Sie sind auf Seite 1von 38

Article No : o06_o03

Chlorinated Benzenes and other


Nucleus-Chlorinated Aromatic Hydrocarbons
UWE BECK, Bayer AG, Leverkusen, Germany
ECKHARD L€oSER, Bayer AG, Wuppertal, Germany

1. Introduction. . . . . . . . . . . . . . .... ..... . 483 3.4. Quality and Analysis . . . . . . . . . . . ..... . 503
2. Chlorinated Benzenes . . . . . . .... ..... . 484 3.5. Storage and Transportation. . . . . . ..... . 503
2.1. Physical Properties . . . . . . . . .... ..... . 484 3.6. Uses . . . . . . . . . . . . . . . . . . . . . . . . ..... . 504
2.2. Chemical Properties . . . . . . . .... ..... . 484 3.7. Toxicology . . . . . . . . . . . . . . . . . . . ..... . 504
2.3. Production . . . . . . . . . . . . . . . .... ..... . 488 4. Chlorinated Biphenyls . . . . . . . . . . ..... . 504
2.3.2. Monochlorobenzene. . . . . . . . . .... ..... . 491 4.1. Physical and Chemical Properties . ..... . 505
2.3.3. Dichlorobenzenes . . . . . . . . . . .... ..... . 491 4.2. Disposal . . . . . . . . . . . . . . . . . . . . . ..... . 505
2.3.4. Trichlorobenzenes . . . . . . . . . . .... ..... . 492 4.3. Analysis . . . . . . . . . . . . . . . . . . . . . ..... . 506
2.3.5. Tetrachlorobenzenes . . . . . . . . .... ..... . 493 4.4. Storage and Transportation. . . . . . ..... . 506
2.3.6. Pentachlorobenzene . . . . . . . . . .... ..... . 493 4.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . ..... . 507
2.3.7. Hexachlorobenzene . . . . . . . . . .... ..... . 494 4.6. Toxicology . . . . . . . . . . . . . . . . . . . ..... . 507
2.4. Quality and Analysis . . . . . . . .... ..... . 494 5. Chlorinated Naphthalenes . . . . . . . ..... . 508
2.5. Storage and Transportation. . .... ..... . 494 5.1. Physical Properties . . . . . . . . . . . . ..... . 508
2.6. Uses . . . . . . . . . . . . . . . . . . . . .... ..... . 495 5.2. Chemical Properties . . . . . . . . . . . ..... . 509
2.7. Toxicology . . . . . . . . . . . . . . . .... ..... . 496 5.3. Production . . . . . . . . . . . . . . . . . . . ..... . 510
3. Chlorinated Toluenes. . . . . . . .... ..... . 498 5.4. Quality and Analysis . . . . . . . . . . . ..... . 510
3.1. Physical Properties . . . . . . . . .... ..... . 498 5.5. Storage and Transportation. . . . . . ..... . 511
3.2. Chemical Properties . . . . . . . .... ..... . 498 5.6. Use . . . . . . . . . . . . . . . . . . . . . . . . . ..... . 511
3.3. Production . . . . . . . . . . . . . . . .... ..... . 499 5.7. Toxicology . . . . . . . . . . . . . . . . . . . ..... . 511
3.3.1. Monochlorotoluenes . . . . . . . . .... ..... . 501 6. Environmental Protection . . . . . . . ..... . 512
3.3.2. Dichlorotoluenes . . . . . . . . . . . .... ..... . 501 7. Economic Aspects . . . . . . . . . . . . . ..... . 513
3.3.3. Trichlorotoluenes. . . . . . . . . . . .... ..... . 502 References . . . . . . . . . . . . . . . . . . . ..... . 514
3.3.4. Tetrachlorotoluenes . . . . . . . . . .... ..... . 502
3.3.5. Pentachlorotoluene . . . . . . . . . .... ..... . 503

1. Introduction Chlorinated aromatic hydrocarbons are of


substantial economic significance. This is partic-
The term ‘‘nucleus-chlorinated aromatic com- ularly true of the chlorinated benzenes, the most
pound’’ as used here refers to a substance con- important being monochlorobenzene, and the
taining a mesomeric p-electron system in a car- chlorinated toluenes. The compounds are now
bocyclic framework in which at least one of the recognized as important starting materials and
ring carbons bears a chlorine substituent rather additives in the production of high-quality
than hydrogen. insecticides, fungicides, herbicides, dyes, phar-
Laboratory work on the compounds making maceuticals, disinfectants, rubbers, plastics, tex-
up this class began long ago. For example, tiles, and electrical goods.
A. LAURENT reported in 1833 that he had obtained In general, the environmental degradability
waxlike compounds in the course of chlorinating of heavily chlorinated organic compounds,
naphthalene. Nevertheless, their industrial man- whether by biotic or by abiotic mechanisms, is
ufacture and use was delayed until the first third low. This persistence has led in recent years to
of the 20th century. such drastic measures as prohibitions, restrictions

 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


DOI: 10.1002/14356007.o06_o03
484 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

on production and use, and legislation regulating forms a eutectic mixture with a solidification
waste disposal. Some highly chlorinated aro- point of þ 1.5  C. Further physical data are
matics have been affected as well. given in Table 1.

Tetrachlorobenzene C6H2Cl4, also occurs


2. Chlorinated Benzenes in three isomeric forms: 1,2,3,4-Tetrachloroben-
zene and 1,2,3,5-tetrachlorobenzene crystallize
2.1. Physical Properties as colorless needles. 1,2,4,5-Tetrachlorobenzene
forms colorless, sublimable needles with a
Monochlorobenzene C6H5Cl, is a colorless strong, unpleasant odor.
liquid which is volatile with steam and is a good All of the tetrachlorobenzenes are insoluble in
solvent. It is miscible with all commonly used water, but they are soluble in many organic
organic solvents and forms many azeotropes [10, solvents, particularly at an elevated temperature.
11]. Monochlorobenzene is flammable and has Further physical data are given in Table 2.
an aromatic odor. Upon addition of 24 % ben-
zene, it forms a eutectic mixture with a solidifi- Pentachlorobenzene C6HCl5, forms color-
cation point of  60.5  C. less needles and is insoluble in water.
Important physical data for monochloroben-
zene are compiled in Table 1. Hexachlorobenzene C6Cl6, forms colorless
and sublimable prismatic crystals. It is insoluble
Dichlorobenzene C6H4Cl2, occurs in three in water, but soluble at an elevated temperature in
isomeric forms. 1,2-Dichlorobenzene is a color- several organic solvents (e.g., benzene, chloro-
less, mobile liquid which is miscible with the form, and ether).
commonly used organic solvents. It is difficult to
ignite and has an unpleasant odor. The properties
of 1,3-dichlorobenzene are similar to those of 2.2. Chemical Properties
1,2-dichlorobenzene. 1,4-Dichlorobenzene is a
white, volatile, crystalline compound soluble in The chlorobenzenes are neutral, thermally stable
many organic solvents. It has a strong camphor compounds. Reactions may occur to replace
odor. 1,4-Dichlorobenzene occurs as a stable hydrogen at unsubstituted positions on the ring
monoclinic a-modification, which is trans- (e.g., halogenations, sulfonations, alkylations,
formed into the triclinic b-form at 30.8  C. nitrations), by substitution of the chlorine (e.g.,
Eutectic mixtures of the dichlorobenzenes hydrolysis), and with de-aromatization (e.g.,
are: 86.0 % 1,2-dichlorobenzene, 14.0 % 1,4-di- chlorine addition).
chlorobenzene, solidification point  23.7  C;
85.3 % 1,3-dichlorobenzene, 14.7 % 1,4-dichlo- Monochlorobenzene. In this compound the
robenzene, solidification point  30.8  C. Fur- chlorine is firmly bound to the aromatic ring and
ther physical data are given in Table 1. can only be substituted under energetic condi-
tions. Chlorobenzene can be hydrolyzed to phe-
Trichlorobenzene C6H3Cl3, occurs in three nol with aqueous sodium hydroxide at 360 – 390
isomeric forms. 1,2,3-Trichlorobenzene forms 
C under high pressure [12–14] or with steam at
colorless tabular crystals. 1,2,4-trichlorobenzene 400 – 450  C over calcium phosphate. Mono-
is a colorless liquid of low flammability, and chlorobenzene reacts with ammonium hydroxide
1,3,5-trichlorobenzene forms long, colorless at high temperature and in the presence of copper
needles. catalysts to give aniline [15].
The trichlorobenzenes are insoluble in water, In electrophilic substitution, e.g., nitration,
slightly soluble in alcohol, and very soluble in the directing influence of the chlorine atom leads
benzene and solvents like petroleum ether, car- to the formation of derivatives in which the add-
bon disulfide, chlorinated aliphatic and aromatic ed substituent is found predominantly in the
hydrocarbons. ortho or para position.
A combination of 34 % of 1,2,3-trichloro- Light-induced addition of chlorine produces
benzene and 66 % of 1,2,4-trichlorobenzene heptachlorocyclohexane [26].
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 485

(Continued)
Table 1. Physical properties of mono- to trichlorobenzenes
486 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8
Table 1. (Continued )
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 487

Table 2. Physical properties of tetra-, penta-, and hexachlorobenzenes

Dichlorobenzenes. The reactivity to further The action of alkaline solutions or alcoholic


substitution on the ring increases from 1,4- via ammonia solution on dichlorobenzene at 200  C
1,2- to 1,3-dichlorobenzene. under pressure gives chlorophenols and dihy-
The position at which a third substituent is droxybenzenes, or chloroanilines and phenyle-
introduced into the ring depends on the direct- nediamines, respectively. The addition of chlo-
ing influence of the two chlorine atoms. Thus, rine leads to octachlorocyclohexane [26].
for example, no 1,3,5-derivatives can be
formed in this way. Electrophilic substitution Trichlorobenzenes. The reactivity of these
of 1,2-dichlorobenzene leads to 4-derivatives compounds toward chlorine decreases in the
as main products and 3-derivatives as bypro- order 1,3,5- > 1,2,3- > 1,2,4-trichlorobenzene.
ducts. Electrophilic substitution of 1,3-dichlo- As expected, electrophilic substitution occurs
robenzene gives 4-derivatives as main product preferentially at certain positions on the aromatic
and 2-derivatives as byproduct, whereas 1,4- ring: With 1,2,3-trichlorobenzene an electrophil-
dichlorobenzene as starting material yields 2- ic substituent is led into the 4-position, with
derivatives. 1,2,4-trichlorobenzene into the 5-position (main
488 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

product) and 3-position (byproduct), and with to only a small extent if at all. The velocity of
1,3,5-trichlorobenzene into the 2-position. chlorination for an individual chlorine compound
The trichlorobenzenes can be hydrolyzed to depends on the compound’s structure and, because
dichlorophenol. of this, both the degree of chlorination and also the
isomer ratio change continuously during the course
Tetrachlorobenzenes. Like the lower chlo- of a reaction. Sets of data on the composition of
rinated benzenes, the tetrachlorobenzenes can be products from different reactions are only compa-
chlorinated and nitrated. The reactivity toward rable with one another if they refer to identical
chlorine decreases from 1,2,3,5- via 1,2,3,4- to reaction conditions and materials having the same
1,2,4,5-tetrachlorobenzene. At a temperature degree of chlorination. By altering the reaction
above 160 – 180  C, the chlorine substituents can conditions and changing the catalyst, one can vary
be hydrolyzed with sodium hydroxide in metha- the ratios of the different chlorinated products
nol. In the preparation of trichlorophenol from within certain limits. Lewis acids (FeCl3, AlCl3,
tetrachlorobenzene, the toxic polychlorinated di- SbCl3, MnCl2, MoCl3, SnCl4, TiCl4) are used as
benzo-p-dioxins – and also the extremely toxic principal catalysts (Table 3). Elevated tempera-
compound 2,3,7,8-tetrachlorodibenzo-p-dioxin – tures in substitution reactions favor the introduc-
may be formed if the very narrowly defined tion of a second chlorine atom in the ortho and meta
reaction conditions are not precisely maintained. positions, whereas para substitution is favored if
cocatalysts and lower temperatures are used. As a
Pentachlorobenzene. Pentachlorobenzene further example of the influence of catalysts on the
can be chlorinated to hexachlorobenzene and composition of the product, attention is drawn to
nitrated to pentachloronitrobenzene. Hydrolysis the formation of 1,2,4,5-tetrachlorobenzene
to 2,3,4,5- and 2,3,5,6-tetrachlorophenol is also (Table 4). The optimal reaction temperature de-
possible. pends on the desired degree of chlorination. Mono-
and dichlorination are carried out at 20 – 80  C. In
Hexachlorobenzene. Hexachlorobenzene, the production of hexachlorobenzene by chlorina-
like the other polychlorobenzenes, can be de- tion of benzene, however, temperatures of about
halogenated to lower chlorinated benzenes 250  C are needed toward the end of the reaction.
with hydrogen or steam at a temperature above The usual catalyst employed in large scale
500  C in the presence of catalysts [27]. At a production is ferric chloride, with or without the
high temperature a mixture of hexachloroben- addition of sulfur compounds. Ferric chloride
zene, chlorine, and ferric chloride gives carbon complexed with 1 mol of water is claimed to
tetrachloride in high yield [28]. Reaction with have the best catalytic effect [43]. Benzene and
sodium hydroxide and methanol leads to chlorine of technical purity always contain some
pentachlorophenol. water, however, thus, it may be that this hydrate
compound is always present in iron-catalyzed
industrial reactions.
2.3. Production The ratio of resulting chlorobenzenes to one
another is also influenced by the benzene : chlo-
Benzene Chlorination in the Liquid rine ratio. For this reason, the highest selectivity
Phase. Chlorobenzenes are prepared industrially is achieved in batch processes. If the same mono-
by reaction of liquid benzene with gaseous chlorine chlorobenzene : dichlorobenzene ratio expected
in the presence of a catalyst at moderate tempera- from a batch reactor is to result from continuous
ture and atmospheric pressure. Hydrogen chloride operation in a single-stage reactor, then a far
is formed as a byproduct. Generally, mixtures of lower degree of benzene conversion must be
isomers and compounds with varying degrees of accepted (as a consequence of a low benzene :
chlorination are obtained, because any given chlo- chlorine starting ratio). The selectivity of a
robenzene can be further chlorinated up to the stage continuous reactor approaches that of a discon-
of hexachlorobenzene. Because of the directing tinuous reactor as the number of reaction stages is
influence exerted by chlorine, the unfavored pro- increased [44]. Mathematical models analyzing
ducts 1,3-dichlorobenzene, 1,3,5-trichloroben- and interpreting benzene chlorination will be
zene, and 1,2,3,5-tetrachlorobenzene are formed found in [44–47] and elsewhere.
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 489

Table 3. Influence of catalysts on the ratio 1,4-:1,2-dichlorobenzene

Catalyst Proportion of 1,4-dichlorobenzene Ratio References


(in %) in the 1,4- : 1,2-
dichlorobenzene fraction dichlorobenzene

MnCl2 þ H2O ca. 50 1.03 [29]


SbCl5 1.5 [30]
FeCl3 or Fe ca. 59 1.49 – 1.55 [31, 35, 38]
Metallosilicon organic
compounds 61 – 74 1.56 – 2.8 [32]
AlCl3 – SnCl4 2.21 [33]
AlCl3 – TiCl4 2.25 [33]
Fe – S – PbO ca. 70 [34]
FeCl3– diethyl ether 2.38 [35]
Aluminum silicate –
hexamethylene-
diamine 2.7 [36]
FeCl3– S2Cl2 ca. 76 [37]
FeCl3 – divalent
organic sulfur
compounds ca. 77 3.3 [38]
L-type zeolite ca. 88 8.0 [39]
TiCl4 (chlorinating
agent is FeCl3) 20 – 30 [40]

Solvents can also influence the chlorination rate Unwanted heat of reaction can be dissipated
as well as the selectivity of the reaction, although either by circulating some of the reactor liquid
solvents are not used in industrial chlorination. through an external heat exchanger or by permit-
ting evaporative cooling to occur at the boiling
Continuous Chlorination. Benzene or a chlo- temperature. Circulation cooling has the advan-
robenzene derivative is treated with chlorine gas in tage of enabling the reaction temperature to be
a suitable reactor in the presence of dissolved ferric varied in accordance with the requirements of a
chloride. The reactants must be mixed as inten- given situation. Evaporative cooling is more
sively as possible. The catalyst can be introduced economical, however.
along with the substrate or it can be allowed to form The reactor must be designed to ensure that
during the reaction on the surface of iron rings in the liquid within it has a suitable residence
the reactor. The reaction is highly exothermic. spectrum, since this favors high chlorination
selectivity. As noted above, the quantity ratio
of the chlorobenzenes to one another is
C6H6 þ Cl2 ! C6H5Cl þ HCl DH ¼  131.5 kJ/mol determined by the benzene : chlorine starting
C6H5Cl þ Cl2 ! C6H4Cl2 þ HCl DH ¼  124.4 kJ/mol
C6H4Cl2 þ Cl2 ! C6H3Cl3 þ HCl DH ¼  122.7 kJ/mol
ratio.
C6H3Cl3 þ Cl2 ! C6H2Cl4 þ HCl DH ¼  115.1 kJ/mol Almost quantitative conversion of chlorine is
achieved in continuously operated plants for the

Table 4. Influence of catalysts on the ratio 1,2,4,5-:1,2,3,4-tetrachlorobenzene

Catalyst Substrate Ratio Ref.


1,2,4,5- : 1,2,3,4-tetrachlorobenzene

FeCl3 1,2,4-trichlo- 2.3 – 2.4 [31],


robenzene [38]
Lewis acids – di- 1,2,4-trichlo- 3 [38]
valent organic robenzene
sulfur compounds
FeCl3 – aromatic 1,2,4-trichlo- 2.7 – 4.6 [41]
iodine compounds robenzene
SbCl3 – I2 benzene 10 – 17 [42]
490 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

manufacture of mono- and dichlorobenzenes Table 5. Solubility (in wt %) of chlorine in benzene and chloroben-
zenes [48]
under normal operating conditions.
Cast iron, steel, nickel, and glass-lined steel Solvent Temperature
can be used as construction materials. Howev-
er, all starting materials must be substantially 20  C 50  C 75  C 100  C
free from water; otherwise, severe corrosion is Benzene 27 6 0.8
caused by the hydrochloric acid formed. Intru- Monochlorobenzene 15 5 1.2
sion of water is dangerous for another reason: 1,2-Dichlorobenzene 9 4 1.1
1,2,4-Trichlorobenzene 6 3.5 1.0
water causes the ferric chloride catalyst to be
inactivated. If this occurs, chlorine collects in
the reactor and exhaust system, and local over- would consist of combined crystallization/distilla-
heating may ensue, causing spontaneous com- tion processes.
bustion of the aromatic hydrocarbon with
chlorine in a highly exothermic reaction to Discontinuous Chlorination. Batch chlori-
form carbon and hydrogen chloride (2 mol of nation of liquid, molten, or dissolved aromatics
HCl/mol of Cl2). Furthermore, above 280  C is carried out industrially in agitator vessels
metallic iron begins to burn in the chlorine equipped with external or internal cooling. The
stream. It is, therefore, advisable to monitor the agitator must provide maximum exchange be-
reaction continuously by observing the heat tween the liquid and gas phases. Gaseous chlo-
production rate and the chlorine content of the rine is introduced through a valve at the bottom of
waste gas. the vessel or through an ascension pipe beneath
On leaving the reactor, the liquid and gas the agitator. The vessel may be constructed of
portions of the reaction mixture are separated. glass-lined steel, cast iron, steel, or nickel. Ab-
The waste gas contains hydrogen chloride and – sence of water must be ensured as a precaution
in proportions corresponding to their vapor pres- against corrosion. The degree of chlorination can
sures at the temperature of the waste gas – be ascertained from density determinations. The
benzene and chlorobenzenes. If the chlorine amount of chlorine which can be introduced in
conversion is incomplete, chlorine may be pres- unit time depends on the heat output of the vessel
ent as well. Concerning the treatment of the waste and on the chlorine conversion rate. It is obvi-
gas, see Chapter 50. ously desirable to keep the chlorine content of the
The liquid phase contains benzene, chloro- off-gas as low as possible. It is also important that
benzenes, hydrogen chloride, and iron catalyst. the reaction begins as soon as chlorine is intro-
Production processes exist in which the product duced (the beginning of the reaction is indicated
mixture is neutralized with sodium hydroxide by a temperature increase and by the formation of
solution or soda before it is subjected to frac- hydrogen chloride). Chlorine is soluble in many
tional distillation. In modern continuous distil- hydrocarbons (see Table 5); therefore, if the
lation trains, the mixture of products can be onset of reaction is delayed, hydrogen chloride
distilled without preliminary treatment, how- may be formed very rapidly, resulting in a sub-
ever. The separated fractions consist of ben- stantial increase in the temperature of the reac-
zene, monochlorobenzene, dichlorobenzenes, tants in the vessel.
trichlorobenzenes, and higher chlorobenzenes.
Iron catalyst is removed along with the distilla-
Other Benzene Chlorination Processes.
tion residue, disposal of which is discussed in
The following additional benzene chlorination
Chapter 50. Dissolved hydrogen chloride is
processes are known:
removed during the benzene distillation and
combined with the waste gas. Unreacted ben-
zene is recycled to the reactor. 1. Chlorination in the vapor phase with chlorine
Whereas chlorobenzene and 1,2-dichloro- 2. Chlorination in the vapor or liquid phase with
benzene are obtainable as pure distillates, the hydrogen chloride and air (oxychlorination)
other fractions are mixtures of close-boiling 3. Chlorination with chlorine-containing
polychlorobenzene isomers. A further separa- compounds
tion, insofar as this is economically justifiable, 4. Electrolysis of benzene and hydrochloric acid
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 491

Apart from oxychlorination these processes rination of chlorobenzene with ferric chloride,
are not industrially important. In oxychlorina- high selectivity in favor of 1,4-dichlorobenzene
tion, benzene vapor and a mixture of hydrogen (1,4 : 1,2-dichlorobenzene ratio till 25) is
chloride and air are reacted at about 240  C in the achieved [40, 70].
presence of catalysts (e.g., CuCl2–FeCl3/Al2O3 Chlorobenzenes can also be produced by
or CuO – CoO/Al2O3). The main product is electrolysis [78, 79], resulting in high selectivity
monochlorobenzene accompanied by 6 – 10 % for monochlorobenzene (98 %) and in the excep-
dichlorobenzene [49–57]. tional yield of 94 % [80].
C6 H6 þHClþ0:5O2 !C6 H5 ClþH2 O
Other Processes. The conversion of substi-
tuted aromatics to chlorobenzenes is of particular
This process was developed in connection with interest in connection with the preparation of not
the production of phenol from chlorobenzene easily accessible isomers, such as 1,3-dichloro-
(Raschig-Hooker process; ! Phenol). The ben- benzene and 1,3,5-trichlorobenzene. The re-
zene conversion must be limited to 10 – 15 % in placement of amino [81, 82], nitro [83–85],
order to control the heat in the catalyst solid bed sulfonic acid or sulfonyl chloride [86–90], or
(222 kJ/mol). An excessively high reaction temper- acyl chloride groups [91] by chlorine leads to
ature favors the formation of dichlorobenzene and a appropriate specialty chlorobenzenes.
side reaction, the highly exothermic oxidation of
benzene to carbon dioxide and water (330 kJ/mol).
Concerning material balance and heat, see 2.3.2. Monochlorobenzene
[58]. The high cost of energy and for a corro-
sion-resistant plant, as well as an insufficient shift Most monochlorobenzene is now produced from
of the ratio of monochlorobenzene to dichloro- benzene and chlorine in continuously operated
benzene, makes the process uneconomical. plants. Depending on the ratio of benzene to
Gulf has developed a process for the oxychlor- chlorine chosen, one can achieve either a low
ination of benzene in the liquid phase under rate of benzene conversion and little dichloro-
pressure with aqueous hydrochloric acid, cata- benzene formation, or almost complete conver-
lytic quantities of nitric acid, and air or oxygen. sion of the benzene with a higher degree of
The process leads to a high rate of benzene dichlorobenzene formation. Which of the two
conversion and good selectivity for monochlor- alternatives is favored depends on a profitability
obenzene [59], but it has not been reported calculation, in which the distillation costs occa-
whether commercial operation has commenced. sioned by the dichlorobenzenes need to be taken
The reaction of benzene and chlorine at 400 to into account. The composition of a chlorination
500  C in the vapor phase [60, 61] is likewise mixture containing the highest possible propor-
uneconomical. One interesting feature is associat- tion of monochlorobenzene has been given as 4 –
ed with vapor phase chlorination catalyzed by non- 5 % unreacted benzene, 73 % monochloroben-
metals, however: the isomer ratio at the dichloro- zene, and 22 – 23 % dichlorobenzene [38].
benzene stage is shifted in the direction of m- The production of monochlorobenzene from
dichlorobenzene (10 % ortho, 66 % meta, 24 % benzene, hydrogen chloride, and air has been
para isomer). This effect is a consequence of the described briefly in Section 2.3.
radical chain mechanism that is followed [62, 63]. Only if special chlorinating agents are used
Chlorine compounds are more selective for benzene can be chlorinated to monochloroben-
chlorination than chlorine itself, and they are thus zene without dichlorobenzene being formed
used in the manufacture of special chloroben- simultaneously [68].
zenes. The range of suitable chlorinating agents
includes metal chlorides (e.g., of iron, antimony,
titanium, and copper) of different valence stages 2.3.3. Dichlorobenzenes
[64–71], sulfuryl chloride [72–75], chlorine
monoxide [76], and chlorosulfuric acid [77]. The Dichlorobenzenes are formed unavoidably in the
latter three compounds are particularly suitable production of monochlorobenzene. They arise as
for the perchlorination of aromatics. In the chlo- isomeric mixtures with a low content of the
492 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

1,3-isomer. A maximum dichlorobenzene concen- p-dichlorobenzene crystallization. Combined


tration of 98 % is obtainable in a batch process in crystallization/distillation processes, extractive
which 2 mol of chlorine is used per mole of benzene distillation [98], or separation on zeolites [99]
in the presence of ferric chloride and sulfur mono- are feasible. However, there also exist synthetic
chloride at mild reaction temperatures. The remain- processes which lead directly to 1,3-
der of the product consists of mono- and trichlor- dichlorobenzene:
obenzene. About 75 % 1,4-dichlorobenzene, 25 %
1,2-dichlorobenzene, and only 0.2 % 1,3-dichloro- Chlorination of benzene in the gas phase at 200 –
benzene are obtained [92]. If the reaction is carried 500  C in a tube or in molten salt [60, 61, 100].
out with only ferric chloride as catalyst the maxi- Sandmeyer reaction of 3-chloroaniline [81, 101]
mum yield of dichlorobenzene is ca. 85 %. For or direct replacement of the amino group by
further information about the effects of catalysts on chlorine [102].
isomer distribution, see Table 3. Reaction of 1,3,5-trialkylbenzene with chlorine
If discontinuous separation of dichloroben- in the presence of I2 or ferric chloride to give
zene isomer mixtures is to be carried out, a 2,6-dichloro-1,3,5-trialkylbenzene, the alkyl
distillation column with at least 60 practical groups then being cleaved in the presence of
plates is needed. At a reflux ratio of about aluminum chloride [103, 104].
35 : 1, monochlorobenzene (if present), 1,3-di- Chlorination of 1,3-dinitrobenzene or chloroni-
chlorobenzene – 1,4-dichlorobenzene mixture, trobenzene at a temperature above 200  C
and 1,2-dichlorobenzene are removed succes- [83–85].
sively at the top of the column. Two-step chlorination of benzenesulfonyl chlo-
The intermediate fractions are recycled, their ride or diphenyl sulfone, with sulfur dioxide
amounts being dependent on the separation ca- being eliminated [89, 90].
pability of the column. Cleavage of sulfur dioxide or carbon dioxide
The 1,4-dichlorobenzene fraction is concen- from the corresponding disulfonyl chlorides
trated from the melt by crystallization – in one or or dicarbonic acid chlorides at temperatures
more steps, depending on the impurities present. above 200/300  C in the presence of catalysts
It can then be separated into pure 1,4-dichloro- [86, 88, 91].
benzene and the eutectic of 1,3-dichlorobenzene Catalytic dechlorination of 1,2,4-trichloroben-
and 1,4-dichlorobenzene (14.7 % 1,4- and 85.3 % zene with hydrogen in the vapor phase
1,3-dichlorobenzene). In industry (for economic [105, 106].
reasons), the fraction is not cooled until the Isomerization of 1,2- and 1,4-dichlorobenzene at
eutectic is obtained. Several different techniques a temperature of 150 – 200  C in the presence
are employed for the melt crystallization [93], of catalysts containing aluminum chloride
e.g., the batch tube bundle crystallizer (a new [107–109]. The conversion to 1,3-dichloro-
development of this type is the Proabd-Raffi- benzene is said to be quantitative if the
neur), the semi-continuous falling film crystal- isomerization is carried out in an antimony
lizer from Sulzer-MWB, or the continuous puri- pentafluoride – hydrogen fluoride system at
fiers from Brodie or Kureha Chem. Ind. 20  C [110].
Small amounts of 1,2- and 1,3-dichloroben-
zene that are present as contaminants in 1,4- Except in the case of the chlorinolysis of 1,3-
dichlorobenzene can be removed chemically by dinitrobenzene, no details are available on the
exploiting the fact that they are considerably extent to which these processes are employed on
more reactive than 1,4-dichlorobenzene. In sul- an industrial scale.
fonation [94, 95], bromination [96], chlorination
[97], and other reactions first the 1,3- and then the
1,2-dichlorobenzene are consumed; this leaves 2.3.4. Trichlorobenzenes
pure 1,4-dichlorobenzene, which can be separat-
ed by some suitable means. 1,2,3-Trichlorobenzene and 1,2,4-trichloroben-
Pure 1,3-dichlorobenzene can be obtained by zene are formed in minor quantities in the pro-
working up the unavoidable 1,3-dichloroben- duction of monochlorobenzene and dichloroben-
zene-containing mother liquor that results from zene. Trichlorobenzenes become the main
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 493

product if the chlorine input is increased to about by chlorination of 3,5-dichloronitrobenzene


3 mol of chlorine per mole of benzene. [125] or 1-bromo-3,5-dichlorobenzene at 300 –
The batch reaction of benzene with a 2.8-fold 400  C [126]. The proportion of the 1,3,5-isomer
molar quantity of chlorine in the presence of fer- in a mixture can be raised by isomerization of the
ric chloride at temperatures increasing to 100  C other trichlorobenzenes with aluminum chloride
gives a chlorination mixture consisting of 26 % [127, 128] or by reacting tetrachlorobenzenes
1,4-dichlorobenzene, 4.5 % 1,2-dichloroben- and higher chlorobenzenes with alkali metal
zene, 48 % 1,2,4-trichlorobenzene, 8 % 1,2,3- amides [129]. Total isomerization is reported to
trichlorobenzene, 8 % 1,2,3,4-tetrachloroben- occur when SbF5 – HF is used as a catalyst sys-
zene, 5.5 % 1,2,4,5-tetrachlorobenzene, and less tem [110]. The three trichlorobenzenes can be
than 1 % pentachlorobenzene. The proportion of separated by distillation and crystallization.
1,4-dichlorobenzene, and thus also of 1,2,4-tri-
chlorobenzene, can be raised by adding sulfur
compounds as cocatalysts. After the chlorination 2.3.5. Tetrachlorobenzenes
mixture has been neutralized it can be separated
by fractional distillation provided a column with 1,2,3,4-Tetrachlorobenzene and 1,2,4,5-tet-
more than 60 practical plates is used. rachlorobenzene are obtained by chlorination of
1,2,4-Trichlorobenzene can be obtained more benzene or of intermediate fractions obtained in
directly by starting with pure 1,4-dichloroben- the production of di- and trichlorobenzene. An-
zene. Because of the directing influence of the timony trichloride – iodine [130] is a catalyst
chlorine substituents present (see Section 2.2), combination that is particularly effective in
only 1,2,4-trichlorobenzene and (to an extent giving 1,2,4,5-tetrachlorobenzene, the industri-
depending on the degree of conversion) higher ally preferred isomer (cf. Table 3). It is advis-
chlorobenzenes are formed. able to discontinue the chlorination before an
Another production method applicable to appreciable amount of hexachlorobenzene has
1,2,4- and 1,2,3-trichlorobenzenes is based on formed, since the low solubility of this com-
the dehydrohalogenation of 1,2,3,4,5,6-hexa- pound makes separation of the chlorination
chlorocyclohexane (stereoisomeric mixture), a mixture difficult. After the lower chlorinated
byproduct of g-hexachlorocyclohexane produc- benzenes have been removed by distillation, the
tion (! Insect Control). In the presence of aque- tetrachlorobenzenes are separated from one an-
ous alkali or alkaline earth solutions [111–114] other by crystallization with or without a solvent
or of ammonia [115], or directly through use of (the eutectic mixture consists of 12 % 1,2,4,5-
catalysts [116–122], hexachlorocyclohexane is and 88 % 1,2,3,4-tetrachlorobenzene and has a
converted at a temperature of 90 – 250  C mainly freezing point of 35  C).
to trichlorobenzene. The yield lies between 80 The 1,2,4,5-tetrachlorobenzene crystals
and 99 %, with the product mixture consisting of which result are of high purity. The fraction
70 – 85 % 1,2,4-trichlorobenzene and 13 – 30 % containing 1,2,3,4-tetrachlorobenzene must be
1,2,3-trichlorobenzene. purified by distillation, however.
It should be pointed out that polychlorinated
dibenzofurans and dibenzodioxins are formed 1,2,3,5-Tetrachlorobenzene which is not
during the reaction. available by direct chlorination of benzene, can
References to further literature on the decom- be obtained by chlorination of 1,3,5-
position of benzene hexachloride will be found in trichlorobenzene.
[123].

1,3,5-Trichlorobenzene is not formed in the 2.3.6. Pentachlorobenzene


course of liquid phase chlorination of benzene
(see Section 2.3). It can be produced, however, by Pentachlorobenzene is of no economic signifi-
Sandmeyer reaction on 3,5-dichloroaniline, by cance. Chlorination of benzene gives a mixture of
reaction of benzene-1,3,5-trisulfonic acid deri- tetra-, penta-, and hexachlorobenzenes, from
vatives with phosgene [88], by vapor phase which pentachlorobenzene can be isolated by
chlorination of 1,3-dichlorobenzene [124], and combined distillation and crystallization steps.
494 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

2.3.7. Hexachlorobenzene robenzene, < 0.5 % trichlorobenzene, remainder


1,4- and 1,3-dichlorobenzene
Hexachlorobenzene can be produced by exhaus- Pure grade: > 99.8 % 1,2-dichlorobenzene,
tive chlorination of benzene, using chlorine in the < 0.05 % chlorobenzene, < 0.1 % trichloroben-
presence of such catalysts as ferric chloride. The zene, < 0.1 % 1,4-dichlorobenzene.
reaction is conducted at a temperature above
230  C in the liquid or vapor phase [131–133]. 1,3-Dichlorobenzene 85 – 99 %, < 0.01 %
Because much of the chlorine remains unreacted chlorobenzene, < 0.1 % 1,2-dichlorobenzene,
and because hexachlorobenzene sublimes, the remainder 1,4-dichlorobenzene.
off-gas from the process is passed through fresh
starting material, in the course of which the 1,4-Dichlorobenzene > 99.8 %, < 0.05 %
chlorine is reacted and the sublimate washed out. chlorobenzene and trichlorobenzene, < 0.1 %
The difficulties caused by sublimed hexachlor- 1,2- and 1,3-dichlorobenzene, bulk density about
obenzene can be eliminated by batch chlorina- 0.8 kg/L.
tion with liquid chlorine in an autoclave [134].
Hexachlorobenzene can also be produced by 1,2,4-Trichlorobenzene > 99 %, < 0.5 %
decomposition of hexachlorocyclohexane in the dichlorobenzenes, < 0.5 % 1,2,3-trichloroben-
presence of chlorine. The resulting lower chlori- zene, < 0.5 % tetrachlorobenzenes.
nated benzenes, mainly trichlorobenzenes, are
converted to hexachlorobenzene without first 1,2,4,5-Tetrachlorobenzene > 98 %,
needing to be isolated [135–137]. < 0.1 % trichlorobenzenes, < 2 % 1,2,3,4-tetra-
High yields of hexachlorobenzene are obtain- chlorobenzene, bulk density about 0.9 kg/L.
able under very mild reaction conditions when
chlorine-containing reagents such as chlorine
monoxide [76] or chlorosulfuric acid/iodine are 2.5. Storage and Transportation
used [77].
The chlorobenzenes are all neutral, stable com-
pounds which can be stored in the liquid state in
2.4. Quality and Analysis steel vessels. The official regulations of various
countries must be adhered with respect to the
The usual separating processes employed in in- equipment of storage vessels, e.g., safety reser-
dustry give chlorobenzenes of high purity. Those voir requirements, overflow prevention, and off-
impurities which remain, as well as their con- gas escape systems.
centrations, depend on the nature of the produc- Chlorobenzenes that are liquid at ambient
tion process and the separating technique temperatures are shipped in drums, containers,
applied. or road/rail tankers. Solid compounds, such as
The method now used almost exclusively to 1,4-dichlorobenzene and 1,2,4,5-tetrachloroben-
determine the quantitative compositions of com- zene, can be transported in the molten state in
mercial chlorobenzenes is gas chromatography, heatable road/rail tankers or as granules or flakes
an approach which is both rapid and reliable. in paper sacks and fiber drums. Steel containers
Glass capillary and specially packed columns are are suitable. Any paper or fiber materials that are
used. For those chlorobenzenes with solidifica- used must be impermeable to vapors arising from
tion points above 0  C, the temperature of solidi- the product.
fication can serve as a criterion of purity of the Liquid transfer must incorporate provisions
main component. Typical analyses of several for gas compensation, as well as protection
commercial chlorobenzenes are as follows: against static charge. Chlorobenzene vapors
form flammable mixtures with air. The com-
Monochlorobenzene > 99.9 %, < 0.02 % pounds are regarded as potential water pollutants
benzene, < 0.05 % dichlorobenzenes. and must not be allowed to enter groundwater.
Spills must be collected (proper precautions
1,2-Dichlorobenzene. Technical grade: being taken to safeguard the health of the workers
70 – 85 % 1,2-dichlorobenzene, < 0.05 % chlo- involved) and burned in a suitable incinerator.
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 495

Table 6. Freight classification

GGVE/GGVS and IMDG Code and IATA-DGR US-DOT


RID/ADR

class number class UN No. pack. group

Monochlorobenzene 3 3 3.3 1134 II UN 1134 Flamm. liquid


1,2-Dichlorobenzene 3 4 6.1 1591 III ORM. A UN 1591
1,4-Dichlorobenzene – 6.1 1592 III ORM. A UN 1592
1,3-Dichlorobenzene 3 4 6.1 1591 III ORM. A UN 1591
Trichlorobenzene 6.1 62 6.1 2321 III Poison B UN 2810
Tetrachlorobenzene – 6.1 2811 III Poison B UN 2811
Hexachlorobenzene 6.1 62 6.1 2729 III Poison B UN 2811

It should be noted that chlorobenzenes may 1,4-Dichlorobenzene is used mainly in the


decompose with the release of hydrogen chloride production of disinfectant blocks and room deo-
if they are exposed to severe heat. dorants and as a moth control agent. After conver-
Freight classifications are given in Table 6. sion into 2,5-dichloronitrobenzene, it finds appli-
cation in the production of dyes. It is also used in
the production of insecticides and, more recently,
2.6. Uses of polyphenylene-sulfide-based plastics, materials
with excellent thermal stability [138, 139].
The chlorobenzenes, particularly mono-, 1,2-di-,
and 1,2,4-trichlorobenzene, are widely used as 1,2,4-Trichlorobenzene is used as a dye
solvents in chemical reactions and to dissolve carrier and (via 2,4,5-trichloronitrobenzene) in the
such special materials as oils, waxes, resins, production of dyes. Other uses are associated with
greases, and rubber. They are also employed in textile auxiliaries and pesticide production (where
pesticide formulations (the highest consumption 2,5-dichlorophenol serves as an intermediate). In
of monochlorobenzene in the United States). the field of electrical engineering, it finds use as an
additive for insulating and cooling fluids.
Monochlorobenzene is nitrated in large The hydrolysis of 1,2,4,5-tetrachloroben-
quantities, the product subsequently being con- zene to 2,4,5-trichlorophenol, an intermediate
verted via such intermediates as nitrophenol, for pesticides, has been almost entirely discon-
nitroanisole, nitrophenetole, chloroaniline, and tinued throughout the world due to the risk of
phenylenediamine into dyes, crop protection formation of 2,3,7,8-tetrachlorodibenzo-p-diox-
products, pharmaceuticals, rubber chemicals, in (TCDD).
etc. The production of phenol, aniline, and DDT Pentachlorothiophenol, a mastication agent
from monochlorobenzene, formerly carried out used in the rubber industry, is obtained from
on a large scale, has been almost entirely dis- hexachlorobenzene. In the Federal Republic of
continued due to the introduction of new pro- Germany, the use of hexachlorobenzene as an
cesses and legislation forbidding the use of active ingredient for pesticides has been prohib-
DDT. ited since 1981.

1,2-Dichlorobenzene after conversion to Producers of chlorinated benzenes are: Anic


1,2-dichloro-4-nitrobenzene, is used mainly in SpA (Italy); Bayer AG (FRG); Hodogaya Chem-
the production of dyes and pesticides. It is also ical Co., Ltd. (Japan); Hoechst AG (FRG); Kur-
used to produce disinfectants and deodorants and eha Chemical Ind. Co., Ltd. (Japan); Mitsui Toat-
on a small scale as a heat transfer fluid. su Chemicals, Inc. (Japan); Monsanto Chemical
Corp. (USA); Nippon Kayaku Co., Ltd. (Japan);
1,3-Dichlorobenzene is used in the produc- Produits Chimiques Ugine Kuhlmann SA
tion of various herbicides and insecticides. It is (France); Rhône-Poulenc Chimie de Base
also important in the production of pharmaceu- (France); Standard Chlorine Chemical Co., Inc.
ticals and dyes. (USA); Sumitomo Chemical Co., Ltd. (Japan).
496 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

2.7. Toxicology Table 8. Physical properties of the monochlorotoluenes

Acute Toxicity. Table 7 shows the LD50’s of


chlorinated benzenes. According to these data, the
acute oral toxicity of chlorinated benzenes is low to
moderate. Absorption through the skin seems to be
minimal, but most of the compounds have some
local irritant potency. In experimental animals,
most chlorinated benzenes induce microsomal liv-
er enzymes and cause porphyria, hypertrophy, and
centrolobular necrosis of the liver. The chlorinated
benzenes can induce kidney damage, changes in
mucous membranes, and irritation of the upper
respiratory tract, depending on the route and time
of administration and on the dose applied. In
addition, mono-, di-, and trichlorobenzenes are
known to act as central nervous depressants, caus-
ing anesthesia and narcosis at higher doses [271,
272].

Chronic Effects. Hexachlorobenzene pro-


duced tumors in studies with mice and hamsters
[271]. There is no evidence for the carcinogenic-
ity of the other chlorobenzenes. None of the
compounds showed mutagenic activity in vali-
dated test systems. No data concerning terato-
genic or embryotoxic effects of the chlorinated
benzenes are available for most of the com-
pounds. p-Dichlorobenzene has been tested in
several species and produced no primary embry-
otoxic or teratogenic effects [292].

Metabolism. Usually the chlorinated ben-


zenes are partially hydroxylated to yield the
corresponding phenols or are partially dechlori-
nated and then excreted in the urine and the feces.
In contrast to rodents, sulfur-containing metabo-
lites cannot be found in monkeys and humans
[271, 293, 294]. Only hexachlorobenzene has
been shown to accumulate in animals and hu-
mans [295, 296].

Table 7. Oral LD50s of chlorobenzenes [291]

Compound LD50 (rat, oral),


mg/kg

Monochlorobenzene 2 910
o-Dichlorobenzene 500
p-Dichlorobenzene 500
1,2,4-Trichlorobenzene 756
1,2,4,5-Tetrachlorobenzene 1 500
Pentachlorobenzene 1 080
Hexachlorobenzene 10 000
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 497

Table 9. Physical properties of the dichlorotoluenes

Hexachlorobenzene has been suggested to clude headache, nausea, throat irritation, and sting-
produce immunotoxic effects in experimental ing of the eyes. Skin irritation is also reported [272].
animals, i.e., alterations of cell-mediated im- No data are available on the effects of trichlor-
mune responses [271]. obenzenes in humans. Only minimal eye and throat
irritation at 3 – 5 ppm in certain people are reported
Effects in Humans. Monochlorobenzene pro- [272]. An outbreak of cutanea tarda porphyria in
duced unconsciousness, vascular paralysis, and Turkey in 1955 was attributed to the uptake of grain
heart failure in a child after accidental oral uptake treated with hexachlorobenzene as fungicide [271].
[271]. o-Dichlorobenzene produced depression in
conditioned reflex activity, demonstrating a cere- Regulations. The following occupational
bral – cortical effect. Erythropoiesis was signifi- exposure limits have been established (MAK
cantly depressed. Symptoms of intoxication in- 2001, TLV 1985):

Table 10. Physical properties of the trichlorotoluenes


498 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

Table 11. Physical properties of tetra- and pentachlorotoluenes

organic solvents, particularly at elevated


Monochlorobenzene: MAK 10 ppm TLV 75 ppm
temperatures.
o-Dichlorobenzene: MAK 10 ppm TLV 50 ppm
p-Dichlorobenzene: Carcinogen in animal TLV 75 ppm
experiments
1,2,4-Trichlorobenzene: Suspected carcinogen 3.2. Chemical Properties

The chlorotoluenes are neutral and stable


compounds.
3. Chlorinated Toluenes Chemical reactions may occur at unsubsti-
tuted positions on the aromatic ring (e.g. haloge-
3.1. Physical Properties nation, nitration, or sulfonation), by replacement
The chlorotoluenes occur in five chlorination of the chlorine substituent (e.g, hydrolysis), and
stages, four of which have several isomers: on the methyl group (e.g., side-chain chlorination
or oxidation).
The influence of the methyl group of toluene
Formula Num- Table in leads to electrophilic substitution at positions 2 and
ber of which phys-
isomers ical data 4, whereas in chlorotoluenes the directing influ-
are given ences of the methyl and chlorine groups overlap
Monochlorotoluenes C7H7Cl 3 8
unpredictably. Introduction of a third substituent
Dichlorotoluenes C7H6Cl2 6 9 (e.g., – Cl, – NO2, – SO3H) into 2-chlorotoluene
Trichlorotoluenes C7H5Cl3 6 10 can lead to all four possible isomers being formed,
Tetrachlorotoluenes C7H4Cl4 3 11 though position 5 is occupied preferentially. In 4-
Pentachlorotoluene C7H3Cl5 11
chlorotoluene, position 2 is the most preferred
position. The chlorine atoms in these compounds
All of the monochlorotoluenes are colorless, are bound very firmly to the aromatic ring and
mobile, flammable liquids with a faint odor, similar cannot be displaced except under forcing condi-
to that of benzene; they form binary azeotropes tions. Nevertheless, the hydrolysis of monochlor-
with many organic compounds [10, 11] (Table 8). otoluene with sodium hydroxide solution is possi-
The dichlorotoluenes, apart from 3,5-dichlor- ble at 350 – 400  C and pressures up to 30 MPa
otoluene, are liquid at room temperature, and (300 bar), the result being isomeric cresol mixtures.
they are likewise colorless and flammable Hydrogenation of chlorotoluenes over noble
(Table 9). The tri, tetra-, and pentachloroto- metal catalysts leads to dechlorination, just as in
luenes are colorless crystalline compounds the case of chlorobenzenes.
(Tables 10, 11). Chlorine substituents can be exchanged for
The liquid chlorotoluenes are good solvents amino groups [140], but this reaction has no
and are miscible with most organic solvents. industrial application.
All chlorotoluenes are insoluble in water. The Under free-radical conditions at elevated
polychlorotoluenes can be dissolved in many temperatures, it is possible to replace sequentially
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 499

the three hydrogen atoms of the methyl group by With most catalyst systems, a high reaction tem-
halogen, leading to ring-chlorinated benzyl-, ben- perature favors ortho and meta substitution as
zal-, and benzotrihalides (see ! Benzyl Chloride well as further chlorination. Reducing the tem-
and Other Side-Chain Chlorinated Aromatic perature favors substitution in the para position
Hydrocarbons). and increases the total yield of monochloroto-
Oxidation of the methyl group leads to chlori- luene. Because of the directing influence of the
nated benzaldehydes and benzoic acids [141, 142]. methyl group, the 3-chlorotoluene fraction of
Catalytic ammonoxidation with oxygen and crude monochlorotoluene is limited to between
ammonia at 350 – 550  C converts the methyl 0.2 and 2 % depending on the catalyst. The influ-
group into a nitrile group [143]. ence of catalysts on the ratio of 2-chlorotoluene to
The polychlorinated toluenes are similar to 4-chlorotoluene is apparent from the data in
one another in their chemical behavior. Their Table 12. Selectivity is seen to be inversely
principal industrial use is in the manufacture of proportional to the activity of the catalyst [144].
side-chain-halogenated products. Solvents also, influence the isomer distribu-
tion. This fact is of little significance, however,
because the toluene reactant in industrial chlor-
3.3. Production inations is not diluted with solvents.
The reaction is usually conducted at a tem-
Toluene Chlorination in the Liquid perature between 20 and 70  C. Chlorination at
Phase. Monochlorotoluenes are produced on temperatures below 20  C is uneconomical be-
a large scale by reacting liquid toluene with cause the rate of reaction is too low.
gaseous chlorine at a moderate temperature and Toluene has a higher p-basicity than benzene,
normal pressure in the presence of catalysts. however, and it therefore, shows a substantially
Mixtures of isomers reflecting various chlorina- higher rate of chlorination than the latter. As a
tion stages are obtained. The chlorination con- result, it can be chlorinated at relatively low
ditions should be such as to give the highest temperatures (Table 13).
possible yield of monochlorotoluene, because This fact permits efficient conversion of tolu-
the dichlorotoluenes, all isomeric forms of which ene to monochlorotoluenes without a substantial
(with the exception of 3,5-dichlorotoluene) re- quantity of dichlorotoluenes also being formed
sult, cannot be separated economically. The rel- (see Table 12).
ative proportions of the various chlorotoluenes At a moderate reaction temperature (below
obtained can be varied within wide limits by 100  C), only traces of side-chain-chlorinated
altering the reaction conditions and catalyst. products are formed, provided activation by light

Table 12. Influences of catalysts on the 2- : 4-chlorotoluene ratio

Catalyst 2- : 4-Chlorotoluene Dichlorotoluene Toluene Ref.


ratio in the chlorination conversion, %
mixture, %

TiCl4, SnCl4, WCl6 or ZrCl4 3.3 1.5 99 [145]


[C6H5Si(OH)2O]4Sn 2.2 [146]
FeCl3 1.9 4.5 75 [147]
SbCl3– diethylselenide 1.9 50 [148]
SbCl3 1.6 [38]
AlCl3– KCl 1.5 <1 16 [149]
SbCl3– thioglycolic acid 1.2 [38]
FeCl3– S2Cl2 1.1 1.0 99 [147]
Ferrocene – S2Cl2 1.06 0.2 67 [150]
Lewis acids – thianthrene 0.91 – 1.1 [151]
FeCl3– diphenylselenide 0.93 91 [148]
PtO2 0.89 2 96 [152]
SbCl3– phenoxathiin derivative 0.66 – 0.88 0.2 – 0.4 96 – 99 [153]
SbCl3– tetrachlorophenoxathiin 0.85 – 0.87 [154]
SbCl3– di- or tetrachlorothianthrene 0.7 – 0.9 0.1 – 0.2 [155]
Fe – polychlorothianthrene 0.76 1.2 95 [156]
500 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

Table 13. Comparison of catalytic chlorination of benzene and toluene Chlorination in the vapor phase with chlorine
Catalyst system Ratio of the chlo- Ref.
[160]
rination rates of Chlorination in the vapor or liquid phase with
toluene to benzene hydrogen chloride and air (oxychlorination)
FeCl3 16 [147] Chlorination with chlorine-containing
FeCl3– S 200 [147] compounds
Glacial acetic acid 345 [157] Electrolysis of toluene and hydrochloric acid

The oxidative chlorination of toluene with


is prevented and effective catalysts are used hydrogen chloride – air at a temperature of
(ones for which amounts of no more than several 150 –500  C in the presence of cupric chloride
tenths of a percent are required). as both catalyst and chlorinating agent gives
Both batch and continuous processes are used mono- and dichlorotoluenes along with varying
commercially, with the former being more amounts of side-chain-chlorinated products [56,
selective with respect to particular stages of chlo- 161–163]. In the Gulf process, the toluene is
rination. For continuous processes, it is necessary chlorinated with hydrochloric acid – oxygen in
to choose a toluene : chlorine starting ratio which the liquid phase in the presence of nitric acid and
gives a lower degree of toluene conversion to an additional strong acid at a temperature of
maximize the formation of monochlorotoluene. 60 – 150  C and pressures of 350 – 1000 kPa. By
The remarks in Section 2.3 on the continuous adding alkanes, e.g., n-octanes, the extent of
and batch chlorination of benzene apply corre- side-chain attack can be reduced to 0.7 %. The
spondingly to the chlorination of toluene. Pro- addition of trialkylphenols is claimed to im-
blems related to reactor design, materials, and prove the selectivity so that only one chlorine
dissipation of heat – 139 kJ is set free per mole of atom reacts with a given aromatic nucleus [164].
monochlorotoluene [158] – are also comparable. Good monochlorotoluene yields are obtained at
The ignition temperature of toluene in gaseous 50  C if ferric chloride is used as a chlorinating
chlorine lies at 185  C. The explosive limits of agent in the presence of Lewis acids, such as
toluene in chlorine lie between 4 and 50 vol %. titanium chloride and aluminum chloride (o-
Conventional refinery toluene is sufficiently pure chlorotoluene : p-chlorotoluene ratio 0.1 –
to serve as the starting material. 0.15) [40, 69, 165, 166]. Polymeric byproducts
Traces of water that are entrained with tech- are also formed but the side-chains are said to be
nical chlorine and toluene have no influence on unattacked.
the composition of the product. They must not be Sulfuryl chloride [72, 167] and chlorine mon-
so large as to reduce the efficiency of the catalyst, oxide [72] are other possible chlorinating agents.
however. Monochlorotoluene can also be manufactured
One process for reducing the water content of electrochemically. Thus, toluene can be chlori-
the toluene below 30 ppm involves stripping with nated electrochemically in methanol to which
hydrogen chloride, and is described in a patent on water and sodium, ammonium, or lithium chlo-
the continuous production of monochlorotoluene ride has been added. High yields of monochlor-
[159]. otoluene result without dichlorotoluene being
As with the chlorobenzenes, the crude chlor- formed [168].
otoluene mixture may be worked up by neutrali-
zation followed by separation in a distillation Other Processes. Only a few of the isomeric
train. If the side-chain contains a detectable chlorotoluenes can be produced economically by
amount of chlorine, then this chlorine should be direct chlorination and separation of the reaction
removed in order to prevent corrosion (e.g., pres- mixture. The other chlorotoluenes must be pro-
sure washing with aqueous alkaline solution may duced by indirect syntheses involving such steps
be carried out before the mixture enters the still). as the replacement of amino substituents by
chlorine [81, 102] or introduction of meta-direct-
Other Toluene Chlorination Processes. ing sulfonic acid groups, which are then removed
The following toluene chlorination processes are after chlorination on the ring [169, 170]. See the
known in addition to liquid phase chlorination: following Sections for additional information.
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 501

3.3.1. Monochlorotoluenes mixtures. Only 2,4-, 2,5-, and 3,4-dichloroto-


luene can be produced economically by direct
Both 2- and 4-chlorotoluene are produced by chlorination of the appropriate pure monochlor-
chlorination of toluene, as described in Section otoluene isomers.
3.3. The economic importance of 4-chloroto-
luene is presently greater than that of 2-chlor- 2,3-Dichlorotoluene. In the chlorination of
otoluene, a circumstance which has led to the 2-chlorotoluene with ferric chloride, approxi-
development of new catalyst systems (see mately 15 % of the product is 2,3-dichloroto-
Table 12), which increase the output of the para luene, accompanied by 2,4-, 2,5-, and 2,6-di-
isomer. The batch chlorination of toluene at chlorotoluene; the former can be separated by
50  C in the presence of ferric chloride (or of distillation. Its production by a Sandmeyer reac-
ferric chloride – sulfur monochloride at 40  C tion on 3-amino-2-chlorotoluene is more eco-
the values for which are given in parentheses nomical, however.
for comparison) gives at most 83 % (98 %)
monochlorotoluene, with 52 % (52 %) of the 2,4-Dichlorotoluene. Chlorination of 4-
product being o-chlorotoluene, 2 % (0.3 %) chlorotoluene in the presence of ring chlorination
m-chlorotoluene, and 28 % (46 %) p-chloroto- catalysts (e.g. chlorides of iron, antimony, or
luene, in addition to 7 % (1 %) unreacted toluene zirconium) leads to 2,4- and 3,4-dichlorotoluene
and 11 % (1 %) dichlorotoluene [147]. in a ratio of ca. 4 : 1; the two can be separated by
2-Chlorotoluene and 4-chlorotoluene are sep- fractional distillation. Only traces of other di-
arated by fractional distillation. Continuous sep- chlorotoluenes are formed [174, 175]. A low
aration is possible with columns having more reaction temperature reduces the formation of
than 200 theoretical plates, leading to a pure 2- trichlorotoluene. According to [167], 2-chloro-
chlorotoluene distillate and a bottom product toluene is converted primarily into 2,4-dichlor-
containing about 98 % 4-chlorotoluene. The boil- otoluene when sulfuryl chloride is used as the
ing points of 3- and 4-chlorotoluene are so nearly chlorinating agent.
alike that these two isomers cannot be separated
by distillation. As in the production of pure 1,4- 2,5-Dichlorotoluene. The proportion of 2,5-
dichlorobenzene (see Section 2.3.3) the latter dichlorotoluene in the dichlorotoluene fraction
separation must be accomplished by crystalliza- can be raised to 60 % by chlorination of 2-chlor-
tion from the melt. The eutectic mixture contains otoluene with sulfur compounds as catalysts or
77.5 % m-dichlorotoluene and 22.5 % p-dichlor- cocatalysts. The product is separated from the
otoluene and has a solidification point of  63.5 reaction mixture by crystallization [176, 177].

C. Consequently, crystallization from the melt Chlorination with iodine catalysis is also possible
must be conducted at low temperatures. [178]. In addition, 2,5-dichlorotoluene can be
4-Chlorotoluene can also be separated from produced by a Sandmeyer reaction on either 2-
mixtures containing 2- and 3-chlorotoluene by amino-5-chlorotoluene or 2,5-diaminotoluene.
adsorption on zeolites at 200  C and 500 kPa
[171]. 2,6-Dichlorotoluene. This isomer can be pro-
3-Chlorotoluene can be produced from m-tolui- duced by chlorination of p-toluenesulfonyl chloride
dine by a conventional Sandmeyer reaction [172] or in the presence of antimonous chloride, followed by
by isomerization of 2-chlorotoluene on acid zeolites desulfonation [169]. Alternatively it can be made
at 200 – 400  C and 2000 – 4000 kPa, separation of by chlorination of 4-tert-butyltoluene or 3,5-di-tert-
the resulting mixture of 2- and 3-chlorotoluene butyltoluene with subsequent dealkylation [179,
being effected by distillation [171, 173]. 180] or by means of a Sandmeyer reaction on 2-
amino-6-chlorotoluene [181]. Distillatory separa-
tion of the 2,6-dichlorotoluene from a chlorination
3.3.2. Dichlorotoluenes mixture (in which it constitutes about 30 % of the
dichlorotoluene fraction) is prohibitively expen-
The isomers of dichlorotoluene have very similar sive. It is impossible at this time to assess the
chemical and physical properties, making it dif- economics of its continuous separation by means
ficult to separate individual components from of adsorption on faujasite-type zeolite [182].
502 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

Table 14. Distribution of the isomeric trichlorotoluenes in the chlorination of toluene

Catalyst 2,3,4- 2,3,6- 2,4,5- 2,4,6-


Trichlorotoluene, % Trichlorotoluene, % Trichlorotoluene, % Trichlorotoluene, %

Ferric chloride 15 46 35 4
Ferric chloride – sulfur
monochloride 11 20 67 2

3,4-Dichlorotoluene. The proportion of 3,4- separation by distillation is impractical. The con-


dichlorotoluene in the product mixture from centration of 2,3,6-trichlorotoluene can be raised to
chlorination of 4-chlorotoluene can be raised to 71 % by fractional crystallization in the absence of
about 40 % if sulfur compounds are used as a solvent. This procedure gives a eutectic mixture
catalysts or cocatalysts. This increase is at the containing 29 % 2,4,5-trichlorotoluene and having
expense of the 2,4-dichlorotoluene [183]. a solidification point of 21.5  C.
Higher yields of 2,3,6-trichlorotoluene are
3,5-Dichlorotoluene. This isomer is not possible from chlorination of 2,3-dichloroto-
formed in the direct chlorination of toluene. Its luene (75 %, in addition to 25 % 2,3,4-trichlor-
indirect synthesis is possible via 2-amino-3,5- otoluene) or 2,6-dichlorotoluene ( 99 %) [84].
dichlorotoluene [184]. 3,5-Dichlorotoluene can 2,3,6-Trichlorotoluene can also be obtained by
also be produced to an extent corresponding to its chlorination of p-toluenesulfonyl chloride or
equilibrium ratio by isomerization of other from 3-amino-2,6-dichlorotoluene by a Sand-
dichlorotoluenes. meyer reaction [186].

2,4,5-Trichlorotoluene. Chlorination of 4-
3.3.3. Trichlorotoluenes chlorotoluene at 20 – 50  C gives > 80 %
2,4,5-trichlorotoluene if ferrous sulfide is used
When toluene is chlorinated with 3 mol chlorine as a catalyst. The product is separated from the
per mole of toluene, four of the six possible chlorination mixture by distillation [188].
trichlorotoluenes are formed in the following
catalyst-dependent ratios (Table 14) [185]. 2,4,6-Trichlorotoluene. The chlorination of
2,4-dichlorotoluene in the presence of ferric
2,3,4-Trichlorotoluene. Chlorination of 4- chloride gives a trichlorotoluene fraction con-
chlorotoluene in the presence of iron trichloride taining 22 % of the 2,4,6-isomer, which can be
leads to a product in which 2,3,4-trichlorotoluene isolated by fractional distillation.
accounts for 22 % of the trichlorotoluene frac-
tion. The compound can be separated from this 3.3.4. Tetrachlorotoluenes
mixture by distillation. It can also be produced
from 3-amino-2,4-dichlorotoluene by using the The three tetrachlorotoluene isomers are all formed
Sandmeyer reaction [186]. when toluene is chlorinated (Table 15) [185].

2,3,6-Trichlorotoluene. The chlorination of 2,3,4,5-Tetrachlorotoluene. The proportion


2-chlorotoluene with an iron powder catalyst gives of the 2,3,4,5-isomer in the tetrachlorotoluene
a trichlorotoluene fraction containing 63 % 2,3,6- fraction can be raised to 49 % by starting with
trichlorotoluene [187]. As 2,3,6- and 2,4,5-tri- 2,4,5-trichlorotoluene. Its separation by distilla-
chlorotoluene have similar boiling points, their tion is possible.

Table 15. Distribution of the isomeric tetrachlorotoluenes

Catalyst 2,3,4,5- 2,3,4,6- 2,3,5,6-


Tetrachlorotoluene, % Tetrachlorotoluene, % Tetrachlorotoluene, %

Ferric chloride 20 44 36
Ferric chloride – sulfur 25 45 30
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 503

2,3,4,6-Tetrachlorotoluene. Yields of 51 % priate specifications. The following are typical


and 66 % of this isomer are obtainable by chlori- analyses found for several chlorotoluenes:
nation of 2,4,5-trichlorotoluene and 2,3,4-tri-
chlorotoluene, respectively. 2,3,4,6-Tetrachlor-
2-Chlorotoluene
otoluene is the exclusive product of chlorination Content >99 %
of 2,4,6-trichlorotoluene [185]. toluene < 0.1 %
4-chlorotoluene < 0.9 %
2,3,5,6-Tetrachlorotoluene. This isomer is 3-chlorotoluene < 0.01 %
4-Chlorotoluene
obtained by exhaustive chlorination of p-tolue- Technical grade with >98 %
nesulfonyl chloride, followed by desulfonation 3-chlorotoluene < 1%
[170]. 2-chlorotoluene < 0.5 %
The various tetrachlorotoluenes are also dichlorotoluenes < 0.5 %
Pure grade with >99.5 %
obtainable from the corresponding amino com- 3-chlorotoluene < 0.2 %
pounds by the Sandmeyer reaction. 2-chlorotoluene < 0.2 %
dichlorotoluenes < 0.1 %
2,4-Dichlorotoluene
Content >99 %
3.3.5. Pentachlorotoluene 4-chlorotoluene < 0.2 %
2,5-dichlorotoluene < 0.3 %
Exhaustive chlorination of toluene gives penta- 2,6-dichlorotoluene < 0.1 %
chlorotoluene. The reaction can be carried out 3,4-dichlorotoluene < 0.4 %
3,4-Dichlorotoluene
with chlorine in either carbon tetrachloride or Content >95 %
hexachlorobutadiene as solvent in the presence 2,4-dichlorotoluene < 5%
of iron powder and ferric chloride as catalysts trichlorotoluenes < 0.5 %
[189], or with chlorine monoxide in carbon tetra-
chloride as solvent in the presence of an acid, e.g., Chlorotoluenes are preferably analyzed by
sulfuric acid [76]. Sulfuryl chloride, used in the gas chromatography. Packed columns are used
presence of sulfur monochloride and aluminum to separate 2-, 3-, and 4-chlorotoluene. The more
chloride catalysts, is also a suitable chlorinating highly chlorinated toluenes can be separated by
agent, the method being that of O. SILBERRAD [72]. means of glass capillary columns.
Further chlorination of pentachlorotoluene in
the presence of a chlorination catalyst at a temper-
ature above 350  C leads to the formation of 3.5. Storage and Transportation
hexachlorobenzene and carbon tetrachloride [190].
The mono- and dichlorotoluenes are stable, neu-
tral liquids. They are shipped in drums, contain-
3.4. Quality and Analysis ers, and road or rail tankers. Steel is a suitable
material for construction of containers.
The industrially important chlorotoluenes can be For information on storage and handling, see
produced such that they have a high degree of Section 2.5.
purity. No general agreement exists as to appro- Freight classifications are given in Table 16.

Table 16. Freight classification

GGVE/GGVS and IMDG Code and IATA-DGR US-DOT


RID/ADR

class number class UN No. pack. group

2- and 4-Chlorotoluene 3 3 3.3 2238 III UN 1993 Flammable liquid


2,3-Dichlorotoluene 3 4 not restricted
2,4-Dichlorotoluene 3 4 not restricted
2,6-Dichlorotoluene 3 4 not restricted
3,4-Dichlorotoluene 3 4 not restricted
504 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

3.6. Uses 2,3,6-Trichlorotoluene. 2,3,6-Trichloroto-


luene is used on a small scale, together with
Isomeric mixtures of the monochlorotoluenes are 2,4,5-trichlorotoluene, to produce 2,3,6-trichlor-
hydrolyzed to cresol on a considerable scale. obenzoic acid, a herbicide precursor.
Chlorotoluenes are also used as solvents in reac- Producers of chlorinated toluenes are: Bayer
tions and to dissolve special products, e.g., dyes. AG (FRG); Enichem (Italy); Hodogaya Chemi-
cals Co. Ltd. (Japan); Hoechst AG (FRG); Ihara
2-Chlorotoluene. 2-Chlorotoluene is a Chemical Ind., Ltd. (Japan); Occidental Chemi-
starting material in the production of 2-chloro- cal Co., Ltd. (USA).
benzyl chloride, 2-chlorobenzaldehyde, 2-chlor-
obenzotrichloride, 2-chlorobenzoyl chloride and
2-chlorobenzoic acid, which are precursors for 3.7. Toxicology
dyes, pharmaceuticals, optical brighteners,
fungicides, and products of other types. 2-Chlor- Little is known about the toxicity of chlorinated
otoluene is also used in the production of toluenes. The toxicity of o-chlorotoluene is con-
dichlorotoluenes (chlorination), 3-chlorotoluene sidered to be relatively low and in the range of
(isomerization), and o-chlorobenzonitrile (am- that of the chlorinated benzenes. The oral LD50 in
monoxidation). rats is greater than or equal to 1600 mg/kg [272].
Sublethal doses of o-chlorotoluene given orally
4-Chlorotoluene. 4-Chlorotoluene is used to rats produce marked weakness; higher doses
mainly to produce p-chlorobenzotrichloride, produce vasodilatation. Inhalation of 14 000 ppm
from which is obtained p-chlorobenzotrifluoride, for 6 h caused loss of coordination, vasodilata-
an important precursor of herbicides (e.g., tion, labored respiration, and narcosis in rats; 175
trifluralin:a,a,a,-trifluoro-2,6-dinitro-N,N-di- 000 ppm was fatal to one of three rats [272]. o-
propyl-p-toluidine). Other side-chain-chlorinated Chlorotoluene produces moderate skin irritation
products or their derivatives are 4-chlorobenzyl and conjunctival erythema in rabbits [272].
chloride (for pharmaceuticals, rice herbicides, p-Chlorotoluene induced no gene conversion
and pyrethrin insecticides), 4-chlorobenzalde- in Saccharomyces cerevisiae [297]. No data are
hyde (for dyes and pharmaceuticals), 4-chloro- available on chronic effects or effects on repro-
benzoyl chloride (for pharmaceuticals and per- duction caused by chlorinated toluenes.
oxides), and 4-chlorobenzoic acid (for dyes). In humans, no cases of poisoning or skin
4-Chlorotoluene is also a starting material in the irritation caused by chlorinated toluenes have
synthesis of 2,4- and 3,4-dichlorotoluene and of been reported [272].
4-chlorobenzonitrile.
Regulations. o-Chlorotoluene TLV 50 ppm
2,4-Dichlorotoluene. 2,4-Dichlorotoluene
is used via its side-chain-chlorinated intermedi-
ates to produce fungicides, dyes, pharmaceuti- 4. Chlorinated Biphenyls
cals, preservatives, and peroxides (curing agents
for silicones and polyesters). Industrial use of the polychlorinated biphenyls
first began in 1929 in the USA [191, 192]. The
2,6-Dichlorotoluene. 2,6-Dichlorotoluene outstanding properties of these compounds, such
is used to produce 2,6-dichlorobenzaldehyde, a as their high chemical and thermal stability, high
dye precursor, and 2,6-dichlorobenzonitrile, a dielectric constant, and the fact that they form
herbicide. only incombustible gases in an electric arc, made
them appear ideally suited for use as insulating
3,4-Dichlorotoluene. 3,4-Dichlorotoluene and cooling fluids for transformers and as dielec-
is used in small amounts in the production of 3,4- tric impregnants for capacitors.
dichlorobenzyl chloride, 3,4-dichlorobenzalde- In subsequent years many other applications
hyde, 3,4-dichlorobenzotrichloride, and 3,4-di- were found as well (see Section 4.5), particularly
chlorobenzoic acid, from which disinfectants, for isomeric mixtures containing two to six atoms
crop protection products, and dyes are produced. of chlorine per mole of biphenyl.
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 505

Table 17. MAK and TLV values of chlorinated biphenyls 8], [25512-42-9] are colorless crystalline
MAK TLV
compounds (the melting points of the pure iso-
(FRG) (USA) mers lie between 18 and 149  C). When burned
mg/m3 mg/m3 in air, they give rise to soot and hydrogen
Chlorinated biphenyls (42 % Cl) 1 III B 1
chloride.
Chlorinated biphenyls (54 % Cl) 0.5 III B 0.5 The most important products are mixtures
whose principal components are trichlorobi-
phenyl [25323-68-6], tetrachlorobiphenyl
In the mid-1960s, improved analytical meth- [26914-33-0], pentachlorobiphenyl [25429-
ods revealed that polychlorinated biphenyls were 29-2], or hexachlorobiphenyl [26601-64-9].
accumulating in nature as a consequence of their Such mixtures are liquid to viscous (pour points
extremely low rates of biological degradation increase with chlorine content from  22 to
(rates which decrease as the chlorine content þ 18  C), and they are fire-resistant. Further
rises). The compounds were detected in fresh chlorination gives soft to brittle thermoplastic
water in all parts of the world, but also in many waxes.
animals (e.g., birds, fish, and plankton). In the Chlorinated biphenyls are soluble in many
late 1970s, it was further discovered that at organic solvents, particularly when heated, but
temperatures of 500 to 800  C in the presence are soluble in water only in the ppm range.
of oxygen, polychlorinated biphenyls can give Although they are chemically very stable, in-
rise to polychlorinated dibenzofurans and diben- cluding to oxygen of the air, they can be hydro-
zodioxins, including (although to a much smaller lyzed to oxybiphenyls under extreme condi-
extent) the particularly toxic compound 2,3,7,8- tions, e.g., with sodium hydroxide solution at
tetrachlorodibenzodioxin [193–198]. 300 – 400  C and under high pressure. Toxic
In the meantime, all but a few of the well- polychlorodibenzofurans may be formed under
known producers (see Section 4.5) discontinued these conditions.
the production of chlorinated biphenyls. More- The fact that the compounds may eliminate
over, in many countries the production, sale, and hydrogen chloride to a small extent at a high
use of polychlorinated biphenyls have been re- temperature explains why hydrogen chloride
stricted or entirely prohibited by legislation. acceptors are often added to transformer fluids
For many years, o-, m- and p-terphenyl mix- based on polychlorinated biphenyls.
tures were chlorinated and then used as plastici- The excellent electrical property data of poly-
zers, flame retardants, and fillers in thermoplastic chlorinated biphenyls, such as high dielectric
pattern and holding waxes. This application like- constant, low power factor, high resistivity, fa-
wise has been substantially discontinued [199], vorable dielectric loss factor, and high dielectric
particularly in view of the persistent nature of the strength, have already been mentioned.
compounds in question and their accumulation in
the environment. Possible toxicological hazards
are either unknown or have not been adequately
4.2. Disposal
investigated (Table 17).
Many products containing chlorinated biphenyls
In view of the above, this article is devoted
are still in use throughout the world, particularly
primarily to a review of recent patents covering
in transformers, rectifiers, and capacitors with
methods for the disposal of polychlorinated bi-
long service lives. Industry and national govern-
phenyls. For information regarding the produc-
ments are now faced with the need to dispose of
tion of these compounds and their specific physi-
these products without causing additional pollu-
cal and chemical properties, attention is directed
tion of the environment. Appropriate official
to earlier surveys [193, 200, 201].
regulations exist in many countries [199,
202–213].
4.1. Physical and Chemical Properties Attention is drawn in the following survey to
patents concerned with the removal of poly-
There are 209 possible chlorinated biphenyls. chlorinated biphenyls from electrical devices and
The mono- and dichlorobiphenyls [27323-18- with the disposal of these compounds. It is im-
506 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

possible to say which of the processes have 4.3. Analysis


actually reached maturity and which are already
being used. The analytical methods most frequently used for
According to the present state of knowledge, detecting chlorinated biphenyls are capillary col-
polychlorinated biphenyls can be destroyed umn gas chromatography coupled with mass
harmlessly by combustion at temperatures above spectrometry in the MID (Multiple Ion Detec-
1000  C and a residence time of 2 s, e.g., in a tion) mode and capillary column gas chromatog-
rotary burner equipped with a scrubbing tower raphy with ECD (Electron Capture Detector).
for hydrogen chloride [199, 213–215]. Regula- These methods are suitable for solution of even
tions in the Federal Republic of Germany specify the most difficult problems. Clean-up steps are
a temperature of 1200  C, a residence time of 0.2 necessary when complex matrices are concerned,
s, and a residual oxygen content in the combus- such as preliminary separation by column chro-
tion gas of 6 % [208]. matography.
Removal of polychlorinated biphenyls from HPLC (High Pressure Liquid Chromatogra-
silicone- and hydrocarbon-based transformer phy) and infrared spectroscopy are applicable to
fluids and heat transfer media is accomplished a limited extent.
through the formation of a separable fraction rich Summary polychlorinated biphenyl determi-
in polychlorinated biphenyls [216], treatment nations are also possible, though not usual. These
with polyalkylene glycol and alkali metal hy- require either exhaustive chlorination and mea-
droxide [217, 218], treatment with sodium surement of the decachlorobiphenyl content or
naphthalenide [219], or heating with a sodium else dechlorination and subsequent measurement
dispersion to 75  C [220]. of the biphenyl content.
Polychlorinated biphenyls are removed from For literature references on the subject of
impregnated electrical parts by irradiation with analysis, see [213, 232–238].
microwaves, which causes gasification of the
compounds [221], or by dry distillation at
500 – 1000  C followed by addition of oxygen 4.4. Storage and Transportation
[222].
Destruction of polychlorinated biphenyls has At a normal temperature the commercially used
been reported to be possible by the following polychlorinated biphenyls are liquid to viscous
methods: treatment with sodium naphthalenide mixtures with a comparatively low vapor pres-
in the presence of metallic sodium [223]; treat- sure (trichlorobiphenyl 6.5105 kPa at 20  C).
ment at 145  C with a dehalogenating reagent Steel and aluminum are suitable as container
prepared from an alkali metal, polyethylene materials. The storage and shipping of these
glycol, and oxygen [224]; reaction with sulfur compounds are subject to a variety of national
in the vapor phase [225]; adsorption on para- regulations. Since these compounds accumulate
magnetic or ferromagnetic material and subse- in the environment they must be handled so that
quent irradiation with microwaves in the pres- release cannot occur.
ence of oxygen [226]; and irradiation with light Exposure of polychlorinated biphenyls to fire
in aqueous solution in the presence of a catalyst may result in the formation of toxic chlorinated
[227]. dibenzofurans and dibenzodioxins [193–198]
Thermal decomposition of polychlorinated and in the evolution of hydrogen chloride.
biphenyls occurs by pyrolysis under oxidative Classification of polychlorinated biphenyls
conditions (oxygen-enriched air) on molten are:
alkali carbonates at 900 – 980  C [228]; by use GGVE/GGVS and RID/ADR: Class 6.1,
of a plasma burner at 3000 – 4000  C [229]; by Number 23
dissolution in kerosene, followed by combus- IMDG-Code and IATA-DGR: Class 9, UN
tion in air and introduction of the combustion Number 2315,
gases into a special decomposition furnace Packaging
[230]; or by evaporation with hydrogen as group II
a carrier gas, followed by combustion in oxygen US D.O.T.: ORM.E, UN
[231]. Number 2315
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 507

4.5. Uses Table 19. Acute oral toxicity of PCBs [298]

Chlorine content, wt % LD50 (rat, oral),


Use of these compounds has fallen drastically g/kg
[239] as a result of the extensive discontinuation 21 3.98
of their production, voluntary renunciation of 32 4.47
their application, and national restrictions. No 42 8.65
details were available concerning products in 48 11.0
62 11.3
which polychlorinated biphenyls are still used, 68 10.9
nor concerning the scale of such use. The fol-
lowing list of important fields of application
should be regarded as retrospective: 4.6. Toxicology

Cooling and insulating fluids for transformers Acute Toxicity. The acute toxicity of mix-
Dielectric impregnating agents for capacitors tures of polychlorinated biphenyls (PCB) seems
Flame-retardant additives for resins and plastics to depend on the chlorine content. Table 19
used in the electrical industry demonstrates the influence of the chlorine con-
Alkali- and acid-resistant plasticizers for lac- tent in mixed isomers of PCBs, in addition to
quers, plastics, adhesives, fillers and sealing their relatively low acute oral toxicity.
compositions The administration of acute or subacute doses
Formulations for paints and printing inks results in liver enlargement, mainly due to enzyme
Water-repellent additives for surface coatings induction; when the doses were increased, fatty
Dye carriers for pressure-sensitive copying paper degeneration and central atrophy of the liver oc-
Additives for thermally-stable lubricants and curred. In addition, hyperplasia and hemosiderosis
gear oils of the spleen were also observed [299, 300]. Poly-
Incombustible hydraulic fluids (particularly suit- chlorinated biphenyls are not likely to possess a
able for use in locations to which access is substantial local irritating potential. Nevertheless,
difficult, e.g., in mines) they seem to be readily absorbed through the skin,
Heat transfer fluids of high heat stability exerting such systemic effects as liver damage.
Inert sealing fluids for vacuum pumps
Dust control agents for road construction Chronic Effects. After oral application, se-
vere liver damage (hypertrophy, fatty degenera-
Mono- and dichlorobiphenyls have been used tion, and centrolobular necrosis) is most likely to
on a small scale as precursors for the correspond- be observed. The skin is also often affected
ing oxybiphenyls. (hyperplasia, hyperkeratosis, and cystic dilata-
Some registered trademarks are listed in tion) [277]. Polychlorinated biphenyls can inter-
Table 18. Most of the listed producers have fere with heme metabolism as shown by an
discontinued production. increased porphyrin content of the liver in rats
[277]. Hepatocellular tumors are produced in rats
and mice after long-term oral application of
PCBs [274], vol. 20. However, the tumor forma-
tion is regarded as a response to tissue damage
Table 18. Trade names of chlorinated biphenyls rather than triggered by a genotoxic mechanism.
The PCBs failed to show positive response in
Apirolio Caffaro, Italy
Aroclor Monsanto, USA, UK
validated mutagenicity test systems. The inter-
Clophen Bayer AG, FRG ference of polychlorinated biphenyls with repro-
Delor Chemco, Czechoslovakia duction could be demonstrated in numerous
Fenclor Caffaro, Italy studies with mammals. The compounds pass
Inerteen Westinghouse, USA
Kanechlor Kanegafuchi Chem. Co., Japan
through the placental barrier and exhibit embry-
Pyralene Prodelec, France otoxic effects [277].
Pyranol Monsanto, UK
Pyroclor Monsanto, USA Absorption, Metabolism, and Excretion.
Sovtol USSR
Polychlorinated biphenyls are readily absorbed
508 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

from the gastrointestinal tract after ingestion or Polychlorinated biphenyls are considered as
from the lung after inhalation. The rates of me- possible teratogens [303] and carcinogens [277].
tabolism and excretion decrease and the storage in
body fat increases with increasing chlorine con-
tent. The compounds are generally metabolized 5. Chlorinated Naphthalenes
by selective hydroxylation. In primates, most of
the metabolites are excreted as conjugates in the The first industrial applications of chlorinated
urine, whereas excretion of free metabolites in the naphthalenes took place at the beginning of the
feces is the major route in rodents [301]. 20th century [240]. The compounds were used
most extensively in the 1930s to 1950s, especial-
Other Effects. Immunosuppressive action of ly in cable and capacitor production, prompted by
polychlorinated biphenyls in mammals could be their dielectric, water-repellent, and flame-
evidenced by a decrease in infectious resistance retardant properties.
with atrophy of the spleen, cortical thymus atro-
phy, and dose-dependent decreased in the pro- More recently, most producers of polychlori-
duction of specific antibodies [271, 277]. In hens, nated naphthalenes have stopped their produc-
growth retardation, high mortality, and subcuta- tion, and output has been reduced drastically in
neous edema could be observed. These findings all parts of the world. The reasons for this follow.
were accompanied by focal necrosis of the liver, First, connections have been established between
hydroperitoneum, and epicardial as well as lung highly chlorinated naphthalenes, especially pen-
edema (chicken edema disease) [271, 277]. tachloronaphthalene and hexachloronaphtha-
lene, and illness. Moreover, because of their high
Experience in Humans. Accidental acute in- chemical and thermal stability, highly chlorinat-
toxications with PCBs are not reported [277]. ed naphthalenes are able to accumulate in the
With workers handling these compounds, acne- environment. Finally, new materials (polyesters
form dermatitis was observed, in addition to liver and polycarbonate) have been introduced as sub-
damage with necrosis [271, 277]. stitutes for chlorinated naphthalenes in the ca-
In 1968, a subacute intoxication of more than pacitor and cable industries.
1000 people in Japan by contaminated rice oil Monochloronaphthalenes, by contrast, are not
was reported (Yusho disease). Initial symptoms considered to be problematic with regard to their
were, for instance, swelling of the eye lids, effects on health and accumulation in the envi-
fatigue, and gastrointestinal disturbances. Later ronment [241].
on, discoloration of the skin and mucous mem- Official regulations relating to chlorinated
branes, headache, signs of sensory nerve injury, naphthalenes differ considerably from country
diarrhea, and jaundice were found. Cases of to country. In Japan, for example, polychlori-
influence on human fetuses have been attributed nated naphthalenes are prohibited entirely. In the
to this high PCB exposure [271, 277]. USA they may still be used without restriction,
Polychlorinated biphenyls accumulate in fat but changes in their production, importation, or
and adipose tissue. They have been demonstrated use must be reported to the U.S. Environmental
in human milk. Because the PCB level was found Protection Agency (EPA) [242], so that the ef-
to be higher in infant blood but lower in umbilical fects of these changes on the environment may be
blood in comparison to maternal blood, the trans- monitored.
fer of PCBs via the milk is probably much more
important than placental transfer [271, 302].
5.1. Physical Properties
Regulations. The following exposure limits
have been established: Naphthalene has 75 chlorinated derivatives. To
date, however, only a few have been synthesized
and isolated in pure form. Only isomeric mix-
Chlorine content 42 %: MAK 0.1 ppm tures characterized according to their chlorine
Chlorine content 54 %: MAK 0.05 ppm content are as a general rule commercially avail-
able. This situation arises because of the fact that
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 509

the most important characteristics of the com- Table 20. Physical data for monochloronaphthalenes*
pounds are a function solely of their degree of 1-Chloronap 2-Chloron
chlorination, as a result of which there is little hthalene aphthalene
demand for the pure compounds. Moreover, [90-13-1] [91-58-7]
precisely because the physical properties of the Melting point,  C 2.3 95.5 – 60
various isomers are very similar, the cost of their Boiling point
separation is unrealistically high. at 101.3 kPa,  C 260.2 258.6
Except for 1-monochloronaphthalene, which Density, g/cm3
at 20  C 1.194 1.178
is a liquid at room temperature, pure chlorinated 80  C 1.144 1.130
naphthalenes are colorless, crystalline com- Temperature corresponding
pounds. Mixtures of the compounds for industri- to vapor pressure ,  C
al use have different degrees of chlorination, and 0.13 kPa 80.6
0.67 kPa 104.6
their softening points lie considerably below the 1.33 kPa 118.6
melting points of the pure components (generally 2.67 kPa 134.4
between  40 and þ 190  C). As the degree of 5.33 kPa 153.2
chlorination increases, a transition occurs from 8.00 kPa 165.6 161.2
13.30 kPa 180.4
liquids, via waxes, to hard solids, which causes 26.70 kPa 204.2
the vapor pressures and water solubilities to fall. 53.30 kPa 230.8
In contrast, the melting points, boiling points, 101.30 kPa 260.2
and densities tend to rise, and any characteristics Refractive index n20
D 1.6326
Viscosity at 25  C, mPa s 2.94
that are dependent on these properties become 
Flash point, C 115
more pronounced. Mono- and dichloronaphtha- Ignition temperature,  C >500
lenes are freely soluble in most organic solvents. *
A eutectic mixture of 75 % of 1-chloronaphthalene and 25 % of
Highly chlorinated naphthalenes are most solu- 2-chloronaphthalene has a solidification point of 17.5  C.
ble in chlorinated aliphatic and aromatic solvents
and in petroleum naphthas. A selection of physical data obtained for pure
Chlorinated naphthalenes have excellent dielec- monochloronaphthalenes and commercial mix-
tric properties. The tri- to hexachloronaphthalenes tures is given in Tables 20 and 21 . For physical
have dielectric constants of 4.5 – 5, a dissipation data on pure polychlorinated naphthalenes, see
factor of 1103 at 800 Hz and 20  C, and a [243].
specific resistivity (100 V, 1 min) above 1014 W cm.
Chlorinated naphthalenes are compatible with
many other commercial products, e.g., chlorinat- 5.2. Chemical Properties
ed paraffins, petroleum waxes, bitumen, various
plasticizers (e.g., tricresyl phosphate), and Reactions of the compounds may occur on the
polyisobutylene. ring (electrophilic substitution), at the chlorine

Table 21. Physical data for commercial chlorinated naphthalene mixtures [241, 243, 244]

CAS reg. no. Average Softening Boiling Vapor Density Flash MAK TLV TWA
chlorine point point pressure at point (FRG) (USA)
content  C 
C kPa 25  C 
C mg/m3 mg/m3
% g/cm3

Monochloronaphthalene [25586-43-0] 22 25 250 – 260 1.2 135


Mono-/dichloronaphthalene [28699-88-9] 26 33 250 – 290 1.22 130
Tri-/tetrachloronaphthalene [1321-65-9] 50 93 304 – 354 8103 1.58 200 5 5
Tetrachloronaphthalene [1335-88-2] 52 115 312 – 360 105 1.65 210 2
Tetra-/pentachloronaphthalene [1321-64-8] 56 120 327 – 371 1.67 230 0.5 0.5
Penta-/hexachloronaphthalene [1335-87-1] 62 137 343 – 384 1.78 250 0.2
Heptachloronaphthalene [32241-08-0]
Octachloronaphthalene [2234-13-1] 70 185 – 197 440 (101.3 kPa) 2.0 >430 0.1
246 (0.067 kPa)
510 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

substituent (e.g., hydrolysis), or with de-aroma- separated and the crude product is fractionated by
tization (chlorine addition). vacuum distillation.
1-Chloronaphthalene participates in electro- Chlorine addition occurs if the chlorination is
philic substitution reactions such as nitration carried out in the absence of a catalyst, resulting
[245], sulfonation, halogenation, and chloro- in the unstable materials 1,2-dichloro-1,2-dihy-
methylation [246]. Reaction is especially favored dro- and 1,2,3,4-tetrachloro-1,2,3,4-tetrahydron-
at the para position relative to chlorine. aphthalene.
Hydrolysis with sodium hydroxide solution Incomplete naphthalene conversion is accept-
takes place at about 300  C in the presence of ed in the production of monochloronaphthalene in
copper catalysts [247] to give 1-naphthol and order to keep the proportion of polychlorinated
also 2-naphthol. naphthalenes small. The best possible result with
In the absence of a catalyst, additive chlori- ferric chloride as catalyst is 75 % monochloro-
nation of 1-chloronaphthalene yields pentachlor- naphthalene and 13 % polychlorinated naphtha-
otrihydronaphthalene and hexachlorodihydro- lenes in an isomer ratio of 90 – 94 % 1-chloro- and
naphthalene [248]. 6 – 10 % 2-chloronaphthalene. If peroxodisulfate
The chemical and thermal stabilities of chlo- and chloride ions are used as chlorinating agents,
rinated naphthalenes increase with the number mainly monochlorinated derivatives are obtained
of chlorine substituents. Highly chlorinated [251]. Because of the large difference between
naphthalenes withstand acids, caustic solutions, their boiling points, the monochloronaphthalene
and oxidizing agents, even at elevated tempera- isomer mixture is easily separated by distillation
tures. An exception is concentrated nitric acid, from the chlorination mixture, and it is of high
which forms nitro derivatives relatively easily purity. The isomers can be separated by crystalli-
with polychlorinated naphthalenes and which at zation [252]. Further information on the industrial
90  C oxidizes octachloronaphthalene to hexa- chlorination of naphthalene will be found in the
chloro-1,4-naphthoquinone and tetrachloroph- preceding edition of this encyclopedia [253].
thalic acid [249]. The preparation of pure isomers representing
If naphthalene is chlorinated beyond the stage the various chlorination stages is only of scien-
of octachloronaphthalene at a temperature ex- tific interest. A review of the procedures is given
ceeding 200  C in the presence of ferric chloride in [243].
catalyst, perchloroindane and carbon tetrachlo- For information regarding the disposal of
ride are formed. This phenomenon is a result of waste gas and chlorinated naphthalene wastes,
chlorine addition and subsequent ring constric- see Section 56.
tion [250], decachlorodihydronaphthalene being
an intermediate.
5.4. Quality and Analysis

5.3. Production The quality of chlorinated naphthalenes is moni-


tored by wet analysis for chlorine content, as well
The chlorination of naphthalene proceeds less as by gas chromatography employing glass cap-
rapidly than that of benzene or toluene. Conse- illary columns. Traces are determined by the
quently, chlorinated naphthalenes are produced same analytical methods that have been devel-
batchwise in agitator vessels. Molten naphtha- oped for polychlorinated biphenyls. For litera-
lene, initially at 80  C, is mixed with gaseous ture on this subject, see [243, 254–261].
chlorine in the presence of ferric chloride or One particular grade of monochloronaphtha-
antimony pentachloride until the desired degree lene is used in wood preservatives and consists of
of chlorination has been reached. As the degree
of chlorination increases, the reaction tempera- 90 – 94 % 1-chloronaphthalene
ture must be raised to keep the mixture above its 6 – 10 % 2-chloronaphthalene
softening point. < 0.1 % dichloronaphthalene
The crude chlorination mixture is neutralized, < 0.01 % trichloronaphthalene and a
e.g., with soda. The neutralizing agent is then chlorine content of 22 %.
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 511

5.5. Storage and Transportation Octachloronaphthalene: ingredient in the


production of carbon elements by carbonization;
The chloronaphthalenes are stable, neutral sub- additive for lubricants used under extreme con-
stances. They can be stored in tanks as liquids, in ditions and for flame-retardant plastics.
which case adequate heating must be provided Trade names for chlorinated naphthalenes.
consistent with the melting point of the material. Most of the producers in the following list either
Steel containers are suitable, although stainless have entirely discontinued the production of
steels should be used for applications in the chlorinated naphthalenes, or else they have re-
electrical industry. Chlorinated naphthalenes that stricted their output and simultaneously reduced
are liquid at ambient temperatures are shipped in the content of highly chlorinated naphthalenes in
drums, containers, or road tankers. Solid chlor- their products.
onaphthalenes are supplied as powder or flakes,
either in fiber drums or in paper sacks. Existing Cerifal types, Caffaro, Italy
national regulations must be complied with in Clonacire types, Prodelec, France
connection with storage and transportation. Halowax types, Koppers Co., Inc., USA
Polychlorinated naphthalenes are not express- Nibren Wax types, Bayer AG, FRG
ly mentioned in the shipping regulations of either Seekay wax types, ICI, Ltd., UK
the EEC or the USA. Monochloronaphthalene
has neither been allocated to a hazard class nor
given a UN number. 5.7. Toxicology

Monochlorinated naphthalenes are of low to


5.6. Use moderate acute toxicity, as shown by their oral
LD50 (Table 22). Subacute to subchronic uptake
The use of chlorinated naphthalenes has dimin- of mixtures of higher chlorinated naphthalenes
ished considerably during the last 30 years. Thus, (predominantly penta- and hexachloronaphtha-
except in special cases, chlorinated naphthalenes lene) resulted in liver injury [271]. In general, the
are no longer used in capacitors or electric cable toxicity of chlorinated naphthalenes increases
coverings. Their use as lubricants has also been with the degree of chlorination [272]. Chlorinat-
largely discontinued. Practice in individual coun- ed naphthalenes irritate the rabbit skin [271].
tries varies, however. In the USA, for example, Ingestion of lubricants containing chloronaphtha-
chlorinated naphthalenes are no longer used as lenes resulted in injury to farm animals (X dis-
wood preservatives. It is impossible to generalize ease). Marked hyperkeratosis of the skin, degen-
concerning which of the following potential ap- erations of the cells in pancreas, liver, and gall
plications are permissible at present. bladder, and damage of the renal cortex could be
observed. Cattle poisoned with highly chlorinated
Monochloronaphthalenes: dye precursor; naphthalenes show a rapid decline in vitamin A
dye dispersant; fungicide and insecticide wood plasma levels [271]. Octachloronaphthalene fed
preservative; engine oil additive for dissolving to rats also greatly enhances the loss of vitamin A
sludges [262]; chemically and thermally stable from the liver [304]. Mixtures of penta- and
sealing fluid; ingredient in special cleaning agents. hexachloronaphthalenes can produce the so-
called chicken edema disease, characterized by
Polychlorinated Naphthalenes: dielectric hydropericardium and ascites in chickens [304].
for impregnation of paper windings in automo-
bile capacitors; insulating, waterproof, and
Table 22. Oral LD50s of monochlorinated naphthalenes [291]
flameretardant dipping and encapsulating com-
pounds for special electrical parts; binder in the Compound Species LD50 (oral),
manufacture of ceramic elements for the electri- mg/kg
cal industry; paper coatings with water-repellent, 1-Chloronaphthalene rats 1540
flame-retardant, fungicidal, and insecticidal mice 1019
properties; plasticizers; electroplating stop-off 2-Chloronaphthalene rats 2078
compound. mice 886
512 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

1-Chloronaphthalene and 1,2,3,4-tetrachloro- Waste Gas Treatment. It is necessary to


naphthalene, when tested for point mutations in distinguish between hydrogen chloride reaction
the Salmonella assay (Ames test), exhibited no gas from the chlorination process and substantial-
positive results [305, 306]. No data are available ly neutral waste gas, e.g. from distillation columns
on the effects of chlorinated naphthalenes on or storage containers. The second of these waste
reproduction. gas streams can be purified in an activated char-
coal tower or incinerator. The hydrogen chloride
Metabolism. Chlorinated naphthalenes are reaction gas is processed in a complex manner to
readily absorbed. Metabolism occurs by conju- recover usable hydrochloric acid:
gation or via hydroxylation to the respective
naphthols or dihydrodiols. The metabolites are
excreted with the urine or the feces [271, 304]. 1. If the reaction gas contains chlorine, this is
removed in a scrubbing tower (e.g., a bubble
Effects in Humans. The main health problem column [263]) containing an easily chlorina-
arising from use and handling of chlorinated table compound, preferably a raw material
naphthalenes is chloracne, which usually occurs used in the chlorination process, and a chlori-
from long-term contact with the compounds or nation catalyst.
exposure to hot vapors. The penta- and hexa- 2. In a second scrubbing tower, organic consti-
chloro derivatives are suggested to have the tuents of the reaction gas are washed out with
greatest potential to generate acne [271]. a high-boiling solvent.
In accidental intoxications, liver damage oc- 3. In addition to (or instead of) being passed
curred independently from chloracne. After loss through the second scrubbing tower, the hy-
of appetite, nausea, and edema of the face and drogen chloride gas is cooled to the lowest
hands, abdominal pain and vomiting followed; possible temperature in a cooler, in which
later on jaundice developed. Autopsy in cases of further organic constituents are condensed out.
fatal intoxication revealed yellow atrophy of the 4. The hydrogen chloride is then absorbed in
liver [304]. water in an adiabatic scrubber, from which it
emerges as about 30 % hydrochloric acid with
Regulations. The following exposure limits < 5 ppm of organically bound carbon.
have been established:
Absorption in calcium chloride solution in the
presence of calcium carbonate lumps has also
been described [264]. In this case, organic com-
Trichloronaphthalene: MAK 5 mg/m3,
TLV 5 mg/m3
pounds are removed with the escaping carbon
Tetrachloronaphthalene: TLV 2 mg/m3 dioxide, and a 33 % calcium chloride solution
Hexachloronaphthalene (skin): TLV 0.2 mg/m3 containing about 4 ppm of organic compounds
Pentachloronaphthalene: TLV 0.5 mg/m3 remains.
Octachloronaphthalene (skin): TLV 0.1 mg/m3
Aqueous hydrochloric acid can be substan-
tially freed from organic substances by extraction
with dodecylbenzene [265].
6. Environmental Protection The hydrogen chloride can also be liquefied in
the absence of water and purified by distillation
In the production of chlorinated aromatics, or- in a pressure column.
ganic compounds are contained in three different The pure hydrogen chloride and its aqueous
waste streams: solution are suitable for chemical processes.
There are also techniques to recover the chlorine
waste gas by electrolysis (e.g., the Hoechst-Uhde process)
wastewater or oxidation (Shell-Deacon process or Kel Chlo-
liquid or solid organic wastes rine process).

The correct disposal of these wastes results in Wastewater Treatment. The biological
no harm to the environment. degradation rate of chlorinated aromatics de-
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 513

Table 23. Production of chlorobenzenes [20, 22] in 103 t/a

Monochlorobenzene 1,2-Dichlorobenzene 1,4-Dichlorobenzene Sum of all chlorobenzenes

USA 1970 220 30 32


1981 130 23 33
1988 11 42
FRG 1970 127
1981 97 34 138
Japan 1981 34 9 16 50

creases as their chlorine content increases. Only Exhaustive chlorination of chlorinated hydro-
chlorinated aromatics with low degrees of chlo- carbons in the vapor phase at a temperature above
rination are degradable in biological wastewater 600  C and pressure up to 200 bar splits the
treatment plants, and then only if their concen- molecules, thus giving high yields of carbon
tration in the wastewater does not exceed certain tetrachloride [18, 19].
levels. Therefore, wastewater streams containing
chlorinated aromatics require preliminary purifi-
cation. The following techniques [266] are suit- 7. Economic Aspects
able: stripping, extraction, and adsorption on
activated carbon or polymeric resins [267]. Overall, it may be said that the use of chlorinated
aromatic hydrocarbons is stagnant or declining
Treatment of Wastes. These wastes may be worldwide (see Tab. 23).
distillation residues, useless fractions from sepa- Monochlorobenzene output in the USA fell
ration processes, or industrial products contain- from 275 100 t in 1960 to 115 700 t in 1982 [20]
ing chlorinated aromatics that are no longer and increased in 1994 to 151 000 t. At the middle
suitable for use. of 1984, Monsanto (at Muscatine, Iowa) discon-
Normally these wastes are disposed of by in- tinued the use of monochlorobenzene as a carrier
cineration. In principle, it is also possible to convert for the herbicide Lasso [21]; this is expected to
chlorinated hydrocarbons into usable compounds lead to a further drop in output.
by hydrodehalogenation or chlorinolysis. It is im- As the production of monochloro-, 1,2-di-
possible to say whether these processes are already chloro- and 1,4-dichlorobenzene is most eco-
being used on an industrial scale. nomical in coproduction, it is becoming increas-
Chlorine-containing aromatics are burned in ingly difficult to adapt the manufacturing condi-
special furnaces that provide reaction tempera- tions to the requirements of the market.
tures above 1000  C and residence times of 1 – 2 s There are no output statistics for chlorinated
[215]. Only then is it certain that no polychlor- toluenes. It is estimated that 30 000 t of 1- and 4-
odibenzodioxins are formed during combustion. chlorotoluene was produced in Western Europe
This risk exists particularly with polychlorinated in 1983 [20].
biphenyls (see Section 48). In an excess of oxy- The production of polychlorinated biphenyls
gen, the chlorinated compounds are converted has been almost completely discontinued
into hydrogen chloride, carbon dioxide and wa- throughout the world (cf. Section 48). Since the
ter. The hydrogen chloride is removed from the first industrial use of polychlorinated biphenyls
flue gas by water scrubbers. at the beginning of the 1930s, about 1 million
Hydrodehalogenation is effected with hydro- tons have been produced [23]; 40 % of this
gen on palladium, platinum, or nickel catalysts at quantity is estimated to be still in use. Consump-
elevated temperature and high pressure. The tion reached its highest level in the 1960s.
nucleus-bound chlorine is substituted by hydro- The production of chlorinated naphthalenes
gen, and hydrogen chloride is thus formed. Mix- has also fallen greatly, with a shift toward less
tures of different chlorination stages down to the highly chlorinated naphthalenes. Output in the
chlorine-free fundamental compound are ob- USA fell from 2270 tons in 1972 [24] to 320 tons
tained [17, 268–270]. in 1978; after the manufacture of chlorinated
514 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

naphthalenes had been discontinued, the quantity 18 Hoechst, EP 51 236, 1980 (D. Rebhan, H. Schmitz).
imported into the USA settled at about 15 tons in 19 Chem. Eng., March 31. 1975, 62.
1980 and 1981 [25]. The output of the USA in 20 Chem, Ind. 37, p. 106, February 1985.
21 Chemical Marketing Reporter, vol. 226, no. 13, Septem-
1972 consisted of 25 – 28 % of mono-/di-, 65 –
ber 24, 1984.
66 % of tri-/tetra-, and about 8 % of penta- to 22 Japan Chem. Week, April 15, 1982, 8.
octanaphthalenes [24]. In the Federal Republic of 23 U.S. Interdepartmental Task Force on PCBs, COM–72–
Germany with an output of about 1000 t of 10419, Washington 1972.
chlorinated naphthalenes in 1972 [26], the pro- 24 F. D. Kover, Environmental Protection Agency, Wa-
duction of polychlorinated naphthalenes has shington, D.C., 1975, EPA 560sol;–75–001, p. 8, p. 11.
likewise been discontinued; only monochloro- 25 U.S. Federal Register, vol. 48, no. 89, May 6, 1983, p. 20
naphthalenes are now produced, output being of 668.
26 Figure from an unpublished survey conducted by Bayer
the order of 100 t/a.
(produced in the FRG for PCN only).
27 Dow Chemical, US 2 886 605, 1959 (H. H. McClure, J. S.
Melbert, L. D. Hoblit).
References 28 Hoechst, BE 660 985, 1964.
29 PPG, US 4 017 551, 1977 (J. E. Milam, G. A. Carlson).
General References 30 K. Shinoda, H. Watanabe, Kogyo Kagaku Zasshi 73
1 Ullmann, 4th ed., 9, 404–420. (1970) no. 11, 2549–2551; Chem. Abstr. 77 (1972) 5072.
2 Winnacker-K€ uchler, 4th ed., vol. 6; ‘‘Organische Tech- 31 S. Yamamoto et al., Kagaku to Kogyo (Osaka) 45 (1971)
nologie II’’, pp. 2–11. no. 9, 456–460; Chem. Abstr. 76 (1972) 99244.
3 Kirk-Othmer, 5, 668–714. 32 Moscow Gubkin Petrochem., SU 514 860, 1976; SU
4 J. J. McKetta, W. Cunningham, Encyl. Chem. Process. 536 185, 1976; SU 540 657, 1976; SU 594 995, 1978 (J.
Des. 8 (1979) 214–270. M. Kolesnikow et al.).
5 C. R. Pearson: ‘‘C1 and C2-halocarbons’’, in: The Hand- 33 Dow Chemical, US 3 636 171, 1972 (K. L. Krumel, J. R.
book of Environmental Chemistry, vol. 3, Springer Ver- Dewald).
lag, Berlin 1982, pp. 69–88. 34 T. Kametani et al., Yakugaku Zasshi 88 (1968) no. 8,
6 Chloroform, Carbon Tetrachloride and other Halo- 950–953; Chem. Abstr. 70 (1978) 19681.
methanes: An Environmental Assessment, National 35 PPG, US 4 235 825, 1980 (J. E. Milam).
Academy of Sciences Washington, D.C., 1978. 36 Sergeev E. V., SU 650 985, 1979.
7 A. Wasselle: C1 Chlorinated Hydrocarbons, Private 37 Nippon Kayaku Co., JP-Kokai 64/3821, 1961.
report by the Process Economic Program SRI Interna- 38 Union Carbide, US 3 226 447, 1965 (G. H. Bing, R. A.
tional, Report No. 126. Krieger).
8 CEFIC-B.I.T. Solvants Chlores ‘‘Methylene chloride– 39 Ihara Chem. Ind. Co., Ltd., EP 118 851, 1984 (Y.
Use in industrial applications,’’ 1983. Higuchi, T. Suzuki).
9 J. Schulze, M. Weiser: ‘‘Vermeidungs- und Verwer- 40 R. Commandeur et al., Nouv. J. Chim. 3 (1979) no. 6,
tungsm€ oglichkeiten von R€uckst€anden bei der Herstel- 385–391; PCUK, DE-OS 3 344 870, 1983 (R. Comman-
lung chloroorganischer Produkte,’’ Umweltforschungs- deur, H. Mathais).
plan des Bundesministers des Innern–Abfallwirtschaft. 41 Dow Chemical, US 4 186 153, 1980; US 4 205 014, 1980
Forschungsbericht 103 01 304, UBA-FB 82–128 (1985). (J. W. Potts).
42 Sanford Chem. Co., US 3 557 227, 1971 (M. M. Fooladi).
Specific References 43 Von den Berg et al., NL 72/1533, 1974; Ind. Eng. Chem.
10 L. H. Hoorsley et al., Azeotropic Data III, Advances in Fundam. 15 (1976) no. 3, 164–171.
Chemistry Series, No. 116, Am. Chem. Soc., Washing- 44 R. B. McMullin, Chem. Eng. Prog. 44 (1948) no. 3, 183–
ton, D.C., 1973. 188.
11 M. Lecat, Tables azeotropiques, 2nd ed., Chez l’Auteur, 45 H. J. H€orig, D. F€orster, Chem. Tech. (Leipzig) 22 (1970)
Brussels 1949. no. 8, 460–461.
12 Dow Chemical, US 1 607 618, 1926 (W. J. Hale, E. C. 46 S. Sacharjan, Chem. Tech. (Leipzig) 31 (1979) no. 5,
Britton). 229–231.
13 J. W. Hale, E. C. Britton, Ind. Eng. Chem. 20 (1928) 114– 47 N. T. Tishchenko, V. M. Sheremet, A. I. Triklio, Khim.
124. Prom-st. (Moscow) 1980, no. 7, 399–401.
14 R. M. Crawford, Chem. Eng. News 25 (1947) no. 1, 235– 48 Ullmanns, 4th ed., 9, p. 506.
236. 49 Raschig GmbH, DE 539 176, 1930; DE 575 765, 1931;
15 Dow Chemical, US 2 432 551, 1947; 2 432 552 (W. H. US 1 963 761, 1934; US 1 964 768, 1933 (W. Prahl, W.
Williams et al.). Mathes).
16 Oiwa et al., Bl. Inst. Chem. Res. Kyoto 29 (1952) 38–56. 50 Hooker Chem. Corp., DE 1 443 988, 1962; CH 432 485,
17 M. Bonnet et al., J. Org. Chem. 48 (1983) 4396–4397. 1962; US 3 644 542, 1972 (W. Prahl et al.).
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 515

51 Union Carbide, BE 636 194, 1962 (C. C. Diffteld, T. T. 84 A. A. Ponomarenko, Zh. Obshch. Khim. 32 (1962) no.
Szabo, C. A. Rivasi). 12, 4029–4040.
52 Vulcan Materials Co., DE 1 518 164, 1963 (E. S. Penner, 85 N. N. Vorozhtsov et al., Zh. Obshch. Khim. 31 (1961) no.
A. L. Malone). 4, 1222–1226.
53 Hodogaya Chem. Ind. Co., JP-Kokai 65/12 613, 1962. 86 Monsanto, GB 948 281, 1962; DE 1 468 241, 1963 (E. B.
54 Asahi Chem. Ind. Co., JP-Kokai 67/3619, 1965. McCall, W. Cummings).
55 W. H. Prahl, DE-OS 2 442 402, 1975. 87 J. Blum, Tetrahedron Lett. 26 (1966) 3041–3045.
56 Sumitomo, JP-Kokai 73/39 449, 1971; DE 2 232 301, 88 Du Pont, DE 1 804 695, 1968 (C. C. Cumbo).
1972 (E. Ichiki et al.); Chem. Abstr. 79 (1973) 91 746. 89 Bayer, DE 2 326 414, 1973; US 3 897 321, 1975; US 4
57 C. A. Gorkowa, A. M. Potapow, C. R. Rafikow, SU 654 012 442, 1977 (H. U. Blank, K. Wedemeyer,
600, 1979. J. Ebersberger).
58 U. Sch€onemann, Chem. Ind, (D€ usseldorf) 5 (1953) no. 7, 90 Mitsui Toatsu Chem. Inc., JP-Kokai 80/104 220, 1979;
529–538. Chem. Abstr. 94 (1974) 30 327.
59 Gulf Res. a. Develop. Co., US 3 591 644; US 3 591 645, 91 Monsanto, GB 957 957, 1962 (E. B. McCall, P. J. S.
1971 (V. A. Notaro, C. M. Selwitz). Bain).
60 ICI, GB 388 818, 1933 (T. S. Wheeler). 92 Dow Chemical, US 1 946 040, 1934 (W. C. St€osser, F. B.
61 Dow Chemical, US 2 123 857, 1938 (J. P. Wibaut, L. van Smith).
de Lande, G. Wallagh). 93 S. Rittner, S. Steiner, Chem. Ing. Tech. 57 (1985) no. 2,
62 C. E. Kooyman, Adv. Free Radical Chem. 1 (1965) 137– 91–102.
153. 94 Politechnika Slaska, PL 78 610, 1976 (W. Zielinski,
63 W. Dorrepaal, R. Louw, Recl. Trav. Chim. Pays-Bas 90 J. Suwinski).
(1971) 700–704; J. Chem. Soc. Perkin Trans 2 (1976) 95 Mitsui Toatsu Chem., Inc., JP-Kokai 78/44 528, 1976.
1815–1818; Int. J. Chem. Kinet. 10 (1978) no. 3, 249–275. 96 Dow Chemical, US 3 170 961, 1965 (E. C. Britton, F. C.
64 P. Kovacic, N. O. Brace, J. Am. Chem. Soc. 76 (1954) Beman).
5491–5494. 97 Dow Chemical, US 1 923 419, 1933 (E. C. Britton).
65 P. Kovacic, A. K. Sparks, J. Am. Chem. Soc. 82 (1960) 98 Rhône-Progil, DE 2 332 889, 1973 (R. Chanel et al.).
5740–5743; J. Org. Chem. 26 (1961) 1310–1213. 99 Mitsui Toatsu Chem., Inc., JP-Kokai 77/6229, 1975 (T.
66 Pullman Inc., DE 1 468 141, 1963 (H. Heinemann, K. D. Kiyoura); Chem. Abstr. 87 (1972) 84 178.
Miller). 100 S. Kikkawa et al., Kogyo Kagaku Zasshi 73 (1970) no. 5,
67 National Distillers Chem. Corp., US 3 670 034, 1972 (R. 964–969; Chem. Abstr. 73 (1970) 87 542.
E. Robinson). 101 E. Pfeil, Angew. Chem. 65 (1953) no. 6, 155–158.
68 J. S. Grossert, G. K. Chip, Tetrahedron Lett. 30 (1970) 102 W. Brackmann, P. J. Smit, Recl. Trav. Chim. Pays-Bas
2611–2612. 85 (1966) no. 8, 857–864; Shell Int. Res., NL 6 515 451,
69 Nikkei Kako, Co., Ltd., Sugai Kogy Ind., Ltd., DE-OS 2 1967.
230 369, 1972 (K. Sawazaki, H. Fujii, M. Dehura). 103 Mobil Oil Corp., US 3 358 046, 1967 (R. D. Offenhauer,
70 Y. Tamai, Y. Ohtsuka, Bull. Chem. Soc. Japan 46 (1973) P. G. Rodewald).
no. 7, 1996–2000. 104 Sumitomo, JP-Kokai 73/86 828, 1972 (H. Suda, S.
71 Monsanto, US 3 029 296, 1962 (W. A. White, R. A. Yamamoto, Y. Sato); Chem. Abstr. 80 (1974) 59 655.
R€uhrwein). 105 Allied, US 2 866 828, 1958 (J. A. Crowder, E. E. Gilbert).
72 O. Silberrad, J. Chem. Soc. (London) 121 (1922) 1015– 106 Ethyl Corp., US 2 943 114, 1960 (H. E. Redman, P. E.
1022; US 259 329, 1925. Weimer).
73 M. Ballester, C. Molinet, J. Castaner, J. Am. Chem. Soc. 107 Columbia-Southern Chem. Corp., US 2 819 321, 1958
82 (1960) 4254–4258. (B. O. Pray).
74 M. Ballester, Bull. Soc. Chim. Fr. 1966, 7–15. 108 BASF, DE 1 020 323, 1956 (E. Merkel).
75 S. Kobayashi, JP-Kokai 74/43 901, 1972; Chem. Abstr. 109 Union Carbide, US 2 666 085, 1954 (J. T. Fitzpatrick).
81 (1974) 35683. 110 Y. G. Erykalov et al., J. Org. Chem. USSR (Engl.
76 Du Pont, US 4 327 036, 1982 (F. D. Marsh). Transl.) 9 (1973) 348–351; SU 392 059, 1973; SU
77 R. J. Cremlyn, T. Cronje, Phosphorus Sulfur 6 (1979) no. 351 818, 1972.
3, 495–504. 111 Kanegabuchi Chem. Ind. Co., JP-Kokai 57/510, 1957 (J.
78 N. C. Weinberg, ‘‘Tech. Elektroorg. Synth.,’’ Tech. Nishida, J. Mikami, S. Kawato); Chem. Abstr. 52 (1958)
Chem. (N.Y.) 5 (1975) Pt. 2, 1–82. 2905 E.
79 Texaco Inc., US 3 692 646, 1972 (W. B. Mather, H. 112 H. Scholz et al., DD 9869, 1955.
Junction, E. R. Kerr). 113 D. Vrzgula, Z. Stoka, J. Auerhan, CS 92 749, 1959.
80 Sumgait Petrochem., SU 612 923, 1978. 114 Mitsubishi, JP-Kokai 75/32 132, 1973; Chem. Abstr. 83
81 C. Galli, Tetrahedron Lett. 21 (1960) no. 47, 4515–4516. (1975) 96 688.
82 S. Oae, K. Shinhama, Y. H. Kim, Bull. Chem. Soc. Japan 115 BASF, DE 1 002 302, 1952 (G. Grassl).
53 (1980) no. 7, 2023–2026. 116 Asahi Glass Co., JP-Kokai 55/7421, 1955 (M. Fujioka et
83 BIOS 986, 151. al.); Chem. Abstr. 51 (1957) 17 989 G.
516 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

117 Ethyl Corp., GB 738 011, 1952 (L. Merritt). 152 Tenneco Chem., US 3 317 617, 1967 (E. P. Di Bella).
118 Diamond Alkali Co., US 2 914 574, 1959 (E. Zinn, J. J. 153 Hodogaya Chem. Co., Ltd., JP-Kokai 81/110 630, 1980;
Lukes). Chem. Abstr. 96 (1982) 34 810. EP 63 384, 1982
119 Pennsalt Chem. Corp., US 2 914 573, 1959 (G. McCoy, (R. Hattori et al.).
C. Inman). 154 Ihara Chem. Ind. Co., Ltd., JP-Kokai 81/105 752, 1980;
120 Österreichische Chem. Werke, AT 261 576, 1967 (H. US 4 289 916, 1981; DE-OS 3 023 437, 1980
Maier). (J. Nahayama, C. Yazawa, K. Jamanski).
121 Uzima Chimica Turda, BG 54 958, 1972 (J. Todea). 155 Hooker Chem. & Plas. Corp., US 4 024 198, 1977 (H. E.
122 Combinatul Chim. Riminicu-Vilcea, BG 61 469, 1976 Buckholtz); US 4 069 263, 1978; US 4 069 264, 1978
(L. Raduly et al.). (H. C. Lin).
123 Ullmann, 4th ed., 9, 508. 156 Hooker Chem. & Plas. Corp., US 4 250 122, 1981 (H. C.
124 Ishihara Sangyo Kaisha, Ltd., JP-Kokai 81/92 227, 1979; Lin, S. Robots).
Chem. Abstr. 95 (1981) 203 526. 157 P. B. De La Mare, P. W. Robertson, J. Chem. Soc. 1943,
125 Hoechst, DE-OS 2 920 173, 1979 (G. Volkwein, 279–281.
K. B€assler, H. Wolfram). 158 H. G. Haring, Chem. Eng. Monogr. 15 (1982) 193–208,
126 Ishihara Sangyo Kaisha, Ltd., JP-Kokai 79/112 827, 208 A.
1978; US 4 368 340, 1983; DE-OS 3 047 376, 1980 159 Hoechst, Krebskosmos GmbH, DE-OS 2 536 261, 1975
(T. R. Nishiyama et al.). (H. Horst et al.).
127 BASF, DE 947 304, 1954 (F. Becke, H. Sperber).
160 J. M. Ballke, J. Liaskar, G. B. Lorentzen, J. Prakt. Chem.
128 Bayer, DE-OS 3 134 726, 1981 (G.-M. Petruck, 324 (1982) no. 3, 488–490.
R. Wambach). 161 A. B. Solomonov, P. P. Gertsen, A. N. Ketov, Zh. Prikl.
129 Rhône Poulenc Ind., EP 43 303, 1982 (G. Soula). Khim. (Leningrad) 42 (1969) no. 6, 1418–1420; Zh.
130 Sonford Chem. Co., US 3 557 227, 1971 (M. M.
Prikl. Khim. (Leningrad) 43 (1970) no. 2, 471–472.
Fooladi). 162 A. M. Potapov, S. R. Rafikov, Izv. Akad. Nauk SSSR, Ser.
131 Dover Chem. Corp., US 3 274 269, 1966 (R. S. Cohen). Khim. 31 (1982) no. 6, 1334–1338.
132 Jefferson Chem. Co., Inc., DE-OS 2 054 072, 1971
163 Ajinomoto Co., Inc., JP Kokai 73/81 822, 1972 (R. Fuse,
(S. Burns). T. Inoue, T. Kato); Chem. Abstr. 80 (1974) 108 160.
133 T. Magdolen, D. Vrzgula, CS 122 646, 1967. 164 Gulf Research and Development Co., US 3 644 543,
134 Hoechst, DE 1 028 978, 1955 (H. Klug, J. Kaupp). 1972 (V. A. Notaro); US 3 717 684, 1973 (V. A. Notaro,
135 Nippon Soda Co., JP-Kokai 75/7572, 1975 (K. Iwabu-
C. M. Selwitz); US 3 717 685, 1973 (H. G. Russell, V. A.
chi); Chem. Abstr. 51 (1957) 17 989 F. Notaro, C. M. Selwitz).
136 Pechiney, US 2 852 571, 1958 (J. Frejacques, H. Guinot). 165 Int. Minerals & Chem. Corp., JP Kokai 74/76 828, 1972
137 C. Popa, C. Raducanu, A. Stefanescu, Rev. Chim. (Bu- (J. T. Traxler); Chem. Abstr. 85 (1976) 6167.
charest) 15 (1964) no. 10, 601–607.
138 Phillips Petr. Co., US 4 096 132, 1978 (J. T. Edmonds Jr. 166 H. Inoue, M. Izumi, E. Imoto, Bull. Chem. Soc. Japan 47
(1974) no. 7, 1712–1716.
139 Bayer, EP 23 314, 1981; EP 40 747, 1981; EP 65 689,
1982 (K. Idel et al.). 167 T. Tkaczynski, Z. Winiarski, W. Markowski, Przem.
140 Swann Research Inc., US 1 954 469, 1934 (C. F. Booth). Chem. 58 (1979) no. 12, 669–670; Chem. Abstr. 92
141 Ullmann, 4th ed., 8, 344, 377–379. (1980) 180 745.
142 Ihara Chem. Ind. Co., Ltd., EP 2 749, 1978 (M. Shi- 168 Sugai Chem. Ind. Co., Ltd., JP Kokai 83/61 285, 1981;
geyasu et al.); Dynamit Nobel AG, EP 70 393, 1982; EP Chem. Abstr. 99 (1983) 79 068.
121 684, 1984 (M. Feld). 169 Shell Int. Res., FR 1 343 178, 1963.
143 Nippon, DE-OS 2 711 332, 1977 (H. Hayami, H. Shi- 170 R. Nishiyama et al., J. Soc. Org. Synth. Chem. Tak. 23
mizu, G. Takasaki). (1965) 515–525.
144 N. N. Lebedev, J. J. Baltadzhi, Zh. Org. Khim. 5 (1969) 171 Hoechst, EP 72 008, 1982 (H.-J. Arpe, H. Litterer, N.
no. 9, 1604–1605. Mayer).
145 Heyden Newport Chem. Co., US 3 000 975, 1961 (E. P. 172 BIOS Final Rep. No. 1145.
Di Bella). 173 Toray, EP 62 261, 1982 (K. Tada et al.).
146 Moscow Gubkin Institute, SU 1 002 297, 1983 (N. N. 174 Tenneco Chem. Inc., FR 1 489 686, 1967; US 3 366 698,
Belov et al.). 1968 (E. P. Di Bella).
147 Ullmann, 4th ed., 9, 512–513. 175 Hooker Chem. & Plas. Corp., DE-OS 2 258 747, 1972;
148 Hooker Chem. & Plas. Corp., US 4 013 730, 1977 (J. C. US 4 006 195, 1977 (S. Gelfand).
Graham). 176 Bayer, DE-OS 2 523 104, 1975 (H. Rathjen).
149 Tokuyama Soda Co. Ltd., JP-Kokai 81/99 429, 1980; 177 Tenneco Chem. Inc., US 4 031 146, 1977 (E. P. Di
Chem. Abstr. 95 (1981) 186 820. Bella).
150 Tenneco Chem., US 4 013 144, 1977 (E. P. Di Bella). 178 Bayer, EP 46 555, 1982 (G.-M. Petruck, R. Wambach).
151 Hooker Chem. & Plas. Corp., US 4 031 142, 1977; DE- 179 Shell Int. Res., GB 1 110 030, 1968 (C. F. Kohll, H. D.
OS 2 634 340, 1976 (J. C. Graham). Scharf, R. Van Helden).
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 517

180 Shell Int. Res., NL 6 907 390, 1970 (D. A. Was). 207 Erste Allgemeine Verwaltungsvorschrift zum Bundes-
181 Rhône-Poulenc Ind., FR 2 475 535, 1981 (J.-C. Lauct, Immissionsschutzgesetz (First General Administrative
J. Bourdon). Provision Issued Pursuant to the Federal Imission Pro-
182 Toray, EP 125 077, 1984 (K. Miwa et al.). tection Act)–Technische Anleitung Luft (Technical
183 Tenneco Chem. Inc., US 4 031 145, 1977 (E. P. Di Guideline – Air). August 28, 1974 (FRG).
Bella). 208 U.S. Public Law 94–469, October 11, 1976, Section 6 (e)
184 T. Asinger, G. Loch, Monatsh. Chem. 62 (1933) 345. of TSCA.
185 Ullmann, 4th ed., 9, pp 513–514. 209 U.S. Environmental Protection Agency 560/ 6–75–004,
186 H. C. Brimelow, R. L. Jones, T. P. Metcalfe, J. Chem. 1976 (Proceedings of the National Conference on PCBs,
Soc. 1951, 1208–1212. Chicago, November 19 – 21, 1975).
187 Tenneco Chem. Inc., US 3 517 056, 1970 (J. F. De 210 U.S. Environmental Protection Agency 230–03/ 79–001,
Gaetano). 1979, Washington, D.C., (Support Document/Voluntary
188 Tenneco Chem. Inc., US 3 692 850, 1972 (E. P. Di Environmental Impact Statement for PCBs).
Bella). 211 NIOSH, Washington, D.C., U.S. Government Printing
189 Kureha Chem. Ind. Co., Ltd., JP-Kokai 70/28 367, 1965 Office, 1977, pp. 40–49 (summary of the literature on the
(M. Ishida); Chem. Abstr. 74 (1971) 3397. toxicity of polychlorinated biphenyls).
190 A. L. Englin et al., SU 1 727 736, 1965. 212 C. Nels, Elektrizit€
atswirtschaft 83 (1984) no. 8, 375–379
191 Swann Research, Inc., US 1 836 180, 1929 (C. R. (disposal of askarels).
McCullough, R. C. Jenkins). 213 M. G. McGraw, Electrical World, (The PCB Problem:
192 C. H. Penning, Ind. Eng. Chem. 22 (1930) no. 11, 1180– separating fact from fiction) February 1983, pp. 49–72.
1182. 214 G. T. Hunt, P. Wolf, P. F. Fennelly, Environ. Sci.
193 K. Soldner, G. Gollmer, Elektrizit€ atswirtschaft 81 Technol. 18 (1984) 171–179.
(1982) no. 17/18, 573–583. 215 NATO-CC MS Report II, (Disposal of Hazardous
194 H. R. Buser, H.-P. Bosshardt, C. Rappe, Chemosphere 1 Wastes – Thermal Treatment) March 23, 1981, pp. 84–89.
(1978) 109–119. 216 General Electric Co., US 4 353 798, 1982 (S. D. Foss).
195 H. R. Buser, C. Rappe, Chemosphere 3 (1979) 157–174. 217 General Electric Co., US 4 353 793, 1982 (D. J.
196 R. R. Bumb et al., Science (Washington, DC) 210 (1980) Brunelle).
no. 4468, 385–390. 218 General Electric Co., US 4 351 718, 1982 (D. J.
197 G. G. Choudhry, O. Hutzinger, Toxicol. Environ. Chem. Brunelle).
Rev. 5 (1982) 1–65, 67–93, 97–151, 153–165 and 295– 219 Goodyear Tire & Rubber Co., US 4 284 516, 1981 (D. K.
309. Parker, R. J. Steichen). D. K. Parker, W. L. Cox, Plant
198 A. Schecter, Chemosphere 12 (1983) no. 4/5, 669–680. Eng. (1980) Aug. 21, 133–134.
199 Environment Committee, Paris, March 1982, Report 220 Sunohio, GB 2 063 908, 1981 (O. C. Norman, L. H.
on the implementation by member countries of deci- Handler); GB 2 081 298, 1982 (O. D. Jordan).
sion by the council on the protection of the environ- 221 ITO T., JP-Kokai 81/111 078, 1980.
ment by control of polychlorinated biphenyls, ENV 222 Fuji Elektric Co., Ltd., DE-OS 3 036 000, 1980 (Masuda
(82) 5. et al.).
200 Ullmann, 4th ed., 9, pp. 515–518. 223 University of Waterloo, US 4 326 090, 1982 (J. G.
201 O. Hutzinger, S. Safe, V. Zitko: The Chemistry of PCB’s, Schmitz, G. L. Bubbar).
CRC Press, Cleveland 1974. 224 The Franklin Institute, DE-OS 3 033 170, 1980; EP
202 Zehnte Verordnung zur Durchf€uhrung des Bundes-Im- 60 089, 1982 (L. L. Pytlewski, K. Krevitz, A. B. Smith).
missionsschutzgesetzes (Tenth Implementing Order Is- 225 ITO T., JP Kokai 82/29 373, 1980; Chem. Abstr. 96
sued Pursuant to the Federal Immission Protection Act of (1982) 222 772.
the FRG); restrictions on PCB, PCT and VC. July 26, 226 Queens University, Kingston ONT, US 4 345 983, 1982
1978. (J. K. S. Wan).
203 Council Directive of July 27, 1976, harmonizing the 227 Tokyo Shibaura Elec., Ltd., JP-Kokai 82/166 175, 1981;
legal and administrative provisions of the member states Chem. Abstr. 98 (1983) 59 404.
restricting the sale and use of dangerous substances and 228 Rockwell Int. Corp., WO 8 002 116; EP 26 201, 1980 (L.
preparations (76/769/EEC). F. Grantham et al.).
204 Gesetz € uber die Beseitigung von Abf€allen (Waste Dis- 229 L. Bjorklund, I. F€aldt, WO 8 200 509, 1980.
posal Act) of January 5, 1977 (FRG). 230 SOTOO Z., JP-Kokai 79/151 953, 1978; Chem. Abstr. 93
205 Verordnung zur Bestimmung von Abf€allen nach x 2 Abs. (1980) 31 358.
2 des Abfallbeseitigungsgesetzes (Order Regulating the 231 ICI Australia, Ltd., WO 8 202 001, 1980 (V. Vasak, K. K.
Classification of Wastes According to x 2 Para. 2 of the Mok, J. Sencar).
Waste Disposal Act), May 24, 1977 (FRG). 232 K. Ballschmiter, M. Zell, Fresenius Z. Anal. Chem. 302
206 Gesetz € uber Maßnahmen zur Sicherung von Alt€olbesei- (1980) 20–31.
tigung (act embodying measures to ensure the disposal 233 H. M. Klimisch, D. N. Ingebrigtson, Anal. Chem. 52
of scrap oil), December 11, 1979 (FRG). (1980) no. 11, 1675–1678.
518 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons Vol. 8

234 P. W. Albro, J. T. Corbett, J. C. Schr€oder, J. Chromatogr. 263 J. Todt, Chem. Ing. Tech. 54 (1982) no. 10, 932.
205 (1981) 103–111. 264 Hodogaya Chem. Co., Ltd., JP-Kokai 79/78 399, 1977
235 D. A. Newton et al., J. Chromatogr. Sci. 21 (1983) 161. (K. Imaizumi, A. Arai, G. Tsunoda); Chem. Abstr. 91
236 E. Schulte, R. Malisch, Fresenius Z. Anal. Chem. 314 (1979) 142 751.
(1983) 545–551 and 319 (1984) 54–59. 265 Sumitomo Chem. Co., Ltd., JP-Kokai 79/43 194, 1977
237 W. J. Dunn et al., Anal. Chem. 56 (1984) no. 8, 1308– (Y. Matsushita, J. Kamimura); Chem. Abstr. 91 (1979)
1313. 76 268.
238 R. H. Lin et al., Anal. Chem. 56 (1984) no. 11, 1808– 266 M. F. Nathan, Chem. Eng. Jan. 30. 1978, 93–100.
1812. 267 Celanese Corp., US 4 276 179, 1981 (J. W. Soehngen).
239 Versar Inc., National Technical Informal Service, Indus- 268 Hooker Chem. Corp., US 2 949 491, 1960 (J. R. Rucker).
trial Use and Environmental Distribution (NTIS 252– 269 Osaka Prefecture, JP-Kokai 78/84 923, 1976 (Y. Hata-
012/3 W P) 1976. no); Chem. Abstr. 89 (1978) 163 306.
240 Fireproof Products Co., US 914 222, 1909; US 914 223, 270 Teijin K. K., JP-Kokai 79/59 233, 1977 (T. Yamaji);
1909; Halogen Products Co., US 1 111 289, 1913 (J. W. Chem. Abstr. 91 (1979) 192 958.
Aylsworth).
241 F. D. Kover, Environmental Hazard Assessment Report, Specific References
Chlorinated Naphthalenes, Environmental Protection 271 T. R. Torkelson, V. K. Rowe in G. D. Clayton, F. L.
Agency 560/8–75–001, 1975. Clayton (eds.): Patty’s Industrial Hygiene and Toxicol-
242 U.S. Federal Register vol. 48, no. 89 of May 6, 1983, pp. ogy, 3rd ed., vol. 2 B, Wiley-Interscience, New York
20 668–20 679; vol. 49, no. 166 of August 24, 1984, pp. 1981, pp. 3433–3601.
33 649–33 654. 272 American Conference of Governmental Industrial Hy-
243 U. A. Th. Brinkman, H. G. M. Reymer, J. Chromatogr. gienists Inc. Documentation of the Threshold Limit
127 (1976) 203–243. Values 1980 (With Annual Supplements) 6500 Glenway
244 AUER-Technikum, no. 10, 1982, Published by Auerge- Bldg. D-5, Cincinnati, OH 45211.
sellschaft GmbH, Berlin 44 (FRG). 273 Commission for Investigation of the Health Hazards of
245 P. Ferrero, C. Caflisch, Helv. Chim. Acta 11 (1928) 795– Chemical Compounds in the Work Environment: Tox-
812. ikologisch-arbeitsmedizinische Begr€ undung von MAK-
246 D. H. S. Horn, F. L. Warrer, J. Chem. Soc. 1946, 144. Werten, Verlag Chemie, Weinheim 1984.
247 Frontier Chemical Co. (Division of Vulcan Materials 274 Monograph on the Evaluation of the Carcinogenic Risk
Co.), US 3 413 357, 1968 (K. F. Bursack, E. L. Johnston, of Chemicals to Humans. Chemicals, Industrial Process-
H. J. Moltzau). es and Industries Associated with Cancer in Humans.
248 E. G. Turner, W. P. Wynne, J. Chem. Soc. 1941, 244–245. IARC Monogr. Suppl. 1–29 (1982) no. 4.
249 W. Schwemberger, W. Gordon, Zh. Obshch. Khim. 2 275 J. A. John, D. J. Wroblewski, B. A. Schwetz: ‘‘Terato-
(1932) 926; 5 (1934) 695. genicity of Experimental and Occupational Exposure to
250 Bayer, DE 844 143, 1951; DE 946 055, 1953 (H. Industrial Chemicals’’ in H. Kalter, ed.: Issues and Re-
Vollmann). views in Teratology, vol. 2, Plenum, 1984, p. 267–324.
251 A. Ledwith, P. J. Russel, J. Chem. Soc. Perkin Trans. 2 276 American Conference of Governmental Industrial Hy-


(1975) no. 14, 1503–1508. gienists. TLV’s Threshold Limit Values for Chemical
252 Dow Chemical Co., US 1 917 822, 1933 (E. C. Britton, Substances in the Work Environment Adopted by the
W. R. Reed). ACGIH for 1985–1986. ACGIH 6500 Glenway Bldg. D-
253 Ullmann, 4th ed., 9, pp. 512–520. 5, Cincinnati, OH 45211.
254 S. Safe, O. Hutzinger, J. C. S. Chem. Commun. 1972, 277 Deutsche Forschungsgemeinschaft: MAK, Verlag Che-
260–262. mie, Weinheim 1984.
255 M. P. Gulan, D. D. Bills, T. B. Putnam, Bull. Environ. 278 ‘‘The Chemical Industry Institute of Toxicology’’: Un-
Contam. Toxicol. 11 (1974) no. 5, 438–441. published data on methyl chloride. Research Triangle
256 U. A. T. Brinkman, A. De Kok, J. Chromatogr. 129 Park, North Carolina 27709.
(1976) 451. 279 B. N. Ames, P. F. Infante, R. H. Reitz, Banbury Report 5.
257 U. A. T. Brinkman et al., J. Chromatogr. 152 (1978) 97– Ethylene Dichloride: A Potential Health Risk, Cold
104. Spring Harbor Laboratory, Maine, USA, 1980.
258 M. Cooke et al., J. Chromatogr. 156 (1978) 293–299. 280 R. J. Kociba, B. A. Schwetz, D. G. Keyes, G. C. Jersey, J.
259 P. W. Albro, C. E. Parker, J. Chromatogr. 197 (1980) J. Ballard, D. A. Dittenber, J. F. Quast, C. E. Wade, C. G.
155–169. Humiston: Environ. Health 21 (1977) 49.
260 P. A. Kennedy, D. J. Roberts, M. Cooke, J. Chromatogr. 281 Ambient Water Quality Criteria for: Halomethanes,
249 (1982) 257–265. Chloroform, Carbon Tetrachloride, Chlorinated
261 J. J. Donkerbroek, J. Chromatogr. 255 (1983) 581–590. Ethanes, Trichloroethylene and Tetrachloroethylene.
262 Koppers Company, Inc., U.S., Product bulletin: Halo- U.S. Environmental Protection Agency, Oct. 1980.
waxes, Chlorinated Naphthalene Oils and Waxlike 282 M. A. Mayes, H. C. Alexander, D. C. Dill, Bull. Environ.
Solids. Contam. Toxicol. 31 (1983) 139–147.
Vol. 8 Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons 519

283 Dow unpublished data. 301 Report of the Cooperative Research Program between
284 C. Bushon, Ecological Effects Branch Chief, Office of the Gesellschaft f€ur Strahlen- und Umweltforschung
Pesticides and Toxic Substances. U.S. EPA, Washing- mbH, M€unchen (GSF) and the Albany Medical College
ton, DC, Dec. 16, 1983. of the Union University, Albany, N.Y., 1974 – 1978,
285 Y. Correia, G. J. Martens, F. H. van Mensch, B. P. Whim, GSF-Bericht Ö 486.
Atmos. Environ. 11 (1977) 1113–1116. 302 B. Bush et al., Arch. Environ. Contam. Toxicol. 13
286 P. R. Edwards, I. Campbell, G. S. Milne, Chem. Ind. 1 (1984) 517.
(1982) 574–578. 303 A. Hofmann et al., Arbeitsmed. Sozialmed. Pr€ aven-
287 K. K. Beutel: Health and Environmental Aspects of tivmed. 18 (1983) 181.
Chlorinated Solvents in Industrial Applications, Juris 304 U. A. T. Brinkman, H. G. M. Reymer, J. Chromatogr.
Druck þ Verlag, Z€urich 1984. 127 (1976) 203.
288 W. L. Dilling in R. A. Conway (ed.): Environmental Risk 305 G. L€ofroth et al., Mutat. Res. 155 (1985) 91.
Analysis for Chemicals, Van Nostrand Reinhold Co., 306 S. Haworth et al., Environ. Mutagen. 5 (1983) Suppl. 1, 3.
New York 1982, pp. 166–174.
289 M. A. K. Khalil, R. A. Rasmussen, Chemosphere 7
(1984) 789–800.
290 ‘‘National Academy of Sciences’’: Nonfluorinated Ha- Further Reading
lomethanes in the Environment, Washington 1978,
p. 97. J. de Boer (ed.): Chlorinated Paraffins, Springer, Berlin
291 NIOSH: Registry of Toxic Effects of Chemical Sub- Heidelberg 2010.
stances, U.S. Dept. of Health, Education and Welfare, G. Kreysa, M. Sch€utze (eds.): Corrosion Handbook, 2nd ed.,
NIOSH (1983) . DECHEMA/Wiley-VCH, Weinheim 2009.
292 E. Loeser, M. H. Litchfield, Fd. Chem. Toxic. 21 (1983) K. A. Marshall: ‘‘Chlorocarbons and Chlorohydrocarbons,
825–832. Survey’’, Kirk Othmer Encyclopedia of Chemical Tech-
293 J. Kohli et al., Can. J. Biochem. 54 (1976) 203. nology, 5th edition, John Wiley & Sons, Hoboken, NJ,
294 R. D. Lingg et al., Drug Metab. Dispos. 10 (1982) 134. online DOI: 10.1002/0471238961.1921182218050504.
295 J. H. Koeman et al., Nature (London) 221 (1969) 126. a01.pub2.
296 L. Acker, R. Schilte, Naturwissenschaften 57 (1970) R. A. Meyers, D. K. Dittrick (eds.): Encyclopedia of Envi-
497. ronmental Pollution and Cleanup, Wiley, New York
297 F. K. Zimmermann et al., Mutat. Res. 133 (1984) 199. 1999.
298 L. Fishbein, J. Chromatogr. 68 (1972) 345. P. Patnaik (ed.): A Comprehensive Guide to the Hazardous
299 M. Ogawa, Fukuoka Igaku Zasshi 62 (1971) 74; cited in: Properties of Chemical Substances, 3rd ed., Wiley, Ho-
J. R. Allen, D. H. Norback, Science (Washington, D.C.) boken, NJ 2007.
179 (1973) 498. C. E. Wilkes, J. W. Summers, C. A. Daniels (eds.): PVC
300 J. H. Miller, Public Health Rep. 59 (1944) 1085. Handbook, Hanser Gardner, Cincinnati, OH 2005.