydroxybenzenesulfonic acid
ized and evaporated to dryness. The sodium salt is used as an additive for electroplating baths.
of the acid is extracted with 78 % ethyl alcohol; By comparison, the acid is relatively unimpor-
yield 78 % [198]. The crude solution obtained tant as a dye intermediate. With ethylene oxide
by acidifying the reaction mass with hydrochlo- it forms poly(ethoxy)oxybenzenesulfonic acid,
ric acid and freeing it from sulfur dioxide by which can be used as a plasticizer and emulsifier.
boiling can be used in the manufacture of dyes
[199]. 4-Methoxybenzenesulfonic Acid
[5857-42-1] (29), C7 H8 O4 S, M r 188.20, am-
monium salt mp 285 ◦ C. The acid is obtained
by sulfonation of anisole. The ammonium salt
of (29) can be obtained in high yield by treat-
ing anisole with an equal mass of sulfamic
(27) acid at 140 – 150 ◦ C [205]. The compound is
used in the manufacture of 4-methoxybenzene-
sulfonylureas, which have hypoglycemic ef-
4-Hydroxybenzenesulfonic Acid [98-67-9] fects.
(28), C6 H6 O4 S, M r 174.17, aniline salt mp
170 ◦ C, S-benzylisothiuronium salt (monohy-
drate) mp 168.7 ◦ C.
(29)
(28) 4-Hydroxy-1,3-benzenedisulfonic Acid

[96-77-5] (30), C6 H6 O7 S2 , M r 254.24, hy-
groscopic crystals, is obtained by hydrolysis of

the dichloride with ethyl alcohol and/or water.
Nitration and reduction of this acid gives 5-
amino-4-hydroxy-1,3-benzenedisulfonic acid.
4-Hydroxy-1,3-benzenedisulfonic acid acceler-
ates the rearrangement of cumene hydroperox-
ide in the Hock – Lang phenol process [206]. (32)
4,5-Dihydroxy-1,3-benzenedisulfonic Acid
[149-46-2] (33), C6 H6 O8 S2 , M r 270.23, is pro-
duced by sulfonation of pyrocatechol with
oleum [211] or by alkali fusion of 2-hydroxy-
1,3,5-benzenetrisulfonic acid: 10 kg of the tetra-
(30)
sodium salt of phenoltrisulfonic acid is intro-
duced into 16 kg of sodium hydroxide at about
4-Hydroxy-1,3-benzenedisulfonyl Chlo- 20 ◦ C. After adding some water, the temperature
ride [1892-33-7], C6 H4 Cl2 O5 S2 , M r 291.13, is gradually raised to 160 ◦ C; at the end of the re-
mp 89 ◦ C, needles (from gasoline), is obtained action the melt is diluted with water and acidified
by treating phenol with chlorosulfuric acid and with sulfuric acid, and sulfur dioxide is driven
introducing the sulfonation mixture into con- off. After cooling, precipitated sodium sulfate
centrated hydrochloric acid [207]. is removed by filtration and excess sulfate ions
are precipitated in fractions. Finally the barium
2,4-Dihydroxybenzenesulfonic Acid salt, which has poor solubility in cold water, is
[6409-58-1] (31), C6 H6 O5 S, M r 190.17, am- precipitated.
monium salt (from ethyl alcohol) mp 190 ◦ C
[208]. The acid is prepared by sulfonating re-
sorcinol with 96 % sulfuric acid in a molar ratio
of 1 : 1. The compound is used as a catalyst in
the curing of resins [209].
(33)
The disodium salt of 33, which is referred to

in the literature as Tiron [212], serves to detect
traces of iron in blood and is used as a reagent for
colorimetric determination of Ti4+ and Mo4+ .
(31) The ability to form water-soluble complex salts,
e.g., with antimony, has been exploited in phar-
3,4-Dihydroxybenzenesulfonic Acid macology [213]. Tiron is claimed to improve the
[7134-09-0] (32), C6 H6 O5 S, M r 190.17, del- storability of silver halogenide emulsions [214].
iquescent crystals; the ammonium salt (flakes,
from aqueous ethanol) melts at 260 ◦ C (de-
comp.). Synthesis: 0.3 mol of disodium 4- 2.8. Chloro-alkylbenzenesulfonic Acids
hydroxy-1,3-benzenedisulfonate is reacted with
1.2 mol of sodium hydroxide for 36 min at 3-Chloro-4-methylbenzenesulfonic Acid
340 ◦ C; the reaction mass is diluted with wa- [98-34-0] (34), C7 H7 ClO3 S, M r 206.65, de-
ter, acidified with sulfuric acid, and boiled to composes above 110 ◦ C. Production is from
remove sulfur dioxide; the product is extracted toluene by sulfonation with anhydrous sulfu-
with ether. Yield 80 %. Pyrocatechol is obtained ric acid, followed by chlorination with gaseous
by hydrolyzing the sulfonic acid group at 190 ◦ C chlorine [215].
[210].
of H2 O. The acid is formed as the main prod-

uct in the sulfonation of 4-chlorotoluene with
100 % sulfuric acid at 100 ◦ C. It is purified
by recrystallizing the barium salt. The com-
pound is used in the production of 5-chloro-2-
formylbenzenesulfonic acid.
(34)
3-Chloro-4-methylbenzenesulfonic acid is
an intermediate in the manufacture of 2-
chlorotoluene, 5-chloro-4-methyl-2-nitroben-
zenesulfonic acid, 2,4-dichlorobenzoic acid, and
(35)
2-chloro-4-sulfobenzoic acid.
3-Chloro-4-methylbenzenesulfonyl Chlo- 4-Chloro-3-(trifluoromethyl)benzene-

ride [42413-03-6], C7 H6 Cl2 O2 S, M r 225.09, sulfonyl Chloride [32333-53-2] (36),
bp32 mbar 166 ◦ C, mp 38 ◦ C, is obtained by chlo- C7 H3 Cl2 F3 O2 S, M r 279.06, bp16 mbar
rination of 4-methylbenzenesulfonyl chloride in 128 – 131 ◦ C, n20
D 1.5158, is obtained from 2-
the presence of iron trichloride or antimony chloro-α,α,α-trifluorotoluene and chlorosulfu-
trichloride. ric acid in 65 % oleum [217]. The compound
A high yield of sulfochloride with only is used as an intermediate in the production of
a small percentage of isomers is obtained if pesticides and dyes [217].
toluene is sulfonated with sulfur trioxide in 1,2-
dichloroethane. The resulting sulfonic acid is
chlorinated in the presence of iodine, and the
resulting chlorobenzenesulfonic acid is reacted
with chlorosulfuric acid. The crude product can
be used immediately in the production of 2,4-
dichloro-α,α,α-trifluorotoluene, which is a pre- (36)
cursor of several herbicides [216].
3,5-Dichloro-4-methylbenzenesulfonic
Acid [2225-18-5], C7 H6 Cl2 O3 S, M r 241.09,
is obtained (in addition to tri- and
tetrachlorotoluenesulfonic acids) from 4-
toluenesulfonic acid by chlorination with chlo-
rine or sulfuryl chloride in sulfuric acid [218],
or by hydrolysis of the sulfonyl chloride (see
next paragraph). The compound is used as
an intermediate in the manufacture of 2,6-
dichlorotoluene.
3,5-Dichloro-4-methylbenzenesulfonyl
Chloride [24653-79-0], C7 H5 Cl3 O2 S, M r
259.54, is formed from 4-toluenesulfonyl chlo-
3-Chloro-4-methylbenzenesulfonamide ride by chlorination with chlorine, antimony
[51896-27-6], C7 H8 ClNO2 S, M r 205.66, melts trichloride being added as a catalyst [219]. The
at 137 ◦ C. compound is used as an intermediate in the
manufacture of 2,6-dichlorotoluene [218].
5-Chloro-2-methylbenzenesulfonic Acid
[133-73-3] (35), C7 H7 ClO3 S, M r 206.65; the
sodium salt crystallizes from water with 1/2 mol
2.9. Amino-alkylbenzenesulfonic Acids
2-Amino-5-methylbenzenesulfonic Acid
[88-44-8] (37), C7 H9 NO3 S, M r 187.22, crystal-
lizes with 1 mol of H2 O. It is produced by baking
p-toluidine sulfate at 180 ◦ C and 97 – 101 mbar,
(39) (40)
dissolving the product in 3 % sodium hydrox-
ide solution, and precipitating the free acid by 4-Amino-3-methylbenzenesulfonic Acid
adding concentrated hydrochloric acid [220, [98-33-9] (41), C7 H9 NO3 S, M r 187.22, crys-
222]. tallizes with 1 mol of H2 O. It is prepared from
o-toluidine and 98 % H2 SO4 via the sulfate,
which is then baked. The sodium salt can be iso-
lated after liming and precipitation of calcium
sulfate [224]. The solution can be used directly
in the manufacture of dyes [225].
(37)
2-Amino-3,5-dimethylbenzenesulfonic
Acid [88-22-2] (38), C8 H11 NO3 S, M r 201.24;
the barium salt crystallizes from water with
2 mol of H2 O; the lead salt is very poorly solu-
(41)
ble in water. Production is from 4-amino-1,3-di-
methylbenzene (m-xylidine) and 96 % sulfuric
acid by baking the sulfate paste in vacuo, subse- 4-Amino-2-methylbenzenesulfonic Acid
quently purifying the product with boiling milk [133-78-8] (42), C7 H9 NO3 S, M r 187.22, crys-
of lime, and finally precipitating the sodium tallizes from water with 3 mol of H2 O. It is
salt with sodium chloride [223]. 2-Amino-3,5- produced analogously to 4-amino-3-methyl-
dimethylbenzenesulfonic acid can also be pro- benzenesulfonic acid by baking of m-toluidine
duced by sulfonation of m-xylidine in 1,1,2,2- sulfate [226].
tetrachloroethane with chlorosulfuric acid and
subsequent boiling until no more hydrogen chlo-
ride is formed.
(42)
(38)
3-Amino-4-methylbenzenesulfonic Acid 2.10. Amino- and

[618-03-1] (39), and 5-Amino-2-methyl- Hydroxycarboxybenzenesulfonic Acids
benzenesulfonic Acid [118-88-7] (40),
C7 H9 NO3 S, M r 187.22; both compounds 2-Amino-4-sulfobenzoic Acid [98-43-1]
are produced analogously to the 3-ami- (43), C7 H7 NO5 S, M r 217.2, 2,4-sulfanthranilic
nobenzenesulfonic acids from the correspond- acid, crystallizes with 1 mol of H2 O; it is freely
ing nitrotoluenesulfonic acids by Béchamp re- soluble in hot water, less soluble in cold water.
duction. The compound is obtained at a moderate yield by
treating 4-methyl-3-nitrobenzenesulfonic acid
with sodium hydroxide solution:
2-Hydroxy-5-sulfobenzoic acid forms a di-

hydrate and is used in analytical chemistry to
detect albumins, iron, and mercury [231]. Appli-
cations described in patents include the use as a
heat stabilizer for polyacrylonitrile [232], as an
additive used in the anodizing of metals [233–
235], and – as a tributyltin compound – as an
agent for the antibacterial protection of organic
This acid is used mainly in the man- materials [236]. The acid is also claimed to be
ufacture of diazoamino compounds of the suitable for a pregnancy test for horses [237].
R−N=N−NH−R type. As mixtures with naph-
thols these compounds have acquired impor-
5-(Chlorosulfonyl)-2-hydroxybenzoic
tance as printing inks (Rapidogen dyes).
Acid [17243-13-9], C7 H5 ClO5 S, M r 236.63,
mp 171 ◦ C (decomp.), is obtained from salicylic
2-Amino-5-sulfobenzoic Acid [3577-63-7],
acid and chlorosulfuric acid [238], [239]. The
(44) C7 H7 NO5 S, M r 217.2, is produced from
compound is used to manufacture the corre-
anthranilic acid by sulfonation with chlorosul-
sponding sulfinic acid and sulfones.
furic acid in anhydrous sulfuric acid or nitro-
benzene or by baking the sulfate of anthranilic
acid at 200 ◦ C [227], [228]. This compound is
used, like its N-alkyl derivatives, as a stabilizer 2.11. Chloro-hydroxybenzenesulfonic
for diazo compounds (see next paragraph). Acids
3-Chloro-4-hydroxybenzenesulfonic Acid
[46060-27-9] (46), C6 H5 ClO4 S, M r 208.62, is
prepared by chlorination of 4-hydroxybenzene-
sulfonic acid or by sulfonation of 2-chlorophe-
nol with 98 % sulfuric acid [240]. The com-
(44) pound can be converted by nitration into 3-
chloro-4-hydroxy-5-nitrobenzenesulfonic acid,
from which 3-amino-5-chloro-4-hydroxyben-
2-Isobutylamino-5-sulfobenzoic Acid, zenesulfonic acid is obtained by reduction.
C11 H15 NO5 S, M r 273.31, is obtained The sulfonic acid group is eliminated easily at
in crystalline form by sulfonating N- 180 – 190 ◦ C.
isobutylanthranilic acid in 98 % sulfuric acid
with 65 % oleum at 80 ◦ C and pumping the
sulfonation mixture into water; yield 93 – 94 %
[229].
2-Hydroxy-5-sulfobenzoic Acid [97-05-2]

(45), C7 H6 O6 S, M r 218.18, needles, mp 120 ◦ C, (46)
soluble in water, ethyl alcohol, and ether, is ob-
tained by heating one part of salicylic acid with
5 parts of concentrated sulfuric acid [230]. It 5-Chloro-2-hydroxybenzenesulfonic Acid
can also be prepared from the sulfochloride. [2051-65-2] (47), C6 H5 ClO4 S, M r 208.62,
is obtained from 2,5-dichlorobenzenesulfonic
acid by partial hydrolysis with sodium hy-
droxide solution in water at 170 – 190 ◦ C and
precipitation with concentrated hydrochloric
acid. Used to prepare 5-chloro-2-hydroxy-3-
nitrobenzenesulfonic acid, which is then re-
(45) duced to 3-amino-5-chloro-2-hydroxybenzene-
sulfonic acid.
(47)
3,5-Dichloro-2-hydroxybenzenesulfonic
Acid [26281-43-6] (48), C6 H4 Cl2 O4 S, M r 243,
forms a poorly water-soluble barium salt.
3-Amino-4-hydroxybenzenesulfonic acid is
an important intermediate in the production
(48) of dyes and is used to manufacture Diamond
Black PV and 3-amino-4-hydroxy-5-nitroben-
zenesulfonic acid.
3,5-Dichloro-2-hydroxybenzenesulfon-
amide [35337-99-6], C6 H5 Cl2 NO3 S, M r 3-Amino-4-hydroxybenzenesulfon-
242.08, melts at 230 ◦ C. It is obtained from the amide [98-32-8], C6 H8 N2 O3 S, Mr
chlorosulfonation of 2,4-dichlorophenol and 188.2. Manufacture: 2-nitrochlorobenzene is
conversion with ammonia or NH4 Cl. It can sulfochlorinated with chlorosulfuric acid; the
be used as a precursor to synthesize some 2- resulting sulfochloride is treated with ammonia
hydroxybenzenesulfonamides that are poorly to give 4-chloro-3-nitrobenzenesulfonamide;
accessible by other routes, by dehalogenation chlorine is replaced by hydroxyl by heating the
with H2 and Pd/C catalyst [241]. product at 100 ◦ C in aqueous sodium hydroxide
solution. Finally, the hydroxybenzenesulfon-
amide is reduced with iron turnings [243].
2.12. Aminohydroxybenzenesulfonic
Acids and 3-Amino-4-methoxybenzenesulfonic Acid
Aminochlorohydroxybenzenesulfonic [98-42-0] (50), C7 H9 NO4 S, M r 203.22, nee-
Acids dles, is freely soluble in water. The compound
is obtained from 2-anisidine and 98 % sulfuric
All the compounds described in this section are acid at 50 – 55 ◦ C [244].
used in the manufacture of dyes.
3-Amino-4-hydroxybenzenesulfonic Acid
[98-37-3] (49), C6 H7 NO4 S, M r 189.19, is freely
soluble in hot water, slightly soluble in cold, di-
lute hydrochloric acid. Obtained by boiling 4-
(50)
chloro-3-nitrobenzenesulfonic acid with sodium
hydroxide solution, followed by Béchamp re-
duction [242]: 3-Acetylamino-4-methoxybenzene-
sulfonyl Chloride [3746-67-6] (51),
C9 H10 ClNO4 S, M r 263.7, mp 152 – 163 ◦ C, is
obtained from 2-acetylaminoanisole and chloro-
sulfuric acid at 35 – 40 ◦ C [245–247]. The com-
pound is used to produce the corresponding
sulfinic acid and Fast Red ITR base.
3-Amino-6-ethoxybenzenesulfonic Acid
[6375-02-6] (54), C8 H11 NO4 S, M r 217.24, nee-
dles, poorly soluble in water and ethyl alcohol.
Manufactured by treating o-dichlorobenzene
with 96 % sulfuric acid and baking the result-
ing sulfate or from phenetidine by reaction with
(51) oleum [250].
3-Acetylamino-4-methoxybenzenesulfon-
amide [85605-29-4], C9 H12 N2 O4 S, Mr
244.27, melts at 226 ◦ C.
(54)
3-Acetylamino-4-methoxy-N-methylbenzene-
sulfonamide, C10 H14 N2 O4 S, M r 258.3, is ob-
tained by treating the chloride with 2 mol of 4-Amino-6-methoxy-1,3-benzenedisulfonic
ethylamine at 25 ◦ C. Other N-alkylamides of Acid (55), C7 H9 NO7 S2 , M r 283.28.
this sulfonic acid are produced in the same way
[248].
5-Amino-4-hydroxy-1,3-benzenedisulfonic
Acid [120-98-9] (52), C6 H7 NO7 S2 , M r
269.25, is obtained by nitration of 4-hydroxy-
1,3-benzenedisulfonic acid and reduction of (55)
the hydroxynitrobenzenedisulfonic acid [84,
p. 148].
4-Amino-6-methoxy-1,3-benzenedisulfonyl
Chloride [670-02-0], C7 H7 Cl2 NO5 S2 , M r
320.17, mp 129 – 130 ◦ C, is obtained by adding
sodium chloride to m-anisidine and chlorosulfu-
ric acid while cooling with ice and then heating
[251].
(52)
3-Amino-5-chloro-2-hydroxybenzenesul-
fonic Acid [88-23-3] (56), C6 H6 ClNO4 S, M r
5-Acetylamino-2-hydroxybenzenesulfo- 223.63, colorless crystals, freely soluble in hot
nic Acid [55034-25-8] (53), C8 H9 NO5 S, M r water, less soluble in cold water, very easily solu-
231.23, needles, freely soluble in water, decom- ble in sodium hydroxide solution. The industrial
position on melting. Manufactured by sulfonat- product has a weak brownish-pink color and is
ing N-(4-hydroxyphenyl)acetamide with 98 % produced by sulfonating 2-amino-4-chlorophe-
sulfuric acid at 80 ◦ C [249] or by acetylating nol or from p-chlorophenol:
5-amino-2-hydroxybenzenesulfonic acid with
acetic anhydride and sodium acetate in water.
(53)
The 5-chloro-2-hydroxy-3-nitroben- H2 O. It is obtained from 4-chloro-3-nitroben-

zenesulfonic acid obtained from p-chlorophenol zenesulfonic acid by reduction; the compound
by sulfonation and nitration is reduced with iron is used for the production of azo dyes.
and hydrochloric acid without being precipi-
tated. After filtering from the iron sludge, the
highly alkaline reduction liquor is concentrated
by evaporation and decolorized with activated
carbon. Upon acidification 3-amino-5-chloro-2-
hydroxybenzenesulfonic acid precipitates. Yield
72 %, based on p-chlorophenol. The acid is (59)
an important intermediate for dyes. It is used
mainly in the manufacture of Diamond Black
P 2 B and of acid chrome blue dyes. 2-Amino-4,5-dichlorobenzenesulfonic
Acid [6331-96-0] (60), C6 H5 Cl2 NO3 S, M r
242.08, crystallizes as needles from water. Man-
3-Amino-5-chloro-4-hydroxybenzenesul-
ufactured by baking 3,4-dichloroaniline sulfate.
fonic Acid (57) is similar in properties and
The compound is used as a component of azo
manufacture to 3-amino-5-chloro-2-hydroxy-
dyes.
benzenesulfonic acid but is less important in-
dustrially [252].
(60)
(57)
2-Amino-4,5-dichlorobenzenesulfonyl
Chloride [36110-12-0], C6 H4 Cl3 NO2 S,
M r 260.53, is obtained by treating 3,4-
2.13. Amino-chlorobenzenesulfonic dichloroaniline with chlorosulfuric acid in the
Acids presence of sodium chloride.
2-Amino-5-chlorobenzenesulfonic Acid 2-Amino-4,5-dichlorobenzenesulfon-
[133-74-4] (58), C6 H6 ClNO3 S, M r 207.64, de- amide [16948-63-3], C6 H6 Cl2 N2 O2 S, M r
composes at 280 ◦ C and crystallizes from water 241.1, mp 183 – 185 ◦ C, crystals from 50 %
with 1 mol of H2 O. Manufactured by baking alcohol, is obtained by treating the chloride
4-chloroaniline hydrogensulfate in vacuo; after with aqueous ammonia [254].
the mass has been pumped into water, the acid is
neutralized with calcium oxide; the solution is 4-Amino-2,5-dichlorobenzenesulfonic
suitable for use in the manufacture of azo dyes Acid [88-50-6] (61), C6 H5 Cl2 NO3 S, M r
[253]. 242.08, is obtained by sulfonating 2,5-
dichloroaniline with 65 % oleum in anhydrous
sulfuric acid; the compound is purified via the
sodium salt [255].
(58)
3-Amino-4-chlorobenzenesulfonic Acid
[98-36-2] (59), C6 H6 ClNO3 S, M r 207.64, nee-
dles (from water), crystallizes with 1 mol of (61)
4-Amino-6-chloro-1,3-benzenedisulfonic 2-Amino-5-chloro-4-methylbenzene-
Acid (62), C6 H6 ClNO6 S2 , M r 287.7. sulfonic Acid [88-53-9] (64), C7 H8 ClNO3 S,
M r 221.66, is a colorless to slightly reddish
crystalline powder. The compound is obtained
by chlorination of p-toluenesulfonic acid to form
3-chloro-4-methylbenzenesulfonic acid, subse-
quent nitration of this acid to a mixture of nitro
isomers, precipitation of the 2-chloro-4-methyl-
(62) 6-nitrobenzenesulfonic acid with sodium chlo-
ride solution, and, finally, Béchamp reduction of
the nitro group with iron and acetic acid [263].
4-Amino-6-chloro-1,3-benzenedisulfonyl
A different synthesis route in which no iso-
Chloride [671-89-6], C6 H4 Cl3 NO4 S2 , M r
mers are formed is as follows [264]:
324.59, mp 142 – 144 ◦ C, is obtained by chloro-
sulfonation of 3-chloroaniline with 11 mol of
chlorosulfuric acid at 130 ◦ C [256–258]; after
the chlorosulfonation mixture is treated with
4 mol of thionyl chloride at 80 ◦ C, the yield is
90 % [259].
4-Amino-6-chloro-1,3-benzenedisulfon-
amide [121-30-2], C6 H8 ClN3 O4 S2 , Mr
285.73, mp 258 – 260 ◦ C, is obtained by treat-
ing the chloride with ammonia in tert-butanol
and concentrating the solution by evaporation;
the yield is 80 % [259]. Condensation with
formic acid gives 6-chloro-7-sulfamoyl-1,2,4- The compound is used as Lake Red C and
benzothiadiazine 1,1-dioxide, an important di- CLT Acid as a diazo component for azo dyes
uretic [260], [261]. The 1-monoamide 63 is an and azo pigments.
intermediate for the production of azo dyes for
polyamide fibers. For manufacture, see [262]. 3-Amino-5-chloro-4-methylbenzene-
sulfonic Acid [6387-27-5] (65), C7 H8 ClNO3 S,
M r 221.66, is a moist, slightly reddish paste in
raw form. It is manufactured by sulfonation of 1-
chloro-2- methyl-3-nitrobenzene [83-42-1] with
oleum, followed by Béchamp reduction [265].
The compound is used as a diazo component for
(63) azo dyes in the dyeing of leather.
4-Amino-6-chloro-N1 ,N2 -dimethyl-

1,3-benzene-disulfonamide [60385-32-2],
C8 H12 ClN3 O4 S2 , M r 313.78, mp 183 ◦ C (crys-
tals from aqueous alcohol), is prepared by boil-
ing the chloride with aqueous methylamine in
dioxane at reflux temperature for 3 h and pre- (65)
cipitating with water [256].
2.14. Amino-chloro- sulfonic Acid [6387-14-0] (66), C7 H8 ClNO3 S,
M r 221.66, needles from water, splits off the
alkylbenzenesulfonic sulfonic acid group in 75 % sulfuric acid at
Acids
150 – 160 ◦ C. It is made by sulfonation of 2-

chloro-6-methylaniline in o-dichlorobenzene
with anhydrous sulfuric acid in vacuo, dur-
ing which the water of the reaction distills off
[266]. Alternative: chlorination of 4-acetylami-
no-3-methylbenzenesulfonic acid in water and
deacetylation. The compound is used as a dye (69)
component.
3. References
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Benzenesulfonic Acids and Their Derivatives: 1. General Aspects

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Benzenesulfonic Acids and Their Derivatives 1

Benzenesulfonic Acids and Their Derivatives

Otto Lindner, Bayer AG, Leverkusen, Federal Republic of Germany

1. General Aspects . . . . . . . . . . . . . 1 2.1. Benzenesulfonic Acid . . . . . . . . . 11

1. General Aspects Aminobenzenesulfonic acids are weak acids;

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

1.2. Chemical Properties

Desulfonation. The sulfonation of aromatic

Figure 1. Sulfonation and desulfonation of benzene (E+ = SO3 or HSO+

1.3.1. Direct Sulfonation C6 H6 + H2 SO4 + SOCl2 −→ C6 H5 SO3 H + SO2 + 2 HCl

liquid phase, sulfur dioxide or dichloromethane

Hydrogensulﬁte addition, followed by the

Most benzenesulfonic acids, chlorides, and

Compound LD50 (rat, oral), Aquatic toxicity Degradation

Benzenesulfonic acid 1170 Zahn – Wellens [57] 90

enameled steel vessel and 10 – 25 mol % of the

creased by using an excess of chlorosulfuric acid chlorosulfonation and subsequent dechlorosul-

Production. Sulfonamides are produced by

Uses. Benzenesulfonamides serve as inter- 2. Individual Benzenesulfonic Acids

Sodium benzenesulfonate decomposes at to a greater or lesser extent. The following meth-

The reaction product is diluted with water and

p-Chlorophenyl Benzenesulfonate and 2,4-

1 – 29 % of diphenyl sulfone disulfonic acid is vapor, a mixture of monosulfonic and disulfonic

[25231-46-3], C7 H8 O3 S, M r 172.20, methyl- They are used as intermediates in the production

Production. The sulfonation of toluene is

3-Methylbenzenesulfonyl Chloride 190.65, bp25 mbar 138 – 139 ◦ C, mp 69 ◦ C.

Methyl 4-(Chloromethyl)benzenesulfonate 4-Methyl-1,3-benzenedisulfonyl Chloride

4-Methyl-1,3-benzenedisulfonic Acid 2,4-Dimethylbenzenesulfonamide [7467-

the sodium salt of 1H-indene-5-sulfonic acid carbazone decomposes at 230 ◦ C. 4-

2.4. Formylbenzenesulfonic Acids

2-Formylbenzenesulfonic Acid [91-25-8]

4-Chlorobenzenesulfonamide [98-64-6], 3,4-Dichlorobenzenesulfonamide [23815-

and 2,4,5-trichlorobenzenesulfonic acid) have reduced to 2,2 -diaminodiphenyl disulﬁde and

4-(Acetylamino)benzenesulfonyl Chloride 5-Amino-1,3-benzenedisulfonyl Chloride,

is removed; the product is then precipitated with 4,6-Diamino-1,3-benzenedisulfonic Acid

The trisulfonic and tetrasulfonic acids formed (24)

(28) 4-Hydroxy-1,3-benzenedisulfonic Acid

groscopic crystals, is obtained by hydrolysis of

The disodium salt of 33, which is referred to

of H2 O. The acid is formed as the main prod-

3-Chloro-4-methylbenzenesulfonyl Chlo- 4-Chloro-3-(triﬂuoromethyl)benzene-

2.9. Amino-alkylbenzenesulfonic Acids

3-Amino-4-methylbenzenesulfonic Acid 2.10. Amino- and

2-Hydroxy-5-sulfobenzoic acid forms a di-

2-Hydroxy-5-sulfobenzoic Acid [97-05-2]

The 5-chloro-2-hydroxy-3-nitroben- H2 O. It is obtained from 4-chloro-3-nitroben-

4-Amino-6-chloro-N1 ,N2 -dimethyl-

150 – 160 ◦ C. It is made by sulfonation of 2-

224. Org. Synth 27 (1947) 88 – 91 248. BIOS 1153, 114, 117.

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