Azo Dyes 1

Azo Dyes
Klaus Hunger, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany (Chaps. 1 – 4,
6 – 10)
Peter Mischke, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany (Chaps. 1 – 4,
6 – 10)
Wolfgang Rieper, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany (Chaps. 1 – 4,
6 – 10)
Roderich Raue, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 5)
Klaus Kunde, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 5)
Aloys Engel, DyStar Textilfarben GmbH & Co. Deutschland KG, Leverkusen, Federal Republic of Germany
(Chap. 5)

1. Introduction . . . . . . . . . . . . . . 2 3.2.1.1. Monoazo Dyes . . . . . . . . . . . . . 22

2. Production . . . . . . . . . . . . . . . 3 3.2.1.2. Disazo Dyes . . . . . . . . . . . . . . . 25
2.1. Diazotization and Coupling . . . . 4 3.2.1.3. Chrome Dyes . . . . . . . . . . . . . . 28
2.1.1. Diazotization . . . . . . . . . . . . . . 4 3.2.1.4. Metal-Complex Dyes . . . . . . . . . 30
2.1.2. Coupling . . . . . . . . . . . . . . . . . 7 3.2.2. Polyamide Dyes . . . . . . . . . . . . 31
2.2. Other Azo Group Syntheses . . . . 11 3.2.3. Silk Dyes . . . . . . . . . . . . . . . . 33
2.2.1. Condensation of Nitro Compounds 3.2.4. Leather Dyes . . . . . . . . . . . . . . 34
with Amines . . . . . . . . . . . . . . 11 3.2.5. Azo Food Dyes . . . . . . . . . . . . . 35
2.2.2. Reduction of Nitro Compounds . . 12 4. Direct (Substantive) Dyes . . . . . 37
2.2.3. Oxidation of Amino Compounds . . 13 4.1. Conventional Direct Dyes . . . . . 38
2.3. Synthesis from Azo Compounds . 13 4.1.1. Monoazo Dyes . . . . . . . . . . . . . 38
2.3.1. Exposure of Concealed or Protected 4.1.2. Disazo Dyes . . . . . . . . . . . . . . . 40
Amino Groups . . . . . . . . . . . . . 13 4.1.2.1. Primary Disazo Dyes . . . . . . . . . 40
2.3.2. Acylation of Amino Azo Com-
4.1.2.2. Secondary Disazo Dyes . . . . . . . 43
pounds . . . . . . . . . . . . . . . . . . 14
4.1.3. Trisazo Dyes . . . . . . . . . . . . . . 43
2.3.3. Alkylation and Acylation of Pheno-
4.1.4. Tetrakisazo Dyes . . . . . . . . . . . . 44
lic Hydroxyl Groups . . . . . . . . . 14
4.1.5. Condensation Dyes . . . . . . . . . . 45
2.3.4. Metal-Complex Formation . . . . . . 15
2.4. Processes without Industrial Im- 4.1.6. Direct Dyes with a Urea Bridge . . 46
portance . . . . . . . . . . . . . . . . . 15 4.1.7. Triazinyl Dyes . . . . . . . . . . . . . 46
2.4.1. Reduction of 4.1.8. Copper Complexes of Substantive
Diazonium Compounds . . . . . . . 16 Azo Dyes . . . . . . . . . . . . . . . . 48
2.4.2. Oxidative Coupling . . . . . . . . . . 16 4.2. Direct Dyes with Aftertreatment . 48
2.4.3. Dehydrogenation 4.2.1. Aftertreatment with Cationic Auxil-
of Diarylhydrazines . . . . . . . . . . 17 iaries . . . . . . . . . . . . . . . . . . . 49
2.4.4. Reaction of Arylhydrazines with 4.2.2. Aftertreatment with Formaldehyde 50
Quinones . . . . . . . . . . . . . . . . 17 4.2.3. Diazotization Dyes . . . . . . . . . . 50
2.4.5. Condensation of Nitroso 4.2.4. Aftertreatment with Metal Salts . . 50
Compounds with Amines . . . . . . 18 5. Cationic Azo Dyes . . . . . . . . . . 51
2.4.6. Azo Compounds from Azido Com- 5.1. Cationic Charge at the Coupling
pounds . . . . . . . . . . . . . . . . . . 18 Component . . . . . . . . . . . . . . . 52
2.5. Equipment for Industrial Produc- 5.1.1. Polyamines as Coupling Compo-
tion of Azo Dyes . . . . . . . . . . . . 19 nents . . . . . . . . . . . . . . . . . . . 52
3. Anionic Azo Dyes . . . . . . . . . . . 20 5.1.2. Heterocycles as Coupling Compo-
3.1. Introduction . . . . . . . . . . . . . . 20 nents . . . . . . . . . . . . . . . . . . . 53
3.2. Acid Azo Dyes . . . . . . . . . . . . . 20 5.1.3. Coupling Components with
3.2.1. Wool Dyes . . . . . . . . . . . . . . . . 21 Alkylammonium Groups . . . . . . . 54

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

10.1002/14356007.a03 245
2 Azo Dyes

5.1.3.1. Coupling Components with 5.2.3.2. Aliphatically Linked Cyclic Ammo-

Dialkylaminoalkyl Groups . . . . . . 54 nium Residues . . . . . . . . . . . . . 64
5.1.3.2. Aromatically Linked Trialkylammo- 5.2.4. Diazo Components with two Differ-
nium Groups . . . . . . . . . . . . . . 54 ent Cationic Residues . . . . . . . . . 64
5.1.3.3. Trialkylammoniumalkyl-Substituted 5.2.5. Diazo Components with Aromatic
Anilines . . . . . . . . . . . . . . . . . 55 Condensed Cyclic Ammonium
5.1.3.4. Other Trialkylammoniumalkyl- Residues . . . . . . . . . . . . . . . . . 65
Substituted Coupling Components . 56 5.2.6. Cyclic Ammonium Compounds
5.1.4. Coupling Components with Dialkyl- Linked in Meta Position to the Azo
hydrazinium Groups . . . . . . . . . 57 Group . . . . . . . . . . . . . . . . . . . 66
5.1.5. Coupling Components with Cyclic 5.3. Different Cationic Charges in
Ammonium Groups . . . . . . . . . . 57 Both the Coupling and the Diazo
5.1.5.1. Heterocyclically Linked Cyclic Am- Component . . . . . . . . . . . . . . . 66
monium Groups . . . . . . . . . . . . 57 5.4. Introduction of Cationic Sub-
5.1.5.2. Aliphatically Linked Cyclic Ammo- stituents into Preformed Azo Dyes 66
nium Groups . . . . . . . . . . . . . . 58 5.5. Cationic Dyes with Sulfur or
5.1.6. Coupling Components with Con- Phosphorus as Charge-Carrying
densed Cyclic Ammonium Residues 59 Atoms . . . . . . . . . . . . . . . . . . 68
5.1.7. Cyclic Ammonium Residues at the 5.6. Dyes with Releasable Cationic
Azo Group . . . . . . . . . . . . . . . 59 Groups . . . . . . . . . . . . . . . . . 68
5.1.8. Coupling Components with two Dif- 6. Developing Dyes . . . . . . . . . . . 69
ferent Cationic Residues . . . . . . . 59 6.1. Developing Dyes for Cotton . . . . 70
5.2. Cationic Charge in the Diazo
6.1.1. Developing Dyes for Dyeing . . . . 70
Component . . . . . . . . . . . . . . . 61
6.1.1.1. β-Naphthol Dyes . . . . . . . . . . . 70
5.2.1. Diazo Components with Aminoalkyl
6.1.1.2. Naphtol AS Dyes . . . . . . . . . . . 70
Moieties . . . . . . . . . . . . . . . . . 61
6.1.2. Developing Dyes for Printing . . . . 77
5.2.2. Diazo Components with Trialkylam-
monium Residues . . . . . . . . . . . 61 6.2. Developing Dyes for Animal
5.2.2.1. Aromatically Linked Trialkylammo- Fibers . . . . . . . . . . . . . . . . . . 85
nium Residues . . . . . . . . . . . . . 62 6.3. Developing Dyes for Hydrophobic
5.2.2.2. Aliphatically Linked Trialkylammo- Fibers . . . . . . . . . . . . . . . . . . 85
nium Residues . . . . . . . . . . . . . 62 7. Disperse Azo Dyes . . . . . . . . . . 86
5.2.3. Diazo Components with Cyclic Am- 8. Azo Pigments . . . . . . . . . . . . . 86
monium Residues . . . . . . . . . . . 64 9. Alcohol- and Ester-Soluble Dyes . 86
5.2.3.1. Aromatically Linked Cyclic Ammo- 10. Fat- and Oil-Soluble Dyes . . . . . 87
nium Residues . . . . . . . . . . . . . 64 11. References . . . . . . . . . . . . . . . 89

1. Introduction [1–6] Due to the simple nature of the synthesis, usu-

ally in aqueous medium, and the almost unlim-
Azo dyes are characterized by a chromophoric ited choice of starting products, an extremely
azo group −N=N−, whose nitrogen atoms are wide variety of azo dyes is possible. The num-
linked respectively to sp2 -hybridized carbon ber of combinations is further increased by the
atoms. At least one of these carbon atoms be- fact that a dye molecule can contain several azo
longs to an aromatic carbocycle (usually a ben- groups.
zene or naphthalene derivative) or heterocycle This diversity of inexpensively produced azo
(e.g., pyrazolone, thiazole), whereas the second dyes permits a wide spectrum of shades and fast-
carbon atom adjoining the azo group may also ness properties suitable for use on a variety of
be part of an enolizable aliphatic derivative (e.g., substrates.
acetoacetic acid). The most common types of Naturally occurring azo dyes are unknown
azo dyes can thus be summarized as follows: (some containing azoxy groups are known), but
aryl−N=N−R, where R can be an aryl, het- the azo dyes represent the most numerous and
eroaryl, or −CH=C(OH)−alkyl. widely manufactured synthetic dyes.
 Azo Dyes 3

Nomenclature. Depending on the number of Dyes listed as examples in the following sec-
azo groups, the azo dyes are called monoazo, tions are cited according to the internationally
disazo, trisazo, tetrakisazo, etc., dyes, and those used designations in the Colour Index. Trade
with three or more azo groups, polyazo dyes. names are compiled in tabular form only for
The structure of an azo dye can be described the individual dye classes; historical common
by means of a structural formula (a), IUPAC names are for the most part included in the text.
nomenclature (b), or practical nomenclature (c),
e.g.: Classification. Azo dyes can be classified ei-
a) ther according to chemical guidelines (charac-
teristic chemical groups) or by color aspects (ap-
plication in dye works). A rigid assignment to
one of the two classification systems is possible,
but not advisable because of overlapping. There
is therefore scarcely a chemical class of azo dyes
that belongs to a single color class or vice versa.
b) 1-hydroxy-2-phenylazo-7-(4
-nitrophenylazo)- Moreover, many materials can be dyed with dyes
8-aminonaphthalene-3,6-disulfonic acid from various color groups. In this article, a com-
c) general formulation: D –1 → K ←2 – D, in promise between the two classification systems
words: p-nitroaniline –1 → H acid ←2 – ani- with emphasis on application in the dye works
line and in reaction equations: seemed to be the most appropriate.
The importance of the azo dyes is due to their
mode of application and to the fact that they
represent a clearly defined concept. They are
briefly described here and dealt with more exten-
sively under special headings: → Disperse Dyes;
→ Metal-Complex Dyes; → Pigments, Organic;
→ Reactive Dyes.
Designation (b) is less commonly used be-
cause of its complexity. The practical nomen-
clature (c) makes use of a genetic scheme of 2. Production
the technically most common synthesis, i.e., it
characterizes the azo dye by the starting com- For additional information see [1–6] and [8–12].
pounds (D = diazo component and K = coupling The processes that are important in the pro-
component) and the direction of coupling. This duction of azo dyes are classified as follows:
nomenclature is shorter and is commonly used Processes involving synthesis of the azo
in industry and technical literature. In the case of group:
disazo and polyazo dyes, the coupling direction
is specified by arrows, the sequence of opera- – diazotization and coupling
tions by appropriate numbers above the arrows, – condensation of nitro compounds with
and the coupling conditions by the abbrevia- amines
tions a (acid) and alk (alkaline). Additional ar- – reduction of nitro compounds
rows at the coupling components show the link- – oxidation of amino compounds
age points of both components across the azo Syntheses with compounds already contain-
groups. All industrially important dyes are also ing the azo group:
classified according to the Colour Index [7]. This
catalog of dyes gives information about trade – exposure of concealed or protected amino
names, coloristic properties, and, if published, groups
the chemical constitution. The dyes are classi- – acylation of aminoazo compounds
fied according to color and chemical properties. – alkylation and acylation of phenolic hy-
Aside from its trade names, the azo dye in for- droxyl groups
mula 1, for example, can be found as C. I. Acid – metal-complex formation
Black 1 or C. I. 20470.
4 Azo Dyes

2.1. Diazotization and Coupling Diazotization of aromatic diamines gives

bisdiazonium compounds and therefore is
Of all the industrially important processes azo called bisdiazotization. The incorrect term
coupling, during which the azo group is synthe- “ tetrazotization ” is frequently found in the tech-
sized, is by far the most important. All other in- nical literature.
dustrially employed processes are advantageous The essential step in diazotization is the elec-
only where azo coupling cannot be utilized, for trophilic nitrosation of the amino group of the
example, because of the unavailability of the primary aromatic amine (2).
starting compounds. Formation of the diazonium ion (4) then fol-
Azo coupling can be summarized as follows: lows via the diazohydroxide (3):
an aromatic amine is linked to a nucleophilic
partner RH (coupling component) in the pres-
ence of a nitrosyl-eliminating compound XNO
to form an aromatic azo compound. The reaction
equation is as follows:

Equation (1) describes the overall azo cou- Reaction sequence (3) is a simplification; in
pling reaction, which consists of two major fact, the reaction rate during diazotization is
steps: formation of the diazonium compound by determined by the formation of the nitrosating
means of the so-called diazotization and synthe- agent (at low acidity) or nitrosation of the amine
sis of the azo dye, the actual azo coupling. (at high acidity). In a strongly acid medium, i.e.,
in the absence of free amines, the protonated
amine surprisingly becomes the nucleophile:
2.1.1. Diazotization
Diazotization is defined as the reaction of pri-
mary aromatic amines with nitrites, preferably
with sodium nitrite, in a usually aqueous min-
eral acid solution at around 0 ◦ C, whereby the
amine is converted into the corresponding dia-
zonium salt: The equilibrium reactions preceding nitro-
sation require excess acid during diazotization
leading to the formation of the nitrosating agent:

Weakly basic amines require a higher acid

concentration, since diazoamino compounds
Ar−N=N−HN−Ar may otherwise form. Very
weakly basic amines, i.e., amines with several
negative (−I/−M) substituents (e.g., tetrahalo- N2 O3 is the nitrosating agent in a weakly
gen anilines, di- and trinitroanilines, halogen- acid medium (Eq. 5), H2 ONO in a more acid
nitroanilines) can only be diazotized after be- medium (Eq. 6), and the nitrosonium ion NO+
ing dissolved in concentrated sulfuric acid and in a strongly acid medium (Eq. 7).
subsequently reacted with nitrosylsulfuric acid, An excess of sodium nitrite must be avoided,
HSO4 NO. since nitrite can react with the coupling agent as
A further reason for using concentrated acids well as with secondary or tertiary amines to form
(concentrated sulfuric acid) is the fact that dia- nitroso compounds during subsequent coupling.
zonium salts of weakly basic amines are readily Excess nitrite can be detected with potassium
hydrolyzable in dilute acids.
 Azo Dyes 5

iodide–starch paper. It is eliminated by adding Many of these compounds can also be used
amidosulfuric acid or urea: as coupling components (see Section 2.1.2), as
shown by the arrow indicating the coupling po-
sition.
Diamines H2 N−A−NH2 . The diamines can
be divided into four groups:
Diazo Components. Diazo components for a) A = phenylene or naphthylene radical, also
the production of azo dyes can be divided into substituted, e.g., by methyl, chlorine, nitro,
the following groups of aromatic amines: methoxy, or sulfonic acid groups. Examples
Aniline and Substituted Anilines. Methyl, are:
chlorine, nitro, methoxy, ethoxy, phenoxy, hy-
droxyl, carboxy, carbalkoxy, carbonamide, and
sulfonic acid groups are primarily used as sub-
stituents.
Examples: Toluidines, nitroanilines, ami-
nobenzoyl amides, and the sulfonic acids of
these compounds.
Naphthylamines and Naphthylamine Sul-
fonic Acids. The following compounds, known
by their common names, are examples of naph- b) A = diphenyl radical, also substituted,
thylamine sulfonic acids: mainly by methyl, chlorine, methoxy, car-
boxylic acid, or sulfonic acid groups. Exam-
ples are:

c)

whereby the aromatic rings can also be

substituted by methyl, chlorine, methoxy,
carboxylic acid, or sulfonic acid groups.
B = oxygen, sulfur, −NH−, −SO2 −,
−N=N−, −CH=CH−, −NHCO−,
−NH−CO−HN−. Examples are:
6 Azo Dyes

d) Diazotization in Organic Solvents. The

water-insoluble or only slightly soluble
amine is dissolved in glacial acetic acid or
other organic solvents and, where neces-
sary, diluted with water. After the addition
of acid it is diazotized in the usual manner
with sodium nitrite solution. Nitrosylsulfu-
ric acid, nitrosyl chloride, alkyl nitrites, or
d) Heterocyclic amines and diamines. Exam-
nitrous gases can also be used to eliminate
ples are:
the nitrite. Temperature, pH, and the concen-
tration of the diazotizing solution often have
a considerable effect on the progress of dia-
zotization. Physical properties (distribution,
particle size) and the addition of emulsifiers
and dispersing agents influence the diazoti-
zation of slightly soluble amines.
Certain aromatic amines require special dia-
zotizing processes:
1-Aminonaphthols, such as 1-amino-2-
naphthol and several 1-aminonaphtholsulfonic
acids, such as 1-amino-2-naphthol-4-sulfonic
Diazotizing Methods. Considering the ba- acid, are oxidized to the respective quinone by
sicity and solubility of the amines being diazo- nitrous acid. Diazotization can however take
tized, the following diazotization methods find place under normal conditions in the presence
industrial use (for further details → Diazo Com- of catalytic quantities of metal salts, such as
pounds): copper or zinc salts.
o-Diamines, such as 1,2-phenylenediamine
a) Direct Diazotization. The primary aromatic or 1,8-naphthylenediamine, undergo cyclization
amine is dissolved or suspended in aque- during the normal diazotization process to form
ous hydrochloric or sulfuric acid to which triazoles:
an aqueous, concentrated sodium nitrite so-
lution is added. An excess of 2.5 to 3 equiva-
lents of acid per equivalent of amine is used.
A temperature of 0 to 5 ◦ C is maintained by
adding ice.
b) Indirect Diazotization. Amines with sulfonic
or carboxylic acid groups are often diffi-
cult to dissolve in diluted acid. Diazotization The desired bisdiazotization with o-
therefore takes place as follows: the amine is phenylenediamine, as well as with m- and
dissolved in water or weak alkalis, and the p-phenylenediamine, is achieved in glacial
calculated amount of sodium nitrite solution acetic acid with nitrosylsulfuric acid. 1,8-
is stirred into the ice-cooled acid solution Naphthylenediamine can be bisdiazotized in
already in the vessel. The acid can also be excess acid.
added to the amine–nitrite mixture already Under normal diazotization conditions, vari-
at hand. ous ortho-substituted aromatic amines also un-
c) Diazotization of Weakly Basic Amines. dergo more or less complete cyclization to form
Weakly basic amines are dissolved in con- benzoheterocycles that are no longer accessible
centrated sulfuric acid and diazotized with to subsequent coupling.
nitrosylsulfuric acid, which is easily pre- Examples are:
pared from solid sodium nitrite and concen-
trated sulfuric acid.
 Azo Dyes 7

formed during the coupling reaction. In order

to maintain an optimal reaction sequence, the
pH must be kept constant by adding alkalis or
buffers. Coupling under strongly alkaline con-
ditions is not possible. According to Equation
(3), the diazonium compound undergoes a re-
verse reaction to form an anti-diazotate, which
cannot be coupled. Under strongly alkaline con-
ditions and with amines as coupling agents,
the diazonium component may react with the
amine nitrogen to form the diazoamino com-
pound R−N=N−HN−Ar. Phenols and enols are
therefore generally coupled in the weakly al-
kaline range (pH 7 – 9), amines mainly in the
weakly acid range (pH 4 – 7).
In the production of developing dyes for tex-
tile printing the formation of diazoamino com-
pounds is desired (see Section 6.1.2, → Diazo
Diazonium compounds are generally stable Compounds).
only in aqueous solution at low temperatures. Substituents with donor effects in the aro-
When heated, they frequently decompose by matic nucleus of the coupling components in-
eliminating nitrogen to form the corresponding crease the reactivity. Conversely, donor sub-
phenol. Some amines, however, can be diazo- stituents on the lower the reactivity, whereas sub-
tized at temperatures up to 40 ◦ C. Light and stituents with acceptor effects increase it. The
heavy-metal ions also accelerate the decompo- coupling energy of substituted anilines as diazo
sition of diazonium compounds. Diazotization, components decreases as follows:
therefore, is usually carried out in wooden vats polynitroanilines > nitrochloroanilines > ni-
or iron stirring vessels with an acid-proof lining troanilines > chloroanilines > anilinesulfonic
or rubber coating (see Section 2.5). acids > aniline > anisidines > aminophenols.
As solids most diazonium compounds are sta- The C-atom with the highest electron den-
ble only to a degree and frequently sensitive to sity is usually the preferred coupling position
heat, impact, and shock (explosive) (→ Diazo of a coupling component. Due to the directing
Compounds). influence of hydroxyl or amino groups in aro-
matic systems, coupling takes place at the or-
tho or para position. If these two positions are
2.1.2. Coupling occupied, there is either no coupling or one of
the substituents is exchanged. Coupling never
Coupling Sequence. The actual azo cou- occurs at the meta position in relation to the di-
pling reaction consists of an electrophilic sub- recting substituent. Components of the naphtha-
stitution reaction of the diazonium compound lene groups generally couple more easily than
with a nucleophilic partner (coupling compo- benzene derivatives.
nent RH): Amines, which tend to form diazoamino
compounds, can easily be coupled at the para
Ar − N+ ≡ NY− + R − H −→ Ar–N = N − R + HY (8) position if they have been reacted with formalde-
hyde and sodium hydrogen sulfite to form N-
Coupling components are aromatic systems methylenesulfonate [13]:
with nucleophilic centers at the aromatic nu-
cleus, particularly phenols, naphthols, and
amines or enolizable compounds with reactive
methylene groups. Phenols react as phenolates,
naphthols as napththolates, and amines as free
bases. According to Equation (8), free acid is
8 Azo Dyes

p-Aminoazo dyes are obtained by splitting from a small quantity of 4-aminoazobenzene (5),
methylenesulfonate from the coupling products diazoaminobenzene (6) as main product:
under acid or alkaline conditions.
Other reaction conditions besides pH also
play an important role in azo coupling. Increased
temperature generally has a greater effect on the
decomposition of the diazonium salt according
4-Aminoazobenzene (5) is obtained by cou-
to Equation (9)
pling in a more strongly acid medium, but better
R − N+ ≡ N Cl− + H2 O −→ ROH + N2 + HCl (9) still by heating diazoaminobenzene (6) in aniline
than on the rate of coupling. The advantages are with addition of aniline hydrochloride.
therefore limited. Coupling can be accelerated Electron donor substituents in the aniline,
by raising the pH and the concentration of the such as methyl or methoxy groups, especially
reactants. In some cases the yield of azo dye can at the meta-position, promote the readiness to
be increased by adding sodium chloride prior to couple; the inclination to couple thus increases
the azo coupling. Some azo dyes can only be in the sequence aniline < o-toluidine < m-
satisfactorily manufactured by adding pyridine toluidine < m-anisidine < cresidine < 1-amino-
or pyridine homologues; examples are the cou- 2,5-dimethoxybenzene (aminohydroquinone di-
pling of diazotized aminoazo compounds and methyl ether) to the extent that without forma-
aminodisazo compounds, as well as o-amino- tion of the diazoamino compound, the last three
phenols for the production of complex forming bases are attached almost quantitatively in the
dyes (→ Metal-Complex Dyes). desired direction, i.e., at the 4-position in rela-
Pyridine acts as proton acceptor in the elec- tion to the amino group.
trophilic coupling reaction and is especially ben- m-Phenylene diamines couple to form
eficial when bulky substituents are present at the monoazo dyes (chrysoidines, see Section 5.1.1)
ortho or peri position in relation to the coupling or disazo dyes.
position of the intermediate product or when the Naphthylamines, Naphthylaminesulfonic
diazonium ion (e.g., in the case of o-diazophe- Acids. Some examples are mentioned here;
nols) exhibits a slight electrophilic reactivity. other compounds can be found among the di-
azo components (see Section 2.1.1), because
Coupling Components. The most impor- most naphthylaminesulfonic acids are capable
tant coupling components can be divided into the of being employed both for diazotization and
following groups. Where there are several possi- for coupling purposes.
bilities for coupling, the preferred coupling po-
sitions are marked by bold arrows and the other
possible coupling positions by ordinary arrows.
Anilines, Diaminobenzenes. Examples are:

Whereas β-naphthylaminesulfonic acids al-

ways couple at the adjacent α-position, with
the α-naphthylaminesulfonic acids, the cou-
pling location is influenced by the position of
the sulfonic acid group: 1,6-, 1,7-, and 1,8-
When reacted with aniline, diazotized ani- naphthylaminesulfonic acids couple at the 4-
line (benzenediazonium chloride) yields, apart
 Azo Dyes 9

position; 1,5-naphthylaminesulfonic acid (Lau- nated during the coupling process. 1-Methyl-2-
rent acid) only couples with very “strong cou- naphthol forms no azo dye.
plers” (e.g., 2,4-dinitroaniline), mainly at the Coupling components in this series that are of
4-position. With diazotized aniline, chloroani- particular industrial importance are 2-hydroxy-
line, or diazotized anilinesulfonic acids the 2- naphthalene-3-carboxylic acid arylamides, in
aminoazo dyes are obtained, but with diazotized particular anilides, which likewise couple at the
nitroaniline, mixtures of the 2- and 4-coupling 1-position (see Section 6.1.1.2).
products form: Phenols and naphthols generally couple
more easily and rapidly than amines; phenol-
3-sulfonic acid can be coupled, but not aniline-
3-sulfonic acid.
The readiness of the phenols to couple in-
creases as the number of hydroxyl groups rises,
as, for example, in the following series:

Naphtholsulfonic Acids. Examples are:

Phenols, Naphthols. Examples are:

Phenols mainly couple at the 4-position, or

at the 2-position if the 4-position is occupied.
p-Hydroxybenzoic acid couples with elimina-
tion of CO2 ; resorcinol couples twice: initially
at the 4-position, with a second equivalent dia-
zonium compound at the 2-position under acid
conditions or at the 6-position under alkaline
conditions. α-Naphthols mainly couple at the 4-
1-Naphtholsulfonic acids mainly couple at
position, in addition to which varying quantities
the 2-position. The 4-coupling products ob-
of 2- and 2,4-coupling products are obtained,
tained as byproducts have to be carefully re-
depending on the diazo component. β-Naphthol
moved from the azo dyes, because unlike the
couples at the 1-position. Substituents in the
2-substitution products, their shade changes as
1-position, such as −SO3 H, −COOH, −Cl,
a function of the pH value (shade intensification
−CH2 OH, or −CH2 N(alkyl)2 , may be elimi-
with rising pH due to formation of phenolate or
10 Azo Dyes

naphtholate resonance structures; see also Sec- However, if this initial coupling is followed
tion 3.2.1). by a metal-complexing process, further coupling
Aminophenols, Aminophenolsulfonic Acids, is possible in the neutral or alkaline range.
Aminonaphtholsulfonic Acids. Examples are: Compounds with Reactive Methylene
Groups. In this series the coupling components
with the greatest industrial importance are the
N-acetoacetyl derivatives of aromatic amines
(acetoacetic arylides):

CH3 CO–CH2 CO–NH–Ar

Anilines substituted by halogen, alkyl, alkoxy,

nitro, and acylamino groups are the aromatic
amines mainly suitable.
Example:

Bis(acetoacetylamino) derivatives, such as

In an alkaline medium m-aminophenol cou- Naphtol AS–G, also enjoy practical importance.
ples at the para position in relation to the hy-
droxy group, in an acid solution p-hydroxy and
p-aminoazo dyes are obtained side by side.
In the case of aminonaphtholsulfonic acids,
orientation is greatly influenced by the pH value
of the coupling medium. For instance, in an acid
medium the azo group enters into the position or- The following coupling components are also
tho to the amino group, in an alkaline medium, listed:
in the position ortho to the hydroxyl group. 1-
Amino-8-naphtholsulfonic acids with free or-
tho positions can couple with two equivalents of
diazonium compound, coupling initially taking
place in the acid medium at the o-amino position,
followed by coupling in the alkaline range at
the o-hydroxy position. Aminonaphtholsulfonic
acids (o-hydroxyazo dyes) initially coupled in Heterocyclic Components. The most impor-
an alkaline medium cannot normally undergo tant compounds in this range are the 5-
further coupling to form disazo dyes: pyrazolones substituted at the 3-position.

Further examples are:

 Azo Dyes 11

that couples easily (e.g., weakly alkaline H acid

solution). If no coloration appears, the coupling
is completed. The presence of unconsumed cou-
pling component can be determined by spotting
with a diazonium salt solution.
Attention must also be paid to the volume of
coupling solution or suspension. With starting
components of low solubility, the physical state
is an important factor. In order to achieve com-
plete reaction of diazo or coupling components
with low solubility, it is often necessary to en-
sure that the reactants are distributed as finely
as possible. This is carried out, for example, by
adding dispersing agents to the diazo component
or to the coupling mixture or by adding emul-
sifiers during acid precipitation of the coupling
component prior to azo coupling. In each case,
the most favorable reaction conditions must be
precisely established and, because of the various
influences that result in undesirable side effects,
Azo Coupling in Practice. The optimum they must be carefully adhered to during manu-
coupling conditions depend first of all on the facture.
nature of the diazo and coupling components See Section 2.5 for suitable apparatus.
used. The acid diazonium salt solution is gener-
ally allowed to enter the solution of the coupling
component. Because, in addition to acid de- 2.2. Other Azo Group Syntheses (See also
rived from the diazotization process, additional Chap. 2.4)
acid is released during coupling, the optimum
pH value must be adhered to by adding bases. 2.2.1. Condensation of Nitro Compounds
Alkali hydroxides, sodium carbonate, sodium with Amines [2, p. 339]
hydrogen carbonate, ammonia, calcium carbon-
ate, magnesium oxide etc., are used for this Aromatic azo and polyazo compounds can be
purpose. Such substances as sodium acetate or produced by condensation of nitro compounds
formiate (weakly acid) or sodium phosphate with amines in accordance with the following
(weakly alkaline) can also be added to buffer equation:
the acid. These substances are added to the re-
R1 –NO2 + H2 N–R2 −→ R1 –N = N–R2 + H2 O (+ O)
action mixture before, during, or after combin-
ing the components. Because at the feed point Because part of the amine is oxidized to the
of the diazonium salt solution the pH value is symmetrical azo compound R2 −N = N−R2 , an
always different than after thorough mixing has excess of amine is expedient. In some conden-
been completed, the type of stirrer and speed sation processes it has been possible to observe
of stirring are also important in many instances. the partial formation of azoxy bridges. Reaction
The sequence in which the two components are takes place on heating the reactants for several
combined can also greatly influence the result. hours to 40 – 120 ◦ C in aqueous sodium hydrox-
The coupling reaction may be completed im- ide solution.
mediately after the components are mixed or Substituents in the aniline component with
after several hours. If the reaction requires a electron-donor effects accelerate condensation;
longer time, it is advisable to cool with ice and electron acceptors retard it. In the nitro compo-
avoid exposure to dazzling light. In order to nent, the substituents have the opposite effect.
check whether excess diazonium compound is Of interest as regards the industrial manufac-
still present, a drop of reaction solution is spot- ture of dye intermediates are condensation reac-
ted onto filter paper together with a component tions of 4,4
-dinitrostilbene-2,2
-disulfonic acid
12 Azo Dyes

with aromatic amines. If specific sodium hy- ing heated with sodium hydroxide solution is
droxide solution concentrations, temperatures, converted into dinitrodibenzyldisulfonic acid
and reaction times are precisely observed, it and dinitrostilbenesulfonic acid. All three nitro
is possible with 1,4-diamines, 4-aminophenols, compounds condense in the presence of alkali,
and their sulfonic and carboxylic acids to pro- both with amino compounds and with each other.
duce homogeneous monoazo and disazo dyes: A number of direct cotton dyes (e.g., C. I. Direct
Yellow 21, 40045 [1325-46-8]) are the result of
complex condensation reactions of this type.
Simple azo compounds free of sulfonic acid
groups can be produced with yields of 40 – 84 %
by condensation of nitrobenzene with o- and
p-anisidine, naphthylamines, and phenylenedi-
amines without solvent in the presence of pow-
dered sodium hydroxide at temperatures of
130 – 190 ◦ C [14].
Because these reactions can proceed very
vigorously, suitable precautionary measures are
necessary.

2.2.2. Reduction of Nitro Compounds [2,

p. 346]
During the reduction of aromatic nitro
compounds, condensation of the nitro and
hydroxylamino derivatives that occur as inter-
mediate steps may result in the formation of
Of importance as regards the industrial pro- azoxy compounds, which in a further reduction
duction of the important direct cotton dyes step can be converted into azo compounds:
for orange, scarlet, and brown shades are con-
densation reactions of 4,4
-dinitrostilbene-2,2
-
disulfonic acid with aminoazo compounds (see
Section 4.1.5). For example, by heating this acid
with an equivalent of 4-aminoazobenzene-4
-
sulfonic acid in aqueous sodium hydroxide so-
lution, the disazo dye 8 is obtained:

The method is only suitable for the synthesis

of symmetrical azo compounds, for when two
different nitro compounds are used, mixtures of
all possible combinations are formed:
Condensation with two equivalents of 4-ami-
noazobenzene-4
-sulfonic acid at 105 ◦ C in 5 %
sodium hydroxide solution results in the corre-
sponding tetrakisazo dye.
Glucose has proved especially suitable as a
The dye synthesis is often followed by an ox-
reducing agent for reductive linkage of aromatic
idative aftertreatment (with chlorine bleaching
nitro compounds, other reducing agents being
liquor) or a reductive aftertreatment in alkaline
alcohols, hydrazine, zinc, iron, and numerous
medium (with sodium sulfide or glucose).
inorganic salts. Only the reduction process with
Instead of 4,4
-dinitrostilbene-2,2
disulfonic
glucose has attained industrial significance in the
acid as starting product, use is frequently made
synthesis of azo dyes, mainly for the linkage of
of 4-nitrotoluene-2-sulfonic acid, which on be-
nitroazo compounds under mild conditions. The
 Azo Dyes 13

process generally takes place in a strongly alka-

line, aqueous medium, less frequently in an alco-
holic medium. For example, the red trisazo dye
C. I. Direct Red, 25015 [6391-13-5] is obtained
by coupling 2-methyl-5-nitroaniline to Nevile-
Winther acid and subsequently treating with glu-
cose and alkali:

2.3. Synthesis from Azo Compounds

Reduction by glucose often does not proceed For specific technical purposes in the production
quantitatively up to the azo stage; instead the azo of azo dyes, further reactions are carried out on
and azoxy compounds are mostly formed side by the azo compound after introduction of the azo
side. Where necessary, therefore, subsequent re- bridge:
duction of the azoxy compound to form the azo
– exposure of concealed or protected amino
dye must follow.
groups
– acylation of aminoazo compounds
– alkylation and acylation of phenolic hy-
2.2.3. Oxidation of Amino Compounds [2,
droxyl groups
p. 371]
– metal-complex formation
Reaction of primary aromatic amines with suit-
able oxidizing agents results in symmetrical azo
compounds, sometimes, by further oxidation of 2.3.1. Exposure of Concealed or Protected
the azo stage, in the mixture with azoxy com- Amino Groups
pounds:
The formation of an amino group in azo dyes is
often necessary for the reaction with acid chlo-
rides, e.g., for the production of reactive dyes,
or for further diazotization and coupling. This
is possible by reduction of nitro groups or by
saponification of acylamino groups.
As the reduction of nitro groups must be car-
Hypochlorites are especially suitable as
ried out while maintaining the azo group, the
oxidizing agents, others being peroxy com-
number of suitable reducing agents is virtually
pounds (hydrogen peroxide, sodium perbo-
restricted to sodium sulfide. Processing is car-
rate), oxygen or air in the presence of a
ried out, depending on the nitro compound, in an
pyridine – Cu(I)chloride catalyst, and chromic
aqueous alkaline solution or suspension at tem-
acid.
peratures between 20 ◦ C and 90 ◦ C. A 10 – 30 %
The main industrial application for the ox-
addition of alkali chloride has proved favorable,
idative linkage of aromatic amines in the syn-
as a result of which most of the dye remains
thesis of azo dyes can be found in the thiazole
undissolved. After reduction the water-soluble
range. The yellow cotton dye C. I. Direct Yel-
sulfide oxidation products are separated, the dye
low 28, 19555 [10114-47-3], for example, is ob-
is dissolved, and the sulfur is separated. The ami-
tained by treating an aqueous solution of the
no azo dye can be further processed straightaway
sodium salt of the so-called dehydrothiotolui-
in this form.
dinesulfonic acid (9) with sodium hypochlorite
The acylamino groups, such as formyl,
in an alkaline medium:
acetyl, or oxalylamino groups can be saponified
in an acid or alkaline medium. As a rule 2 – 10 %
14 Azo Dyes

sulfuric acid or 2 – 6 % sodium hydroxide solu- For the production of substantive dyes two
tion is used at temperatures up to the boiling identical or different aminoazo dyes are linked
point of the reaction mixtures. together by means of cyanuric chloride. The
third chlorine atom remains either in the
molecule or, preferably, is condensed with am-
2.3.2. Acylation of Amino Azo Compounds monia or simple aromatic amines at tempera-
[2, p. 390]; [5, vol. VI, p. 1] tures of 80 – 100 ◦ C. The reaction with cyanuric
chloride not only enables the inner-molecular
Acylation reactions of aromatic amino com- blend to be varied at will but also considerably
pounds are important both for the production increases substantivity.
of reactive dyes, i.e., dyes that in the dyeing Phosgene, which is introduced into the so-
of textiles form a covalent bond with the fiber lution of the amino azo compound at 20 – 35 ◦ C
(→ Reactive Dyes), and for the synthesis of di- and at a neutral pH, is used as a bifunctional acy-
rect dyes (see Section 4), i.e., dyes that, because lation agent to link two amino azo compounds
of their pronounced affinity for cellulosic fibers (see Section 4.1.6).
(substantivity), are adsorbed directly onto the Numerous commercial dyes of a substan-
cotton fiber from an aqueous solution. tive nature have urea bridges of this kind, e.g.,
Acylation agents that contain at least two the direct dye C. I. Direct Yellow 50, 29025
reactive centers in the molecule and are capa- [8004-79-3], which is produced from diazotized
ble of selective reactions under certain condi- 2-aminonaphthalene-4,8-disulfonic acid and m-
tions, e.g., cyanuric chloride and cyanuric fluo- toluidine by reaction of the azo dye with phos-
ride (10), 2,3-dichloroquinoxaline-6-carboxylic gene:
acid chloride (11) and chlorotrifluoropyrimidine
(12), are used for the synthesis of a relatively
large number of reactive dyes.

2.3.3. Alkylation and Acylation of Phenolic

Hydroxyl Groups [2, p. 403]

The reactive dyes most widely used so far Alkylation. To overcome the poor alkali fast-
are the chlorotriazinyl dyes, which can be pro- ness of p-hydroxyazo dyes (see Section 3.2.1)
duced on an industrial scale from dyes –NH
f the phenolic OH groups can be converted into
2
containing amino groups and cyanuric chloride, alkyl ether with such alkylation agents as dialkyl
with cleavage of hydrogen chloride, in an aque- sulfate, alkyl halides, epoxides, etc. Depend-
ous organic medium at 0 – 5 ◦ C and at a pH- ing on the water solubility of the p-hydroxyazo
value of 6.5 – 7.0. They can be condensed with dyes, processing is carried out in weakly alkaline
an aliphatic or aromatic amine or even with a aqueous solution or in organic solvents, such as
second dye –NH
f ◦ dimethylformamide or ethylene glycol dimethyl
2 at 40 to 50 C to form the
less reactive monochlorotriazinyl dyes: ether, under alkylation conditions, such as are
usual with aromatic hydroxy compounds. The
synthesis of p-alkoxyazo compounds by heating
hydroxyazo compounds in an alcoholic medium
with the addition of acid is of interest, e.g.:
 Azo Dyes 15

The reaction represents the inversion of the The azo dye anion always acts as a divalent
acid-catalyzed hydrolysis of azoaryl ethers. ligand in threefold coordination. The remaining
On a large industrial scale hydroxyazo com- coordination positions of the metal ions are filled
pounds are mainly reacted with ethyl chloride by addition of further ligands with lone electron
in aqueous alkaline solution (sodium carbonate, pairs (e.g., H2 O, NH3 , amines) or by another azo
sodium hydroxide) by heating for several hours dye anion (formation of 1 : 2 metal complexes).
to temperatures of around 100 ◦ C in a closed Suitable complex-forming metals are in par-
system. ticular the trivalent chrome and trivalent cobalt
(coordination number 6) and also the divalent
Acylation. Here aryl sulfonation plays a par- copper and nickel (coordination number 4),
ticularly important role. In order to convert whose complex dyes have great industrial im-
them into arylsulfonic acid esters, hydroxyazo portance.
dyes are reacted with arylsulfonic acid chlo- One of the hydroxyl groups in the ortho posi-
rides, mainly p-toluenesulfonic acid chloride or tion relative to the azo bridge can only be formed
benzenesulfonic acid chloride in an aqueous al- during metallizing by cleavage of an o-methoxy
kaline medium. The formation of arylsulfonic group. This demethylating metallizing process
acid esters not only overcomes the poor alkali has been introduced on an industrial scale be-
fastness of p-hydroxyazo dyes but, with wool cause of the wide variety of diazo components
dyes, also improves the fastness to washing and to choose from [15].
milling and the neutral affinity. The addition of copper to the molecule in an
oxidative process, in which a hydrogen atom in
the ortho position relative to the azo group is
2.3.4. Metal-Complex Formation converted into the appropriate hydroxyl group
by means of oxidizing agents, such as hydrogen
For more details → Metal-Complex Dyes and peroxide, has acquired technical significance
[15], [2, p. 434]. [16]:
Azo dyes with certain structural groupings
are capable of forming metal-complex com-
pounds. Here even the coupling component,
such as salicylic acid, can form a complex:

Chrome-complex dyes are best used as dyes

for wool, polyamide, and leather and for col-
oring paints and plastics; copper complexes are
Technically far more important than these used as cotton and leather dyes and also as pig-
metal complexes, most of which are produced ments; and chrome and cobalt complexes, as
on the fiber (see chrome dyes, Section 3.2.1.3), spirit-soluble dyes.
are those dyes whose metal complexes are pro-
duced within the dye itself. Here the complex is
always formed with the participation of the azo 2.4. Processes without Industrial
group. These dyes have complex-forming sub- Importance
stituents in the o,o
position relative to the azo
bridge and are, for instance, capable of forming Of the processes for producing azo dyes via syn-
1 : 1 metal complexes of the general formula 13. thesis of the azo group, the following are worth
mentioning, although they have attained no in-
dustrial importance so far:
– reduction of diazonium compounds
– oxidative coupling
– dehydrogenation of diarylhydrazines
– reaction of arylhydrazines with quinones
16 Azo Dyes

– condensation of nitroso compounds with Whereas in the Lange reaction (see Eq. 10)
amines the two aryl radicals are identical, Suckfüll
– azo compounds from azido compounds and Dittmer were able to expand the reaction
of diazonium salt and diazosulfonate for the syn-
thesis of asymmetrical azo compounds and, with
2.4.1. Reduction of Diazonium Compounds certain restrictions, extend it to the azo series.
[2, p. 320, 323] The significance of the reaction lies in the ac-
cess to azo compounds that are very difficult to
When aromatic diazonium compounds are re-
synthesize by conventional means, e.g.:
acted with ammoniacal copper(I) salt solution,
diarylazo compounds or diaryls are obtained
with elimination of nitrogen

The course of the reaction depends on the

type of substitution on the aromatic nucleus:
whereas electron-attracting substituents result in
diaryl formation, diazonium salts in which the 2.4.2. Oxidative Coupling
substituents on the nucleus are electron donors
can be converted to symmetrical azo compounds Of interest from the preparative and theoretical
(Vorländer reaction) [17], [18]: aspects is the oxidative azo coupling process dis-
covered by S. Hünig, through which many hete-
rocyclic azo compounds have become accessible
[21].
A precondition of the reaction is the presence
of a heterocyclic hydrazone, which couples with
The action of sulfurous acid or its salts on aromatic amines, phenols, or compounds with
diazonium compounds of the naphthalene se- active methylene groups in the presence of de-
ries results in the formation of symmetrical azo hydrogenating agents to form the corresponding
compounds; the starting compounds may also azo compounds, e.g.:
contain electron-attracting substituents (Lange
reaction) [19], e.g.:

As regards the coupling components and the

coupling location, the reaction resembles the azo
coupling process. As electrophilic component, a
diazonium ion 14 is suggested, which is formed
from the hydrazone component through the ac-
tion of the dehydrogenating agent and reacts by
Studies by Suckfüll and Dittmer have electrophilic substitution with the coupling com-
shown that in this process the diazonium salt re- ponent with the loss of two hydrogen atoms to
acts with the diazosulfonate formed from sulfite form the azo compound.
and diazonium ion [20]:
 Azo Dyes 17

In the case of phenols and α-naphthols, the 2.4.4. Reaction of Arylhydrazines with
attack in principle always takes place at the p- Quinones [2, p. 355]
position. Only when the p-position is occupied
does coupling occur at the o-position. The opti- Benzo- and naphthoquinones as well as
mum phenylazo compound yield (approx. 90 %) quinones of some polycondensed aromatics re-
is attained at pH 9. The dehydrogenating agents act in an acid aqueous or aqueous alcoholic
mainly used for this purpose are potassium hex- medium or in acetic acid to form hydroxyazo
acyanoferrate(III), copper(II) sulfate, silver ni- compounds, tautomers of quinone hydrazones,
trate, sodium hypochlorite, or lead(IV) oxide. e.g.:
The optimum pH range for oxidative cou-
pling with aromatic amines and enamines is
pH 1 – 3, diluted hydrochloric acid or glacial
acetic acid being preferred as reagents. Well-
tried dehydrogenating agents for this purpose are
iron(III) chloride, red lead, lead(IV) oxide, and
lead(IV) acetate.
In order to obtain an optimum yield, reagent
and oxidizing agent should in each case be care- The reaction proceeds along the lines of
fully matched to the coupling component used. this condensation process only if the oxidizing
Oxidative coupling has so far rarely been used power of the quinone and the reduction poten-
for industrial production of azo dyes. tial of the hydrazine are not at such a high level
that formation of hydroquinone takes place via a
redox reaction. Quinones with a high oxidation
2.4.3. Dehydrogenation of Diarylhydrazines potential (e.g., p-benzoquinone) can thus only
[2, p. 377] be reacted with arylhydrazines (e.g., o- and p-
nitrophenylhydrazine) and vice versa.
N,N
-Diarylhydrazines can be dehydrogenated Of significance is the reaction of the quinones
to form azo compounds: with arylhydrazines to form azo compounds,
when the latter are difficult to obtain by azo cou-
pling, e.g., 1-hydroxy-2-phenylazonaphthalene:

Oxidizing agents frequently used are sodium

hypochlorite or air in the alkaline, or iron(III)
chloride or sodium dichromate in the acid
medium, as well as nitrous acid. The method ac-
quires importance when the azo compounds to Instead of quinones, it is possible to react their
be synthesized are not accessible by coupling monoximes with arylhydrazines, e.g.:
or condensation reactions, or only with diffi-
culty, and the relevant diarylhydrazines can be
obtained by simple reactions, e.g.:

The hydroxylaminoazo compounds formed

(15) react with nitrous acid to form azo diazo-
18 Azo Dyes

nium compounds (16), preliminary stages for the Whereas nitroso – amine condensation is not
synthesis of polyazo dyes. generally possible in the naphthalene range, its
Arylhydrazines can also be converted into use in the benzene range mainly serves the
azo compounds by condensation with other production of asymmetrically substituted azo
dioxo compounds, provided this possibility is compounds and the formation of polyazo com-
permitted by the keto-enolic tautomerism. An pounds. It has no industrial importance in the
interesting example of this is the reaction of production of azo dyes.
dioxosuccinic acid with two equivalents of
phenylhydrazine-4-sulfonic acid, which with si-
multaneous formation of the pyrazolone ring re- 2.4.6. Azo Compounds from Azido
sults in tartrazine (C. I. Acid Yellow 23, 19140 Compounds
[1934-21-0]), the oldest dye in this class:
Compounds containing active methylene groups
react with organic azido compounds in the pres-
ence of a base, with formal substitution of a di-
azo group for two hydrogen atoms (diazo group
transfer) [22]:

The resulting diazo compound (19) can be

coupled with a second molecule of the methy-
lene compound (18) to form a symmetrical azo
compound (20):

p-Toluenesulfonic acid azide (17, R =

2.4.5. Condensation of Nitroso Compounds CH3 C6 H4 SO2 −), readily obtainable from p-
with Amines [2, p. 332] toluenesulfonic acid chloride, has, in particular,
proved to be a suitable azido compound.
Azo and polyazo compounds can be produced The method permits the synthesis of a num-
by condensation of amines with nitroso com- ber of interesting heterocyclic azo compounds,
pounds, very good yields being frequently ob- e.g.:
tained:

Depending on the substitution of the aro-

matic rings, the reactions are carried out at room
temperature or at temperatures of up to about
100 ◦ C. The reagent used is almost always acetic
acid on its own or in mixtures with other or-
ganic solvents. Other reagents, such as water or
alcohols, cause a sharp decrease in yield. The So far, however, it has been of no industrial
influence of substituents on the reaction rate is importance.
analogous to that in nitro – amine condensation
(see Section 2.2.1).
 Azo Dyes 19

2.5. Equipment for Industrial such as saponification, esterification, acylation,

Production of Azo Dyes or metal-complexing processes, which if neces-
sary must be carried out under pressure and at
Production of azo dyes on an industrial scale is higher temperatures.
still carried out on a batchwise basis. Following the synthesis and any thermal af-
The main items of equipment for industrial tertreatment process that may be required, azo
diazotization and coupling are the diazotizing dyes insoluble in water (e.g., pigments, disperse
vessel, the dissolving tank for dissolving the dyes) can be directly isolated by means of filter
coupling component, and the central coupling presses or suction filters. For large-volume prod-
tank with capacities between 25 and 80 m3 . Cou- ucts, preference is given to continuously operat-
pling batches of up to 8 kmol per batch can thus ing rotary filters.
be processed. Water-soluble azo dyes (e.g., reactive dyes,
Figure 1 illustrates the flow diagram and main acid dyes, or direct dyes) must be precipitated
items of equipment in a simple industrial azo dye from the coupling solution (coupling liquor) by
synthesis. salting out or changing the pH. If in addition to
the salt content other impurities in the dye are
permissible, the spray drying process is used for
separating water-soluble azo dyes from the re-
action solution.
Depending on the requirements regarding
corrosion resistance and ability to withstand
compressive and thermal stress, the materials
used for industrial equipment are iron, stain-
less steel, rubber-coated steel with or without
an acid-proof lining, enameled steel, glass fiber
reinforced synthetic resins, and wood.
In general, diazotizing, dissolving and cou-
pling vessels are nowadays made from rubber-
coated steel. The hard rubber lining can be ex-
posed without damage to temperatures of up to
100 ◦ C; contact with organic solvents should be
avoided. Use has also been made of coupling
Figure 1. Equipment diagram for the production of an azo tanks made from glass fiber reinforced synthetic
dye
a) Diazotizing tank; b) Dissolving tank; c) Clarifying press; resins (low weight, low cost, easy to repair),
d) Coupling vessel; e) Filter press; f) Drying and milling which are resistant to hydrochloric acid and can
be exposed to temperatures of up to 100 ◦ C.
In the simplest case, the solution of the cou- Wooden vats are still of importance in the in-
pling component is transferred to the coupling dustrial manufacture of azo dyes, primarily be-
vessel after mechanical and adsorptive clarifica- cause of their corrosion resistance in aqueous
tion by means of a clarifying press or a filter, systems, combined with low capital expendi-
and the diazonium salt solution, likewise after ture and repair costs. For reactions in an alka-
clarification, is added slowly above or below the line medium and in organic solvents, as well
surface of the coupling component solution. The as for reactions under pressure, stainless steel
solutions can also be added in the reverse se- tanks are employed. Stainless steel tanks and
quence or both at the same time from the dia- other items of equipment made from this mate-
zotizing and dissolving tank. The constancy of rial are not resistant to corrosion by mineral acid
the reaction temperature and of a narrow pH solutions. Stainless steel must also be avoided
range is a decisive factor as regards the cou- for reactions of weakly acid or salt-containing
pling process and must be continuously moni- solutions carried out under pressure. Enameled
tored by means of suitable measuring devices. equipment is used for reactions in acid media
The coupling reaction can be followed in the performed under pressure, but is not resistant to
coupling tank or other vessels by other reactions, alkalis. Its advantage lies in its easy cleaning.
20 Azo Dyes

For reactions under pressure in an acid medium, Reactive Dyes. From the chemical stand-
rubber-coated and brick-lined steel tanks with point the group of anionic azo dyes includes
agitators, heating coils, and thermometer tubes a large proportion of the reactive dyes which,
made from Hastelloy (nickel alloys with varying in addition to the usual structural characteris-
Mo, Cr, Mn, Cu, Si, Fe, and C contents) have also tics, also contain certain reactive groups capa-
proved suitable. Brick-lined vessels are chiefly ble of reaction with functional groups of the
employed in large-capacity equipment, when the fiber during the dyeing process, for example,
use of enameled vessels is dispensed with be- with the hydroxyl groups of cellulose, the ami-
cause of the high capital expenditure and repair no and mercapto groups of wool and silk, or
costs involved. the amino and carbonamide groups of synthetic
In the industrial production of azo dyes in polyamides. Owing to the covalent dye – fiber
equipment that cannot be placed under pres- bond these dyeings usually exhibit good fastness
sure (wooden vats, drums made from synthetic to wet processing.
resins), pumps are needed in order to convey the For structures of reactive dyes for wool and
tank contents from vessel to vessel or via clarify- polyamide → Reactive Dyes.
ing presses and filter presses. When steel drums
are used, the solutions and suspensions are often Metal-Complex Dyes. The anionic azo dyes
transferred by air or nitrogen pressure. also including the metal-complex dyes, which
are derived from o,o
-disubstituted azo dyes and
which can be metallized not only on the fiber but
3. Anionic Azo Dyes [1], [3], [4], [7], [5, whose metal-complex compounds are applied
largely in the form of a complete dye (cf. Sec-
vol. I, p. 480; vol. III, p. 268]
tion 2.3.4). They serve for the dyeing of wool
(see Section 3.2.1.4), silk and leather (Section
3.1. Introduction 3.2.4) and polyamide (see Section 3.2.2), and
also for cotton (see Section 4.1.8) and as alcohol-
Anionic dyes include many compounds from and ester-soluble dyes (see Section 6.1.2). This
the most varied classes of dyes, which ex- dye class, too, is discussed only briefly here; for
hibit characteristic differences in structure (e.g., details → Metal-Complex Dyes.
azoic, anthraquinone, triphenylmethane, and ni-
tro dyes) but possess as a common feature
water-solubilizing, ionic substituents. The an- 3.2. Acid Azo Dyes
ionic azoic dyes, which are discussed here, con-
stitute the most widely used group of this class This group of substances also includes dyes
of dyes. that are classified under other headings,
Most often sulfonic acid groups serve as hy- → Anthraquinone Dyes and Intermediates,
drophilic substituents, because they are read- → Nitro and Nitroso Dyes; → Triarylmethane
ily introduced and, as strong electrolytes, are and Diarylmethane Dyes.
completely dissociated in the acidity range used Azo dyes with relatively low molecular
in the dyeing process. Almost invariably the masses and one to three sulfonic acid groups
products manufactured and employed are water- serve as so-called acid azo dyes for dyeing
soluble sodium salts of the sulfonic acids. and printing wool, polyamide, silk, and basic-
modified acrylics and for dyeing leather, fur, pa-
Direct Dyes. In principle the anionic dyes per, and food. The main area of application is
also include direct dyes, but the latter, because the dyeing of wool and polyamide.
of their characteristic structures, are used to dye Individual dyes also play a part in the manu-
cellulose-containing materials and go onto the facture of color lakes, which are used to pigment
fiber from a neutral dye bath. Because the clas- printing inks and for coloring plastics.
sification used here is based chiefly on the dyes’ Disazo and polyazo dyes containing sulfonic
application in the dyehouse, direct dyes are dis- acid groups are also frequently used in the above
cussed in a separate chapter (see Chap. 4). applications. Many of them are also sold as sub-
stantive dyes for cotton because of their pro-
 Azo Dyes 21

nounced affinity toward cellulosic fibers (see satisfactory because of an inadequate migra-
Chap. 4). tion property. In consequence the range of
The term “acid dye” derives from the dyeing applications of milling dyes is also limited.
process, which is carried out in an acidic aque- 3) Dyes with intermediate molecular size not
ous solution (pH 2 – 6). only form a saltlike bond with the wool fiber
Protein fibers contain amino and carboxyl but are also bonded to the fiber by inter-
groups, which in the isoelectric range (approx- molecular forces and have properties lying
imately pH 5) are ionized mostly to –NH+ 3 in an intermediate position between those of
and −COO− . In the acid dyebath the carboxyl the leveling and the milling dyes. They are
ions are converted to undissociated carboxyl used mainly where average requirements are
groups owing to the addition of acid HX (sulfu- placed on the wetfastness and levelness of the
ric or formic acid), which causes the positively dyeing.
charged wool (H3 N+ −W−COOH) to take up an
Concerning the possibility of influencing the
equivalent amount of acid anions X− (hydrogen
rate of dyeing and the leveling power during the
sulfate, formate) [23]:
dyeing process by the addition of acid or color
salt → Dyes, General Survey.

3.2.1. Wool Dyes

The standard dyes for wool are divided essen-

tially into four groups according to their differ-
ent dyeing behaviors (cf. Table 1).
The actual dyeing process consists of a re-
Table 1. Names of important ranges of acid wool dyes
placement of the absorbed acid anions X− by
the added dye anions  f − , since the latter ex- Manu- Ranges
hibit a much greater affinity for the substrate facturer Group A Group B Group C Group D
than the much smaller acid anions. Thus the dye
is bonded to the wool not only by electrostatic Bayer Acilan Supracen Supranol Supramin
Ciba-Geigy Erio Eriosin Polar
attraction (salt formation) but also by its more Hoechst Amido Lanaperl Alphanol
or less strong affinity for the fiber. Fast
ICI Lissamin Coomassie Carbolan
Acid dyes are divided into three groups based Sumitomo Suminol Suminol
on their differences in affinity, which is primarily leveling milling
a function of the molecular size. Sandoz Sandolan- Sandolan-
E N
1) Leveling dyes are relatively small molecules
which form a saltlike bond with the protein Group A contain the low-priced, usually
fiber. This not very tight bond imparts good older leveling dyes with moderate light fastness.
migration properties to such dyes on wool. These dyes are still used in larger quantities for
The interplay between the bonded dye and cheap articles.
the dye still in the dyebath results in very Group B also includes leveling dyes, which
uniform, level dyeings. On the other hand are applied in a strongly acid bath but which ex-
they possess only poor wetfastness, so that hibit very good light fastness.
the use of leveling dyes is severely limited. Group C contains the milling dyes, which are
2) Milling dyes are large-volume dye applied in a weakly acid to neutral bath.
molecules, for which salt formation with Group D contains the acid dyes with
the fiber plays only a secondary role and the good leveling properties, intermediate molecu-
adsorption forces between the hydrophobic lar sizes, and for the most part good light fast-
regions of the dye molecule and those of nesses.
the protein fiber predominate. The resulting The product ranges of the various dye manu-
tighter bond yields good wetfastness, but facturers do not completely fulfill the demands
the levelness of the dyeings is not always made on the dyes in respect of the individual
22 Azo Dyes

fastnesses, and within a manufacturer’s range Aromatic Amines as Coupling Compo-

the properties of the dyes can be individually nents. One of the oldest azo dyes is C. I.
specified. Acid Yellow 36, 13065 (metanil yellow) (21)
In describing the separate dye types it is use- [587-98-4].
ful to distinguish between the monoazo and the
disazo dyes, and to further break down the dis-
azo dyes into primary and secondary types on
the basis of chemico-structural principles.
In the industrial manufacture of acid azo dyes
usually aniline derivatives are used as the di- Because of the basic group suitable for salt
azo components and for disazo dyes also diami- formation the dye is not fast to acid, but it is still
nodiphenyl derivatives and other bifunctional di- used today for dyeing wool and in special areas
amines. The coupling components for orange (leather and paper) primarily for price reasons.
to blue shades are commonly aniline, naphthy- Coupling H acid to 1-(phenylamino)naphtha-
lamine, naphthol, and aminonaphthol deriva- lene-8-sulfonic acid (N-phenylperic acid) yields
tives, whereas phenylpyrazolones are much used C. I. Acid Blue 92,13390 (22) [3861-73-2].
for preparing dyes in the yellow and orange
shades.
In regard to the stability of the shade to
changes in pH, care must be taken that hydroxyl
or amino groups lie adjacent to the azo group
in order to form a hydrogen bridge with the
latter. This hydrogen bridge prevents a disso- On wool the product turns out a very pure
ciation of the hydroxyl groups or a protonation blue of good light fastness and with moderate
of the amino groups and hence avoids an un- wet fastness and adequate leveling power.
wanted change in shade in response to moderate
pH shifts. Groups that are not in the ortho posi- Naphthols and Naphtholsulfonic Acids as
tion must be alkylated or acylated (see Section Coupling Components. In this series two im-
2.2.3). portant acid dyes with very similar struc-
tures are C. I. Acid Red 88, 15620 (23)
[1658-56-6], derived from diazotized naph-
3.2.1.1. Monoazo Dyes thionic acid and 2-naphthol, and C. I. Acid
Red13, 16045 (24) [2302-96-7], from naph-
Among the acid monoazo dyes are a number thionic acid and Schäffer’s acid:
of much used wool dyes that possess no out-
standing coloristic properties but that are distin-
guished by brilliance of shade, very good level-
ing power, and particularly low cost, while their
wash fastness and light fastness meet only low to
medium requirements. Partly influenced by the
introduction of the International Woolmark to
label high-quality wool articles, the fastness re- Both are all-purpose dyes which, because of
quirements have risen considerably in the last 20 their attractive red shades, are still in use today in
years, which has necessitated the development many areas of textile dyeing and also for leather
and manufacture of particularly fast dyes. For and paper dyes. Wool dyeings produced with
this reason many, and above all the older, acid these dyes exhibit moderate fastness levels.
dyes have lost all importance for the dyeing of A long-known, inexpensive, but only moder-
wool and are used today only for the coloring of ately fast dye is C. I. Acid Orange 7, 15510 (Or-
paper, soaps, food, and cosmetics. ange II) (25) [633-96-5]. As a wool dye it is now
In the following discussion the acid monoazo of secondary importance, but is used in special
dyes are classified according to the type of cou- areas such as leather dyeing, paper coloration,
pling component. and the manufacture of color lakes.
 Azo Dyes 23

with good light and wetfastnesses can be pro-

duced. Example: C. I. Acid Violet 14, 17080 (30)
[4404-39-1].

A previously much used red wool dye is C. I.

Acid Red 14, 14720 (26) [3567-69-9], which is
now used to a limited extent in wool dyeing for
inexpensive articles.
The usually very low wetfastness of these
Of interest is the manufacture of 4-ami-
simple acid azo dyes can be improved at the
no-3-(4
-toluenesulfonyl)acetanilide, which
expense of leveling power by the introduction
is used as the diazo component: p-
of special, large-volume substituents. Example:
phenylenediamine is oxidized with iron(III)
C. I. Acid Orange 19, 14690 (27) [3058-98-8],
chloride to 1,4-benzoquinonediimine, to which
is a very important acid dye for wool and
p-toluenesulfinic acid is added. The final step is
polyamide with good fastness properties and yet
partial acetylation:
with good leveling power.

Aminonaphtholsulfonic Acid as the Cou-

pling Component. Important coupling compo-
Further examples are: C. I. Acid Red 32,
nents are γ acid (2,8-aminonaphthol-6-sulfonic
17065 (31) [6360-10-7], and C. I. Acid Blue 117,
acid) and H acid (1,8-aminonaphthol-3,6-
17055 (32) [10169-12-7].
disulfonic acid), from which many important
wool dyes are derived, some of which exhibit
very good light and wetfastness.
Especially in acid coupling γ acid yields dyes
with very good light fastness, which is presum-
ably attributable to the formation of a hydrogen
bridge between the azo bridge and the hydroxyl
group peri to the azo bridge.
As examples are cited two outstandingly
lightfast dyes of good leveling power whose dye-
ings on wool exhibit moderate wetfastness: C. I.
Acid Red 42, 17070 (28) [6245-60-9], and C. I.
Acid Red 37, 17045 (29) [6360-07-2].

On wool both dyes exhibit quite good wet-

fastness and high leveling power.
In order to achieve valuable dyes with alka-
line coupling to γ acid, the amino group must
be acylated or arylated. Example: C. I. Acid Red
68, 17920 (33) [6369-40-0].
Through the choice of suitably substituted di-
azo components, bluish red to blue wool dyes
24 Azo Dyes

1-Phenyl-5-pyrazolones as Coupling Com-

ponents. Especially lightfast yellow shades are
obtained by using 1-phenyl-5-pyrazolones as
coupling components. The first representative
of the class to appear was Tartrazine, C. I. Acid
Yellow 23, 19140 [1934-21-0], which is formed
On wool it exhibits high leveling power and in a smooth reaction when phenylhydrazine-4-
yields light- and wetfast dyeings. sulfonic acid is heated with dioxosuccinic acid
N-arylation of γ acid results in a strong (see Eq. 11, Section 2.4.4). Today the start-
deepening of the shade. The usually brown to ing compound is 1-(phenyl-4
-sulfonic acid)-3-
black dyes thus obtained are fast to light and carboxy-5-pyrazolone, which can be obtained
milling and go onto wool and silk from a neu- from oxaloacetic ester and phenylhydrazine-4-
tral liquor. Example: C. I. Acid Brown 20, 17640 sulfonic acid and can be coupled with diazotized
(34) [6369-33-1]. sulfanilic acid. Tartrazine is an intense yellow,
moderately fast dye that is still important in wool
dyeing but is also used in the dyeing of leather,
the coloring of paper, soap, and food, and in the
lake form as a pigment.
For price reasons the 1-aryl-3-methyl-5-
pyrazolones and their derivatives are preferred to
the corresponding 3-carboxypyrazolones. There
An important coupling component is H acid. is such a wide range of possible variations that
Realization that acylation of its amino group dyes in this series extend from greenish yellow
substantially improves the light fastness and in to reddish orange. Examples: C. I. Acid Yellow
addition yields dyes with good leveling power 17, 18965 (37) [6359-98-4].
led to many valuable light- and wetfast prod-
ucts that even today occupy a firm position on
the market. A relatively simply structured wool
dye, C. I. Acid Red 1, 18050 (35) [3734-67-6]
is obtained by the alkali coupling of diazotized
aniline to N-acetyl H acid.

On wool the product yields a clear, superbly

lightfast yellow with good to very good general
Valuable dyes can also be made with N- fastness properties, but relatively poor milling
benzoyl H acid and N-toluenesulfonyl H acid. fastness.
An interesting development is the Carbolans C. I. Acid Yellow 76, 18850 (38) [6359-88-2],
of ICI. Their neutral affinity to wool and very is obtained by coupling diazotized 4-aminophe-
good wetfastness properties are achieved by in- nol to the pyrazolone component and then es-
corporating long hydrophobic hydrocarbon rad- terifying with p-toluenesulfonic acid chloride
icals [5, vol. III, p. 268]. Example: C. I. Acid Red in an alkaline medium. The toluenesulfonic es-
138, 18073 (36) [15792-43-5]. ter group substantially improves the fastness to
milling and makes the shade obtained largely
independent of pH; the light fastness is not quite
as good as that of Acid Yellow 17.
 Azo Dyes 25

an important product, which through shading

with yellow, orange, or red forms the basis of
most black acid dyes. To manufacture this type
of dye, coupling is always first carried out in
an acid medium with the more strongly elec-
trophilic diazonium salt, here with diazotized
4-nitroaniline, then in the alkaline range with
diazotized aniline:

3.2.1.2. Disazo Dyes

Dyes with two azo groups are divided on Abbreviated manufacturing instructions for
chemico-structural principles into primary and C. I. Acid Black 1, 20470: Stir 260 kg of 4-
secondary disazo dyes. Primary disazo dyes are nitroaniline with 1200 L of water and a 23 %
manufactured either according to the scheme solution of 132 kg sodium nitrite for about 1/2 h.
D1 → K ← D2 from a bifunctional coupling Run this suspension into a mixture of 4000 L wa-
component K and two identical or different di- ter, 530 L 31 % hydrochloric acid, 500 kg ice,
azo components D1 and D2 , or according to the and a 23 % solution of 1.2 kg sodium nitrite at
scheme K1 ← D → K2 by coupling a bisdiazo- no more than 10 ◦ C. Add about 1000 kg of ice
tized diamine D to the coupling components K1 and then 2600 L of an aqueous solution of 485 kg
and K2 , which may be the same or different. Sec- H acid within a period of 1 – 2 h with thorough
ondary disazo dyes are manufactured according stirring. Coupling is complete at the end of 3 h.
to the scheme D → M → K (M = middle compo- Meanwhile diazotize 165 kg of aniline in
nent) from a diazotized aminoazo dye (D → M) 300 L water, 1500 kg ice, and 440 L 31 % hy-
and a coupling component K (series coupling). drochloric acid by adding 124 kg of sodium ni-
trite as a 23 % solution. This yields a volume
Primary disazo dyes of the type of 3000 L. Then dissolve the monoazo dye by
D1 → K ← D2 are obtained by twofold cou- adding 360 L of 30 % sodium hydroxide solution
pling to, for example, resorcinol. These orange and cool with about 3000 kg of ice. To this run
to brown dyes have poor light and wetfast- in the solution of diazotized aniline and then im-
ness and are used only for inexpensive leather mediately 1800 L of 15 % soda solution within
dyeings. Among the naphthalene derivatives H 2 – 3 min. The volume is 22000 – 23000 L. Af-
acid is one of the most important; it serves as ter 6 h add common salt (9.5 % calculated on
a bifunctional coupling component K for the the volume) to cause salting out and continue
manufacture of many wool dyes now in use. stirring overnight. Filter off the precipitated dye
Dye synthesis following the above scheme and dry; the yield is about 1900 kg.
generally permits little variation of the shade Usually the acid coupling of 4-nitroaniline
(black, dull brown, and blue), because com- is not continued to completion, because this re-
pletely conjugated chromophoric systems are quires too much time. Consequently, the com-
formed. mercial product normally contains a small pro-
One of the most important acid dyes is C. I. portion of red monoazo dye, which together with
Acid Black 1, 20470 (39) [1064-48-8]. the greenish black disazo dye yields the desired
neutral black shade.

Primary Disazo Dyes of the Type

K1 ← D → K2 (K1 = K2 or K1 = K2 ). This
series includes many milling dyes because of
the molecular size achieved (cf. Table 1, group
It dyes wool in blue-black shades with very
C). Depending on the type of coupling compo-
good light fastness but only moderate wetfast-
nents K1 and K2 , which may be phenols, pyra-
ness. Nevertheless, because of its high affin-
zolones, acetoacetic acid arylamides, or naph-
ity and good leveling power it has remained
26 Azo Dyes

tholsulfonic acids, clear yellow to red shades disulfonic acid −→2-naphthol

are obtained. The preferred diazo components
are diaminodiphenyl derivatives and similarly and C. I. Acid Yellow 42, 22910 [6375-55-9]
structured diamines. Once important dyes de-
rived from unsubstituted benzidine are now of benzidine-2,2 - −→ 2 equivalents of
no further importance because of the latter’s car- 1-phenyl-3-methyl-disulfonic acid −→ 5-pyrazolone
cinogenic activity (→ Benzidine and Benzidine
Derivatives). Because the coupling of bisdia-
zotized diamines to form monoazo and disazo Instructions for manufacturing C. I. Acid Yel-
dyes proceeds with different rates, asymmetri- low 42, 22910: Dissolve 250 kg of benzidine-
cal disazo dyes are readily manufactured. For 2,2
-disulfonic acid in 2500 L of water at 50 ◦ C
example, the milling and wetfast red wool dye that was made weakly alkaline with about 90 kg
C. I. Acid Red 114, 23635 (40) [6459-94-5], is of soda. Then add 100 kg of sodium nitrite in
manufactured by coupling bisdiazotized 3,3
-di- the form of a 30 % solution. Run the entire so-
methylbenzidine with one equivalent of Gacid; lution into 4000 L of water at 25 ◦ C, containing
the monoazo compound obtained is further cou- 350 L 31 % hydrochloric acid and 675 kg rock
pled with phenol to yield the disazo dye, the salt. The total volume is 7500 L, the temperature
p-hydroxyl group of which is subsequently es- 30 ◦ C. Stir for about 15 min during the diazoti-
terified with toluenesulfonic acid to improve the zation process.
fastness properties and pH stability. In the coupling vat add 264 kg of 1-phenyl-
3-methyl-5-pyrazolone to 2000 L of water con-
taining 80 kg of soda and dissolve at 80 ◦ C. Then
add another 80 kg of soda and cool with 2000 kg
of ice to 20 ◦ C. Run in the diazonium salt solu-
tion in about 30 min; no diazo reaction should
occur during this procedure. Stir overnight, dur-
ing which coupling takes place. Then draw off
An important discovery was the realization the dye and dry; the yield is about 720 kg.
that benzidines substituted in the 2,2
-position In addition to benzidine derivatives another
are outstandingly suitable for the manufacture class of substances of interest as bifunctional
of very wash-fast and milling-fast wool dyes, diazo components consists of special diamines
while the substantivity toward cellulosic fibers is that can be manufactured through the reaction
reduced. A number of important acid wool dyes of aromatic amines with benzaldehyde or cyclo-
have been developed on this basis, for example, hexanone, e.g.:
C. I. Acid Yellow 44, 23900 (41) [2429-76-7].

Dyes based on these compounds possess, in

In the manufacture of this dye bisdia-
addition to good light fastness, excellent wet-
zotized 5,5
-dimethylbenzidine-2,2
-disulfonic
fastness and are usually neutral dyeing on wool.
acid is coupled to two equivalents of N-
This, although of no importance for dyeing pure
acetoacetylaniline. The clear, intense, greenish
wool, plays an important role in dyeing blended
yellow dyeing obtained on wool is milling fast
spun yarn and blended fabrics of wool and cotton
and exhibits excellent wetfastness but only mod-
or wool and viscose staple. The neutral dyeing
erate light fastness.
acid dye can be used in combination with direct
Other members of this series are C. I. Acid
dyes (union wool recipes). Examples are C. I.
Orange 56, 22895:
Acid Yellow 56, 24825 (42) [6548-24-9],
benzidine-2,2 - −→ 1-phenyl-3-methyl-5-pyrazolone
 Azo Dyes 27

A product with a similar structure is C. I. Acid

Red 73, 27290 (46) [5413-75-2], which is impor-
tant today in wool dyeing and in paper coloration
and leather dyeing because of its outstandingly
clear shade and good leveling power.

and C. I. Acid Red 154, 24800 (43; R = CH3 )

[6507-79-5].

The most important dyes of the type D → M

→ K are, however, black and navy blue wool
dyes, which contain as the middle component M
chiefly 1-naphthylamine or 1-naphthylamine-7-
C. I. Acid Red 134,24810 (43; R = OCH3 ) sulfonic acid and as the coupling component K
[6459-69-4], is another interesting dye for wool N-phenylperi acid [= (1-phenylamino)naphtha-
and polyamide. lene-8-sulfonic acid], N-tolylperi acid, and
Particularly good milling fastness is naphthol or 1-naphthylamine derivatives.
achieved by the introduction of 4,4
-diami- Examples of these high-yield and very wash-
nodiphenylthioether as the diazo component, fast and lightfast dyes are C. I. Acid Black 24,
for example in the yellow wool dye C. I. Acid 26370 (47) [3071-73-6], which is manufac-
Yellow 38, 25135 (44) [13390-47-1]. tured by coupling diazotized 1-naphthylamine-
5-sulfonic acid to 1-naphthylamine, further di-
azotization of the aminomonoazo dye and cou-
pling to N-phenylperi acid; and C. I. Acid Blue
113, 26360 (48) [3351-05-1]. This blue dye
is very important in the dyeing of wool and
polyamide.

Secondary Disazo Dyes. The secondary

disazo dyes, which can be manufactured
by series coupling according to the scheme
D → M → K (D = diazo component; M = middle
component; K = coupling component), offer
much greater possibilities for variation than
the primary disazo dyes. This group includes
red dyes and, above all, important navy blues
and blacks. Some of the red dyes of this type are
manufactured from aminoazobenzene, amino- Manufacturing instructions for C. I. Acid Blue
azotoluene, or the corresponding sulfonic acids 113, 26360: Dissolve 250 kg of 100 % aniline-
by diazotization and coupling to naphtholsul- 3-sulfonic acid in about 3000 L of neutral wa-
fonic acids. ter, add about 1000 kg of ice and 400 L of 31 %
One of the oldest disazo dyes is Sudan IV, hydrochloric acid, and diazotize at 10 ◦ C with a
C. I. Acid Red 66, 26905 (45) [4196-99-0], 23 % solution of 100 kg sodium nitrite. Then dis-
which today is scarcely of any importance. solve 220 kg 100 % 1-naphthylamine in 2000 L
water with 185 L 31 % hydrochloric acid at the
boil. Quickly run the solution into the diazotized
aniline-3-sulfonic acid to which 4000 kg of ice
has been added. Then in about 45 min partly neu-
tralize to about pH 4 with 400 L of 15 % sodium
28 Azo Dyes

hydroxide solution, temperature 10 ◦ C, volume the hydrophilic groups in the molecule. It also
of 15000 L. After adding 25 % by volume rock results in a deepening and dulling of the shade,
salt, stir for 2 h and again add 360 L of 15 % so that these dyes do not yield brilliant colors.
sodium hydroxide solution. Consequently, for combination dyeing the range
After cooling to 0 ◦ C with about 1000 kg of of chrome dyes has been supplemented with
ice, add 120 kg of sodium nitrite as a 23 % so- brilliant acid dyes, which cannot form chrome
lution and then quickly 600 L of 48.5 % sulfuric lakes and survive the chroming process without
acid. After 4 h separate the diazonium salt of the change.
aminomonoazo dye in a filter press and stir the Chrome dyes are applied to the fiber chiefly
press cake into 1500 L of water and 400 kg of with the aid of the afterchroming method and
ice. special products also by the one-bath chroming
Dissolve 438 kg of 100 % N-phenylperi acid method (metachrome process). For ecological
in 2000 L of water at about 80 ◦ C and then ad- reasons chrome dyes are of severely limited im-
just to a volume of 8500 L and a temperature portance.
of 10 ◦ C with about 1500 kg of ice and water.
Finally add 230 L of 15 % sodium acetate solu- Dyes for the Afterchroming Method. In
tion and adjust to pH 3 – 4 with about 10 L of afterchroming the dye is allowed to go onto
31 % hydrochloric acid. Then simultaneously the fiber from an acid bath, and this is followed
feed into this solution 400 L of 15 % sodium ac- by treatment with dissolved alkali dichromate,
etate solution and the suspension of the diazo- which is reduced by the cystine group of the
nium salt press cake. Stir thoroughly and adjust wool to trivalent chromium compounds. The
this dispersion to the alkaline range by adding chromium complex formed on the wool fiber
250 L of 30 % sodium hydroxide solution and contains two azo dye radicals for each metal
cause to dissolve by heating to 80 ◦ C. Add 10 % atom (1 : 2 complex compound).
by volume rock salt and continue stirring for 3 h. In the reversal of this process with so-called
Separate the dye in a filter press at 70 ◦ C. The mordant dyes, first the chromium salt is applied
final volume is 19000 L; the yield is 800 kg of to the fiber (premordanting) and then the dye.
dried product. Mordant dyeing is essentially only of historical
A very wash-fast black wool dye is C. I. Acid interest.
Black 26, 27070 (49) [6262-07-3]. The afterchroming dyes have lost their former
importance because of the considerable amount
of time required by the dyeing process, but they
are still used in wool dyeing because of their low
price. For the names of important afterchroming
dye ranges see Table 2.
Table 2. Important ranges of afterchroming dyes
It contains 4-amino-diphenylamine-2- Manufacturer Range
sulfonic acid as the diazo component, 1-
naphthylamine as the middle component, and Bayer Diamantchrom
Ciba-Geigy Eriochrom
2-naphthol-6-sulfonic acid as the final coupling Sandoz Omegachrom
component.
Furthermore, dyes of this type are still pro-
3.2.1.3. Chrome Dyes [3, p. 464], [15, p. 680] duced in large amounts in the COMECON coun-
tries and in the People’s Republic of China.
Azo dyes with certain groupings can be con- In the yellow and orange types the salicylic
verted on the fiber with chromium salts to acid grouping dominates. One of the most im-
chromium complexes that are more or less sol- portant chrome-developed yellow dyes is C. I.
uble (see Section 2.3.4). This “chroming” of Mordant Yellow 1, 14025 (50) [584-42-9]. After
largely acid monoazo dyes improves the light chroming it yields a somewhat dull yellow with
fastness of the dyeings and above all their wet- good fastness properties.
fastness, because the complex formation blocks
 Azo Dyes 29

in the molecule (55). Two other important black

dyes are C. I. Mordant Black 3, 14640 (56,
R = H) [3564-14-5], and C. I. Mordant Black 11,
14645 (56, R = NO2 ) [1787-61-7].

C. I. Mordant Yellow 5, 14130 (51)

[6054-98-4], possesses two salicylic acid
groups. After chroming the product is greenish
yellow and exhibits very good general fastness
properties. Because diazotized aminosalicylic
acid is not sufficiently electrophilic, the dye C. I. Mordant Black 11 is also used as an indi-
is manufactured by coupling diazotized 5-ami- cator in the complexometric titration of various
no-2-chlorobenzoic acid to salicylic acid and bivalent metals with which the dye forms com-
saponifying the activated chlorine atom. plexes [24].
The complex formation on the salicylic acid The o,o
-dihydroxyaminoazo and o-
group has little influence on shade and light hydroxy-o
-aminoazo compounds with phenols
fastness, in contrast to o,o
-disubstituted ary- or aniline derivatives as coupling components
lazo compounds, on which complexing brings yield largely brown shades on chroming; they
about a considerable deepening of shade and include one of the most important brown dyes
usually marked increase in light fastness. Ex- with very good fastness properties, C. I. Mor-
amples: C. I. Mordant Red 7, 18760 (52) dant Brown 33, 13250 (57) [3618-62-0].
[3618-63-1], dyes wool a dull orange, which
through chroming becomes a clear red with very
good fastness properties.

The rarely used chrome-developed disazo

dyes mostly contain the salicylic acid grouping,
Red, blue, and primarily black afterchroming which in the type D → M → K (see page 27) is
dyes contain naphthalene radicals in the diazo or usually introduced into the molecule in the form
coupling component. of aminosalicylic acid as the diazo component.
A blue dye, for example, is C. I. Mordant Blue Dyes of the type K1 ← D → K2 (see page 25) are
13, 16680 (53) [1058-92-0]. manufactured by coupling bisdiazotized benzi-
dine derivatives (D) to two equivalents of sali-
cylic acid (K1 = K2 ) or to one equivalent each
of salicylic acid (K1 ) and naphtholsulfonic acid
(K2 ).

Dyes for the One-Bath Chroming Method

One of the most important black dyes is C. I. (Metachrome Process). In this method the
Mordant Black 9, 16500 (54) [2052-25-7]. metal complex is formed on the fiber by the
simultaneous action of chrome dye and dichro-
mate. Compared with the afterchroming method
metachrome dyeing has the advantage of simpler
application, but the number of usable dyes for
this process is more severely limited. Whether a
dye is suitable for the metachrome process de-
Oxidation of the dye during chroming with pends on its hydrophilic character and its rate of
dichromate creates a naphthoquinone structure complex formation [15, p. 680].
30 Azo Dyes

The method is used at present for wool dyeing molecule or for every two dye molecules. These
primarily because of price considerations. products generally yield dyeings of high light
Examples of typical one-bath chroming dyes and wetfastness but of somewhat muted shades.
are: C. I. Mordant Yellow 30, 18710 (58)
[10482-43-6], C. I. Mordant Red 19, 18735 (59) 1 : 1 Metal-Complex Dyes. Among these
[1934-24-3], C. I. Mordant Red 30, 19360 (60) dyes primarily the 1 : 1 chromium complexes
[6359-71-3], C. I. Mordant Brown 48, 11300 containing sulfonic acid groups have achieved
(61) [6232-53-7], and C. I. Mordant Blue 7, commercial importance. They must be applied
17940 (62) [3819-12-3]. from a strongly acid bath, which imposes certain
limits on their range of applications. The 1 : 1
metal complexes are not suitable for polyamide,
which is partially decomposed under the dyeing
conditions for these products. Their main area
of application is in the dyeing of wool, but they
are also suitable for leather dyeing. See Table 3
for a list of ranges.
Table 3. Important ranges of 1 : 1 metal-complex dyes

Manufacturer Range

BASF Palatin Fast

Ciba-Geigy Neolan

The 1 : 1 metal-complex dyes are also pro-

duced in large amounts in the COMECON coun-
tries and in the People’s Republic of China; man-
ufacturers in, for example, India or Greece are
of lesser significance.
The manufacture of 1 : 1 chrome complex
dyes takes place in two operations: manufac-
ture of the azo dye capable of chrome devel-
opment and formation of the chromium com-
plex. Similarly as for the one-bath chroming
dyes, negatively substituted o-aminophenols
but also o-aminonaphthols and their sul-
fonic acids are used as diazo components;
2-naphthol, 2-naphtholsulfonic acids, pyra-
zolones, acetoacetic acid aryl amides, and 2,4-
dihydroxyquinoline serve as the coupling com-
ponents.
3.2.1.4. Metal-Complex Dyes
1 : 2 Metal-Complex Dyes. Because of
(cf. Section 2.3.4) their complexed structure 1 : 2 metal-complex
Only a short overview of the subject will dyes exhibit anionic character. Those which
be given here (for detailed treatment → Metal- have gained commercial importance are primar-
Complex Dyes). Metal-complex dyes are man- ily the ones that are free of sulfonic acid groups
ufactured in the complete dye form before the and for which adequate water solubility is pro-
dyeing process and usually contain chromium vided by nonionic, hydrophilic substituents,
or cobalt ions, rarely copper or iron ions, bound such as methylsulfone or sulfonamide groups
in the molecule. A distinction is made between [15, p. 689], [25].
1 : 1 and 1 : 2 metal-complex dyes, depending The introduction of 1 : 2 metal-complex
on whether there is one metal ion for each dye dyes, which are applied from a neutral to weakly
 Azo Dyes 31

acid bath, represented a significant technical ad- Table 5. Important ranges of 1 : 2 metal-complex dyes containing
vance over the strong-acid-dyeing 1 : 1 chrome monosulfonic and disulfonic acid groups
complex dyes. It has meant better protection of Manufacturer Range
the fiber material, simplification of the dyeing
process, and improvement of the fastness prop- BASF Acidol M
Bayer Isolan S
erties. Ciba-Geigy Lanacron S
Because these dyeings, like all metal- Hoechst Azarin
ICI-Francolor Neutrichrom S
complex dyeings, usually exhibit subdued Sandoz Lanasyn S
shades, the 1 : 2 metal-complex dyes are com-
bined with small amounts of acid dyes or suitable
The 1 : 2 metal-complex dyes with two sul-
reactive dyes to brighten the tint.
fonic acid groups are a more recent develop-
Owing to their outstanding wetfastness, high
ment.
light fastness, and good fiber levelness, the 1 : 2
Contrary to the opinion frequently expressed
metal-complex dyes are of major importance in
in the literature that such dyes would exhibit in-
dyeing wool and polyamide. Important ranges
adequate levelness when applied in a weakly
of these dyes are listed in Table 4.
acid bath and inadequate stability to acid in a
Table 4. Important ranges of 1 : 2 metal-complex dyes strongly acid dyebath, they are very well suited
for dyeing wool and polyamide if certain pH
Manufacturer Range
conditions are observed. These products are very
BASF Ortolan soluble in water, have high tinctorial strength,
Bayer Isolan and are very high-yield dyes with a relatively
Ciba-Geigy Irgalan
Sandoz Lanasyn simple structure (for further details → Metal-
Complex Dyes).
The extent of variation is extremely large as a
result of the great number of available diazo and 3.2.2. Polyamide Dyes [5, vol. III, p. 276]
coupling components, the choice of complex-
forming metal (primarily chromium or cobalt), Synthetic polyamides have a structure similar
and the possibility of synthesizing 1 : 2 metal to those of wool and silk but differ in having a
mixed complexes. low acid-binding power and in their capacity to
Substituted o-aminophenols and also an- dissolve nonpolar compounds. In consequence
thranilic acid and its derivatives are the most materials of polyamide can be dyed with dis-
important diazo components. The main cou- perse dyes as well as with selected acid dyes,
pling components are pyrazolones, acetoacetic including metal-complex dyes.
acid arylamides, naphthols, N-substituted ami- When choosing acid dyes for polyamides it
nonaphthols, and naphthylamines. must be borne in mind that owing to the lower
For subdued shades the 1 : 2 metal-complex acid-binding power dyes with two and more sul-
dyes with one or two sulfo groups continue to fonic acid groups in the molecule go onto the
play an important role. Dyes with one such group fiber much more slowly and to a much lower
contain the sulfonic acid group in one of the saturation value than dyes with one sulfonic
two parts bound to the azo group and com- acid group. Consequently, these dyes cannot be
plexed to chromium or cobalt. They are built mixed or combined with one another, which has
up stepwise via the 1 : 1 metal-complex. Com- been taken into account in composing the prod-
pared with the 1 : 2 metal-complex dyes with uct ranges.
nonionic hydrophilic groups they exhibit better Since acid dyes on polyamide behave as they
solubility in water but poorer leveling power, and do on wool in regard to leveling power, build-up,
therefore they are always used together with spe- and fastness properties (see Section 3.2.1), they
cially selected leveling auxiliaries. The ranges of fall into two classes (cf. Table 6):
these dyes (Table 5) contain primarily navy blue, Group A: acid dyes with good leveling power
black, dark brown, and olive shades. and low substantivity for polyamide; they
yield dyeings with reasonably good wetfast-
ness.
32 Azo Dyes

Group B: acid dyes with lower leveling

power, higher substantivity and high wetfast-
ness standard on polyamide. Many of these
acid dyes with a lower leveling power rather
clearly reveal differences in fiber structure
that may result from, for example, differ-
ences in the degree of drawing (so-called
streakiness), so that it is usually necessary
to add leveling and retarding auxiliaries Group B dyes are used almost exclusively
(→ Textile Dyeing). for clothing textiles for which more stringent re-
quirements are placed on wetfastness. Some of
Table 6. Important ranges of polyamide dyes the typical azo dyes of this type are C. I. Acid
Yellow 42, 22910 (67) [6375-55-9], C. I. Acid
Manufacturer Range Yellow 65, 14170 (68) [6408-90-8], C. I. Acid
Group A Group B Red 114, 23635 (69) [6459-94-5], C. I. Acid Blue
113, 26360 (70) [3351-05-1].
BASF Acidol Acidol
Bayer Telon Supra Telon Fast
Ciba-Geigy Erionyl Erionyl
Tectilon
Crompton & Knowles Nylanthrene Nylanthrene
ICI Nylomine A Nylomine C
Nylomine B
Sandoz Nylosan E Nylosan F
Nylosan N

The main area of application for the acid

polyamide dyes characterized in group A is in
carpet dyeing, but they are also used in other
areas of textile dyeing where the fastness re-
quirements are not too stringent. A few struc-
tures are presented below to illustrate the types
of azo dyes used: C. I. Acid Yellow 25, 18835
(63) [6359-85-9], C. I. Acid Orange 67, (64)
[12220-06-3], C. I. Acid Red 42, 17070 (65)
[6245-60-9], C. I. Acid Red 32, 17065 (66)
[6360-10-7].

Other acid disazo dyes for polyamide are sec-

ondary disazo dyes (D → M → K) with one or
two sulfonic acid groups bound to aromatic nu-
clei or with an external sulfate group, which
is situated mainly in the diazo component D.
Aniline, 1-naphthylamine, and their derivatives
preferably serve as the middle component M,
whereas the coupling components of the phenol
and arylamine series common in disperse dyes
are used as the final hydrophobic component K
[26–30], as illustrated by the general structure
71.
 Azo Dyes 33

Table 7. Important ranges of dispersed 1 : 2 metal-complex dyes

Manufacturer Range

BASF Vialon
Ciba-Geigy Avilon
ICI-Francolor Amichrom

R1 and R2 = alkyl groups, partially substi-

tuted
The patent literature indicates that polyamide
dyes of this type are generally characterized by 3.2.3. Silk Dyes
high tinctorial strength and light fastness and a
good capacity to compensate for nonuniformity Because natural silk, as a protein fiber of ani-
in the material. mal origin, resembles wool fiber in its chemi-
Because of increasing standards of wetfast- cal structure, it can be dyed with nearly all the
ness, lightfast reactive dyes are also being used classes of dyes used for wool. The choice of dyes
in polyamide printing, especially to produce depends essentially on the fastness properties re-
pastel shades. However, only selected represen- quired.
tatives of the cotton reactive dyes so far offered Of great importance for the dyeing of natural
on the market are suitable for polyamide. Essen- silk are selected members of the class of acid
tially the products recommended for polyamide wool dyes (see Section 3.2.1). The occasionally
contain monosulfonic and disulfonic acid inadequate wetfastness of these dyeings can be
groups with β-sulfatoethylsulfone, α-bromo- substantially improved by the proper aftertreat-
acrylamide, α,β-dibromopropionylamide, ment (e.g., with potassium sodium tartrate and
monochlorodialkylaminotriazine, and tri- tannin).
halopyrimidyl groups, particularly 2,4-difluoro- Selected acid 1 : 1 chrome complex dyes, be-
5-chloropyrimidyl groups (→ Reactive Dyes). cause of their good wetfastness and light fastness
Because of their high fastness standards the and their very good leveling power, and also 1 : 2
1 : 2 metal-complex dyes have also acquired chrome complex and 1 : 2 cobalt complex dyes
some importance in the dyeing of polyamide. with hydrophilic groups (see page 30) have suc-
They are used primarily in the clothing sector to cessfully come into use as silk dyes.
achieve deep shades. The first complete range of Furthermore, direct dyes (see Chap. 4) are
these dyes for polyamide fibers was developed among the most important silk dyes. Their fast-
in 1940 – 1943 at the Ludwigshafen works of ness properties can be improved by aftertreat-
the then I. G. Farbenindustrie, but owing to the ment with metallic salts or formaldehyde.
events of the day they never reached the market. If suitably selected, cationic dyes (see
The range consisted of dyes with and without Chap. 5) can also be used for dyeing weighted
nonionic, hydrophilic groups. silk, toward which they exhibit special affinity,
Later these dye types were further devel- in addition to having good leveling power and
oped by other companies and uniform ranges very good wetfastness. On the other hand, the
were placed on the market. Dyes with nonionic, light fastness of these dyeings is not always sat-
hydrophilic groups are offered for wool and isfactory.
polyamide dyeing (see page 30), while the use Reactive dyes have also found a place in silk
of water-insoluble 1 : 2 metal-complex dyes is dyeing. These dyeings are characterized by very
restricted to polyamide dyeing; Table 7 shows fast and bright shades with exceptionally good
ranges of these products. In a process compa- wetfastness.
rable to disperse dyeing, these dyes are applied Initially the development of synthetic fibers
to polyamide from a finely dispersed aqueous greatly reduced the importance of silk dyeing.
suspension and yield extremely lightfast and The processing of silk has undergone a marked
wetfast dyeings (for further details → Metal- increase owing to the growing quality conscious-
Complex Dyes). ness of buyers, who appreciate the outstanding
wear properties of silk, and because of the inten-
sified activities of China on the world market.
34 Azo Dyes

In addition to China the countries that are still here are already familiar from the textile
prominent in silk processing today are Japan and field.
Italy. Group C is composed of acid dyes and direct
dyes. Unlike group A, they are mainly dye
mixtures that give marked coloration of the
3.2.4. Leather Dyes leather as well as good surface coverage.
Group D consists of pigment preparations
Leather is produced by tanning skins of different
that are important for the treatment of leather
origin and the tanning process has a decisive in-
and are applied by different methods (spray-
fluence on the dyeability of the pretreated prod-
ing, padding, curtain coating). The ranges
ucts. The differences in the dyeing behavior of
contain both organic and inorganic pigments
leather of various origins that has been tanned in
and mixtures of the two. They are marketed
different ways are about as marked as those of
as binder-containing or binder-free, finely
the different textile fibers.
dispersed aqueous pigment preparations and
Many of the anionic, cationic, metal-
have high covering power and in most cases
complex, and direct dyes employed in the textile
very good light fastness.
field are also used for dyeing leather. In addi-
tion ranges have been developed that are par- The large number of cationic dyes suitable
ticularly suitable for dyeing leather. The choice for dyeing leather cannot be grouped under one
of dye depends largely on the tanning method, specific range. They have very good covering
the fastness properties required, and the end use, power and give a high yield and brilliant shades.
and a distinction is made, depending on the Their light fastness is generally only moderate.
depth of penetration of the dyes, between sur- They are used for vegetable tanned leathers and
face dyeing, part-penetration dyeing, and full- as a so-called top dyeing for chrome leather.
penetration dyeing (for more details on the dye- To obtain the good fastness to buffing that
ing of leather → Leather). is particularly important in the dyeing of suede,
The main shades used are different browns special dyes are used which, in addition to ade-
and blacks, as well as bordeaux, reds, yellows, quately deep and level surface dyeing, also give
blues, and greens. Most of the leather dyes be- good penetration so that no change in shade oc-
long to the azo class. They are marketed both curs when the leather is subsequently buffed.
as individual dyes and in the form of mixtures. Some typical anionic azo dyes for leather
The most important ranges are listed in Ta- are: C. I. Mordant Brown 33, 13250 (72)
ble 8. Because of the many different classes of [3618-62-0]: strong penetration, poor coverage;
dyes used, several ranges are available:
Group A includes both anionic and di-
rect dyes. They are used mainly for dye-
ing chrome leather and alum-tanned glove
leather. The basic difference between acid
and direct dyes, which is pronounced in tex-
tile dyeing, is less marked in the dyeing C. I. Acid Brown 105, 33530 (73) [8003-78-9]:
of leather. Therefore, the two groups often poor penetration, good coverage;
tend to be combined under the term “anionic
dyes”. The dyeings obtained have good light
fastness and good to very good wetfastness,
rub fastness, and fastness to washing.
Group B contains acid 1 : 1 chrome-complex
dyes as well as 1 : 2 chrome- and 1 : 2 cobalt-
complex dyes with hydrophilic groups (see
C. I. Acid Black 24, 26370 (74) [3071-73-6]: no
Section 3.2.1.4). Particularly stringent de-
penetration, good coverage;
mands can be made on these dyes in terms
of light, wet, and perspiration fastness and
leveling properties. Some of the ranges used
 Azo Dyes 35
Table 8. Names of important ranges of leather dyes and pigments

Manufacturer Ranges

Group A Group B Group C Group D

BASF Luganil Luganil C Lurazol Lepton

Eukesolar liq. Lumin Helizarin
Corial Fast

Bayer Baygenal Baygenal L Aciderm Eusin

Benzo Leather Eukanol
Chrome Leather Baysin
Bayderm
Isoderm

Ciba-Geigy Sella Fast Sellacron Sellaflor Irgafin

Neolan
Lanacron
Irgalan
Irgaderm liq.

FMC/ICI Coriacide
Inoderm

Hoechst Coranil Coranil Fast Remaderm Melustral

(with Cassella) Melustral Coating

Sandoz Derma Derma Light Relca

Sandoderm Relcasyn
Relcasol

From the chemical viewpoint some of the

most frequently used synthetic food dyes belong
to the azo series.
The dyes approved for food coloration in the
EEC are listed in the guidelines for colorants
of 23. Oct. 1962, which are continually updated.
C. I. Acid Yellow 36, 13065 (75) [587-98-4] The member states of the EEC must convert
(metanil yellow): strong penetration, poor cov- these guidelines to national law.
erage; The azo dyes listed below bear, in addition
to the L number of the Dye Commission of the
Deutsche Forschungsgemeinschaft (DFG, Ger-
man Research Association), an EEC number (E)
under which they are registered in the EEC: C. I.
Food Yellow 4, 19140, L-Yellow 2, E 102, Tar-
trazine, (76) [1934-21-0]

3.2.5. Azo Food Dyes

In terms of quantity and value food dyes play

only a relatively minor role in the dye-making
industry.
A brief survey is given here of the azo dyes
that have been approved for food coloration.
For a detailed treatment of the subject, includ- C. I. Food Yellow 3, 15985, L-Orange 2, E 110,
ing legislation and official regulations, → Foods, Yellow Orange S, (77) [2783-94-0]
3. Food Additives.
36 Azo Dyes

The food dyes permitted in the USA are

compiled in the Code of Federal Regulations,
Vol. 21, Food and Drugs, Parts 1 to 99; continual
amendments are published in the Federal Reg-
ister.
A synthetic dye is permitted for dyeing food
only if thorough toxicological studies reveal no
C. I. Food Red 9, 16185, L-Red 3, E 123, Ama- danger of toxic effects to the consumer. Food
ranth S, (78) [915-67-3] dyes are among the food additives that have been
subjected to the most thorough toxicological ex-
aminations.
Purity Requirements: Food dyes that are placed
on the market must meet special purity require-
ments, which have been fixed by law for the
Federal Republic of Germany in the Directive
on Additives of 20. 12. 1977. According to this
C. I. Food Red 7, 16255, L-Red 4, E 124, Pon- regulation the following substances must not
ceau 4 R, (79) [2611-82-7] be detectable in food dyes:Barium compounds
that are soluble in dilute hydrochloric acid; cad-
mium, mercury, selenium, tellurium, thallium,
uranium and chromates; polycyclic aromatic hy-
drocarbons with 3 or more fused nuclei; and
2-naphthylamine, benzidine, and 4-aminobiphe-
nyl (xenylamine).
Upper limits have been specified for the fol-
C. I. Food Red 3, 14720, L-Red 1, E 122, Azo lowing contaminants:
Rubine, (80) [3567-69-9]
arsenic max. 5 mg/kg
lead max. 20 mg/kg
antimony, copper, individually max. 100 mg/kg
chromium, zinc,
barium sulfate
max. 200 mg/kg
together
aromatic amines max. 100 mg/kg
portions extractable max. 0.2 %
C. I. Food Black 1, 28440, L-Black 1, E 151, with ethyl ether∗
water-insoluble max. 0.2 %
Brilliant Black BN, (81) [2519-30-4] portions∗

∗ Only in the dyes E 102 – 110, E 122 – 132, E 142 and E 154.

Furthermore, special purity requirements

have been placed on individual dyes.
In the Federal Republic of Germany the an-
The use of dyes for pharmaceutical prepa- alytical methods for testing the degree of purity
rations is regulated in the EEC by guidelines have been published by the Dye Commission of
from 1978 and 1981 and the Directive concern- the DFG.
ing Pharmaceuticals Dyes of 1982. Here practi- In the USA the regulations for the purity of
cally the same dyes are permitted as for food. food dyes are specified in the Code of Federal
For other areas of application different regu- Regulations. The Food and Drug Administration
lations apply. These regulations differ from one (FDA) is responsible for the registration and cer-
another in respect of the dyes permitted (for tification of food dyes.
example, in the cosmetics sector the cosmetics
guidelines and the Directive on Cosmetics).
 Azo Dyes 37

4. Direct (Substantive) Dyes characteristics are necessary for high substan-

tivity:
Direct or substantive dyes are colored com-
pounds that are mainly used to dye materials a) Coplanarity of the Dye Molecules. The
made from natural or regenerated cellulose (e.g., importance of coplanarity is shown by
cotton, jute, viscose, or paper) without employ- the example of 4,4
-diaminodiphenyl
ing mordants as auxiliaries. The essential re- derivatives. Whereas 3,3
-disubstituted
quirement for classification of a dye in this group diaminodiphenyls (e.g., o-tolidine or o-
is its substantivity, i.e., its absorption from an dianisidine) as diazo components pro-
aqueous salt-containing solution onto cellulosic duce high absorptive power in dyes,
materials. Absorption onto cotton takes place in this substantivity is neutralized in 2,2
-
a neutral to soda alkaline medium and onto paper disubstituted derivatives and coplanarity of
in a weakly acid to neutral medium. these molecules is no longer possible.
Substantivity was initially attributed to sec- b) Long Chain of Conjugated Double
ondary valence bonding between fiber and dye. Bonds.Dye molecules of this kind (see also
The fact that coplanar molecules are always Schirm’s rule [34]) can contain bridges,
more substantive than nonplanar ones later led such as −CH=CH−, in addition to the
to the coplanarity theory with its assumption that aromatic rings, thus ensuring the devel-
coplanar dyes are in contact with the cellulose opment of resonance forms across the en-
molecule along their entire length. tire molecule. Exceptions to this rule are
The presence of hydrogen bonds has also the bridges −NHCONH−, −CONH−, and
been expounded as a possible explanation for −NH−, which increase substantivity in spite
high affinity between fiber and dye [31]; how- of the interruption in the conjugated sys-
ever, such bonds are probably prevented by a tem. In these groups, the ability to form
water layer between fiber and dye [32]. hydrogen bonds is the decisive factor. Other
The nature of substantivity has been very con- groups causing an interruption in the conju-
vincingly explained [33]. gated system, e.g., −CH2 −, −CH2 CH2 −,
According to this explanation, single dye −CO−, −S−, −SO2 −, and cyclohexylene,
molecules are adsorbed by the intermicellary decisively lower substantivity. Only the sub-
cavities of the cellulosic fibers and, unlike non- stantivity of the linked segments remains.
substantive dyes, they form aggregates in these On the basis of the structural characteristics
cavities. described, direct dyes based on benzidine can be
Because of their size, these aggregates can commended for their good substantivity. In fact
no longer be directly washed out with water, but this group was for a long time a significant con-
only after further solvation has taken place. stituent of all important direct dye ranges in the
Because direct dyes become aggregated in shade spectrum from red to brown, blue, green,
aqueous solutions at normal temperatures, sub- and black.
stantivity often cannot take effect until the tem- Because of the carcinogenic properties of un-
perature has risen. Only then diffusion into the substituted benzidine in humans about 15 – 20
fiber is possible. years ago almost all major dye manufacturers in
The tendency toward aggregation is therefore the most important western industrialized coun-
characteristic of substantive dyes, which also ex- tries stopped production of dyes based on this
plains why coplanar dyes possess greater sub- substance.
stantivity than nonplanar ones. This development led to an intensive search
There is no exact delineation between sub- for substitute dyes, the results of which are re-
stantive and nonsubstantive dyes, the boundaries flected in particular in the patent literature. The
between them are fluid. significance of this development is also dis-
Structural Characteristics. Azo dyes com- cernible in the number of direct dyes newly reg-
prise the major proportion of the direct dyes; istered with the Colour Index between 1971 and
apart from these, only a few azine, phthalocya- 1982. The research efforts are especially appar-
nine, and nonazo metal-complex dyes possess ent in the case of black, with 21 new registra-
a certain significance. The following structural tions; yellow, brown, and blue, each with 19;
38 Azo Dyes

and red, with 17. However, of a total of 115 di- Because of their ease of application and mod-
rect dyes, the constitution has as yet only been erate price, direct dyes still represent one of the
stated in 7 instances. It is therefore not possi- largest groups of azo dyes, although their wet-
ble to evaluate the patent literature results with fastness, in particular, often only satisfies mod-
regard to the industrial significance of the prod- erate to average requirements. The only slight
ucts. decrease in consumption of direct dyes follow-
Starting Compounds. Based on the require- ing the appearance of the wetfast reactive dyes
ments mentioned, the following starting com- is due to the markedly higher price of reactive
pounds are especially suited for the synthesis of dyes. For product ranges see Table 9.
direct dyes: Direct dyes are classified according to their
a) 3,3
-Disubstituted 4,4
-diaminodiphenyl method of application:
derivatives, but not 2,2
-disubstituted ones. a) Conventional Direct Dyes. They include
These are, therefore, diamines with the struc- monoazo, disazo, trisazo, and tetrakisazo
ture dyes. It is advantageous to subdivide them
according to the nature of their chemical
structure. Disazo dyes, for example, can
be divided according to chemical synthe-
sis principles into primary and secondary.
Conventional azo direct dyes further include
where X = CH3 , OCH3 , Cl, SO3 H. 1,4- symmetric urea derivatives, dyes obtained
Diaminophenyl derivatives also belong to by oxidation of amines, and triazinyl and
this group. copper-containing dyes.
b) Compounds of the type b) Direct Dyes with Aftertreatment. This group
includes direct dyes that after being applied
to the fiber by the usual method undergo one
of the following aftertreatments:
where X = NH, SO2 , −N=N−, Aftertreatment with cationic auxiliaries
−CONH−, −CSNH−, −SO2 NH−, Aftertreatment with formaldehyde
−CH=CH−, −HNCONH−, −HNCSNH−, Diazotization of the dye on the fiber and
−O2 SNHSO2 −. coupling with suitable components (dia-
c) 1,4-Diaminonaphthalene and 1,5-diami- zotization dyes)
nonaphthalene Aftertreatment with metal salts
d) m-Phenylenediamine and other 1,3-
disubstituted diamines, e.g., 2,6-diami-
notoluene-4-sulfonic acid or bis(3-ami-
nophenyl)urea. 4.1. Conventional Direct Dyes
e) Heterocyclic diamines
4.1.1. Monoazo Dyes

Only a few monoazo dyes possess the necessary

substantivity to render them suitable for direct
dyeing of cellulosic fibers.
Of practical importance as diazo com-
ponents are only the derivatives of 2-(4
-
aminophenyl)-6-methylbenzthiazole, of the so-
called dehydrothio-p-toluidine (82):
 Azo Dyes 39
Table 9. Designations of important ranges of direct dyes (The names in brackets are the U.S. products of the relevant Western European
company)
Manufacturer Product range

Western Europe
BASF (FRG) Lusantin, (Phenamine)
Bayer (FRG) Benzamin, Benzo, Benzocuprol, Sirius, Sirius Supra
Ciba-Geigy (Switzerland) Cuprophenyl, Diphenyl, Solophenyl, (Diazophenyl)
Croda (United Kingdom) Covazol, Diazin
Hoechst/Cassella (FRG) Cotonerol, Diamin, Duasyn, (Rayon)
ICI (United Kingdom) Chlorazol, Durazol
PCUK/ICI (France) Cuprodiazol Light, Diazamine, Diazol, Diazol Fast, Diazol Light, Metadiazol
Rovira (Spain) Hispadiazo, Hispaluz, Hispamin
Sandoz (Switzerland) Cuprofix, Cuprofix C, Indosol, Solar, (Lumicrease, Pyrazol)

United States
Amer. Cyanamid Calcomine
Atlantic Atlantic, Atlantic Diazo, Atlantic Direct, Atlantic Resin
Crompton & Knowles Diazo, Direct-, Intrabond, Intralite, Intramet, Sol-Aqua-Fast, Superlitefast
Internat. Dyestuff Elcofast, Elcomine
Org. Chem. Corp. Orcoform, Orcolitefast, Orcomine

Japan
Hodogaya Aizen Direct, Aizen Primula, Direct
Mitsubishi Diacotton, Diacupro, Dialuminous, Direct
Mitsui Toatsu Direct, Suprazo
Nippon Kayaku Kayafect, Kayaku Direct, Kayarus
Sumitomo Direct, Japanol, Nippon, Sumilight, Sumilight Supra

The compound 82 is obtained by melting p- used. Naphtholsulfonic acids are of only

toluidine with sulfur at 130 – 230 ◦ C. The deriva- minor importance here. Dehydrothio-p-tolu-
tives (83) – (86) are used to produce monoazo idinesulfonic acid (83) and the sulfonated
direct dyes: primulin base are also used as diazo components
for certain orange disazo direct dyes.
Examples. Diazotization of dehydrothio-p-
toluidinesulfonic acid (84) and coupling to ace-
toacetic acid o-anisidide results in the light-
fast yellow C. I. Direct Yellow 27, 13950 (87)
[10190-68-8].

Coupling the diazotized monosulfonic acid

of the primulin base to acetoacetic acid anilide
produces the clear, greenish yellow C. I. Direct
Yellow 22, 13925 (88) [10190-69-9].

Whereas 83 and 84 are obtained by sulfona-

tion of dehydrothio-p-toluidine (82) with oleum,
compounds 85 and 86 are formed in a mixture
with 82 during the sulfur melting process and
are separated by vacuum distillation. Substantive yellow monoazo dyes with very
Acetoacetic acid arylides and pyrazolone good light fastness are also obtained by oxida-
derivatives are the coupling components mainly tion of dehydrothio-p-toluidine and its deriva-
40 Azo Dyes

tives (see Section 2.2.3). Oxidation of the

sodium salt of the monosulfonic acid of the
primulin base in the alkaline pH range with
sodium hypochlorite results, for example, in C. I.
Direct Yellow 29, 19556 (89) [6537-66-2].
As with the corresponding oxidation of
Both as regards the number of products on
dehydrothio-p-toluidinesulfonic acid (83),
the market and the consumption in terms of vol-
which results in C. I. Direct Yellow 28, 19555
ume, the disazo dyes of the bisdiazotized ben-
(see Section 2.2.3), in addition to the azo dye,
zidine were for a long time the most important
diphenazines (90) are obtained as byproducts,
substantive dyes. Today, no individual chemical
e.g., which in some cases have to be separated
group enjoys such significance. Instead, besides
the substituted 4,4
-diaminodiphenylene, sev-
eral other groups, including heterocyclicones,
have taken the place of benzidine.
o-Dianisidine as bisdiazo component has a
certain significance in blue direct dyes of the
congo red type. Coupling with two equivalents
when they impair the shade and fastness prop- of H acid results in C. I. Direct Blue 15, 24400
erties of the dyes. (92) [2429-74-5].

4.1.2. Disazo Dyes

4.1.2.1. Primary Disazo Dyes

Primary disazo dyes are obtained in accordance With chromotropic acid (1,8-dihydroxy-
with the pattern K1 ← D → K2 by bisdiazotiza- naphthalene-3,6-disulfonic acid) as coupling
tion of a bifunctional diazo component D and component, C. I. Direct Blue 10, 24340
coupling to two equivalents of coupling com- [4198-19-0], is obtained (see page 41).
ponent K1 and K2 , or according to the pattern A very clear pure blue is obtained through the
D1 → K ← D2 by coupling of two equivalents of alkaline coupling of bisdiazotized o-dianisidine
diazo component (D1 and D2 ) to one equivalent to two equivalents of Chicago acid SS (1-ami-
of a bifunctional coupling component. Depend- no-8-hydroxynaphthalene-2,4-disulfonic acid):
ing on whether K1 and K2 or D1 and D2 are the C. I. Direct Blue 1, 24410 (93) [2610-05-1].
same or different, symmetrical or asymmetrical
dyes are obtained.

Type K1 ← D → K1 Primary symmetrical

disazo dyes with benzidine as bisdiazo compo-
nent were long considered to be the prototype
of direct dyes. Development of this dye class o-Tolidine is also occasionally encountered
commenced with congo red, C. I. Direct Red 28, as diazo component, e.g., in C. I. Direct Blue
22120 (91) [573-58-0]. 14, 23850 (94) [72-57-1].
 Azo Dyes 41

The dye enjoyed major significance and in The product is obtained by coupling bis-
addition was one of the first chemotherapeutics diazotized 4,4
-diaminostilbene-2,2
-disulfonic
to be used as a remedy for protozoal diseases acid with two equivalents of phenol and sub-
(Trypan Blue). sequent ethylation. It is a very high-strength
Other important diamines used for the reddish yellow with very good leveling power
synthesis of symmetrical substantive disazo and average fastness properties, which is excel-
dyes are 4,4
-diaminostilbene-2,2
-disulfonic lently suited for the dyeing of fabric blends, e.g.,
acid (95) and 4,4
-diaminodiphenylurea-3,3
- cotton – polyamide. For manufacturing specifi-
dicarboxylic acid or -3,3
-disulfonic acid (96): cations see below.
An example of the use of 96 as diamine is
C. I. Direct Red 75, 25380 (98) [2829-43-8].

Other direct dyes with the diphenylurea

group can be produced from aminomonoazo
dyes by subsequent treatment with phosgene
The diamine 95 is obtained by heating 4- (see Sections 2.3.2 and 4.1.6).
nitrotoluene-2-sulfonic acid in diluted sodium
hydroxide solution with sodium hypochlorite, Type K1 ← D → K2 Primary Asymmetri-
4,4
-dinitrostilbene-2,2
-disulfonic acid being cal Disazo Dyes. Since the coupling reac-
formed in the process, and subsequent reduc- tions of substituted 4,4
-diaminodiphenylene to
tion with iron and hydrochloric acid. Com- monoazo or disazo dye proceed at different rates,
pounds 96 can be produced from 4-nitroaniline- asymmetrical coupling reactions can be carried
2-carboxylic acid or -2-sulfonic acid by treat- out. The first (acid coupling) proceeds from bis-
ment with phosgene and subsequent reduc- diazotized o-dianisidine with one equivalent of a
tion. The sodium salt of 4,4
-dinitrostilbene- coupling component to a monoazo intermediate
2,2
-disulfonic acid itself belongs to the group compound, which now together with a second
of stilbene dyes. It is mainly used as C. I. Direct (different) coupling component forms an asym-
Yellow 11, 40000 [1325-37-7] for the coloration metrical disazo dye.
of paper. Example: C. I. Direct Blue 22, 24280
Stilbene dyes are different self-condensation (99) [2586-57-4], is obtained by coupling o-
products of 4-nitrotoluene-2-sulfonic acid pro- dianisidine to Chicago acid SS and β-naphthol:
duced with of sodium hydroxide solution. The
various types are synthesized depending on the
concentration of sodium hydroxide, the reac-
tion temperature, and the reaction time. In some
cases a subsequent reaction with arylamines is
carried out.
An example of the combination with 95 is
C. I. Direct Yellow 12, 24895 (97) [2870-32-8], Production. The following abridged specifica-
also known as chrysophenine: tions are intended to illustrate processes for the
42 Azo Dyes

manufacture of symmetrical and asymmetrical

disazo direct dyes.
C. I. Direct Yellow 12,
24895, (97) [2870-32-8]: 590 kg of 4,4
-
diaminostilbene-2,2
-disulfonic acid are ad-
justed with water and ice to a volume of ap-
proximately 5500 L and a temperature of 5 ◦ C
and bisdiazotized with 220 kg sodium nitrite as
23 % solution; volume 6000 – 7000 L, tempera-
ture 20 – 22 ◦ C.
Next, 312 kg of phenol are dissolved with Dyes with a urea bridge, −HN−CO−NH−,
1500 L of water and 150 L of 30 % sodium hy- are also obtained by phosgene treatment of ami-
droxide solution and 225 kg of soda are added. noazo compounds (see Section 4.1.6). The so-
To this is transferred the above bisdiazotized called I acid imide (101), resorcinol and m-
solution. Then, 160 L of 30 % sodium hydrox- phenylenediamine are also of importance. Ex-
ide solution is added over 1 h. On the following amples of dyes are: C. I. Direct Orange 26,
morning, the solution is heated to 70 ◦ C, and af- 29150 (102) [3626-36-6],
ter addition of 240 L of 30 % hydrochloric acid,
the dye is salted out with 12 % rock salt, calcu-
lated on the volume. Yield: 2090 kg.
Approx. 5500 kg of the damp press cake,
corresponding to 2940 kg of 100 % product,
3500 kg of 94 % ethanol, 520 kg of soda, 870 L
of 30 % sodium hydroxide solution, and 840 kg C. I. Direct Red 250, 29168 (103),
of ethyl chloride are kept in a closed stirrer ves-
sel for 24 h at 100 ◦ C (5 – 5.5 bar). The mixture is
then cooled to 70 ◦ C and transferred at its own
pressure to a distilling vessel, from which the
ethanol is distilled with direct steam via a col-
umn. After being cooled to 80 ◦ C, the mixture is
suction filtered and dried at 100 ◦ C. and C. I. Direct Red 23, 29160 (104)
C. I. Direct Blue 15, 24400 (92) [2429-74-5]. [3441-14-3].
105 kg of dianisidine dihydrochloride is charged
into 6000 L of water and 400 L of 31 % hy-
drochloric acid. Then 2000 kg of ice is added
and the solution is bisdiazotized at 0 ◦ C with
200 kg of sodium nitrite and stirred for 4 h.
To 210 kg of H acid as neutral solution 4000 L The dye 104 is obtained by simultaneous cou-
of a 20 % sodium carbonate solution is added and pling of one equivalent each of diazotized aniline
then 3000 kg of ice to cool to 0 ◦ C. This solu- and 4-aminoacetanilide to I acid urea (100). Al-
tion is run in the bisdiazonium salt solution and though it only possesses average fastness prop-
stirred overnight. erties, it enjoys great importance and because of
Then the solution is heated to 80 ◦ C, 4600 kg its good leveling power is used for dyeing union
of sodium chloride is added, and the dye is fil- fabrics, polyamide, and chrome leather.
tered and dried in vacuo at 95 – 100 ◦ C. Yield: By coupling diazotized dehydrothio-p-tolui-
7600 kg. dinesulfonic acid to resorcinol and subsequent
coupling of diazotized aniline to the monoazo
Types D1 → K ← D1 and D1 → K ← D2 dye formed one obtains C. I. Direct Orange 18,
The most important coupling component for 20215 (105) [5915-59-3]. The product likewise
these types is the compound 100, which is pro- represents an important substantive dye.
duced by phosgene treatment of the I acid.
 Azo Dyes 43

as o-tolidine, 4,4
-diaminobenzanilide (DABA),

or 4,4
-diaminodiphenylamine-2-sulfonic acid
(DADPS).
The most important synthesis principle in this
range is the type K1 ← D1 → K2 ← D2 . The se-
quence of the three couplings depends on the
nature of the components.
An example is C. I. Direct Green 85, 30387
4.1.2.2. Secondary Disazo Dyes (108).

Type D → M → K. For the manufacture of

secondary disazo dyes, a diazotized amine D is
coupled to an amine M with free para position,
which in turn is diazotized and coupled to a cou-
pling component K (series coupling).
Dyes of this type mostly have a straight-chain
structure and often contain groups that increase
substantivity, such as I acid, I acid derivatives,
in particular with acylated amino groups, urea The reaction commences with stepwise cou-
bridges, or benzoylamino groups. The shades in pling of the o-tolidine and then aniline with H
this range extend from orange through red, vio- acid, followed by coupling of this aminodisazo
let, and blue to black. intermediate with phenol.
Examples: From 4-aminoazobenzene-4
- With C. I. Direct Black 166, 30026 (109),
sulfonic acid and benzoyl I acid C. I. Direct the first step is the acid coupling of 3,3
-diami-
Red 81, 28160 (106) [2610-11-9], is obtained. nobenzanilide to H acid, followed by alka-
This dye represents an important red grade. line coupling of aniline to the monoazo dye
and finally coupling of the disazo dye to m-
phenylenediamine.

C. I. Direct Black 51, 27720 (107)

[3442-21-5], is produced by coupling a mix-
ture of diazotized 3- and 5-aminosalicylic acid
to 1-naphthylamine and subsequent alkaline
coupling to γ acid. C. I. Direct Black 150, 32010 (110)
[6897-38-7], is produced by double (alka-
line) coupling of bisdiazotized 4,4
-diaminodi-
phenylamine-2-sulfonic acid to γ acid and sub-
sequent single coupling to m-phenylenediamine.

4.1.3. Trisazo Dyes

The trisazo dyes include in particular blue,

green, and black grades. Benzidine, which here,
too, used to be an important bisdiazo compo- Among the trisazo dyes, the synthesis prin-
nent, has been replaced by other diamines, such ciple of series coupling of the type D → M1
44 Azo Dyes

→ M2 → K is also of importance. This group 2000 kg of ice. The diazotizing solution is added
contains a number of dyes with good to very at 0 – 12 ◦ C over the course of 1/2 h. After a fur-
good general fastness properties. ther hour, 375 kg of sodium hydrogen carbonate
Anilinesulfonic acids are chiefly used as is added and after 1 h has expired, the mixture
starting component D, naphthylamine and Cleve is heated to 60 ◦ C by indirect steam. Following
acids as middle components M1 and M2 , and I the addition of 8 % rock salt, the temperature is
acid, its N-phenyl derivatives, H acid, γ acid, maintained at 60 ◦ C for a further hour, and the
and their derivatives as final component K. This dye is filtered and dried at 110 ◦ C (drum drier
type mainly possesses blue and green shades. or circulating air cabinet). Then yield is approx.
Example: C. I. Direct Blue 78, 34200 (111) 360 kg.
[2503-73-3]. Other possible combinations are only of mi-
nor importance compared with the trisazo dyes
manufactured according to the synthesis princi-
ples mentioned.

4.1.4. Tetrakisazo Dyes

2-aminobenzene-1,4-disulfonic acid → Cleve acid-7 → Numerous syntheses are possible for these dyes,
1-naphthylamine → N-phenyl I acid which all yield only dark shades. Here, too, only
a few types are of industrial importance.
In the manufacture of trisazo dyes, good yield A further extension to the trisazo dyes on the
and purity during final coupling are often ob- principle of series coupling D → M1 → M2 →
tained only in the presence of pyridine or other M3 → K offers no advantages, because the in-
bases as coupling accelerators [35]. Intermedi- termediate isolation that is frequently necessary
ate isolation and separation of impurities prior leads to yield losses and a chain extension is
to continuation of coupling are also frequently therefore ruled out on economic grounds. This
necessary. is also reflected in the number of polyazo dyes
The use of pyridine during final coupling given in the Colour Index [7, vol. 4, p. 4325]. Al-
(pyridine coupling) is illustrated in the following though 78 tetrakisazo dyes with eleven different
abridged manufacturing specification for C. I. synthesis principles are listed, only 14 dyes with
Direct Green 33, 34270: five and more azo groups are mentioned, two of
which are specified with eight azo groups (see
2-aminonaphthalene-8-sulfonic acid → 3,5-xylidine → top of next page).
2-ethoxy Cleve acid-6 → N-acetyl H acid An example of type D → M1 → M2 → M3
→ K is C. I. Direct Dye, 35850 [8002-98-0]
(brown).
Final Diazotization: The disazo dye produced by
the usual method aminocroceic acid → sym. m- sulfanilic acid → m-toluidine → Cleve acid-6 →
xylidene → 2-ethoxy-Cleve acid-6 (batch size: m-toluidine → 1-nitrophenylene-2,4-diamine
81 kg aminocroceic acid 100 %) is stirred in the
form of a press cake in 600 L of water with 500 L A number of important direct dyes are derived
of 50 % acetic acid. Then 26.5 kg of sodium ni- from type K1 ← M1 ← D → M1 → K 1 : C. I. Di-
trite in the form of a 30 % solution is added at rect Black 22, 35435, (112) [6473-13-8] is pro-
25 ◦ C. After stirring overnight, a reddish-brown duced via the primary disazo dye from 4,4
-
solution is obtained. Final coupling: To 104 kg diaminodiphenylamine-2-sulfonic acid and two
of H acid 100 %, dissolved in 500 L of water, equivalents of γ acid. This dye is bisdiazo-
are added 32 L of 40 % sodium hydroxide so- tized and coupled to two equivalents of m-
lution and 17 kg of soda; the mixture is heated phenylenediamine.
to 70 ◦ C and 50 kg of acetic acid anhydride is
added. After acetylation is completed, the mix-
ture is transferred to 1500 L of pure pyridine and
 Azo Dyes 45

produces a number of highly fast substan-

tive dyes with industrial importance, espe-
cially in the shades orange, scarlet, and brown
[36]. Example: C. I. Direct Orange 39, 40215
[1325-54-8], is obtained by condensation of
4-aminoazobenzene-4
-sulfonic acid with dini-
Another example is C. I. Direct Black 151, trostilbenedisulfonic acid in aqueous sodium hy-
35436 (113) droxide solution. The main product formed is the
tetrakisazo dye of the stilbene-2,2
-disulfonic
acid (115), as well as the corresponding azoxy
compounds. No uniform product is obtained,
since part of the aminoazo compound is con-
Here, too, the disazo dye is initially prepared sumed as reducing agent. Condensation dyes
from bisdiazotized 4,4
-diaminodiphenylamine- are often purified by aftertreatment with reduc-
2-sulfonic acid with 2 equivalents of γ acid. Cou- ing agents or such as glucose or sodium sulfide.
pling is then again carried out stepwise to γ acid Abridged specification: 468 kg of 100 % 4,4
-
and finally to m-phenylenediamine. dinitrostilbene-2,2
-disulfonic acid as sodium
C. I. Direct Black 19, 35255 (114) salt is stirred with 1000 L of water and adjusted
[6428-31-5], is also an important dye. It is to a weakly alkaline pH value with sodium hy-
obtained by coupling two equivalents of p- droxide solution. Then 440 L of 30 % sodium hy-
nitraniline to H acid, sulfhydrate reduction of droxide solution is added and 346 kg of 100 % 4-
the two nitro groups, and coupling of the bis- aminazobenzene-4
-sulfonic acid introduced as
diazotized intermediate compound with two sodium salt. After the contents of the tank have
equivalents of m-phenylenediamine (see top of been diluted to 4500 L, the temperature is raised
page 45). and maintained for 14 h at 100 ◦ C. The conden-
sation product is transferred into 10000 L of wa-
ter and 39 kg of sodium sulfide is then added.
4.1.5. Condensation Dyes The temperature is raised to 85 ◦ C and main-
tained there for 1/2 h; then salting-out carried
These dyes are produced by condensation of ni- out with 12 % rock salt, calculated on the total
tro compounds (see also Section 2.2.1). volume. Isolation is carried out at 70 ◦ C using
Alkaline condensation of dinitrostil- a filter press. The dye is given a final washing
benedisulfonic acid with aminoazo compounds
46 Azo Dyes

with 9000 L of a 10 % rock salt solution heated

to 50 ◦ C. The yield is approx. 780 kg dry.
Table 10 shows further examples of conden-
sation dyes obtained from the corresponding
aminoazo compounds and 4,4
-dinitrostilbene-
2,2
-disulfonic acid.
By mixing two different aminoazo com-
pounds A–NH2 and B–NH2 and subsequent
4.1.6. Direct Dyes with a Urea Bridge phosgene treatment, the asymmetrical dipheny-
lurea direct dye 118 is obtained in addition to
By the end of the 19th century, BASF had dis- the two symmetrical members.
covered that the reaction of aminoazo dyes with
phosgene in an aqueous solution in the presence
of soda resulted in valuable symmetrical urea
azo dyes [37]:
There are a number of yellow substan-
tive dyes synthesized by this principle. Ex-
ample: C. I. Direct Yellow 41, 29005 (119)
[8005-53-6], is obtained by phosgene treat-
ment of an equimolar mixture of bases
A (sulfanilic acid → cresidine) and B (p-
The urea bridge can also be introduced nitroaniline → salicylic acid and reduction of the
into direct dyes with 4,4
-diaminodiphenylurea NO2 group). The mixture additionally contains
derivatives by means of bisdiazotization and the two corresponding symmetrical dyes.
coupling (see (98) in page 40). C. I. Direct Yel-
low 50, 29025 (116) [3214-47-9]

4.1.7. Triazinyl Dyes

is obtained, for example, by phosgene treat-
ment of two equivalents of aminoazo dye pre- The principle of linking two or three azo dyes
pared from diazotized 2-aminonaphthalene-4,8- by means of a triazine ring was established by
disulfonic acid coupled to m-toluidine. Ciba patents [38]. The triazine bridge increases
Other examples of symmetrical direct dyes the substantivity of the dyes, in a similar man-
with a urea bridge are shown in Table 11. ner to the −NH−CO−NH− group. Production
Aminodisazo and aminotrisazo dyes can also is based on cyanuric chloride, the three chlo-
be treated with phosgene, largely red and brown rine atoms of which can be replaced in stages by
shades being obtained. nucleophilic radicals under different conditions
Example: C. I. Direct Red 80, 35780 (see Section 2.3.2).
[2610-10-8], is rendered accessible by phosgene The procedure that can be adopted is for in-
treatment of the aminodisazo dye 117: termediate products with amino groups (e.g., H
 Azo Dyes 47
Table 10. Examples of condensation dyes made from aminoazo compounds and 4,4
-dinitrostilbene-2,2
-disulfonic acid

Table 11. Aminoazo compounds for symmetrical direct dyes with a urea bridge

acid) to be condensed with cyanuric chloride and

the reaction product subsequently attached to the
diazo component, or aminoazo dyes are reacted
directly with cyanuric chloride. In the relevant
commercial azo dyes, the third chlorine atom
in the cyanuric chloride is usually reacted with
aniline or ammonia and less frequently left un-
changed.
Of interest, here, are dyes that yield green
shades through combination of a blue and yel-
low component.
Example: C. I. Direct Green 26, 34045 (120)
[6388-26-7]. The blue component (H acid → cresidine → H
acid) is linked with the triazine ring by means
of the amino group of the H acid; after reduc-
tion of the nitro group, the yellow component
(p-nitroaniline → salicylic acid) replaces the
second chlorine atom of cyanuric chloride and
aniline the third chlorine atom. The dye consti-
48 Azo Dyes

tutes a very pure, clear, bluish green with very fast blue grades, such as C. I. Direct Blue 98,
good fastness properties. 23155 [6656-03-7], a copper complex of 121;

4.1.8. Copper Complexes of Substantive Azo

Dyes

Under certain structural conditions, azo dyes are

capable of forming metal complexes (see Sec- and C. I. Direct Blue 84, 23610 [13569-92-1], a
tion 2.3.4). A process for the complexing of o,o
- copper complex of 122.
dihydroxyazo dyes with copper by reaction of
these dyes with copper sulfate in a weakly acid
solution was described for the first time in 1915
[39].
The introduction of copper into conven-
tional substantive dyes often increases their
light and wetfastness considerably, since com-
The following additional examples of sub-
plexing blocks the hydrophilic groups. Copper
stantive copper complex dyes can be mentioned:
complexes of o,o
-disubstituted azo dyes are
C. I. Direct Violet 47, 25410 [13011-70-6], a
chiefly of interest for direct dyes. Substituents
copper complex of 123;
especially capable of complexing are hydroxyl,
methoxy, carboxy, and carbomethoxy groups.
BASF developed the oxidative copper treatment
process in which on the basis of o-hydroxyazo
dyes, copper complexes of the corresponding
o,o
-dihydroxyazo dyes are obtained [40].
The possibility of first converting suitable azo
compounds into copper complexes, and subse- and C. I. Direct Green 23, 31985, a copper com-
quently using them as coupling components for plex of 124.
the synthesis of azo direct dyes, was also de-
scribed.
As in the case of the metal-free direct dyes,
a large diversity of structures is encountered;
here, too, there are direct dyes with pyrazolones,
substituted 4,4
-diphenylamines, or the 1,3,5-
triazine ring, urea and stilbene derivatives, and
condensation dyes.
For each dye it is necessary to establish the 4.2. Direct Dyes with Aftertreatment
most favorable conditions under which copper-
containing products with improved properties For supplementary literature see [41] and [42,
are obtained. Because none of the known com- vol. 2, p. 46]
plexing processes provides optimum results in In spite of the reactive dyes with their out-
all instances, the production of certain dyes or standing wetfastness, the direct dyes continue
complexing variations is protected by a large to hold a large share of the market for inexpen-
number of patents. sive cellulose and paper dyes. Apart from the
Especially for ecological reasons, however, new developments to replace the old established
the importance of copper complex dyes is de- benzidine dyes, considerable efforts are being
creasing. This applies in particular to the copper made to improve the fastness properties of direct
aftertreatment. dyes by aftertreatment. The various aftertreat-
A demethylating copper treatment of dyes ment methods are described below in the order
synthesized with o-dianisidine results in light- of their present importance.
 Azo Dyes 49

4.2.1. Aftertreatment with Cationic use of circulating liquor dyeing machines, be-
Auxiliaries cause even with addition of aftertreatment agent
in portions (e.g., in the case of wound pack-
Aftertreatment of substantive dyeings with or- ages) no completely uniform aftertreatment can
ganic, cationic substances has lately begun to be guaranteed.
gain increasingly in importance. Improvements The action of quaternary ammonium com-
are obtained in particular in wetfastness proper- pounds on the dyed fiber in many cases produces
ties, especially fastness to water, washing, and a change of shade.
wet pressing, as well as fastness to perspiration A further disadvantage is the possible elim-
and cross-dyeing. ination of aliphatic amines, e.g., in an alkaline
The cationic compounds precipitate the (an- medium in the presence of anionic substances or
ionic) dyes from their aqueous solutions and on at excessive drying temperatures. This can cause
the fiber form higher molecular mass, scarcely an unpleasant (fishy) odor to arise. In such cases,
soluble, saltlike compounds with the dyes. Re- an acid aftertreatment is necessary.
moval of the latter from the fiber is thus made
more difficult. A number of companies have Cationic Formaldehyde Condensation
compiled their own ranges of this type of af- Resins. An appreciable improvement in wet-
tertreatment agent. fastness properties is obtained by aftertreating
Cationic textile auxiliaries can be divided into the dyeings with polymeric condensation resins
two groups: quaternary ammonium compounds containing strongly basic groups. This leads to
and cationic formaldehyde condensation resins. the formation of insoluble salts from resin cation
and dye anion.
Quaternary Ammonium Compounds. The most important resins of this type are ob-
These contain aliphatic and/or cycloaliphatic tained from dicyanodiamide (125) by condensa-
radicals (R1 to R4 in Eq. 12), of which at least tion with formaldehyde and hydrochloric acid:
one represents a long-chain alkyl radical (with
more than five C atoms). The compounds react
with the dyes in accordance with the following
pattern:

Suitable blending of ammonium salts of

fairly strongly basic amines (e.g., melamine
or guanidine) and acid condensation with
formaldehyde enables favorable conditions to
be obtained with regard to solubility and cross-
Use is made, for example, of cetyldi- linking of the cationic condensation resins.
methylbenzylammonium chloride and pyri- The water-soluble resins are inexpensive,
dinium compounds of the type and compared with quaternary ammonium com-
pounds relatively small quantities often suffice
to achieve a marked improvement in wet fastness
and fastness to perspiration. A disadvantage is
a certain influence on light fastness. This may
be lowered by one to two steps on the eight-
In addition, the quaternary ammonium com- step blue scale, when these resins are used on
pounds mostly possess strong affinity for the materials dyed by substantive dyes. Formalde-
cellulosic fiber, whereby the insoluble reaction hyde condensation resins are therefore used es-
product is anchored even more firmly with the pecially for articles in which wet fastness and
dye on the fiber. This high affinity can, however, fastness to perspiration are important, but light
also result in nonuniform improvements in fast- fastness is less crucial, e.g., lining fabrics.
ness properties. This behavior also prevents the
50 Azo Dyes

4.2.2. Aftertreatment with Formaldehyde Diazotization dyes now enjoy only minor im-
portance.
The wetfastness properties of substantive azo Example: C. I. Direct Red 145, 17805 (126)
dyes containing free amino or hydroxyl groups [6771-94-4], yields a clear yellowish red when
as terminal groups (final component of coupling, developed with β-naphthol.
e.g., resorcinol or m-phenylenediamine) can be
improved by aftertreating the dyed fiber material
with aqueous formaldehyde solution. The con-
ditions for the presence of free amino groups
can also be satisfied by subsequent reduction of
nitro groups or hydrolysis of acylamino groups.
During reaction with formaldehyde, methylene
bridges are formed between two dye molecules;
i.e., an enlargement of the molecule occurs and 4.2.4. Aftertreatment with Metal Salts
hence an improvement in wetfastness, whereas
light fastness is not influenced. This method is dealt with briefly, mainly on his-
Because of a lack of storage stability in dye- torical grounds, because for reasons connected
ings treated by this method, the formaldehyde with wastewater pollution and because of cer-
aftertreatment is mainly confined to dark shades tain performance drawbacks it is hardly used any
(brown and black). longer.
The first patent on this aftertreatment method Metal complexing (see Section 4.1.8) cannot
was granted to Geigy as early as 1899 [43]. Al- be carried out until after the fiber has been dyed.
though the basic, simple process has remained This aftertreatment, mainly with copper salts
virtually unchanged, its importance has lately (sulfate, acetate), takes place under mild condi-
declined sharply for ecological reasons. tions, so that, for example, no metal complexing
with an o-methoxyazo group occurs. Suitable
complexing systems, on the other hand, are o,o
-
4.2.3. Diazotization Dyes dihydroxy-, o-hydroxy-o
-carboxy-, o-hydroxy-
o
-carbomethoxy-, and o-carboxy-o
-aminoazo
Direct dyes containing one or more diazotizable groups.
amino groups in the dye molecule permit fur- 4,4
-Diaminodiphenyl-3,3
-dicarboxylic
ther diazotization on the fiber and subsequent acid (127), 4,4
-diaminodiphenyl-3,3
-
coupling with a “developer.” β-Naphthol can bisoxyacetic acid (128), and 4,4
-diami-
be used as a developer for orange, red, brown, nodiphenylurea-3,3
-dicarboxylic acid (129)
blue, and black shades, 1,3-phenylenediamine have proved successful as diamino components
and 2,4-diaminotoluene for brown, gray, and for the synthesis of disazo copper-aftertreated
black shades. dyes.
The shade of the dye applied to the mate-
rial usually changes considerably as a result of
this aftertreatment. wetfastness and fastness to
perspiration are greatly improved, light fastness
remains unchanged. The amino group needed
for diazotization is introduced by final coupling
with an amine, an aminonaphtholsulfonic acid,
or an amino-acylaminonaphtholsulfonic acid or
by reduction of a nitro or hydrolysis of an
acylamino group. “Development” results in en-
largement of the dye molecule without further
solubilizing groups being added.
The time-consuming process necessitates
careful handling. Exposure to sunlight or par-
tial drying of the diazotized dyeing should thus
be avoided.
 Azo Dyes 51

Metal complexing results in blocking of sol-

ubilizing groups; aggregation increases, the dye
becomes less soluble, and an improvement in
wet fastness occurs. Although the light fastness
is generally also improved by this aftertreatment,
fastness of the dyeings to perspiration is fre-
quently reduced. The shades generally become
duller and flatter. Catalytic action of traces of
heavy-metal ions that are present can cause fiber
tendering to occur in the presence of detergents
containing oxidizing agents (peroxides). 132At an intermediate position, compound 133
An example of a direct dye suitable for cop- has its positive charge much less delocalized be-
per aftertreatment is C. I. Direct Blue 167, 24560 cause of the high energy of the quinoid reso-
(130), see top of the page. nance extreme 133b.

5. Cationic Azo Dyes

Cationic azo dyes carry a positive charge in
the colored portion of the molecule. The salt-
forming counterion is, in most cases, the col-
orless anion of a low molecular mass inorganic
or organic acid. The positive charge is gener-
ally carried by nitrogen, but there are also dyes
in which this function is taken on by sulfur or
phosphorus (see Section 5.5).
The positive charge may be either localized Finally, in compound 134 the structure does
at an ammonium group (see, e.g., 131) not permit a charge delocalization from the ben-
zimidazolium ion to the back ring azo dye sub-
stituent.

131
134
or delocalized across the dye cation. The transi-
tion between the two dye classes is continuous. Both 133 and 134 confer a similar orange-
At one extreme, this leads to the dark blue com- red color to polyacrylonitrile and are classified
pound 132, which is no longer considered an as cationic azo dyes.
azo dye but classified as a diazacyanine dye
(→ Methine Dyes and Pigments). History. Basic dyes of the azo class are
among the earliest known synthetic dyes. They
were used originally for dyeing cotton mor-
danted with tannin and potassium antimonyl tar-
52 Azo Dyes

trate and wool from neutral solution. They con- 2,6-toluylenediamine, or mixtures of these di-
tinue to occupy a place of minor importance for amines. These dyes confer muted yellow to or-
dyeing leather, paper, plastics, and waxes, and ange shades to paper, leather, and polyacryloni-
as constituents of graphic arts colors. trile fibers. When they are mixed with malachite
The preparation of the first cationic azo green and fuchsin, medium-fast black shades
dye, Vesuvin, was described by C. Martius are obtained on polyacrylonitriles. A mixture of
in 1863. It is obtained by coupling diazo- chrysoidine with Crystal Violet or Victoria Pure
tized m-phenylenediamine to an excess of Blue is used to adjust the color of nigrosine hec-
the same amine. An analogous dye from tograph inks [44].
toluylenediamine was reported by P. Gries in Examples are C. I. Basic Orange 1, 11320
1878. Chrysoidines, coupling products of ani- (135) [4438-16-8] the azo dye from diazotized
line or toluidines to m-phenylenediamine or aniline and 2,4-diaminotoluene,
toluylenediamine, were reported by H. Caro
in 1875 and O. N. Witt in 1876. These
were followed in 1886 by cationic safra-
nine azo dyes, obtained by coupling dia-
zotized diethylphenosafranine to phenols or
aromatic amines (→ Azine Dyes), and by 135
dyes produced by coupling diazotized ami-
nophenyltrimethylammonium chloride to phe- and C. I. Basic Orange 2, 11270 (136)
nols and aromatic amines. Both groups formed [532-82-1] the dye from aniline and m-
the basis of the Janus dye product line, which phenylenediamine.
gained great importance for a time in dyeing
weighted silk.
When polyacrylonitrile fibers appeared on
the market, an intense research effort in the area
of cationic azo dyes was stimulated worldwide 136
at all the leading dye plants. These materials now The dye Astrachrysoidine RR is a mixture of
occupy a place of importance in all significant several compounds.
product lines. A mixture of 13 g aniline, 12.5 g o-toluidine,
Azo dyes with several cationic charges, and 3.0 g p-toluidine is diazotized in aqueous hy-
which are substantive dyes for cellulose, are in- drochloric acid solution at 0 ◦ C using 66.5 mL
creasingly being used for coloring bleached sul- of a 30 g/100 mL sodium nitrite solution. Excess
fite cellulose. nitrite is destroyed prior to coupling using sul-
The cationic charge may be introduced into famic acid. The diazotized solution is added in
the dye molecule via either the diazo component a thin stream and at 0 ◦ C to a solution of 16.5 g
or the coupling component. of m-phenylenediamine and 18.5 g of 2,4-diami-
notoluene in 1000 mL of water. The coupling so-
lution is then adjusted to pH 3 – 3.5 by addition
5.1. Cationic Charge at the Coupling of dilute aqueous sodium acetate. After com-
Component pleted coupling, the pH of the reaction mixture
Amino groups, amidine residues, trialkylammo- is adjusted with hydrochloric acid using congo
nium, or cyclic ammonium groups may serve as red indicator. The precipitated dye is collected
carriers of the cationic charge in the coupling by filtration and dried to yield 75 g of a dark
components. orange powder.
Chrysoidine dye salts of dodecylbenzenesul-
fonic acid are soluble in glycols and glycol ethers
5.1.1. Polyamines as Coupling Components and are used in the production of inks, printing
inks, and varnishes [45].
Chrysoidines are obtained by coupling di-
azonium salts of aniline, toluidines, or mix-
tures thereof to 1,3-phenylenediamine, 2,4- or
 Azo Dyes 53

Mono- and disazodyes from diazotized ani- ered to 8 – 10 ◦ C and, at this temperature, 47 g
lines and 2,4,6-triaminotoluene dye wool and sodium nitrite is added in portions over a period
cotton [46]. of 1.5 h. After addition is completed, the mixture
Vesuvin and Bismarck Brown products are is stirred for 1/2 h, 10 g m-phenylenediamine is
obtained when m-phenylenediamine, 2,4- and added, and stirring is continued for another 3 h
2,6-diaminotoluene, or mixtures thereof are at 8 – 13 ◦ C. Finally, the reaction is warmed to
treated with nitrite in acidic solution, or when 35 – 40 ◦ C for 1 h followed by chilling of the dye
a mixture of the amines and nitrite is acidi- solution.
fied. The final products consist of mixtures of Vesuvines are used chiefly for dyeing paper
monoazo, disazo, and polyazo dyes, with the dis- containing wood pulp.
azo species probably predominating in commer-
cial products. In the presence of sodium chlo-
ride, the dye is salted out immediately after its 5.1.2. Heterocycles as Coupling Components
formation and thereby the formation of polyazo
dyes is prevented. If heterocyclic polyamines, e.g., 2,4-diamino-6-
Astravesuvin R (137), C. I. Basic Brown 4, hydroxypyrimidine, are used as coupling com-
21010, serves as an example: ponents with aromatic diazonium compounds,
dyes are obtained that color polyacrylonitrile in
lightfast yellow shades and that are character-
ized by excellent leveling properties [52]. An
example is 138 [6979-64-2].

137
138
A mixture of 2,4- and 2,6-diaminotoluene
(28.5 g, molar ratio 2 : 3) and 25 g of m-
phenylenediamine is dissolved in 1200 mL wa- Coupling Components with Amidine Moi-
ter at room temperature and mixed with 67 mL of eties. Well-leveling azo dyes are also obtained
30 g/100 mL aqueous sodium nitrite. After ad- when pyrazolones substituted in the 1-position
dition of 450 g of sodium chloride and 800 g by an amidine residue are used as coupling
of ice, which results in a temperature of − 10 components. The diazo components are pre-
to − 12 ◦ C, 86 mL of concentrated hydrochloric dominantly substituted by methyl and methoxy
acid is added rapidly. Finally, the pH is adjusted groups [53]. An example is 139 [68936-08-3].
to 3 – 3.5 by the addition of dilute sodium ac-
etate solution. After several hours, the coupling
solution is adjusted to pH 1 and the precipitated
dye is collected by vacuum filtration and dried
to yield 90 g of a yellow-brown powder.
Liquid Vesuvin dye solutions may be ob-
tained by diazotization and coupling of aromatic 139
diamines [47–49] or, if desired, also in mixture
with aromatic monoamines [50] in carboxylic By reaction of these dyes with formaldehyde
acid solutions. The dye mixtures can be alky- and acetone, condensation products suitable for
lated with alkylene oxides [51]. wetfast dyeing of cotton are obtained [54].
m-Phenylenediamine (105 g) is added to a
mixture of 360 g glacial acetic acid, 80 g water,
and 60 g ethylene glycol followed by stirring and
warming to dissolve. The temperature is low-
54 Azo Dyes

5.1.3. Coupling Components with Copper complexes of these materials or of the

Alkylammonium Groups analogous γ acid (1-hydroxy-7-aminonaphtha-
lene-3-sulfonic acid) dyes confer gray-violet
Numerous cationic azo dyes contain a [56] or blue hues [57], [58] to paper, respectively,
dialkylaminoalkyl or a trialkylammonium group or dye particles of glass in navy blue tones [59].
as the charge carrier in the coupling component. A commercial product of this series is Cartasol
Red K-2B (Clariant).
5.1.3.1. Coupling Components with These kinds of triazine moieties may also be
Dialkylaminoalkyl Groups part of pyrazolone and pyridone coupling com-
Dyes bearing one or more dialkylaminoalkyl ponents [60], [61].
substituents have found favor for coloring paper The dialkylaminoalkyl residue may also be
because they behave as substantive dyes which, connected directly to the phenyl residue of the
when properly substituted, result in a practically acetoacetanilide. By coupling with diazotized
colorless waste liquor. A suitable starting mate- 2-(4-aminophenyl)benzimidazole, a yellow dye
rial for the preparation of such dyes is the reac- suitable for paper is formed [62].
tion product of 2 mol dialkylaminopropylamine The dialkylaminoalkyl group may be con-
with 1 mol cyanuric chloride. This may be con- nected to the N-1 atom of 3-methylpyrazolone
verted to an acetoacetarylide, which, [63], to the amide nitrogen atom of N-
phenylpyrazolone-3-carbonamide [64], to the
N-2 atom of 3-cyano-2,4,6-trisaminopyridine
[65], or to the amino group of 2-amino-4,6-
dihydroxypyridine [66].
3- or 6-hydroxy-2-naphthoic acid amides
bearing dialkylaminoalkyl residues on the ni-
trogen atom lead to orange dyes for poly-
acrylonitrile or paper when coupled with di-
azotized aniline [67], [68], or to red dyes,
soluble in glycol ethers and useful for
ink-jet printing, when coupled with diazo-
tized 3-amino-4-methoxybenzenesulfonic acid-
140 N,N-diethylamide [69], or to substantive red
dyes when the diazo component is a 2-(4
-
when coupled with diazotized 2-(4
-ami-
aminophenyl)benzotriazole [70]. Dialkylami-
nophenyl)-5-methylbenzothiazole, yields the
noalkyl amides of J acid have been used to pre-
yellow dye 140 [91458-38-7] with greenish cast
pare red dyes for polymeric materials, especially
suitable for coloring paper [55].
paper, with 4-acetylaminoaniline as diazo com-
By reaction of a similar triazine component
ponent [71], [72].
with J acid (1-hydroxy-6-aminonaphthalene-3-
sulfonic acid), followed by coupling with dia-
zotized 4-aminoazobenzene, the cationic sub-
5.1.3.2. Aromatically Linked
stantive azo dye 141 [71032-95-6] is obtained,
Trialkylammonium Groups
which colors paper in red hues.
Exhaustive alkylation of aminonaphthols, such
as 2-amino-7-naphthol, and coupling with dia-
zotized aromatic amines generates yellow, or-
ange, red, and brown cationic azo dyes [73],
[74]. Compound 142 dyes human hair and poly-
acrylonitrile in brown shades [75].

141
 Azo Dyes 55

5.1.3.3. Trialkylammoniumalkyl-
Substituted
Anilines

Dialkylanilines that carry a cationic substituent

at one of the alkyl groups are among the most
important coupling components of cationic azo
dyes.
142
By reaction of N-ethyl-N-(2-chloro-
Exhaustively alkylated 4-aminodiphenyl- ethyl)aniline or of N-ethyl-N-(2-chloroethyl)-
amine is also suitable as a coupling component. m-toluidine with trimethylamine, ammonium
Dyes (e.g., 143) [41025-69-8] obtained by re- salts are obtained that, upon coupling with dia-
action with diazotized nitroanilines confer fast zotized aromatic amines, yield a large number
yellow, orange, and red shades to polyacryloni- of valuable dyes for coloring polyacrylonitrile.
trile [76]. C. I. Basic Red 18, 11 085 (146) [25198-22-5]
is derived from the diazo component 2-chloro-
4-nitroaniline [80].

143
146
By exhaustive alkylation of 3-ami- It is a component of all major product lines
nophenylpyrazolone compounds, a trimethy- used for dyeing polyacrylonitrile.
lammonium moiety may be introduced into Commercial products are Astrazon Red GTL
this coupling component. The disazo dye 144 (DyStar), Diacryl Red GTL-N (Mitsubishi),
[86565-98-2] colors paper in orange shades [78] Sumiacryl Red F-GTL (Sumitomo), and Ta-
(see bottom of page). iacryl Red GTL (T&T Ind.).
The trialkylammoniumphenyl group may The corresponding dye from 2,6-dichloro-4-
also be part of acetoacetic acid arylides [77] or nitroaniline as the diazo component is also of
be connected to the coupling component via an commercial importance.
ether link (see 145) [84041-74-7] [79]. Other suitable diazo components are
4-nitroaniline (orange), 2,6-dichloro-4-
nitroaniline (yellow-brown) [81], 2-cyano-
4-nitroaniline (red) [82], 2,6-dichloro-4-
(N,N-dimethylsulfamoyl)aniline (orange),
4-aminobenzophenone (yellow), 2,4,6-
trichloroaniline (yellow), 2,4,6-tribromoaniline

145

144
56 Azo Dyes

(yellow), 2,6-dibromo-4-nitroaniline (yellow nization to the trialkylammonium residue may

brown) [83], and 2-cyano-5-chloroaniline (or- also be carried out using dialkyl phosphites or
ange). phosphonates [95].
Heterocyclic diazo components include 2- With aromatic diamines as the diazo compo-
aminothiazole substituted with ester groups nents, such as 4,4
-diaminodiphenylsulfone, ba-
[84], and the coupling product of diazotized sic disazo dyes are obtained which are suitable
4-nitroaniline with 2-amino-3-cyanothiophene for dyeing acid-modified polyamide materials
[85]. An especially favored starting material is 3- [96].
phenyl-5-amino-1,2,4-thiadiazole, which is also The diamine of dye 144 leads to cationic dis-
used in the production of disperse dyes. It yields azo dyes that color paper in brilliant orange hues
very bright dyes for coloring polyacrylonitrile [97].
[80]. An example is 147 [85283-77-8].

5.1.3.4. Other
Trialkylammoniumalkyl-Substituted
Coupling Components

The coupling component 2,6-dihydroxypyridine,

147 already an acknowledged component of high-
intensity chromophores in disperse dyes, has
A commercial product is Astrazon Red BBL
also been applied successfully to the synthesis of
(DyStar).
cationic azo dyes. The trialkylammoniumalkyl
By coupling aminobenzothiazoles to the qua-
group may be linked either to the pyridine ni-
ternary ammonium bases red cationic dyes (e.g.,
trogen [98] (149) [71873-54-6] or to C-3 of the
148) are obtained [86].
pyridine ring [99] (150).

148

This is to be contrasted with the blue di-

azacyanines, which derive from the quaternized
benzothiazole residue.
Dye affinity to polyacrylonitrile and, thereby, 149
the dyeing rate may be enhanced by introducing
an aralkyl residue [87] or an aryloxyalkyl residue
[88] in place of an alkyl group at the trialkylam-
monium group.
The solubility of these dyes is signifi-
cantly enhanced by introduction of alkenyl [89],
hydroxypropyl [90], or polyetheralkyl [91] moi-
eties into the trialkylammonium group. The tri- 150
alkylammonium group may also be a component Dyes with cationically substituted deriva-
of a heterocyclic ring [92]. When the trialkylam- tives of 2-hydroxy-6-aminopyridine [100], of
monium residue contains an alkyl chain of more 2,6-diaminopyridine [101], and of 5-hydroxy-
than 11 carbon atoms, the dyes become solu- 3-methyl-1-phenylpyrazolone [102] as the
ble in aliphatic and alicyclic hydrocarbons and coupling components have also been de-
can be used for the production of printing inks scribed. Coupling components based on 4-
[93]. Also C. I. Basic Black 8 is recommended hydroxynaphthalimide, which carry the trialky-
as a dye for ink-jet printing [94]. The quater- lammoniumalkyl substituent at the imide nitro-
 Azo Dyes 57

gen, have been used for the synthesis of red Red dyes are obtained with 3-phenyl-5-ami-
cationic azo dyes [103]. no-1,2,4-thiadiazole as the diazo component
Aromatic coupling components may have the [118].
trialkylammoniumalkyl linked via a carboxam-
ide group [104], e.g., 151.
5.1.5. Coupling Components with Cyclic
Ammonium Groups

By reaction of heteroaromatics, such as pyridine,

with intermediates that contain anionically dis-
placeable groups, coupling components are ob-
tained that derive their positive charge from a
151 cyclic ammonium group. Alternately, the hete-
Also described as linking groups are ether rocycle may be linked to the coupling compo-
[105], thioether [106], carbonyl [107], car- nent by other means for later quaternization.
boxylic ester [108], carbonamide [109–112] and
sulfonamide [113] moieties.
Monofluortriazine reactive dyes, in which 5.1.5.1. Heterocyclically Linked Cyclic
a trialkylammoniumalkyl group is bound to Ammonium Groups
the heterocycle by an amino group are rec-
ommended for blends of polyacrylonitrile with Reaction of chloroacetamide with pyridine, fol-
wool, synthetic polyamides or cellulosics [114– lowed by condensation with acetoacetic esters
116]. in alcoholic sodium hydroxide, leads to a 2,6-
dihydroxy-4-methylpyridine that is substituted
in the 3-position by a pyridinium moiety. If this is
5.1.4. Coupling Components with coupled with diazotized aromatic or heterocyclic
Dialkylhydrazinium Groups amines, yellow to red cationic azo dyes (e.g.,
153) [92691-25-3] are obtained [119], [120].
A number of valuable cationic azo dyes con-
tain the dialkylhydrazinium group as the charged
moiety of the coupling component. The aromatic
amines used as the diazo components are the
same as those described for the dyes mentioned
in Section 5.1.3.3. The red dye 152 [4531-45-7]
is formed with 2-chloro-4-nitroaniline:
153

With aromatic diamines and triamines as the

diazo components, cationic substantive disazo
and trisazo dyes (e.g., 154) [62073-65-8] are ob-
tained, which are suitable for bulk dyeing of pa-
152 per [121], [122], [123] or ink-jet printing [124].
A yellow dye is obtained with 1-amino-2,6- A commercial product is Cartasol Yellow K-
dichloro-4-(N,N-dimethylsulfamoyl)benzene, GL (Clariant).
an orange dye with 1-amino-2,5-dichloro-4- Also known are 2,6-dihydroxypyridine dyes
(N,N-dimethylsulfamoyl)benzene, a yellow that carry a quaternized benzothiazole [125],
brown dye with 1-amino-2,6-dichloro-4-nitro- benzimidazole [126], or imidazole [127], [128]
benzene, a ruby dye with 1-amino-2-cyano-4- moiety in the 3- or 4-position.
nitrobenzene, and a violet species with 1-ami-
no-2,4-dinitro-6-bromobenzene [117].
58 Azo Dyes

154

5.1.5.2. Aliphatically Linked Cyclic nitro-7-bromobenzisothiazole (blue with a red

Ammonium Groups cast) [137], and 2-amino-4-chloro-3-cyano-5-
formylthiophne (blue) [138].
By reaction of N-ethyl-N-chloroethylaniline, The solubility of these dyes is enhanced when
N,N-bis(chloroethyl)aniline, or N-ethyl-N- picolines are used for quaternization in place of
chloroethyl-m-toluidine with heteroaromatics, pyridine [139].
especially pyridine, coupling components are Concentrated aqueous solutions of these dyes
obtained that carry cyclic ammonium groups. are obtained by dissolving the bicarbonate salts
of the dyes in aqueous organic acids, e.g., acetic
acid [140].
If monoalkylanilines are reacted with vinyl-
heterocycles, especially vinylpyridine, and if the
heterocyclic nitrogen is then quaternized, cou-
155
pling components are obtained that carry the
pyridinium component by way of a carbon link-
The red cationic azo dye 155 [36986-04-6], age [141], e.g., 157.
obtained with 2-chloro-4-nitroaniline [129], is
represented in numerous cationic dye prod-
uct lines: e.g., Maxilon Red 2GL (Ciba), and
Yoracryl Red 2G (YDC).
Introduction of a second pyridiniumalkyl
residue (156) [24447-84-5] leads to a brighten-
ing of the hue to orange.
157

The place of the pyridinium residue may

also be taken by the 1,2,4-triazolium [142],
the benzimidazolium [143], or the imidazolium
[144] moieties. An example is the dye 158
[47660-05-9].

156

Here again, all compounds cited in Sec-

tions 5.1.3.3 and 5.1.4 are used as the di-
azo components. In addition, the follow-
ing have been described as diazo compo-
nents: 2,5-dichloro-4-nitroaniline (red) [130], 2- 158
chloro-5-trifluoromethylaniline (yellow) [131], The cyclic ammonium residue may also be
4-nitro-2-trifluoromethylaniline (red) [132], linked to the coupling component via a sulfon-
2-amino-5-trifluoromethyl-1,3,4-thiadiazole amide [145] or an ester [146] group.
(red) [133], 3-methylmercapto-5-amino-1,2,4- A yellow cationic substantive paper dye
thiadiazole (red) [134], 3-methyl-4-nitro-5-ami- is obtained by coupling diazotized 2-(4
-ami-
noisothiazole (blue violet) [135], 2-amino-6- nophenyl)-5-methylbenzothiazole onto an ace-
chlorobenzothiazole (red) [136], 3-amino-5-
 Azo Dyes 59

toacetic arylide, e.g., N-aryl-acetoacetamide, In a similar manner 6-amino-1,3-di-

substituted by a pyridinium residue [147], or methylbenzotriazolium chloride may be con-
by coupling tetraazotized 4,4
-diaminostilbene verted into the 6-hydroxy compound for use as
with the coupling component of dye 155 [148]. a coupling component [153].

5.1.6. Coupling Components with 5.1.7. Cyclic Ammonium Residues at the

Condensed Cyclic Ammonium Residues Azo Group
Heterocyclic compounds wherein the condensed
benzene ring is substituted by a hydroxyl or an If azo dyes from aromatic diazonium com-
amino function may be coupled with diazonium pounds and 1-phenyl-3-methyl-5-pyrazolone or
compounds and may also be quaternized, ei- 1-phenyl-3-methyl-5-aminopyrazole are quater-
ther prior or subsequent to the coupling reac- nized at the 2-nitrogen of the pyrazole, cationic
tion, to yield cationic azo dyes. 1,2-Dialkyl-6- azo dyes are obtained. A resonance charge ex-
nitroindazolium salts are reduced to the 6-ami- change is prevented through lack of a donor
no compounds and then coupled with diazonium function at the aromatic moiety [154], [155]. An
salts of aromatic amines. These dyes (e.g., 159) example is dye 162.
color polyacrylonitrile in bright yellow to orange
shades [149].

162

159 Azo dyes from aromatic diazonium com-

pounds and indolizine derivatives may also be
6-Amino-1,3-dimethylbenzotriazolium converted into cationic azo dyes by quaterniza-
chloride may also be used as the coupling tion [156].
component [150]. By hydrolysis of 6-amino-
1,2-dialkylindazolium chloride in dilute sulfu-
ric acid at 180 – 190 ◦ C, a hydroxyl group is 5.1.8. Coupling Components with two
introduced into the 6-position. The 6-hydroxy- Different Cationic Residues
1,2-dialkylindazolium salt formed is suitable for
the generation of mono- [151] (160) and disazo Mono- and polyazo dyes have been prepared, in
dyes [152] (161) [92888-19-2]. which the coupling component carries at least
two different basic and/or cationic groups. Of
these, mostly yellow to orange dyes are derived
from pyridones with a cyclic ammonium group
and an amino- or trialkylammoniumalkyl group.
To obtain a technically sufficient affinity to cel-
lulose fibers disdiazo components are preferred
either with the same coupling component [157–
160
161] (e.g., 163) or with different ones [162],
[163] (e.g., 164).
A step further is the connection of two suit-
able molecules with the help of a dihaloalkane
[164], [165] (e.g., 165).
Dyes of this kind can be used to color anodi-
cally generated oxide layers on aluminum [166].
161
60 Azo Dyes

163

164

165

A commercial product is Cartasol Yellow K-

3GL liq.
Orange, red and violet dyes can be ob-
tained by using as coupling components aminon-
aphtholsulfonic acids that are connected via
the N atom to a 1,3,5-triazine with dif-
ferent aminoalkylamino, trialkylammonium-
alkylamino or cyclic ammonium substituents in 167
positions 4 and 6 [167] (e.g., 166).
Between the N atom of the ami-
nonaphtholsulfonic acid and the triazine ring,
spacer groups can be introduced, e.g., ami-
noaroyl or aminophenylcarbamoyl groups
[169], [170].
A different way to synthesize a coupling com-
ponent with two different basic groups is to re-
166 act N-dibromopropionylaminonaphtholsulfonic
For example, 167 dyes paper in a scarlet acids with dialkylaminoalkylamines to give
shade [168]. aziridine derivatives; red dyes are obtained by
coupling these with a diazonium salt of p-ami-
noazo-benzene [171] (e.g., 168).
 Azo Dyes 61

phthalic acid residue. By diazotization of 4-

methoxy-3,5-bis(aminomethyl)aniline trihydro-
chloride and coupling with 3-hydroxynaphthoic
acid arylides, red cationic substantive paper dyes
are obtained [173]. Of importance in the manu-
facture of cationic substantive paper dyes are re-
action products of cyanuric chloride with 2 mol
168 dialkylaminoalkylamine and 1 mol 1,3- or 1,4-
diaminobenzene.
Yellow paper dyes (e.g., 169) are obtained
5.2. Cationic Charge in the Diazo by diazotization of these aromatic amines and
coupling with acetoacetarylides [174], [175].
Component By coupling to derivatives of J acid, sub-
stantive dyes (e.g., 170) are obtained wherein
Diazo components may contain the cationic the charge on the sulfonic acid group is more
charge at amino, dialkylamino, trialkylammo- than compensated for by the multiple cationic
nium, or cycloammonium groups. charges. These dye paper in shades of red [176].
Dyes wherein the dialkylaminoalkyl group is
connected to the diazo component via the ester
5.2.1. Diazo Components with Aminoalkyl group of anthranilic acid [177–180], a carbox-
Moieties amide [181], a sulfonamide [184], [182] or an
ether [183] residue have also been described.
Yellow dyes are prepared by aminomethylation
of 2-(4
-aminophenyl)-5-methylbenzothiazole
followed by diazotization and coupling with 5.2.2. Diazo Components with
acetoacetarylides. Red cationic dyes are ob- Trialkylammonium Residues
tained with naphthols or hydroxynaphthoic acid
arylides. All are suitable for dyeing paper. The The trialkylammonium group may be linked to
bleachability of these dyes is important for the diazo component either via aromatic substi-
the recycling of waste paper [172]. The ami- tution or by way of an aliphatic residue.
nomethylation of aromatic amines is carried
out by reaction with formaldehyde and phthal-
imide, followed by hydrolytic scission of the

169

170
62 Azo Dyes

5.2.2.1. Aromatically Linked still contain a primary amino group by dimer-

Trialkylammonium Residues ization using phosgene [193], [194] or cyanuric
chloride [195].
Aminophenyltrimethylammonium chloride was Coupling with β-naphthol results in a yel-
already an important diazo component of the low dye suitable for polyacrylonitrile [196], cou-
Janus line of dyes. The fastness of these dyes, pling with 2,5-dimethoxyaniline gives an or-
e.g., 171, on polyacrylonitrile is enhanced by ange dye that is recommended for hair coloration
introduction of halogens. Mono- and dialkylan- [197].
ilines are suitable coupling components [185].

5.2.2.2. Aliphatically Linked

Trialkylammonium Residues

The Friedel – Crafts acylation of acetanilide with

chloroacetyl chloride yields 1-acetamido-4-
171 chloroacetylbenzene. The trimethylammonium
Disazo dyes of this series (e.g., 172) are group is introduced by reaction with trimethyl-
suitable for dyeing polyacrylonitrile and paper amine, followed by hydrolysis of the acetamide
[186]. group. This diazo component is a constituent
of numerous yellow, orange, and red cationic
azo dyes. Using diethyl-m-toluidine as the cou-
pling component, the lightfast red dye (174)
[67905-12-8] is obtained [198].

172

A commercial product is Anilan Golden Yel-

low RL (Ciech).
4-Hydroxynaphthalimide as a coupling com-
ponent yields cationic dyes that confer an
orange-red shade to polyacrylonitrile [187]. 174
Heterocyclic coupling components that Introduction of an unsaturated alkyl residue
have been coupled with diazotized ami- improves the solubility of the dye [199]. N-
nophenyltrimethylammonium chloride are Methyl-N-cyanoethylaniline yields an orange
5-hydroxy-1-phenylpyrazole-3-carbonamide dye. The shade is shifted to yellow with a red
[188], 1-alkyl-6-hydroxy-2-pyridone [189], 1- cast using N-cyanoethyl-2-chloroaniline (175)
amino-3-hydroxy-isoquinoline [190], and 2,4- [72208-25-4].
diamino-6-hydroxypyrimidine [191]. The tri-
alkylammoniumaryl residue may also be con-
nected to the aromatic diazo component via a
sulfone or a sulfonamido function [192]. Dis-
azo dyes in this series (e.g., 173) [77901-21-4]
may also be generated from monoazo dyes that

173
 Azo Dyes 63

The trialkylammonium alkyl residue may

also be attached directly to the aryl residue of
the diazo component [209]. Dyes that derive
from aminomethylated 2-aminonaphthalene and
contain acetoacetarylides, naphthols, or pyra-
zolones as the coupling components are suit-
able for dyeing paper. An example is the yellow
175
monoazo dye 178.
Commercial products are Sevron Yellow 3RL
(CKC), and Sumiacryl Yellow E-3RD (Sumit-
omo).
Use of 2-methylindole as the heterocyclic
coupling component has led to commercially
important dyes (e.g., 176) [25784-16-1] [200].

178

Disazo dyes are obtained by using coupling

components with a primary amino group and
dimerization with phosgene [210]. The diazo
components are prepared by exhaustive alkyl-
176
ation of aminomethylated 2-aminonaphthalene-
However, dyes have also been gener- 1-sulfonic acid, followed by scission of the sul-
ated from 1-phenyl-3-methyl-5-aminopyrazole fonic acid group in the presence of mineral acids
[200], 2,4-dihydroxyquinoline [201], 2,6- [211].
dihydroxypyridine [202], 2,6-diaminopyridine The trialkylammonium residue may also be
[203], 2,4,6-triaminopyridine [204], and 3- connected to the diazo component by way of an
phenyl-5-hydroxyisoxazole [205]. The solubil- ether [212], a carbonamide [213], [214], a sul-
ity of such dyes may be enhanced by introduc- fone [215], or a sulfonamide group [216], [217].
tion of polyether moieties [206]. Bis-cationic metal-complex dyes are suit-
Cationic dyes with reactive functional able for dyeing leather. Cationic monoazo dyes
groups, e.g., dichlorotriazine or vinylsulfone, wherein a trialkylammonium group is linked via
suitable for dyeing wool and silk, have also been a carboxamide group to the diazo component
generated in this series [207]. Bis-cationic dyes, [218] and disazo dyes are known. The latter
for instance 177, are suitable for dyeing mixed- are prepared from dialkylamino compounds by
fiber fabrics containing acid-modified and un- quaternization using alkylene dibromides. They
modified polyamide, whereas the latter does not are suitable for dyeing paper [219].
take up the dye [208]. Azo dyes with 2-(4
-aminophenyl)-5-
methylbenzothiazole as the diazo component
and carrying trialkylammoniumalkyl residues
are suitable for dyeing paper in the same man-
ner as the dyes described in Section 5.2.1 [172],
[220]. Also described as carriers of the cationic
charge were dialkylhydrazinium residues linked
to the diazo component via a sulfonamide [221]
or a carboxamide group [222].

177

A commercial product is Sevron Red YCN

(CKC).
64 Azo Dyes

5.2.3. Diazo Components with Cyclic

Ammonium Residues

The cyclic ammonium residue may either be

linked directly to the aromatic ring or attached
to the diazo component via an aliphatic residue.

5.2.3.1. Aromatically Linked Cyclic 180

Ammonium Residues
The chloroethylsulfonamide may also be re-
For the preparation of a diazo component that acted with 1,2,4-triazole [231].
contains a 1,2,3-triazolium residue in the para Dyes containing the pyridinium group linked
position, p-nitrophenylazide in acetone solution to the diazo component via a carboxylic ester
is first reacted with acetylene in an autoclave to function (e.g., 181) [32017-47-3] are obtained
give 1-(4-nitrophenyl)-1,2,3-triazole. The nitro by condensation of 4-nitrobenzoyl chloride with
group is then reduced, the resultant amine acety- chloroethanol, reaction of the ester with pyri-
lated, and the triazole moiety is quaternized with dine, reduction of the nitro to an amino group, di-
dimethyl sulfate. After hydrolysis of the acetyl azotization, and coupling with aromatic amines
group, the resultant amine may be diazotized and [232].
treated with ethylcyanoethylaniline to give dye
179 [47553-94-6] [223]. The dye colors poly-
acrylonitrile to a lightfast orange.

181

This dye imparts an orange shade to polyacry-

lonitrile. The cyclic ammonium residues may
also be linked to the diazo component via a car-
boxamide [233] or an ether group [234] or di-
179 rectly by means of an alkyl residue [235].
The triazole moiety may also be linked in
the 2-position with respect to the azo link-
age [224]. Among cyclic ammonium residues 5.2.4. Diazo Components with two Different
linked via carbon bonds to the aromatic ring Cationic Residues
of the diazo component have been cited:
1,3-dialkylbenzimidazolium [225], benzothia- Mono- and disazo dyes have been prepared in
zolium [226], methylpyridiniumoxazole [227], which the diazo compound carries at least two
and pyridinium [228] moieties, linked via ni- different basic and/or cationic groups.
trogen, as well as the benzotriazolium moiety Reaction of 2,4- or 2,5-diaminobenzene-
[229]. sulfonic acids with 2-chloro-1,3,5-triazines that
are substituted in the 4- and 6-positions by
aminoalkylamines and cyclic ammoniumalky-
5.2.3.2. Aliphatically Linked Cyclic lamines, respectively, leads to diazo compo-
Ammonium Residues nents which, when diazotized and coupled with
derivatives of aminonaphtholsulfonic acids, give
Upon reaction with pyridine azo dyes that carry rise to dyes for cotton, leather, and especially
a chloroethylsulfonamido group in the diazo paper [236]. An example is 182, which colors
component form cationic azo dyes, e.g., 180 paper in a violet hue.
[33869-97-5], which color polyacrylonitrile in
brilliant shades [230].
 Azo Dyes 65

182

183

Reaction of chloromethyl derivatives of

4
-aminophenyl-2-benzothiazoles with e.g.
N
,N

,N


-permethyldiethylene-triamine leads
to compounds with alkylaminoalkylammonium
residues that can be diazotized and coupled
with, e.g., acetoacetarylides [237]. An example
is 183, which colors paper in a greenish shade
of yellow.
184

5.2.5. Diazo Components with Aromatic By exhaustive alkylation, dyes are obtained
Condensed Cyclic Ammonium Residues that are suitable for polyacrylonitrile [239].
Introduction of halogen yields dyes with es-
Polynuclear N heterocycles that carry an ami- pecially valuable properties. A suitable diazo
no group in the carbocyclic aromatic ring may component is 4-amino-6-chlorobenzimidazole.
be diazotized and then joined to azo dyes using The sequence of diazotization, coupling with
aromatic or heterocyclic coupling components. aromatic amines, and quaternization gives col-
Quaternization at the heterocyclic nitrogen atom orants (e.g., 185) [36116-31-1] that confer fast
may occur before or after coupling. The azo orange and red shades to polyacrylonitrile [240].
dye 184, from 2-methyl-5-aminobenzimidazole
and 1-phenyl-3-methyl-5-pyrazolone, used in
the form of its hydrochloride, dyes paper and
leather in clear yellow shades [238].

185
66 Azo Dyes

Trifluoromethyl-substituted aminobenzimid- polyacrylonitrile in fast yellow shades and ex-

azole compounds have also been described as hibit excellent leveling characteristics [247].
diazo components [241].
A bathochromic shift is obtained by us-
ing 4-amino-6-chlorobenzotriazole in place
of the benzimidazole. The quaternized cou-
pling products with dialkylanilines (e.g., 186)
[36116-25-3] dye polyacrylonitrile in red shades 188
with a blue cast [242]. This dye is also recommended for dyeing of
human hair [248], as well as the dye containing
2-methylindole as coupling component [249],
[250].

5.3. Different Cationic Charges in Both

the Coupling and the Diazo Component
186

Red dyes for polyacrylonitrile are obtained A further means to introduce different basic
with 6- or 7-aminoindazole as the diazo compo- and/or cationic residues (cf. Sections 5.1.8 and
nent [243], (e.g., 187). 5.2.4) into a dye has been developed by combin-
ing diazo and coupling components that each
carry different basic or cationic groups. They
are synthesized according to the procedures that
have been described in Sections 5.1 and 5.2.
Dyes have been prepared that color paper in
187 hues ranging from orange [251] (e.g., 189, see
next page)
Other heterocyclic diazo components that to red [252–254] (e.g., 190)
have been used to generate cationic dyes
are 4-amino-7-nitrobenzisothiazole [244], 2-
methyl-6-aminoquinoline [245], and 5-ami-
noimidazo[1,2-a]pyridine compounds [246].

5.2.6. Cyclic Ammonium Compounds

Linked in Meta Position to the Azo Group
190
Coupling of diazotized N-heterocyclic amino
compounds that carry the amino group in the 2- to black [255] (e.g., 191)
or 4-position to the heterocyclic nitrogen to aro- The yellow dye 192
matic or heterocyclic coupling components and can be used in ink-jet systems to flocculate
subsequent quaternization of the heterocyclic ni- anionic pigment dispersions, thus improving the
trogen leads to diazacyanine dyes (→ Methine bleedfastness [256], [257].
Dyes and Pigments).
If the starting materials are heterocyclic ami-
no compounds with the amino group in a 5.4. Introduction of Cationic
meta position, a mesomeric charge exchange is Substituents into Preformed Azo Dyes
not possible. Therefore, dyes of this type are
grouped with the cationic azo dyes. Cationic substituents may also be introduced
By coupling of diazotized 3-aminopyridine into preformed azo dyes. In this manner, mix-
to 2-naphthol, followed by quaternization, dyes tures of isomers are obtained which may carry
(e.g., 188) [41313-61-5] are obtained that color
 Azo Dyes 67

189

191

192

193

one to four cationic groups in various positions. amide on azo dyes in sulfuric acid medium, fol-
The multiplicity of isomers is a cause for good lowed by displacement of the reactive chloro
water solubility. These dyes are predominantly substituent by pyridine or trialkylamine. Of spe-
used for coloring paper. cial significance for dyeing paper are dyes that
Reaction of chlorosulfonic acid with mono- are prepared by coupling of diazotized 2-(4
-
[258] or disazo dyes [259] yields sulfonyl aminophenyl)−5-methylbenzothiazole to ace-
chlorides, which can then be transformed into toacetarylides, pyrazolones, naphthols [260], or
cationically substituted sulfonamides by reac- barbituric acid derivatives [261], followed by
tion with dialkylaminoalkylamines. The cou- reaction with N-hydroxymethylchloroacetam-
pling product of diazotized 2-anisidine with 2- ide and pyridine or N-methyl-1,3-diaminopro-
hydroxynaphthoic acid arylide upon such treat- pane [262] . The azo dye obtained by ox-
ment dyes paper red and the azo dye from tetraa- idative dimerization of 2-(4
-aminophenyl)−5-
zotized dianisidine and 1-phenyl-3-methyl-5- methylbenzothiazole may also be subjected to
pyrazolone gives yellowish orange shades. this conversion [263]. Dye 193 colors paper yel-
Numerous cationic azo dyes are prepared low.
by the action of N-hydroxymethylchloroacet-
68 Azo Dyes

194

195

Disazo dyes with β-naphthol as the coupling By reacting dyes that contain a chloroethyl
component give red shades [264]. group with thiourea, the cationic charge may
By removal of the chloroacetyl residue ami- be introduced in the form of an isothiouronium
nomethylated dyes are obtained which are used residue (e.g., 197) [269].
for coloring paper either as such or upon further
alkylation [265]. An example is the yellow dye
194.
Reaction of azo dyes with formaldehyde and
4-methylimidazole, followed by alkylation, pro-
duces cationic azo dyes that dye paper with ex-
cellent wetfastness [266]. An example is the dis-
azo dye 195, which confers a brilliant red shade 197
to paper. To introduce phosphorus as the charge-
A commercial product is Cartasol Brilliant carrying moiety, dyes that contain haloalkyl
Yellow K-5GL (Clariant). groups are reacted with phosphines, such as di-
methylphenylphosphine (e.g., 198) [270].
5.5. Cationic Dyes with Sulfur or
Phosphorus as Charge-Carrying Atoms
When dyes containing anionically displaceable
groups are reacted with thioethers, cationic dyes
(e.g., 196) are obtained in which the sulfonium
moiety carries the charge [267]. The sulfonium
group may also be linked directly to the aromatic 198
coupling component [268].

5.6. Dyes with Releasable Cationic

Groups

Dyes with releasable cationic groups are con-

verted to water-insoluble dyes when heated in
196
the dye bath. They can then enter textile mate-
 Azo Dyes 69

rials that are amenable to dyeing with disperse 4.2.3). As a result of the diazotization of di-
dyes. Using this method, for instance, it is pos- rect dyes with free amino groups and subse-
sible to dye polyester materials without having quent reaction with suitable coupling com-
first to generate a finely dispersed form of the ponents, an azo dye of higher molecular mass
colorant with the aid of surfactants. An example with especially good adhesion is synthesized
of such a releasable group is the isothiouronium on the fiber.
moiety [271]. Dyes with isothiouronium groups Developing dyes from another dye
are also suitable for wool [272]. class are the phthalocyanine develop-
Reaction of dyes containing a primary amino ing dyes (e.g., Phtalogen dyes (Bayer)
group with dimethylformamide and an inorganic → Phthalocyanines).
acid chloride, e.g., phosphoryl chloride, permits Developing dyes whose color-imparting
introduction of the formamidinium group, which structure is synthesized before they are ap-
is also scissioned off upon heating in the dye bath plied to the substrate in the form of soluble
(e.g., 199) [273]. derivatives; they are converted into an insol-
uble form by aftertreatment on the fiber.
These include the polycondensation dyes,
in particular in the azo range, which con-
tain thiosulfate groups (–S–SO3 –) as water-
solubilizing groups. In the presence of con-
densing agents (e.g., sodium sulfide), these
199 compounds undergo polycondensation on
the fiber to form insoluble dyes, S–S bridges
A similar reaction occurs with the trialkylhy- being formed at the same time (e.g., Inthion
drazinium moiety obtained by reacting formyl- dyes from Hoechst) [275], [276].
substituted azo dyes with dialkylhydrazines and A further example is that of esterified Naph-
subsequent quaternization [274]. tol AS dyes. If azo dyes formed from Naphtol
AS components and diazotized color bases
are reacted with suitable acylation agents
6. Developing Dyes containing sulfo groups, soluble esters of
azo compounds, which can be applied to the
General Survey. There is no standard defi- fiber, are obtained. By saponification in an al-
nition of the term developing dyes. They can kaline medium the esters are then converted
include all dyes that are synthesized on the fiber on the fiber into insoluble dyes, e.g., Neoco-
or converted there into their final form. In this ton dyes (Ciba); Tinogenal dyes (Geigy) and
respect it is possible to distinguish between two Neogenol dyes (Sandoz) [277].
main groups:
Developing dyes in the second group have
Developing dyes whose final chromophoric never been able to maintain their market position
system is synthesized on the fiber with for- over a lengthy period: they are only mentioned
mation of an insoluble dye. In the azo dye se- here because their mode of action is of interest
ries, these mainly include the β-naphthol and from the chemical aspect.
Naphtol AS dyes, which are directly synthe- The first group of developing dyes, on the
sized on the fiber; the substrate impregnated other hand, includes products of major industrial
with the coupling component is “developed” interest. Among all the developing dyes, by far
in a suitable diazonium salt solution. When the greatest importance attaches to the insoluble
dyeing or printing the fiber, it is also possible dyes known as Naphtol AS dyes, which are pro-
for coupling component and diazo compo- duced on the fiber from 2-hydroxy-3-naphthoic
nent to be applied simultaneously; not until acid amides and other carboxylic acid amides
an aftertreatment is carried out is the cou- capable of coupling (Naphtol AS components)
pling process then initiated. and suitable diazo components. Only members
The diazotization dyes are also frequently of this class of compounds are dealt with in detail
numbered among this group (see Section
70 Azo Dyes

in this chapter. In accordance with dyeing and (so-called because of the ice used during diazo-
performance aspects they can be divided into tization); see Table 12.
developing dyes for cotton Table 12. Amines for the development of cotton impregnated with
β-naphthol and shades obtained
developing dyes for animal fibers
developing dyes for hydrophobic fibers 5-Nitro-2-aminotoluene orange
5-Nitro-2-aminoanisole pink
The large number of dyeing and printing 4-Chloro-2-aminoanisole scarlet
4-Nitroaniline red
methods used will be discussed under the key- 1-Naphthylamine bordeaux
words → Textile Dyeing and → Textile Printing. 3,3
-Dimethoxy-4,4
-diaminodiphenyl
(with Cu salts) blue
3,3
-Dimethyl-4,4
-diaminodiphenyl brown
Mixture of 4,4
-diaminodiphenylamine
6.1. Developing Dyes for Cotton [5, and 4-dimethylamino-4
-aminoazobenzene black

vol. III, p. 290], [42, vol. 1, p. 502], [278–280]

Numerous disadvantages of β-naphthol dye-
The principal fields of application are the dye- ing (difficulty in obtaining uniform fixation of
ing and printing of textiles made from cellulosic the coupling component when drying material
fibers (natural or regenerated), of which cotton impregnated with β-naphthol; very limited fast-
is the main material. Cotton dyeing with devel- ness of the dyeings to light, chlorine, washing,
oping dyes was being practiced by the end of and rubbing) pushed subsequent developments
the 19th century (ice colors); it received a boost in the direction of the so-called Naphtol AS dyes.
with the introduction of Naphtol AS components
in 1911. Ten years later, the Rapid Fast range
(see page 82) made possible an especially sim- 6.1.1.2. Naphtol AS Dyes
ple method of application in the printing of cot-
In Offenbach (now Hoechst) in 1911,
ton. Cotton dyeing and printing on the basis of
A. Winther, L. Laska, and A. Zitscher dis-
developing dyes have now reached such an ad-
covered that instead of β-naphthol it is more
vanced stage of development, and the dyeings
advantageous to use the anilide of 2-hydroxy-3-
obtained possess such a high quality level, that
naphthoic acid, listed in the technical literature
this class of dye is likely to continue to maintain
under its trade name Naphtol AS; AS is short for
its market position in the future.
“Amid einer Säure” (amide of an acid). Com-
pared with that of β-naphthol, the sodium salt
of this coupling component possesses the great
6.1.1. Developing Dyes for Dyeing
advantage of having a certain degree of substan-
tivity, i.e., it is absorbed onto the cotton fiber like
6.1.1.1. β-Naphthol Dyes
a direct dye. Uniform fixation on the substrate is
thus guaranteed. Moreover, in comparison with
β-Naphthol dyes are only of historical inter-
β-naphthol, the alkaline solutions of Naphtol AS
est. The initial results achieved in the dyeing
possess higher air resistance, with the result that
of cotton by producing an azo dye on the fiber
the moist cotton fibers impregnated with it can
were patented by Th. and R. Holliday (1880).
be exposed to air for a prolonged period without
They impregnated cotton with an alkaline so-
undergoing a change. The dyeings obtained on
lution of β-naphthol and, after drying, “devel-
the fiber after development with suitable diazo
oped” the impregnated material by immersing it
components are distinguished by a high fastness
in an acetate-buffered solution of diazotized α-
level.
or β-naphthylamine. In particular the attractive
With the development of a large number of
red (para red) obtained by Gallois and Ull-
substituted anilides of 2-hydroxy-3-naphthoic
rich (1889) using 4-nitroaniline as diazo com-
acid (known as “β-oxynaphthoic acid arylides”)
ponent was for a long time of importance in the
and related compounds as Naphtol AS cou-
dyeing and textile printing industries. The intro-
pling components (the various products are de-
duction of further suitable diazo components led
noted by additional letters following the AS) and
to a whole range of shades in these “ice colors”
a selection of suitable aromatic amines (“Fast
 Azo Dyes 71

Color Bases”) and their stabilized diazonium phosphorus trichloride being added slowly at
salts (“Fast Color Salts”) as diazo components, 70 – 80 ◦ C to a mixture of one equivalent each
the Naphtol AS dyeing sector underwent rapid of carboxylic acid and amine in an inert solvent
expansion. (usually toluene and polychloroalkanes). The re-
World production of Naphtol AS compo- action mixture is then boiled for some hours and,
nents, Fast Color Bases, and Fast Color Salts for after cooling, treated with soda to remove the
dyeing and printing of cellulosic fibers amounts acid. The Naphtol AS compound is filtered off,
in 1982 to approx. 24000 t (around 6000 t are in the solvent recovered. The yield is almost quanti-
addition used for production of azo pigments). tative. The addition of formaldehyde to alkaline
This is equivalent to just under 5 % of colorant solutions of 2-hydroxy-3-naphthoic acid amides
consumption in the textile sector as a whole, al- improves the air stability of the damp impregna-
though as a result of a decrease in the proportion tions. The stabilizing action of the formaldehyde
of world fibers demand accounted for by cotton, can be explained by the reversible formation of
a declining trend can be observed in the percent- hydroxymethyl compounds, the sodium salts of
age rate. which possess improved hydrolysis resistance.
The percentage of Naphtol AS developing By varying the substituents in the aryl amide
dyes in the dyestuffs requirement for textiles radical and in the hydroxynaphthoic acid moiety,
made from cellulosic fibers has for years re- a wide range of coupling components was syn-
mained constant at around 8 %, although the use thesized. The substituents naturally influence the
of reactive dyes, particularly since the start of the shade and fastness properties of the azo dyes ob-
1970s, has gained increasingly in importance. tained after development. For example, the in-
Around 60 % of Naphtol AS dyes are employed troduction of alkoxy groups in the aryl amide
for dyeing, around 40 % in the printing sector. radical has a favorable influence on light fast-
Table 13 provides a survey of the most im- ness.
portant ranges of coupling and diazo compo- With the commercial products compiled in
nents for Naphtol AS dyeing (and printing). The Tables 14 and 15, the shades obtained with dia-
manufacturing countries are combined into three zotized color bases, such as chloro- or nitroani-
large groups: Western Europe and USA, India lines, are almost always orange, red, or bor-
and Japan, and the state-trading countries. The deaux. Therefore, these Naphtol AS derivatives
first group accounts for about 50 % of production can also be referred to as “Red Naphtols.”
volume, and the other two have approximately The classification principle used in the Ta-
equal importance. bles is largely that adopted in the Colour Index
The trade names indicate that the spelling [7], which is based on the chemical constitution.
Naphtol AS is reserved for the Hoechst range. The trade names are mainly those of the Hoechst
Naphthol AS components belong to other range, since as a result of the historical develop-
ranges. The Hoechst spelling is the one mainly ment, the field of Naphtol AS developing dyes
used below. is an undisputed domain of this manufacturer. A
number of compounds are listed under the dif-
Coupling Components. The following fac- ferent designations of other manufacturers (e.g.,
tors were of major importance to the rapid de- Naphthol, Naphtanilid). Only in some cases do
velopment of numerous new coupling compo- the letter combinations in the trade names of dif-
nents and their use in cotton dyeing: a sim- ferent firms agree with regard to one and the
ple synthesis process for substituted 2-hydroxy- same compound.
3-naphthoic acid aryl amides, improved dye- Whereas with 2-hydroxy-3-naphthoic acid
ing properties (substantivity, fastness, shades for amides, only red shades (apart from a few red-
combinations), and reduction in the sensitivity dish brown shades) can be obtained by varying
of the moist impregnated material to air. the aryl amide radical in combination with sim-
2-Hydroxy-3-naphthoic acid can be pro- ple diazo compounds, coupling components de-
duced under pressure by reaction of carbon diox- rived from o-hydroxycarboxylic acids of other
ide with the sodium salt of β-naphthol (Kolbe- ring systems yield brown and black shades.
Schmitt synthesis). The aryl amides are obtained Here, derivatives of carbazolecarboxylic acid
by one-step reaction, 0.4 – 0.5 equivalents of
72 Azo Dyes
Table 13. Trade names of important coupling components and diazo components for Naphtol AS dyeing and their manufacturers

Country Manufacturer C. I. Azoic Cou- C. I. Azoic Diazo Component

pling Component Bases Stabilized salts

Germany, Hoechst Naphtol AS- Echt-Base Echt-Salz

Fed. Rep. Azanil-Salz
Variaminblau

Switzerland Rohner Naphtanilid Fast Base Diazo Fast

USA Blackman Uhler Naphtol AS- Fast Base Fast Salt

Pfister Chem. Naphtol AS- Azoene Fast Base Azoene Fast Salt

India Amar Dye Amarthol AS- Amarthol Fast Base Amarthol Fast Salt
Atul Prod. Tulathol AS- Tulabase Fast –

Japan Daito Chem. Ind. Daito Grounder Daito Base Daito Salt
Sanyo Colour Works Sanatol Sanyo Fast Base Sanyo Fast Salt
Sumitomo Naphthoide (Fast) Base Salt
Showa Chem. Co. Kako Grounder Kako Base Kako Salt

China, P.R. Youhaothol AS- Fast Base Fast Salt

Youhaoriamin Blue

Czech Rep. Ultrazol Fast Base Fast Salt

Poland Ciech Naphtoelan Naphtoelan Fast Base Naphtoelan (Fast) Salt

fromer Soviet Union Azotol Azoamin Diazol

and dibenzofurancarboxylic acid are of partic- product of a blue dye (nickel phthalocyanine
ular importance (see Table 16). sulfochloride) and a coupling component in the
Yellow dyeings are not obtainable by combi- yellow range (aminophenyl pyrazolone deriva-
nation of o-hydroxyarylcarboxylic acid amides tive) yields in combination with suitable diazo
with color bases. The coupling components components brilliant yellowish greens with out-
used for yellow shades are derived from acetyl- standing light fastness [281]. Since the coupling
and benzoylacetic acid amides. Although in the component possesses virtually no affinity for the
chemical sense they are therefore not naphthol cellulosic fiber, the product was mainly used for
derivatives, they are classified as Naphtol AS textile printing by the Rapidogen process (see
components and in accordance with their col- page 83). Green dyeings are now obtained al-
oristic properties are often called “Yellow Naph- most exclusively by combination of phthalocya-
tols” (Table 17). nine developing dyes, e.g., Phtalogen (Bayer),
In contrast to the red Naphtols (Tables 14 and with yellow Naphtol AS dyes.
15) and heterocyclic coupling components (Ta-
ble 16), the yellow Naphtols are stable in alkaline Diazo Components. A large number of dia-
solution; therefore, no addition of formaldehyde zotizable aromatic amines are available for azoic
is necessary, and because of side reactions it is coupling with the coupling component (see Ta-
even inadmissible. ble 18). The diazo components are sold either
Apart from the coupling components listed in as nondiazotizable bases, so-called “Fast Color
the tables, mention should also be made of those Bases” (both as free amines, if they are stable
that as a special structural characteristic contain and nontoxic, and as hydrochlorides or sulfates),
azo groups, e.g., Naphthol AS-BN (Blackman or as stabilized diazonium salts, so-called “Fast
Uhler) (C. I. Azoic Coupling Component 43, ex- Color Salts” (for trade names see Table 13).
act constitution not as yet published). The diazonium compounds are isolated (“pre-
An interesting development during the six- cipitated”) in the form of chlorides, sulfates, hy-
ties was Naphtol AS-FGGR (Bayer) (C. I. Azoic drogen sulfates, double salts of zinc chloride,
Coupling Component 108): the condensation fluoroborates, oxalates, and neutral or acid 1,5-
 Azo Dyes 73
Table 14. Naphthol AS components: 2-hydroxy-3-naphthoic acid amides
74 Azo Dyes
Table 14. (Continued)

∗ A former Hoechst product, no longer manufactured by any company.

naphthalenedisulfonates and other aromatic sul- that can be combined with the same Naphtol
fonates, the optimum conditions depending on AS components to give blue and violet shades.
the type of base. Final stabilization is achieved Here, chief mention can be made of: N-aroyl-
by mixing (“adjusting”) with inert salts (usually p-phenylenediamine derivatives, which contain
aluminum sulfate). For further details → Diazo no negative substituents, and 4-aminodiphenyl-
Compounds. amine derivatives. With compounds of the latter
With the diazo components, too, the chemi- type (Variamin Blue bases and salts; Hoechst)
cal constitution naturally has a great influence attractive blue shades are obtained and in com-
on fastness properties and shade of the dyeing bination with Naphtol AS-GR (C. I. Azoic Cou-
obtained with a coupling component. It has been pling Component 36, 37585; see Table 16) green
found that negative substituents (halogens, nitro, dyeings as well. 4-Aminoazobenzene deriva-
nitrile, RO2 S, and, in particular, CF3 groups) in tives produce black dyeings in combination with
the aromatic nucleus exert a favorable influence Red Naphtols.
on light fastness. In addition to suitable substi- The diazo components compiled in Table 18
tuted aniline derivatives, which in combination have been classified first by coloristic aspects
with 2-hydroxy-3-naphthoic acid amides almost (shades) and second by constitutional character-
without exception yield red shades (orange, red, istics (in accordance with the Colour Index [7]).
bordeaux), color bases have been developed The shades specified in the trade names relate,
 Azo Dyes 75
Table 15. Naphthol AS components: derivatives of 2-hydroxy-3-naphthoic acid amides

with only a few exceptions to the dyeings ob- C. I. Azoic Diazo Components 135 – 137
tained with Red Naphtols. (bases I, II, III from Hoechst, now withdrawn by
Basically speaking it is possible for the dyer the manufacturer on price grounds) [282–284],
to combine any aromatic base with any Naph- [15, p. 676].
tol AS component. However, only a limited se-
lection of all conceivable combinations fulfil
the preconditions for a coloristically high-grade
dyeing. The dyeings generally possess high fast-
ness to rubbing, washing, chlorine, and light.
Many of the Naphtol AS dyes obtained on the
fiber attain fastness levels of Indanthren dyes,
without being chemically related to these com-
pounds, which are usually polycyclic (examples
see Table 19). A further development concerns improve-
ment in the dyeing methods. The conventional
two-bath technique (impregnation of the mate-
Other Developments. A new development
rial with the alkaline solution of the substantive
in Naphtol AS dyeing, which commenced at
coupling component, removal of the excess, and
the start of the 1960s, utilized the tendency of
subsequent treatment with the diazonium salt
certain azo dyes to form metal complexes. Het-
solution) can often be considerably simplified
eroaromatic amines that fulfil certain structural
and shortened by using the so-called one-bath
pre-conditions (see Section 2.3.4) are used as di-
method: a highly substantive Naphtol AS im-
azo components and the dyeings obtained on the
pregnating component and the developing com-
fiber with Naphtol AS components by the usual
ponent are prepared together in one bath. Not
method are converted into especially lightfast
until the acid has been added is formation of the
metal complex dyeings by aftertreatment with
dye initiated. Diazo components suitable for this
heavy-metal salts (copper, cobalt):
purpose consist of a diazoamino compound not
76 Azo Dyes
Table 16. Naphthol AS components: o-hydroxy compounds of polycondensed and heterocyclic arylcarboxylic acid amides

capable of coupling in the neutral and alkaline simply pouring in the relevant liquid brand into
range, which in the presence of acid is regener- aqueous diluted sodium hydroxide solution. The
ated into the active diazonium salt (see Section liquid brands of the diazo components are ei-
6.1.2). The addition of dispersing agents to the ther molecular solutions or dispersions: aro-
developing component ensures that the insolu- matic amines with low melting points (down
ble dye formed in the liquor remains in colloidal to approx. 80 ◦ C) are dissolved as free bases
dispersion and can be removed during the subse- in monoalkyl ethers of diethylene glycol (oc-
quent washing process (Azanil Color Salts from casionally with the addition of dimethylsulf-
Hoechst) [285–288]. oxide or N-methylpyrrolidone); higher melting
The introduction of liquid brands of azoic amines (mp above 100 ◦ C) can in the presence
coupling components and azoic diazo compo- of suitable surfactants and other auxiliaries (eth-
nents results in a considerable simplification ylene glycol, glycerol, or sorbitol) be processed
of important steps in the dyeing and printing in more highly concentrated dispersions. Apart
with Naphtol AS developing dyes. The for- from dust-free handling, all liquid brands of di-
mer are 25 – 45 % solutions of monoalkali salts azo components are distinguished by particu-
of Naphtol AS components in high-boiling al- larly rapid and complete diazotizability without
cohols (usually ethylene or diethylene glycol) troublesome side reactions [289] (see also page
miscible with water. These highly concentrated 82).
molecular solutions with good storage stabil-
ity permit dust-free handling of the coupling
component and enable ready-to-use impregnat-
ing baths to be prepared especially quickly by
 Azo Dyes 77
Table 17. Naphthol AS components: acylacetic acid amides

6.1.2. Developing Dyes for Printing [5, solution of a sodium naphtholate and, after dry-
vol. III, p. 290 – 301], [278–280], [290] ing, the thickened solution of the diazotized Fast
Color Base is printed onto the material.
For details of the printing method → Textile In contrast to cotton dyeing, with the wide di-
Printing. versity of Naphtol AS derivatives that are used,
price, coloristic, and substantivity reasons dic-
Two-Stage Printing Processes. As with the tate that only two components capable of cou-
dyeing of cotton fibers, two-stage methods can pling are in the main used for impregnation of
also be employed when printing. Depending on the textile to be printed: Naphtol AS (C. I. Cou-
whether the coupling component (as sodium pling Component 2, 37505, see Table 14) as red
salt) or the diazo component (as diazonium salt) component and Naphtol AS-G (C. I. Coupling
is applied during the printing process, a distinc- Component 5, 37610, see Table 17) as yellow
tion is made between naphtholate printing pro- component. The cotton impregnated with the
cesses and base printing processes. sodium salts of these Naphtols by padding and
In the naphtholate printing process, the subsequent drying has good, if only limited, sta-
sodium salts of the Naphtol AS compounds in bility when stored in a cool, dark place. Because
the form of aqueous, thick pastes (additions of of their low substantivity for the cellulosic fiber,
high-swelling, nonionic or anionic polysaccha- Naphtol AS and Naphtol AS-G additionally sat-
rides) are printed on the textile material and then isfy the important requirement that after the base
developed as azo dyes on the fiber by treatment printing process they can be completely washed
with the solution of a diazotized base. off again from the unprinted parts.
Naphtholate printing has always been of only By combining the two Naphtols with numer-
secondary importance. ous azoic diazo components, a relatively wide
In the so-called base printing process, the range of printed shades is possible. The addi-
cellulosic material is first impregnated with the tion of Naphtol AS enables shades in the or-
78 Azo Dyes
Table 18. Color bases and color salts
 Azo Dyes 79
Table 18. (Continued)
80 Azo Dyes
Table 18. (Continued)
 Azo Dyes 81
Table 18. (Continued)
82 Azo Dyes

ange, scarlet, red, bordeaux, violet, navy blue, longer needs to be buffered; during the subse-
and black range to be obtained, Naphtol AS-G quent printing process it couples rapidly and
is used in the yellow to brown range. If higher re- completely with the Naphtol in the impregnated
quirements must be met with regard to light fast- fabric [289], [292].
ness, Naphtol AS-G can be replaced by Naphtol The possibility of diazotizing mixtures of dif-
AS-IRG (C. I. Coupling Component 41, 37613, ferent azoic diazo components at the same time
see Table 17). in a single paste has proved to be a particular ad-
Right into the 1940s, the base printing pro- vantage of the diazotization process described.
cess enjoyed considerable industrial impor- The use of mixed coupling products thus opened
tance, but in comparison with the one-stage pro- up a further possible method of shade matching.
cess it then receded into the background. The
development of reactive dyes resulted in a world- One-Stage Printing Processes. Especially
wide revival of the two-stage base printing pro- simple methods of printing cotton fibers were
cess, because vinyl sulfone dyes, in particular, developed using the one-stage direct printing
can in many cases be applied together with color process. In this technique, the diazo component
salts or diazotized color bases. The possibility in the form of a stabilized diazo compound, i.e.,
of printing a broader range of shades on cot- not initially capable of coupling, is applied at
ton, which had long been desired, can thus be the same time as the coupling component and
achieved [291]. coupling is then initiated by a damp aftertreat-
The additional combination of the yellow to ment in an acid medium or by acid, or frequently
golden yellow azoic developing dyes with the also neutral steaming.
blue phthalocyanine developing dyes, in par- Three different diazo derivatives are em-
ticular with a cobalt-phthalocyanine derivative ployed in textile printing as stabilized diazo
of clear, dark blue color (C. I. Ingrain Blue 5, compounds (a more appropriate term is con-
Phtalogen Blue IBN [37370-33-5] from Bayer) cealed diazo compounds): antidiazotates, di-
makes it possible to match deep green shades azo sulfonates, and diazoamino compounds
and thus close a gap in the color range. (for properties and production → Diazo Com-
These subsequent developments have re- pounds).
sulted in the base printing method acquiring con- Combinations with diazoamino compounds
siderable importance, in particular for so-called were of particular industrial importance, but
African and Java prints. with the appearance of the reactive dyes, they,
too, receded into the background.
Other Developments. In the conventional Because of its relatively complicated chem-
diazotizing process, the differences in the re- ical background, the one-stage printing process
activity of aromatic amines frequently lead to must be dealt with in somewhat more detail.
the uncontrolled release of nitrous gases and un-
desired side reactions, in spite of the fact that Combinations with Antidiazotates. Un-
ice is used. With the use of liquid brands (see like the unstable syndiazotates, the stable antidi-
page 75) instead of the powder of the free base, azotates do not couple with alkaline β-naphthol
it was possible to increase the rate of diazo- solution, or if so only very slowly.
tization considerably and to eliminate the for-
mation of byproducts. A further refinement of
this technique led to an especially elegant vari-
ation of the base printing process, the so-called
DIP process (“Diazotization in the paste”): the
aqueous – alcoholic dispersion or molecular so-
lution of the base is stirred into a paste of sodium Not until the acid treatment is carried out
nitrite which without being cooled is then mixed is the diazonium ion formed with subsequent
with the aqueous paste of a medium-strong acid rapid azo coupling. This fact acquired impor-
(it is best to use phosphoric acid). Diazotation tance in textile printing, diazotates of weakly
is completed quickly without any formation of basic, mainly chlorinated amines being used in
nitrous gases. The diazo salt paste obtained no
 Azo Dyes 83

particular, because of their good stability and Combinations with Diazosulfonates. Dia-
development ability. zosulfonates Ar−N=N−SO− 3 , obtained by re-
Antidiazotates are obtained in a simple man- action of diazonium salts with sulfites, do not
ner by introducing a diazonium salt solution into couple in their stable anti form with 2-hydroxy-
concentrated aqueous alkali and heating to tem- 3-naphthoic acid amides, or if so only slowly.
peratures above 100 ◦ C, whereby the syndiazo- The diazonium compound capable of coupling
tate formed initially is rearranged into the anti is reformed when exposed to light or when the
compound. temperature increases.
Mixtures of sodium salts of 2-hydroxy-3- The Rapidazol dye range introduced in 1932
naphthoic acid amides and other coupling com- utilizes this property: ready-to-use mixtures of
ponents in the Naphtol AS range with antidia- diazosulfonates, in particular from the 4-ami-
zotates in the form of pastes and powder brands nodiphenylamine range (Variamin Blue bases,
have been marketed since 1921 as Rapid Fast see Table 18), with coupling components of the
dyes. If the fibers impregnated or printed with Naphtol AS type are printed on the fiber and
them undergo an acid aftertreatment, regenera- then developed into azo dyes in neutral steam,
tion of the active diazonium salt and coupling especially in the presence of oxidizing agents.
of the azo dye take place on the substrate. A In spite of its limited color scale, the range,
number of combinations and the shades obtained with its high-quality blue and black brands, was
with them are compiled in Table 20, consider- a welcome addition to the diazotate mixtures.
able importance attaching in particular to Rapid It was especially important at a time when no
Fast Blue BN. diazoamino compounds capable of being devel-
Table 19. Combinations for developing dyes in the Naphtol AS range
oped in a neutral medium were available.
with high fastness properties
Naphtol Color base Dyeing Combinations with Diazoamino Com-
obtained pounds [6, p. 177]. Among the Naphtol AS
AS-L4G Fast Orange RD yellow
combinations for printing, it is the stable
AS-OL Fast Orange GGD orange diazoamino compounds that are mainly used.
AS-OL Fast Scarlet GGS scarlet Since the release (1930) of the first Rapidogen
AS-LT Fast Scarlet LG red
AS-ITR Fast Red ITR red dyes up to the worldwide introduction of the re-
AS-ITR Fast Bordeaux BD bordeaux active dyes, standardized mixtures of these com-
AS-E Variamin Blue FGC blue
AS-FGGR Fast Yellow GC green
binations had enjoyed major industrial impor-
AS-BT Fast Scarlet TR brown tance. The most important commercial ranges
AS-SG Fast Red B black based on diazoamino compounds are compiled
in Table 21.
Table 20. Examples of printing combinations with antidiazotates Table 21. Designations of important ranges of Naphtol AS printing
combinations with diazoamino compounds
Dye Antidiazotate of Coupling Country Manufacturer Ranges
component
Germany, Bayer Rapidogen
Rapid Fast Yellow GH Fast Scarlet GG Base Naphtol AS-G Fed. Rep.
Rapid Fast Orange RH Fast Scarlet GG Base Naphtol AS-PH France ICI-Francolor Neutrogen
Rapid Fast Red RH Fast Red RC Base Naphtol AS-OL Switzerland Rohner Ronagen, Sinagen
Rapid Fast Bordeaux Fast Red R Base Naphtol AS-BS USA Blackman Uhler Printing
RH Pfister Chem. Azogen
Rapid Fast Blue BN Fast Blue B Base Naphtol AS
Rapid Fast Brown IBH Fast Red R Base Naphtol AS-LB India Amar Dye Stabagene
Atul Prod. Tulagene
Japan Kiwa Chem. Ind. Polydogen
The generally limited storage stability of the Sanyo Col. Works Thiugen
mixtures has proved to be a disadvantage of the Sumitomo Sumika Fast
process described, because slow splitting of the Poland Pologen
antidiazotate takes place in the alkaline printing
paste.
Diazoamino compounds (further details
→ Diazo Compounds) are obtained by reacting
84 Azo Dyes

a diazonium salt (200) with a primary or sec- As amine component, the so-called stabilizer,
ondary aliphatic or aromatic amine: use is thus generally made of non-diazotizable
secondary amines, or the equilibrium is influ-
enced by 2nd order substituents in the stabiliz-
ing amine (decreasing basicity). When aromatic
stabilizers are used, the o- and p-position in re-
In the case of aromatic amines, the diazoami- lation to the amino group is usually blocked by
no compound only forms if blocking or deacti- substituents, with the result that after splitting of
vation of the coupling positions in the aromatic the diazoamino compound no coupling to ami-
nucleus prevents the formation of an aminoazo noazo products can occur. If a possible coupling
compound. The reaction (13) is reversible, i.e. position is free, the azo coupling is handicapped
the addition of acid causes the diazoamino com- by the deactivating influence of carboxylic acid
pounds to be split again into their initial compo- or sulfonic acid groups. These substituents ad-
nents. If a primary amine R–NH2 (201) is used, ditionally impart the desired water solubility to
the resulting triazene (202) is in balance with its the diazoamino compound used in the printing
tautomer (202a): combinations.
Stabilizers frequently used are sarcosine, N-
methyltaurine and anthranilic acid derivatives:

Sarcosine N-Methyltaurine

The splitting process can thus lead to the for-

mation of a new diazonium salt (201a) (“redia-
zotization”).
The tautomer equilibrium 202
202a is de-
Anthranilic acid derivatives
pendent on the nature of the two radicals Ar
and R: as the basicity of amine Ar−NH2 (200a)
increases and that of amine R−NH2 (201) de- The diazoamino compound (for further de-
creases, the equilibrium shifts in favor of the tails → Diazo Compounds) is generally obtained
diazoamino compound (202), which is split in by adding a diazonium salt solution to the neu-
the desired manner to form the original diazo- tral or alkaline solution of the stabilizer in the
nium salt. form of its sodium salt. The reactivity of the di-
For practical usage as a stabilized diazo azonium salt determines the speed of the reac-
compound in printing combinations, only those tion. The diazoamino compound precipitated or
diazoamino compounds are suitable that satisfy salted out is filtered, dried, ground, and adjusted
the following conditions: with the sodium salt of a Naphtol AS compo-
nent.
Well-defined splitting without rediazotiza- After the textile fabric has been printed with
tion. the printing combination, the dyeing is devel-
No possibility for the diazonium salt ob- oped by acid steaming (in the presence of acetic
tained after splitting to couple with the amine and formic acid vapors). The reaction of the two
component. soluble components on the fiber to form the in-
Solubility of the diazoamino compound in soluble azo dye is illustrated by the example of
water. Rapidogen Red GS (205).
 Azo Dyes 85

For use of diazoamino compounds for the

dyeing of cotton, see page 77, and of synthetic
polyamide fibers, see Section 6.3.

6.2. Developing Dyes for Animal Fibers

Compared with the dyeing and printing of hy-

drophilic cellulosic fibers, the dyeing of animal
fibers (protein fibers) with products in the Naph-
tol AS range has never attained industrial im-
portance. In this connection, mention is made
here only of the Hoechst ranges of Ofna-Lan and
Rauna dyes, which are no longer on the market
and were used for the dyeing of wool – cellulosic
blends and furs. The problem with this dyeing
203: Diazoamino compound of Fast Red KB base and sar- method proved to be the alkalinity of the impreg-
cosine.
204: Naphtol AS-D
nating baths (alkaline solutions of the Naphtol
AS coupling components), because of the sen-
sitivity to hydrolysis of the peptide compounds
The diversity of combinations on the market of animal fibers [293].
makes it possible to obtain dyeings of any shade Pure silk can be dyed in the same way as cel-
from greenish yellow through orange, scarlet, lulosic fibers, since, unlike wool, silk is largely
red, bordeaux, violet, blue, green to black. insensitive to alkali.
The need for acid development has occasion-
ally proved to be a certain disadvantage. This
step can be avoided by using a steam-volatile 6.3. Developing Dyes for Hydrophobic
organic base, such as diethylaminoethanol, in- Fibers
stead of the alkali employed in the Naphtol
AS diazoamino combinations. During neutral Naphtol AS dyes have also been used com-
steaming, the alkali component in the printing mercially for dyeing hydrophobic synthetic
mixture then escapes and azo coupling takes fibers, particularly polyester and polyamide.
place, especially in the presence of salts which Two methods were developed [294]:
in the steam undergo hydrolysis to form com- In the modified azo process, the coupling
pounds with an acid reaction (e.g., ammonium component and the azoic diazo component are
or pyridinium salts). Selection of suitable modi- applied to the fiber consecutively or from an
fied stabilizers, such as 206 or 207, also enables aqueous bath at 80 – 130 ◦ C, if necessary in the
the splitting tendency of the diazoamino com- presence of a carrier, and the fiber impregnated
pounds to be so carefully “counterbalanced” that by this means is then treated with nitrous acid.
the relevant printing combinations can be devel- Development of the dyeing takes place with di-
oped in neutral steam (Rapidogen N, Neutrogen azotization and simultaneous coupling.
dyes, etc., see Table 21). Products are being introduced that in the op-
timum mixture ratio contain selected combina-
tions of coupling and diazo components capa-
ble of development (Intramin dyes, Hoechst;
Ronasyn dyes, Rohner). The process only gained
206
importance in the inexpensive black dyeing of
polyester fibers (C. I. Azoic Black 16, e.g., In-
tramin Black G, Hoechst). Multicolored shades
are more advantageously obtained with disperse
dyes.
207
86 Azo Dyes

When using diazoamino compounds (so- Azo pigments, like all other organic pig-
called Ofnaperl process, Hoechst) a suitable ments, serve for the coloration of polymeric
diazoamino compound is added to the alkaline materials such as plastics, elastomers, rubber,
bath, in which the Naphtol AS component is dis- paints and other coating materials, and for print-
solved. After the fiber is impregnated in this bath ing pastes. The relatively inexpensive azo pig-
at 60 – 80 ◦ C, the development process is initi- ments have gained noticeable importance due to
ated in the warm acid bath by liberating the con- the rapid economic and industrial development
cealed diazonium salt. Unlike the components of in the past three decades.
the printing combination, the diazoamino com-
pounds used contain no carboxylic acid or sul-
fonic acid groups; they have only limited solubil- 9. Alcohol- and Ester-Soluble Dyes
ity in water but must be readily dispersible (C. I.
Azoic Diazo Components 127, 128, and 130, Of- With the exception of the blue copper phthalo-
naperl Salts, Hoechst). The process has proved cyanine derivatives, these products are azo dyes
especially effective for the dyeing of polyamide soluble in polar solvents, such as alcohols, gly-
fibers (perlon, nylon). cols, esters, glycol ethers, and ketones. Dyes
soluble in alcohol and esters are used in protec-
tive lacquers for the transparent coating of metal
7. Disperse Azo Dyes (→ Disperse Dyes) (aluminum) foils and other materials, such as
wood (greening lacquers); in flexographic inks
Disperse dyes are dyes sparingly soluble in wa- for the printing of metal foils, cellophane and
ter which are used for dyeing synthetic fibers. paper; as well as for the coloration of cellulose
The dyes are added to the aqueous dye bath in esters, celluloid, and poly(vinyl acetates), and,
finely dispersed form and are uptaken out of this in the office supplies sector, for stamping inks
dispersion by the hydrophobic fiber. and pastes for pressure recorders. See Table 22
The fiber hereby represents the organic phase, for important product ranges.
in which the disperse dyes are more soluble than
Table 22. Designation of important alcohol- and ester-soluble dye
in the aqueous dyebath. ranges
About half of all disperse dyes belong to the
Manufacturer Range
azo range. Originally developed for cellulose ac-
etate fibers, disperse dyes are nowadays used in BASF Neozapon, Zapon Fast
Bayer Irisol Fast
large quantities for dyeing polyester fibers. Ciba-Geigy Grasol Fast, Irgacet, Oracet, Orasol
GAF Azosol Fast
ICI Methasol
Sandoz Savinyl
8. Azo Pigments (→ Pigments, Organic)
In modern formulations for foil lacquers,
Pigments are coloring matters that are practi- dyes with better solubility in esters are given
cally insoluble in the application media (DIN preference over the older products, which are
55944). Coloring matters are all color-spending mainly soluble in alcohols. As regards chemical
materials according to DIN 55945. constitution, there is no precise delineation bet-
Azo pigments are the most important class ween alcohol- and ester-soluble dyes, nor bet-
within the group of organic pigments. Mono- ween these two groups and the fat- and oil-
and disazo pigments are the two main ranges. soluble dyes described in Chapter 10.
Whereas in English a strict differentia- In accordance with chemical aspects, the
tion exists between pigments (insoluble color- most important alcohol- and ester-soluble azo
ing matters) and dyes (soluble coloring mat- dyes can be divided into three groups:
ters) in German some confusing terms are
still occasionally used, e.g., “Pigmentfarb- 1 : 2 Metal complexes of (mainly mono-
stoffe”, “Körperfarben”, “Farbkörper”, “Lack- ) azo dyes, without sulfonic or carboxylic
farbstoffe”. These terms should be discontinued acid groups, and trivalent metals (→ Metal-
and only “pigments” and “dyes” used. Complex Dyes).
 Azo Dyes 87

The metals chiefly suitable are chromium Cyclohexylamine, dodecylamine, and sul-
and cobalt, as well as nickel, manganese, fonium or phosphonium compounds serve
iron, or aluminum. Diazo components are as bases, whereas derivatives of the xan-
mainly chloro- and nitroaminophenols or thene range (rhodamines) are mainly used
aminophenol sulfonamides, coupling com- as cationic dyes. Example: C. I. Solvent Red
ponents are β-naphthol, resorcinol, and 1- 109 [53802-03-2] is composed of Solvent
phenyl-3-methlylpyrazolone (5). Formation Yellow 19, 13 900 : 1, (210) [10343-55-2]
of a complex from an azo dye and a metallic and Solvent Red 49, 45 170 : 1, (211)
salt generally takes place in the presence of [81-88-9]:
organic solvents, such as alcohols, pyridine,
or formamide. An example is C. I. Solvent
Red, 12715 (208) [33270-70-1].

210

208

1 : 1 Metal-complex azo dyes that contain

sulfonic acid or carboxylic acid groups and
211
are present in the form of internal salts. Here,
azamethin – metal complexes are also of im- These dyes are saltlike compounds of a
portance. An examples is C. I. Solvent Yel- metal-complex azo dye acid and a base.
low 32, 48045 (209) [61931-84-8].

10. Fat- and Oil-Soluble Dyes

Fat- and oil-soluble dyes are also soluble in
waxes, resins, lacquers, hydrocarbons, halo-
genated hydrocarbons, ethers, and alcohols, but
not in water. It is not possible to differentiate
209 clearly between them and the alcohol- and ester-
In the case of C. I. Solvent Orange 56, sim- soluble dyes (see Chap. 9).
ilar to 18745 : 1 [13463-42-8], also a metal Table 23. Designations of important fat- and oil-soluble dye ranges
complex, diazotized 2-hydroxy-3-amino-5-
Manufacturer Range
nitrobenzene sulfonic acid is coupled to 1-
phenyl-3-methylpyrazolone (5). Amer. Cyanamid Calco
C. I. Solvent Yellow 82, similar to 18690, is BASF Sudan
Bayer Ceres
a 1 : 1 metal complex of the azo dye ob- Bitterfeld Sudan
tained from anthranilic acid and 1-phenyl- Du Pont Oil
Ethyl Corp. Oil Soluble
3-methylpyrazolone (5). Hoechst Fat
Reaction products of acid azo dyes, acid 1 : 1 ICI Waxoline
metal-complex azo dyes, or 1 : 2 metal com- Siegle Sico Fat
Williams Oil
plex azo dyes without acid groups, with or-
ganic bases or cationic dyes.
With the exception of the blue anthraquinone
derivatives, all fat- and oil-soluble dyes belong
88 Azo Dyes

to the azo range. These azo dyes are gener- C. I. Solvent Black 3, 26150 (216)
ally based on simple components. According to [4197-25-5]
their degree of solubility they usually contain
hydroxy and/or amino groups, but not sulfonic
acid and carboxylic acid groups. See Table 23
for important product ranges.
As examples, mention can be made of some
of the most important fat- and oil-soluble azo
216
dyes produced on an industrial scale: C. I. Sol-
vent Yellow 56, 11021 (212) [2481-94-9] The products are sold in powder form, as
granules, or as flakes, and some dyes also as liq-
uid brands. The liquid brands are highly concen-
trated solutions of fat-soluble dyes in aromatic
hydrocarbons, in some cases also solvent-free
212 100 % liquid products.
C. I. Solvent Yellow 14, 12055 (Orange) (213) Fat- and oil-soluble dyes are used on a large
[842-07-9] scale in a wide variety of industrial sectors. Main
fields of application are the coloration of prod-
ucts in the mineral oil and plastics industries,
as well as of wax products (e.g., candles, shoe
polish, floor polishes).
Mineral oil products (fuels, fuel oil, lubricat-
ing oils, and greases) are colored as a means of
distinguishing between different grades (super-
213
grade petrol) or for compulsory identification,
C. I. Solvent Yellow 16, 12700 (214) [4314-14-1] e.g., of diesel and fuel oils, for duty purposes.
The plastics industry values the fat- and oil-
soluble dyes for the highly transparent colorings,
usually with very good light fastness, that are
obtainable with them. Products in this dye class
are most frequently used for the coloration of
polystyrene, as well as for incorporation in poly-
methacrylate and unsaturated polyester casting
214
resins.
An interesting factor is the high degree to
C. I. Solvent Red 23, 26100 (215; R = H) which the light fastness of fat- and oil-soluble
[85-86-9]; C. I. Solvent Red 24, 26105 (215; dyes is dependent on the medium colored.
R = CH3 ) [85-83-6] Whereas, for example, 0.05 % colorations of the
dye Solvent Yellow 56, 11021, in candle mate-
rials possess only moderate light fastness (step
3 on the eight-step Blue Scale), transparent col-
orations in polystyrene are distinguished by out-
standing light fastness (step 8).
Other fields of application are the pyrotech-
nics industry (high sublimation tendency of the
dyes), the office supplies industry (inks for felt-
215 tip pens, oil-based stamping inks), the lacquers
industry (especially coloration of transparent
lacquers on aluminum foil) and the cosmetics
industry (approval restricted to a few products).
 Azo Dyes 89

11. References 23. T. Vickerstaff: The Physical Chemistry of

Dyeing, Oliver and Boyd, London –
1. P. Rys, H. Zollinger: Farbstoffchemie, 3rd ed., Edinburgh 1954.
Verlag Chemie, Weinheim 1982. 24. E. M. Diskant, Anal. Chem. 24 (1952) 1856.
2. Houben-Weyl, 10/3, 213 – 465, 467 – 485. 25. G. Schetty, J. Soc. Dyers Colour. 71 (1955)
3. H. R. Schweizer: Künstliche organische 705.
Farbstoffe und ihre Zwischenprodukte, 26. Sandoz, BE 717458, 1967 (M. Studer).
Springer Verlag, Berlin 1964. 27. Bayer, DE-OS 1923680, 1969 (H. Nickel, F.
4. W. Seidenfaden: Künstliche organische Suckfüll).
Farbstoffe und ihre Anwendungen, Enke 28. Toms River Chem. Corp., DE-OS 1931691,
Verlag, Stuttgart 1957. 1969 (H. A. Stingl).
5. K. Venkataraman: The Chemistry of Synthetic 29. Crompton & Knowles, DE-OS 1957115, 1969
Dyes, Academic Press, New York, vol. I (J. F. Feeman).
(1952), vol. II (1952), vol. III (1970), vol. IV 30. Bayer, DE-OS 1960816, 1969 (K. L. Moritz).
(1971), vol. VI (1972), vol. VII (1974). 31. J. Boulton, J. Soc. Dyers Colour. 67 (1951)
6. H. Zollinger: Azo and Diazo Chemistry, 522.
Interscience, New York – London 1961. 32. I. D. Rattee, M. M. Breuer: The Physical
7. Colour Index, Society of Dyers and Colourists Chemistry of Dye Absorption, Academic
and American Association of Textile Chemists Press, London – New York 1974.
and Colorists, 3rd ed., Bradford 1971, First 33. H. Bach, E. Pfeil, W. Phillippar, M. Reich,
Revision 1975, Second Revision 1982. Angew. Chem. 75 (1963) 407.
8. K. Holzach: Die aromatischen 34. E. Schirm, J. Prakt. Chem. 144 (1935) no. 2,
Diazoverbindungen, Enke Verlag, Stuttgart 69.
1947. 35. H. Zollinger, Helv. Chim. Acta 38 (1955)
9. Houben-Weyl, 10/3, 1 – 212. 1597, 1623; R. Pütter, Angew. Chem. 63
10. N. N. Woroshzow: Grundlagen der Synthese (1951) 186.
von Zwischenprodukten und Farbstoffen, 4th 36. Cassella, DE 204212, 1907 (A. Greßly).
ed., Akademie Verlag, Berlin (DDR) 1966. 37. BASF, DE 46737, 1888; DE 47902, 1889
11. H. E. Fierz-David, L. Blangey: Grundlegende (C. L. Müller).
Operationen der Farbenchemie, 8th ed., 38. Ciba, DE 436179, 1923.
Springer Verlag, Wien 1952. 39. Ciba, DE 335809, 1915.
12. P. F. Gordon, P. Gregory: Organic Chemistry in 40. BASF, DE 807289, 1948 (H. Pfitzner, H.
Colour, Springer Verlag, Berlin – Heidelberg Merkel); H. Pfitzner, H. Baumann, Angew.
– New York 1983. Chem. 70 (1958) 232.
13. A. Eibner, Justus Liebigs Ann. Chem. 316 41. J. Offenbach: Deutscher Färbekalender, Eder
(1901) 126; H. Bucherer, A. Schwalbe, Ber. Verlag, Stuttgart 1972, pp. 185 – 194.
Dtsch. Chem. Ges. 39 (1906) 2798. 42. L. Diserens: Die neuesten Fortschritte in der
14. M. Martynoff, Bull. Soc. Chim. Fr. 18 (1951) Anwendung der Farbstoffe, vol. 1, 3rd ed.,
214. 1951; vol. 2, 2nd ed., 1949, Birkhäuser, Basel.
15. H. Baumann, H. R. Hensel: “Neue 43. Geigy, DE 114634, 1899.
Metallkomplexfarbstoffe. Struktur und 44. GAF, DE 901419, 1950; DE 901540, 1950.
färberische Eigenschaften”, Fortschr. Chem. 45. BASF, DE-OS 2557561, 1975 (H. Kast, G.
Forsch. 7 (1967) no. 4. Riedel).
16. H. Pfitzner, H. Baumann, Angew. Chem. 70 46. Tekhnolog Constr. Techn. Bur., RU 21 02 415,
(1958) 232. 1994.
17. D. Vorländer, F. Meyer, Justus Liebigs Ann. 47. BASF, DE-OS 3011235, 1980 (K. Schmeidl).
Chem. 320 (1902) 122. 48. BASF, DE-OS 37 13 618, 1987 (K. Schmeidl).
18. D. C. Freemann, C. E. White, J. Org. Chem. 49. BASF, EP 341 325, 1988 (K. Schmeidl).
21 (1956) 379. 50. Bayer, DE-OS 3025557, 1980 (K. Linhart, H.
19. H. H. Hodgson, F. Leigh, G. Turner, J. Chem. Gleinig, R. Raue, H.-P. Kühlthau).
Soc. 1942, 744. 51. Bayer, DE-OS 33 03 512, 1983 (R. Raue).
20. F. Suckfüll, H. Dittmer, Chimia 15 (1961) 137. 52. Amer. Cyanamid, DE-AS 1072222, 1958.
21. S. Hünig et al., Angew. Chem. 70 (1958) 215; 53. Bayer, DE-AS 1044310, 1956.
74 (1962) 818. 54. VEB Bitterfeld, DE-OS 2038411, 1970.
22. M. Regitz, Angew. Chem. 79 (1967) 786. 55. Bayer, DE-OS 3048998, 1980 (K. Kunde).
90 Azo Dyes

56. Sandoz, DE-OS 2915323, 1979; 3030197, 90. Bayer, DE-OS 2309528, 1973; DE-OS
1980 (R. Pedrazzi). 3030918, 1980 (K. Linhart, H. Gleinig, G.
57. Sandoz, DE-OS 33 11 091, 1982 (J. Troesch, Boehmke, K. Breig); DE-OS 3101140, 1981
W. Portmann). (K. Linhart, H. Gleinig, G. Boehmke).
58. Sandoz, DE-OS 33 29 817, 1982 (J. Troesch, 91. Bayer, DE-OS 2508884, 1975; DE-OS
W. Portmann). 2631030, 1976 (W. Kruckenberg).
59. Sandoz, DE-OS 34 12 762, 1983 (J. Troesch). 92. Ciba, DE-OS 2011428, 1970 (G. Hegar).
60. Sandoz, DE-OS 35 03 844, 1984 (R. Pedrazzi). Sandoz, CH 546269, 1964; CH 552032, 1964
61. Sandoz, EP 341 214, 1988 (H. A. Moser, R. (R. Entschel). Du Pont, US 3890257, 1973;
Wald). US 3987022, 1973 (D. S. James).
62. Bayer, DE-OS 3133360, 1981 (K. Kunde). 93. Pentel K.K., JP 77101125, 1976.
63. Nippon Chem. Works, JA 04 93 365, 1990. 94. Mitsubishi Kasei, JA 01 284 570, 1988.
64. BASF, EP 281 920, 1987 (J. Dehnert). 95. Bayer, DE-OS 2533428, 1975 (G. Boehmke,
65. Bayer, EP 632 104, 1993 (K. Hassenrueck, P. U. Hendricks).
Wild). 96. Sumitomo, JP 7237675, 1969.
66. Bayer, EP 312 838, 1987 (A. Engel). 97. Ciba-Geigy, EP 696 619, 1994 (A. Kaeser).
98. Sandoz, DE-OS 2118536, 1970; DE-OS
67. Intreprenderea “Sintofarm”, RO 88 681, 1984.
2712265, 1976; DE-OS 2741010, 1976;
68. BASF, DE-OS 42 02 566, 1992 (E. Hahn, H.
DE-OS 2805264, 1978 (M. Greve); BE
Hengelsberg, U. Mayer).
756820, 1970; CH 549629, 1971. Montedison,
69. Orient Chem. Works, JA 08 048 924, 1994.
DE-OS 2851373, 1977 (F. Merlo).
70. Nippon Chem. Works, JA 04 183 754.
99. ICI, DE-OS 2200270, 1971; DE-OS 2364592,
71. BASF, DE-OS 42 35 154, 1992 (U. Schloesser,
1973; DE-OS 2364593, 1972.
U. Mayer).
100. Sandoz, DE-OS 2313526, 1972 (W.
72. BASF, EP 666 287, 1994 (U. Schloesser, U.
Steinemann).
Mayer). 101. Ciba-Geigy, DE-OS 2429927, 1973 (V.
73. Wella, EP 852 942, 1996 (U. Lenz, E. Nowald). Ramerathan).
74. L’Oreal, WO 97/20 545, 1997 (H. Samain). 102. Sandoz, DE-OS 31 17 127, 1980 (P. Doswald,
75. Sandoz, DE-OS 1644138, 1966. E. Moriconi, H. Moser, H. Schmid).
76. Ciba, FR 1322766, 1961. 103. Mitsubishi, JP 4957169, 1972; JP 4990327,
77. Bayer, DE-OS 32 31 398, 1982 (P. Wild, F.-M. 1972; JP 49109422, 1973; JP 5000179, 1973;
Stoehr). JP 5003123, 1973; JP 5031181, 1973; JP
78. Bayer, DE-OS 3138182, 1981 (K. Kunde, P. 5246184 1973.
Wild). 104. Ciba, BE 587048, 1959. GAF, FR 1295862,
79. ICI, GB 951667, 1961. 1960.
80. Bayer, DE-AS 1011396, 1955 (W. 105. I. Gmai et al., SU 287217, 1966.
Kruckenberg). 106. Inst. f. Org. Ind., PL 64734, 1968.
81. VEB Chem. Bitterfeld, DDR 227 148, 1984 107. Du Pont, DE-OS 2003540, 1969.
(E. Guhl, G. Knochel, H. Noack, J. Schlykow). 108. Ciba-Geigy, DE-OS 2509596, 1974.
82. VEB Chem. Bitterfeld, DDR 227 149, 1984 109. Sandoz, DE-OS 20 61 964, 1969 (H. Moser, H.
(R. Freitag, E. Guhl, G. Knochel, H. Noack, J. von Tobel).
Schlykow). 110. Ciba-Geigy, EP 15 233, 1979 (P. Galafassi,
83. Bayer, DE-OS 2850706, 1978 (K. Leverenz, J. J.-M. Adam, P. Loew, H. Scheidegger).
Reppert). 111. Ciba-Geigy, DE-OS 38 21 627, 1987 (W.
84. Chemie Bitterfeld-Wolfen, DE-OS 41 28 490, Stingelin).
1991 (H. Hartenstein et al.). 112. Ciba-Geigy, EP 294 330, 1987 (W. Stingelin).
85. Mitsubishi Chem., JA 59 170 147, 1983. 113. Ciba, BE 672152, 1964, Amer. Aniline, US
86. Sumitomo, JP 7313753, 1969. 3881866, 1972 (E. E. Renfrew). ACC, US
87. Bayer, DE-OS 2024184, 1970; DE-OS 4204994, 1979; US 4211697, 1979 (K. A.
2036952, 1970; DE-OS 2036997, 1970; Desai).
DE-OS 2041690, 1970; DE-OS 2065685, 114. Mitsubishi Chem., JA 59 140 265, 1983.
1970 (W. Kruckenberg). ICI, DE-OS 2646967, 115. Mitsubishi Chem., JA 61 151 269, 1984.
116. Mitsubishi Chem., JA 62 263 262, 1986.
1975 (P. Gregory).
117. Sandoz, FR 1325176, 1961.
88. Sandoz, DE-OS 2338729, 1972 (B. Henzi).
118. Sandoz, CH 508709, 1969. Bayer, DE-OS
89. Bayer, DE-OS 2059947, 1970.
2042662, 1970.
 Azo Dyes 91

119. Sandoz, DE-OS 2054697, 1969 (W. 145. ICI, GB 1282281, 1967; GB 1290321, 1967.
Steinemann); DE-OS 2752282, 1976 (M. 146. Ciba-Geigy, CH 745871, 1974; CH 745872,
Greve). ICI, DE-OS 2638051, 1975; DE-OS 1974.
2656879, 1975; DE-OS 2657147, 1975; 147. Ciba-Geigy, EP 16726, 1979 (J. M. Adam, P.
DE-OS 2657149, 1975; DE-OS 2702777, Galafassi).
1976; DE-OS 2702778, 1976 (B. Parton). 148. Ciba-Geigy, EP 306 452, 1987 (W. Stingelin).
120. TU Dresden, DDR 289 043, 1989 (P. 149. Kuhlmann, BE 626882, 1962; DE-OS
Bellmann, K. Gewald, H. Schafer). 2314406, 1972 (J. P. Stiot, C. Brouard).
121. Sandoz, DE-OS 2627680, 1975 (M. Greve, H. 150. Kuhlmann, FR 1364560, 1962.
Moser); CH 601433, 1976; FR 2360632, 1976 151. Kuhlmann, FR 1364647, 1963.
(H. Moser). Ciba-Geigy, DE-OS 3223436, 152. Kuhlmann, FR 1389432, 1963; FR 1414876,
1981 (V. Ramanathan, W. Stingelin). 1964; DE-OS 2140511, 1970; DE-OS
122. Hodogaya Chem. Ind., JA 03 192 158, 1989. 2314406, 1972 (J. P. Stiot, C. Brouard).
123. Nippon Kayaku, JA 01 283 269, 1988. 153. Kuhlmann, FR 1467822, 1965.
124. BASF, DE-OS 38 01 945, 1988 (H. Bruder, R. 154. Kuhlmann, FR 1403092, 1964. Geigy, FR
Dyllick-Brenzinger, U. Mayer, S. J. Bares). 1322747, 1961.
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Miederer). (B. Parton, F. L. Rose).
127. BASF, EP 482 508, 1990 (M. Ruske, U. 157. Sandoz, DE-OS 36 09 590, 1985 (H. A. Moser,
Mayer). R. Wald).
128. BASF, DE-OS 19 809 994, 1997 (M. Ruske, P. 158. Sandoz, DE-OS 35 16 809, 1984 (J. Doré).
Erk, H. Hengelsberg). 159. Sandoz, DE-OS 37 15 066, 1986 (H. A. Moser,
129. Ciba, BE 698730, 1966; BE 698917, 1966; EP R. Wald).
55221, 1980 (P. Loew). Yorckshire Dyeware 160. Sandoz, DE OS 33 40 483, 1982 (M. Greve, H.
Corp., GB 1047293, 1964; GB 1157867, 1967; Moser).
GB 1349511, 1970 (J. F. Dawson, J. 161. Sandoz, DE-OS 33 11 294, 1983 (H. Moser, W.
Schofield). ICI, GB 2009208, 1977 (M. G. Samhaber, H. Schmid).
Hutchings). 162. Sandoz, DE-OS 35 38 517, 1984 (H. A. Moser,
130. ICI, GB 1211078, 1967. R. Wald).
131. Yorckshire Dyeware Corp., GB 1233729, 163. Sandoz, DE-OS 19 629 238, 1995 (J. Geiwiz,
1968. H. Moser, R. Pedrazzi, H. A. Moser).
132. GAF, DE-OS 2244459, 1971. 164. Sandoz, DE-OS 39 32 566, 1988 (H. A. Moser,
133. Yorckshire Dyeware Corp., GB 1380571, R. Wald).
1971. 165. Sandoz, DE-OS 19 500 203, 1994 (H. A.
134. ICI, GB 1247683, 1968. Moser).
135. ICI, DE-OS 2331953, 1972. 166. Sandoz, DE-OS 44 39 004, 1994
136. Yorckshire Dyeware Corp., GB 1361542, (J.-P-Chavannes, G. Schöfberger, G. Scheulin).
1972. 167. Bayer, DE-OS 31 14 088, 1981 (F.-M. Stöhr,
137. Ciba-Geigy, DE-OS 2125911, 1970. ICI, H. Nickel).
DE-OS 3008899, 1979 (P. Gregory, D. Thorp). 168. Sandoz, DE-OS 36 25 576, 1985 (J. Doré, R.
138. BASF, DE-OS 36 11 228, 1986 (K. H. Etzbach, Pedrazzi).
G. Hansen, H. Reichelt, E. Schefczik). 169. Bayer, DE-OS 31 33 568, 1981 (F.-M. Stöhr,
139. ICI, DE-OS 2548879, 1974; DE-OS 2703383, H. Nickel).
1976; DE-OS 2817638, 1977 (P. Gregory). 170. Clariant, WO 97/35925, 1996 (R. Pedrazzi).
Sandoz, CH 627487, 1977 (U. Blass). 171. Ciba-Geigy, EP 122 458, 1983 (J.-M. Adam,
140. Ciba-Geigy, EP 514 336, 1991 (A. Nicopoulos, H. Schwander).
H. Birri, G. Hanika). 172. Sandoz, DE-OS 2250676, 1971 (H. Moser).
141. Sandoz, BE 668688, 1964. ICI, DE-OS 173. Sterling Drug, DE-OS 2604699, 1975 (N. C.
2817638, 1977; DE-OS 3008899, 1979; GB Crounse).
2074598, 1980 (P. Gregory). 174. Bayer, EP 54616, 1980; EP 74589, 1981;
142. ICI, GB 1374801, 1971. DE-OS 3222965, 1982 (K. Kunde).
143. Ciba-Geigy, DE-OS 2154477, 1970. 175. Bayer, DE-OS 35 02 927, 1985 (K. Kunde, N.
144. BASF, DE-OS 2046785, 1970. Petzeit).
92 Azo Dyes

176. Sandoz, DE-OS 2915323, 1978 (R. Pedrazzi). 209. Sterling Drug, GB 1299080, 1968; JP
177. BASF, DE-OS 33 26 812, 1983 (H. Loeffler). 4702127,1970; US 3935182, 1973; US
178. BASF, DE-OS 34 13 022, 1984 (H. Colberg). 3996282, 1974. Scott Paper, GB 2020703,
179. BASF, DE OS 34 18 672, 1984 (H. Colberg, 1978.
H. J. Degen, J. P. Dix). 210. Bayer, DE-OS 3114075, 1981; DE-OS
180. BASF, DE-OS 35 02 693, 1985 (H. Colberg, E. 3114087, 1981 (H. Nickel, P. Wild, F. M.
Hahn). Stöhr).
181. Sandoz, DE-OS 3030196, 1980 (R. Pedrazzi). 211. Bayer, DE-OS 3048694, 1980 (H. Nickel, P.
182. Nippon Chem. Works, JA 04 183 755, 1985. Wild).
183. Ciba-Geigy, DE-OS 34 20 777, 1983 (V. 212. Mitsubishi, JP 49118721, 1973.
Ramanathan). 213. Ciba-Geigy, EP 263 073, 1986 (W. Stingelin).
184. Sterling Drug, US 4376729, 1980 (N. C. 214. Ciba-Geigy, EP 434 623, 1989 (W. Stingelin).
Crounse). 215. Eastman Kodak, US 3804823, 1972. Hoechst,
185. Hoechst, DE-OS 2028217, 1970; DE-OS DE-OS 2339713, 1973 (E. Fleckenstein).
2057977, 1970. 216. Toyo Ink, JA 05 125 290, 1991.
186. Mitsubishi, JP 2181/66, 1963. ICI, GB 217. Bayer, DE-OS 2315637, 1973 (K. L. Moritz,
1516978, 1974 (P. Gregory). Bayer, DE-OS K.-H. Schündehütte). Sandoz, DE-OS
3110223, 1981 (P. Wild, H. Nickel). 2120878, 1970; EP 41040, 1980; EP 93828,
187. Mitsubishi, JP 4986424, 1972; JP 49116384, 1980; EP 93829, 1980 (P. Doswald, E.
1973. Moriconi, H. Moser, H. Schmid). Kuhlmann,
188. Chemie Bitterfelden-Wolfen, DDR 296 501, DE-OS 2119745, 1970. Eastman Kodak, US
1990 (E. Forst, E. A. Jauer, R. Muehlberg, W. 3836518, 1972 (G. T. Clark).
Mueller, H. Noack). 218. Bayer, DE-OS 2101999, 1971 (M. Wiesel, G.
189. ICI, NL 6918341, 1968; DE-OS 2216206, Wolfrum). Mitsubishi, JP 5043284, 1973.
1971. 219. Sandoz, DE-OS 3313965, 1982.
190. Hoechst, DE-OS 2347756, 1973. 220. Sandoz, DE-OS 2251041, 1971 (H. Moser).
191. Hoechst, FR 1601787, 1967. 221. Sandoz, DE-OS 2120590, 1970; DE-OS
192. Sandoz, CH 555876, 1971 (R. Entschel). 2120878, 1970.
193. Bayer, EP 24322, 1979 (H. Nickel, F. Müller, 222. Sandoz, CH 516622, 1968.
P. Mummenhoff). 223. Bayer, DE-OS 1544529, 1965.
194. BASF, EP 324 415, 1988 (H. Bruder, U. 224. Hoechst, FR 1484099, 1965.
Mayer). 225. Hoechst, FR 1484503, 1965. Amer. Cyanamid,
195. Bayer, EP 24321, 1979 (H. Nickel, F. Müller, DE-AS 1155547, 1957; DE-AS 1162014,
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196. Nippon Chem. Works, JA 05 132 629, 1991. 226. IG Farbenind., DE 477913, 1927. ICI, DE-OS
197. Warner-Jenkinson, DE-OS 19 752 665, 1996 2319090, 1972.
(R. W. Pengilly, F. C. P. McLoughlin, 227. Ciba-Geigy, EP 284 567, 1987 (J. M. Adam).
R. G. J. C. Twigg). 228. ICI, DE-OS 2421822, 1973 (J. L. Leng, D. F.
198. Du Pont, DE-AS 1054616, 1954. Newton); GB 2011454, 1977 (M. G.
199. Bayer, DE-OS 2135152, 1971. Hutchings). Ciba-Geigy, GB 1257346, 1968.
200. Ciba, DE-AS 1156188, 1959. 229. Kuhlmann, FR 1391676, 1963.
201. Du Pont, US 2965631, 1958. 230. ICI, GB 1246632, 1967; GB 1365625, 1972
202. Ciba, DE-OS 1956142, 1968. Sandoz, CH (J. S. Hunter, J. L. Leng, C. Morris).
553241, 1969 (R. Entschel, C. Müller, W. 231. Bayer, DE-OS 2141987, 1971 (M. Wiesel, G.
Steinemann). Wolfrum).
203. Hoechst, DE-OS 2222099, 1972 (E. 232. GAF, DE-OS 2050246, 1969 (N. A. Doss).
Fleckenstein, R. Mohr, E. Heinrich). 233. Sandoz, CH 554917, 1969 (R. Entschel,
204. Ciba-Geigy, DE-OS 2263109, 1971. C. Müller, W. Steinemann). Hodogaya, JP
205. ICI, GB 1414503, 1972 (D. B. Baird, J. L. 7130110, 1968.
Lang, D. F. Newton). 234. Ciba, DE-OS 1644110, 1966.
206. Bayer, DE-OS 2559736, 1975 (W. 235. MLB Hoechst, DE 105202, 1898. Bayer, DE
Kruckenberg). 272975, 1911. Geigy, DE 473 526, 1927.
207. Hodogaya, JP 7215473, 1969; JP 7215476, 236. Sandoz, DE-OS 37 17 869, 1986 (R. Pedrazzi).
1969. 237. Sandoz, DE-OS 33 40 486, 1982 (M. Greve, H.
208. Du Pont, DE-OS 2137548, 1970. Moser).
 Azo Dyes 93

238. Bayer, DE 181783, 1906. 267. ICI, BE 601144, 1960.

239. Kuhlmann, FR 1380628, 1963. VEB 268. CZ 182 658, 1976 (J. Kroupa, V. Chmatal, J.
Bitterfeld, DE-OS 2031561, 1970. Dvorak).
240. Hoechst, DE-AS 1242773, 1963; FR 2019355, 269. ICI, BE 601145, 1960; BE 601146, 1960;
1968; DE-OS 2516687, 1975; DE-OS DE-OS 2436138, 1973 (C. W. Greenhalgh,
2522174, 1975 (R. Mohr, E. Mundlos, K. D. S. Phillips).
Hohmann). 270. ICI, BE 603028, 1960. V. V. Kormachev, G. P.
241. Hoechst, DE-OS 1816985, 1968. Pavlov, V. A. Kukhtin, R. S. Tsekhawski. Zh.
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3936435, 1974 (G. T. Clark). 276. G. Kaufmann, Melliand Textilber. 44 (1963)
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251. Ciba-Geigy, EP 116 513, 1983 (V. (1954) 429.
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253. Sandoz, DE-OS 33 13 965, 1982 (J. Doré, R. Kirst); DE 1088060, 1959 (R. Mohr, H.
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254. Sandoz, DE-OS 34 40 777, 1983 (J. Doré, R. Hertel, W. Kirst, R. Mohr).
Pedrazzi). 283. A. Rückert, Melliand Textilber. 41 (1960)
255. Sandoz, DE-OS 34 16 117, 1983 (M. Greve, H. 1541.
Moser, R. Pedrazzi, R. Wald). 284. R. Gross, Text. Prax. 15 (1960) 1046.
256. Lexmark, GB 23 15 493, 1996 (J. F. Feeman, 285. W. Kirst, Z. Gesamte Textilind. 68 (1966) 772.
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259. Sterling Drug, US 4379089, 1980. (1983) 286.
260. Sandoz, DE-OS 2403736, 1973 (H. Moser). 290. W. Seidenfaden, Melliand Textilber. 28 (1947)
261. Ciba-Geigy, EP 84372, 1982 (J. M. Adam). 432.
262. Bayer, EP 321 778, 1987 (G. Franke, P. Wild). 291. E. Fees, Melliand Textilber. 47 (1966) 1162,
263. Ciba-Geigy, EP 14677, 1979 (J. M. Adam, V. 1300.
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264. Ciba-Geigy, EP 57159, 1981 (J. M. Adam). Karacsonyi, H. Curtius).
265. Sandoz, DE-OS 1903058, 1969; DE-OS 293. Naphtol Chemie Offenbach, DE 848639, 1948
1965994, 1968. Sterling Drug, DE-OS (W. Kirst).
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