1. * GB780031 (A)
Description: GB780031 (A) ? 1957-07-31
Acid amide derivatives of azo-dyestuffs and process for making them
Description of GB780031 (A)
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CH313170 (A) DE943901 (C) NL89904 (C) US2774755 (A)
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and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
PATENT SPECIFICATI0N
780,031
Date of Application and filing Complete Specification: Dec. 16, 1953.
No. 35107/53.
Application made in Switzerland on Dec. 24, 1952.
Application made in Switzerland on Nov. 12, 1953.
Complete Specification Published: July 31, 1957.
Index at acceptance:-Classes 2(2), B2B2, F2F; 2(4), D1L, G, P1A(1C3:
2B2A: 3: 4B: 5), P1B(1:
2:3:4), P2G(2A: 2B), P2G2C(1:3:5:6:7:8:9:10), P2G(3:4:5C1:6A:
6X), P2H(3: 6: 7: 9: 11: 12: 15: 17: 18: 20), P2J, P(3X: 4X), P9A(3A1:
3F:
4B: 7B: 7D); 2(5), RIC14, R2C(14:16), R(22C14:29C14: 29C16: 33C14);
2(6), PIO(C10: C20Dl: 20D3: DIA); and 2(7), T6J4.
International Classification:-C08b, f, g. C09b. D01f.
COMPLETE SPECIFICATION

2. Acid Amide Derivatives of Azo-Dyestuffs and process for making them
We, CIBA LIMITED, a body corporate organised according to the laws of
Switzerland, of Basle, Switzerland, do hereby declare the invention,
for which we pray that a patent may be granted to us, and the method
by which it is to be performed, to be particularly described in and by
the following statement.The present invention provides a process for
the manufacture of acid amide derivatives of azo-compounds, wherein an
amine which is free from groups imparting solubility in water and
contains at least two reactive amino groups is condensed at each of
the amino groups with a carboxylic acid halide free from groups
imparting solubility in water, at least one of the amino groups being
condensed with a carboxylic acid halide of an azo compound of which at
least one azo linkage is bound on one side to an aryl nucleus which
contains a carboxylic acid ester group in a position vicinal to the
azo linkage, and on the other side to the residue containing the
carboxylic acid halide group.
In the process of the invention there are used starting materials
which are free from groups imparting solubility in water such as
sulphonic acid groups, sulphonic acid amide groups and carboxylic acid
groups. The amines used as starting materials must contain at least
two reactive, that is to say, primary or secondary, amino groups. Good
results are obtained with non-vattable aromatic diamines. As such
diamines there may be mentioned mono-nuclear diamines such as 1: 4 -
diaminobenzene, 1: 4 - diamino - 2: 5dialkoxybenzenes and 1:
4-diaminobenzenes which may contain various substituents in the 2- and
5-positions, such as nitro groups, halogen atoms, alkoxy groups or
alkyl groups.
In many cases especially good results are obtained by using binuclear
or polynuclear amines, for example, by using 4:4'-diaminodiphenyl and
derivatives thereof, such for example, as 3: 3 -dichloro-, 3: 3
'-dimethyl-, 45 3: 3 '-dialkoxy-4: 41-diaminodiphenyl, 3: 5:
3': 51-tetrachloro-4: 4'-diaminodiphenyl and 3:5:3':51 - tetramethyl -
4:41 - diaminodiphenyl. In general valuable acid amide derivatives are
also obtained by using diamines 50 of the benzene series, in which two
identical or different benzene nuclei are connected together by a
suitable bridging member, for example, by oxygen, or -SO2,- as in the
case of 4:4'-diaminodiphenylsulphone, 3: 31diamino-4:
4'-dichlorodiphenylsulphone and 3:31 - diamino - 4:41 -
dimethoxydiphenylsulphone; or by -CO- as in the case of 3:
31-diaminodiphenyl ketone, 3: 31-diamino4: 41-dichlorodiphenyl ketone
and 3: 31diamino-4: 41-dimnethoxydiphenyl diketone; or by -CH-- as in
the case of 3: 3 1-diaminodiphenyl - methane, 3:31 - diamino -
4:4'dichlorodiphenyl - methane, 4: 41 - diamino3:31 - dichlorodiphenyl
- methane, 4:41 -diamino - 3: 5: 3': 51 - tetrachiorodiphenylmethane;

3. or by -NINHCO-, -NHCONIIH-, -SO0NH-, -CH = CH-, --CI--CH-2-,
-HN--CO-C2H4--CO--, -NH- or -N= N-. Finally there may be used 70
diamines of quite a different kind, for example, 2: 8 -
diaminochrysene, 4: 11 - diaminofluoranthene, 2: 6- or 1:
5-diaminonaphthalenes, and diaminobenzthiazoles such as
2-(41-aminophenyl)-6-aminobenzthiazole. 75 The carboxylic acid halides
serving as starting matenials in the present process may be prepared
by treating with an acid halide forming agent an azo-compound, of
which at least one azo linkage is bound on one side to 80 an aryl
nucleus containing a carboxylic acid ester group in ortho-position to
the azo linkage and on the other side to a residual which contains
asAhe sole group impartin, _ .
solubility a free carboxylic acid group, such as azo compounds of the
formula R1-N= N-R--COOHin which R, represents the residue of a diazo
component of the benzene or naphthalene series containing a carboxylic
acid ester group as a substituent in a position vicinal to the azo
linkage, and -R2-COOHrepresents the residue of a coupling component
containing a hydroxyl group and bound to the azo linkage in a position
vicinal to that group, or of the formula COO-AI.
R,-N- N-R2-COOH in which the -COO-Agroup is in orthoposition to the
azo linkage, A represents a benzene residue or an alkyl group of 1 to
4 carbon atoms, R, represents a benzene or a naphthalene residue, and
R. represents the residue of a coupling component containing a
hydroxyl group and bound to the azo linkage in a position vicinal to
that group. Advantageously these azo-compounds contain a single azo
group, and they are advantageously prepared by coupling a diazotised
amine of the naphthalene or advantageously of the benzene series,
which contains a carboxylic acid ester group in a position vicinal to
the diazotised amino group, with a coupling component containing a
carboxylic acid group as a substituent, and a hydroxyl group in
ortho-position to the couplable carbon atom.
The carboxylic acid ester group may, for example be a carboxylic acid
aryl ester group, for example, a carboxylic acid phenyl ester group of
which the phenyl nucleus may contain as further substituents alkyl
groups such as methyl or ethyl, alkoxy groups such as methoxy or
ethoxy or halogen atoms such as chlorine. Of special interest are
diazo-components which contain carboxylic acid alkyl ester groups,
especially those containing alkyl residues of low molecular weight
such as a carboxylic acid methyl, ethyl, n-propyl, isopropyl or butyl
ester group. As examples of diazo components containing carboxylic
acid ester groups there may be mentioned, for example,
1-aminobenzene-2-carboxylic acid phenyl ester,
1-aminobenzene-2-carboxylic acid 41-chloro-phenyl ester,
1-aminobenzene12-carboxylic acid methyl or ethyl ester,

4. 1aminobenzene-2-carboxylic acid n-butyl ester, 1-amino-4- or
-5-chlorobenzene-2-carboxylic acid methyl ester, 1-amino-4:
6-dichlorobenzene-2-carboxylic acid methyl ester,
2aminonaphthalene-3-carboxylic acid methyl ester and
2-aminonaphthalene-3-carboxylic acid ethyl ester.
For the preparation of the carboxylic acids containing azo linkages
the above mentioned or other amines of the kind described above 6 may
be coupled with any desired carboxylic acids, but advantageously with
those capable of coupling in a position vicinal to a hydroxyl group,
for example, oxy-carbazole carboxylic acids, especially
2-oxycarbazole-3-carboxylic 6' acid and N-alkyl-derivatives thereof,
2-oxyanthracene-3-carboxylic acid, and also
3-oxydiphenylene-oxide-2-carboxylic acids or
3oxy-diphenylene-sulphide-2-carboxylic acid.
As coupling components there may also be 7( used open-chain or
heterocyclic compounds containing enolisable keto groups, with the use
of which it is generally recognised that after coupling they are
present in the enol form, that is to say they contain a hydroxyl group
7' in a position vicinal to the azo linkage. Among coupling components
of this kind there are especially suitable pyrazolone carboxylic
acids, for example, 1-aryl-5-pyrazolone-3carboxylic acids or
aryl-pyrazolones, which 8( contain a carboxyl group bound to the aryl
residue; and as examples there may be mentioned
1-phenyl-5-pyrazolone-3-carboxylic acid and also
1-phenyl-3-methyl-5-pyrazolone4'-carboxylic acid. As open-chain
coupling 85 components containing enolisable keto groups there may be
mentioned arylides of /l-ketocarboxylic acids containing carboxyl
groups such, for example, as 1-acetoacetylaminobenzene-2- or -3- or
-4-carboxylic acid and 90 1 - benzoylacetvlamino - benzene- 3- or
-4carboxylic acid.
However, especially valuable results are obtained by using 2 -
oxynaphthalene- 3carboxylic acid as coupling component. 95 For the
preparation of the carboxylic acid halides serving as starting
materials in the present process the above carboxylic acids containing
azo linkages are treated with acid halide forming agents. As acid
halide form- 10( ing agents there are to be understood agents which
are capable of converting carboxylic acids into their acid halides,
for example, the bromides or chlorides. As such agents there may be
mentioned, more especially, phos- 10' phorus halides, such as
phosphorus pentabromide, phosphorus trichloride or phosphorus
pentachloride, and phosphorus oxyhalides.
There are advantageously used acid chloride forming agents, that is to
say, agents which 11 are capable of converting carboxylic acids into
their acid chlorides, such as phosphorus pentachloride or thionyl

5. chloride.
The treatment with the acid halide forming agents is advantageously
carried out in an 11' inert organic solvent, such as dimethylformamide
or chlorobenzenes, for example, mono- or di-chlorobenzene, toluene,
xylene, benzene or nitrobenzene.
For the preparation of such acid halides it 124 is usually of
advantage first to dry azo-compounds prepared in an aqueous medium or
to free them from water by boiling azeotropically in an organic
solvent. The azeotropic drying 780,031 accelerate the reaction it is
generally of advantage to remove the hydrogen halide formed in the
condensation, for example, by continuous distillation, boiling under
reflux or by the addition of an acid-binding agent, such as anhydrous
sodium acetate, pyridine or anhydrous ammonia. The resulting dyestuffs
are generally obtained in very good yield and in a pure state. It may
be of advantage, in order to prepare especially pure dyestuffs,
previously to isolate the acid chlorides obtained from the carboxylic
acids and, if desired, to recrystallise the acid chlorides. In some
cases, however, the isolation of the acid chloride may be dispensed
with without impairing the results, and then the condensation may
directly follow the preparation of the acid chloride.
The new acid amide derivatives of azo-compoufids obtainable by the
present process are free from groups imparting solubility, and contain
the residue of an amine having at least two acylated amino groups, at
least one of which acyl residues is that of a carboxylic acid of an
azo-compound of which at least one azo linkage is bound on one side to
an aryl nucleus containing a carboxylic acid ester group, in
ortho-position to the azo linkage and on the other side to the residue
containing the carbonyl group. As will be understood from the
foregoing description, there are of special interest those acid amide
derivatives which correspond to the general formula may, if desired,
immediately precede the treatment with the halogenating agent.
In accordance with the present process the acid halides obtainable as
described above are reacted with amines, which contain at least two
reactive amino groups.
For example, 1 mol of a diamine may be condensed with 1 mol of a
carboxylic acid halide of an azo-compound containing a carboxylic acid
ester group vicinal to the azo group and with 1 mol of another acid
halide free from groups imparting solubility and having any desired
constitution, and which is free from or contains an azo linkage.
However, it is generally desirable to condense a diamine at each of.
the amino groups with a carboxylic acid halide of an azo-compound
which contains a carboxylic acid ester group in a position vicinal to
the azo group, and, in the interests of uniformity and ease of control
of the course of the reaction, it has been found advantageous to

6. condense 1 mol of a diamine with 2 mols of a single acid halide having
the constitution given above.
The condensation of the carboxylic acidd halides with the amines is
advantageously conducted in an anhydrous medium. Under these
conditions the condensation generally takes place surprisingly easily
even at temperatures within the boiling range of normal organic
solvents such as dimethyl-formamide, toluene, monochlorobenzene,
dichlorobenzene, trichlorobenzene, and nitrobenzene. In order to R1,-N
= N-R--CO-NH-R3 -NH--OC-R2-N = N-Rl in which R, represents a residue
of a diazo component of the benzene or naphthalene series containing a
carboxylic acid ester group as a substituent in a position vicinal to
the azo linkage, -Ro-CO- represents the residue of a coupling
component containing a hydroxyl group and bound to the azo linkage in
a position vicinal to the hydroxyl group, and -HN-R,-NHI- represents
the residue of an aromatic diamine.
The new acid amide derivatives are valuable pigments. They are
especially suitable for colouring polyvinyl compounds, for example, by
being incorporated during rolling into polyvinyl foils, and they are
in general distinguished by an especially good fastness to light and
migration, and also by their resistance to heat and solvents. This is
also of value for the so-called pigment printing, that is to say, for
printing processes which depend on fixing pigments by means of
suitable adhesives such as casein, hardening artificial materials,
especially urea-formaldehyde or melamineformaldehyde condensation
products, polyvinyl chloride or polyvinyl acetate solutions - or
emulsions, or other emulsions (for example, oil-in-water or
water-in-oil emulsions), on a substratum, especially on a textile
fibre or on another sheet-like structure such as paper (for example,
wallpapers) or fabrics of glass fibres. The pigments obtained by the
present process are also well suited for other purposes, for example,
in a finely dispersed form for colouring artificial silk or viscose or
cellulose ethers or esters or superpolyamides or superpolyurethanes in
the spinning mass, and also for preparing coloured lacquers or lacquer
formers, solutions and products from acetylcellulose, nitrocellulose,
natural resins or artificial resins, such as polymerisation or
condensation resins, for example, aminoplasts, phenoplasts,
polystyrene, polyethylene, polyacryl, rubber, casein or silicones.
Preparations which contain such pigments in a finely dispersed form,
can be prepared in known manner by intensive mechanical treatment, for
example, on roller mills or in suitable kneading apparatus. The choice
of the dispersing medium enabling the intensive mechanical treatment
to be performed depends on the purpose in view, for example for making
preparations capable of being dispersed in water there may be used
sulphite cellulose waste liquor or salts of

7. naphthylmethane-disulphonic acid, and for making cellulose acetate
artificial silk spinning preparations there may be used
acetyl-cellulose mixed with a small amount of a solvent.
780,031 By virtue of the especially favourable physical form in which
the products of the invention are generally obtained, and by virtue of
their chemical inertness and good heat resistance, they can be easily
dispersed in the normal manner in masses or preparations of the kind
described above, and they are advantageously so dispersed at a stage
in which the masses or preparations have not yet reached their final
shape. The operations necessary for shaping, such as spinning,
pressing hardening, casting, adhesion or the like, can then be carried
out in the presence of the pigment without preventing any chemical
reactions of the substratum such as further polymerisation,
condensation, etc.
As compared with the products which are obtained according to
Specification 528,268 and Specification 427,208, as open to public
inspection under Section 91 of the Patent Act 1907-46 by the coupling
method and which, because of their unfavourable physical form, give in
polyvinyl foils practically useless dyeings, there are obtained by the
present process valuable products which are particularly suitable for
dyeing polyvinyl foil in which, owing to their greater dispersibility,
they give much more intense dyeings.
The following Examples illustrate the invention, the parts and
percentages being by weight unless otherwise stated and the
relationship of parts by weight to parts by volume being the same as
that of the kilogram to the litre.
EXAMPLE I.
parts of the monoazo-dyestuff from diazotised
l-amino-benzene-2-carboxylic acid methyl ester and
2-oxy-naphthalene-3carboxylic acid of the formula -cop:H.3 -CO5HS are
introduced, while stirring, into 500 parts of chlorobenzene. 20 parts
of thionyl chloride are added to the mixture and the whole is heated
at a gentle boil. After about 1 hour the acid chloride of the dyestuff
dissolves. The whole is stirred at the boil for about 2 hours longer
and then allowed to cool. The crystalline acid chloride which
precipitates is filtered off with suction, and washed with a small
amount of cold chloro-benzene and dried in vacuo at 70-80 C. The acid
chloride melts at 205-206 C.
73.7 parts of the acid chloride so obtained are introduced into 2000
parts of dry chlorobenzene and 20 parts of pyridine. 10.8 parts of 1:
4-diaminobenzene are added to the mixture, and the whole is heated at
the boil, while stirring, for about 24 hours. When the condensation
ceases the pigment so formed is 60 filtered off while hot, then washed
with warm chlorobenzene and subsequently with hot alcohol, and dried.

8. The resulting disazo-dyestuff of the formula O.C-OCH. H,>.O-HN-( N-oC
'oH.3o-Cis a red-brown pigment which is sparingly soluble to insoluble
in the usual solvents and, when incorporated by rolling into polyvinyl
chloride foils, yields strong red-brown tints of good fastness to
migration and light. The 70 pigment dissolves in concentrated
sulphuric acid with a red-violet coloration.
The above mentioned monoazo-dyestuff is prepared as follows:
30.2 parts of 1-aminobenzene-2-carboxylic 75 acid methyl ester are
introduced into 300 parts of water and 58 parts of hydrochloric acid
of 30 per cent. strength, and the mixture is stirred for about hour in
order to form the hydrochloride. The mixture is then cooled 80 with
ice to 0s C., and 50 parts by volume of a 4N-solution of sodium
nitrite at 0-5 C.
is run in through a dropping funnel below the surface of the liquid.
The whole is stirred for a further 1 hour until the diazotisadion is
finished and dissolution is almost complete, and the nearly colourless
diazo-solution is then filtered. The diazo-solution is run at 0-10 C.
into a filtered solution of 37.6 parts of
2-oxynaphthalene-3-carboxylic acid 90 in 500 parts of water, 28 parts
of sodium hydroxide solution of 30 per cent. strength and 40 parts of
sodium carbonate. The whole is further stirred until the coupling is
finished, and is then filtered and the filter 95 residue is washed
with water. The filter residue is suspended in 1500 parts of cold
water and, in order to form the free dyestuff acid, is mixed with
about 58 parts of hydrochloric acid of 30 per cent. strength (until
100 the reaction is acid to Congo). The whole is stirred for about 3
hours longer at room temperature, filtered, and the filter residue is
washed with cold water until neutral to Congo.
The dried and ground monoazo-dyestuff of 105 the above formula is a
red powder, which dissolves very sparingly in aqueous alkaline
solutions with an orange coloration. The dyestuff dissolves in
concentrated sulphuric acid with a red-violet coloration. 110 EXAMPLE
2.
parts of the monoazo-dyestuff obtained as described in Example 1 from
diazotised 1aminobenzene-2-carboxylic acid methyl ester and
2-oxynaphthalene-3-carboxylic acid are 115 converted into the chloride
of the dyestuff acid as described in Example 1.
as described in Example 1.
7802031 warm chlorobenzene and subsequently with hot alcohol, and
dried. If desired, in order to remove the last traces of the organic
solvent, such as chlorobenzene, which often persistently adheres to
the finely dispersed pigment, the product may be subjected to
distillation with steam before the drying operation. The resulting
disazo-dyestuff of the formula 73.7 parts of the acid chloride so

9. obtained are introduced into 2000 parts of dry chlorobenzene and 20
parts of pyridine. 25.3 parts of 3: 31-dichloro-4: 41-diaminodiphenyl
are added to the mixture, and the whole is heated at the boil while
stirring, for about 24 hours.
When the condensation ceases the pigment formed is filtered off while
hot, washed with C-cC-G 1'0 CO -F:N--Q H-OC OHF 94.CO-Co CS N= U_ Cl
Cl cN=1c is a red powder which is sparingly soluble to insoluble in
the usual solvents and, when incorporated by rolling into polyvinyl
chloride foils yields strong scarlet red tints of good fastness to
migration and light. The pigment dissolves in concentrated sulphuric
acid with a red-violet coloration.
EXAMPLE 3.
76.9 parts of the dyestuff from diazotised 4-chloro-
1-amino-benzene-2-carboxylic acid methyl ester and
2-oxynaphthalene-3carboxylic acid are introduced, while stirring, in
1000 parts of nitrobenzene. 20 parts of thionyl chloride are added to
the mixture, and the whole is heated at 130-150 C. After about hour
the acid chloride dissolves. The whole is stirred for about 2 hours
longer at 130-150 C. and then allowed to cool. The crystalline
precipitated acid chloride of the dyestuff is filtered off with
suction and washed with a small amount of cold benzene, and dried in
vacuo at 70-80 C. The acid chloride melts at 227-228 C.
80.6 parts of the acid chloride so obtained are introduced into 2000
parts of dry chloro benzene and 20 parts of pyridine. 25.3 parts of 3:
3 -dichloro-4: 41-diaminodiphenyl are added to the mixture, and the
whole is heated at the boil, while stirring, for about 24 hours.
When the condensation has ceased, the pigment formed is filtered off
while hot, washed with warm chlorobenzene and then with hot alcohol,
and dried. The resulting disazo-dyestuff of the formula =.C--{ K;) O
-HMH-CC O H,{Oc--C-=O Ctlr=N - t et - -43-b - CL is a red-orange
pigment, which is sparingly soluble to insoluble in the usual solvents
and, when incorporated by rolling into polyvinyl chloride foils,
yields strong red-orange tints of good fastness to migration and
light. The pigment dissolves in concentrated sulphuric acid with a
violet coloration.
By using in this Example 3:3 1-dimethyl4: 41-diaminodiphenyl, instead
of 3: 3 dichloro-4:41-diaminodiphenyl, the condensation dyestuff is
obtained in the form of a dark brown pigment, which is sparingly
soluble to insoluble in the usual solvents and, when incorporated by
rolling into polyvinyl chloride foils, yields strong brown tints of
good fastness to migration and light.
EXAMPLE 4.
83.8 parts of the dyestuff from diazotised 4: 6 - dichloro - 1 -
aminobenzene - 2carboxylic acid methyl ester and

10. 2-oxynaphthalene-3-carboxylic acid are introduced, while stirring,
into 500 parts of chlorobenzene. 20 parts of thionyl chloride are
added to, the mixture, and the whole is heated to the boil. After
boiling for about hour the acid chloride of the dyestuff dissolves.
The whole is stirred for a further 2 hours at the boil and allowed to
cool. The precipitated product is filtered off with suction, and
washed with a small amount of cold chlorobenzene and dried in vacuo at
70-80 C.
The acid chloride melts at 210-211 C.
87.5 parts of the acid chloride so obtained are introduced into 2000
parts of dry chlorobenzene and 20 parts of pyridine. 18.4 parts of
4:41-diaminodiphenyl are added to the mixture, and the whole is heated
at the boil, while stirring, for about 24 hours. When the condensation
has ceased, the pigment formed is filtered off while hot, washed with
warm chlorobenzene and then with hot alcohol, and dried. The
disazo-dyestuff of the formula O=C-OCH3 HO C0-HN-Ng-OC OH H3CO-C=O
cl_- - -t]-- LP--C 780,031 _5 is a red-orange pigment, which is
sparingly soluble to insoluble in the usual solvents and, when
incorporated by rolling into polyvinyl chloride foils, yields strong
red-orange tints of good fastness to migration and light. The pigment
dissolves in concentrated sulphuric acid with a violet coloration.
EXAMPLE 5.
80.1 parts of the dyestuff from diazotised 1-aminobenzene-2-carboxylic
acid methyl ester and 1 - (21 - chlorophenyl) - 5 - pyrazolone -
3carboxylic acid are introduced, while stirring into 800 parts of
chlorobenzene. 20 parts of thionyl chloride are added to the mixture
and the whole is heated to a gentle boil. After about - hour the acid
chloride of the dyestuff dissolves. The whole is stirred for a further
_II c 13N-Co N 1 C=N CL is a greenish yellow pigment, which is
sparingly soluble to insoluble in the usual solvents and, when
incorporated by rolling in polyvinyl chloride foils, yields strong
greenish yellow tints of good fastness to migration and light.
The pigment dissolves in concentrated sulphuric acid with an orange
coloration.
In the following Table are given further 2 hours at lhe boil, and is
then allowed to cool. The precipitated product is filtered off with
suction, and washed with a small amount of cold chlorobenzene and
dried in vacuo at 70-80' C. The acid chloride melts at 208209 C.
83.8 parts of the acid chloride so obtained are introduced into 2000
parts of dry chlorobenzene and 20 parts of pyridine. 18.4 parts of 4:
4-diaminodiphenyl are added to the mixture, and the whole is heated at
the boil, while stirring for about 24 hours. When the condensation has
ceased, the pigment formed is filtered off with suction while hot,
washed with warm chlorobenzene and then with hot alcohol, and dried.

11. The disazo-dyestuff of the formula CI _ C_- 1 (___?.;, CL N= -. / k.-.
I valuable pigments which can be obtained in the manner described in
the foregoing Examples by condensing (in the molecular ratio 2: 1) of
the monoazo-dyestuffs obtainable from the diazo components given in
Column I and the coupling components given in Column II, with the
diamines given in Column III:
1-aminobenzene-2carboxylic acid methyl ester
1-aminobenzene2-carboxylic acid ethyl ester
2-oxynaphthalene3-carboxylic acid , 3:31-dimethyl4:41-diamino-diphenyl
1:5-diaminonaphthalene 1:4 diamino-benzene rust red brownish orange
pure, yellowish red 3:31-dimethyl4:41-diamrnino-diphenyl
3:31-dichloro4:41-diaminodiphenyl 1:5-diaminonaphthalene brownish
bordeaux scarlet reddish orange 780,031 Iv Colour obtained by rolling
the I II pigment into Diazo Coupling III polyvinyl chloride Components
Components Diwmines foils.
4-chloro- l-aminobenzene2-carboxylic acid methyl ester
5-chloro-l-aminobenzene2-carboxylic acid methyl ester
4.:6-dichloro-laminobenzene-2carboxylic acid methyl ester
2-aminonaphthalene3-carboxylic acid ethyl ester
1-aminobenzene2-carboxylic acid methyl ester1-aminobenzene2-carboxylic
acid ethyl ester )-oxynaphthalenei-carboxylic acid C I
2-oxynaphthalene3-carboxylic: acid 1-phenyl-5-pyrazolone-3-carboxylic
acid 1P(21-chlorophenyl)5-pyrazolone-3carboxylic acid
1-phenyl-3-methyl5-pyrazolone-41carboxylic: acid
4-chloro-l-amninobenzene2-carboxylic acid methyl ester
:4I-diaminoLiphenyl :4-diamnino-benzene [:S-diaminoiaphthalene
:3'dimethoxy1:41-diamino-diphenyl 4:4'-diaminodiphenyl
3:3'-dimethyl4:41-diamninodiphenyl 1:4-diamino-benzene 1:5-diamino,
naphthalene 3:31-dimethyl4:4'-diaminodiphenyl 4:41-diaminodiphenyl
3:31-dimethyl4:4'-diaminodiphenyl 1:4-diamino-benzene 3:31-dichloro,
4:41-diamino-diphenyl 1:5-diaminonaphthalene 4:41-diamino-diphenyl
3:31-dimethyl4:41-diamino-diphenyl 3:31-dichloro4:41-diwnino-cliphenyl
ure, yellowish carlet yellowish red bluish red brownish red bright
scarlet brown pure, yellowish scarlet yellowish brown brownish
bordeaux reddish yellow yellow orange yellow greenish yellow yellow )
F S 11 780,031 U j! IV Colour obtained by rolling the I II pigment
into Diazo Coupling III polyvinyl chloride Components Components
Diamines foils.
5-chloro-laminobenzene-2carboxylic acid methyl ester
4:6-dichloro-laminobenzene-2-.
carboxylic acid methyl ester 1-aminobenzene2-carboxylic acid-n-butyl
ester 1-aminobenzene-2carboxylic acid methyl ester
1-phenyl-3-methyl5-pyrazolone-41carboxylic acid
2-oxynaphthalene-3-carboxylic acid 3:31-diaminro-dpey

12. 4:4'-diamino-diphenyl 3:31-dichloro4:4'-diamino-diphenyl
di-(p-aninobenzenesulpho)-imine 1:3-diamino4:6-dimethyl-benzene
1:3-diamino-benzene 1:4-diamino2:5-dichloro-benzene
1:4-diamino2:5-diethoxy-benzene 1 6-dipaminobenzoylamino)-n-hexane
3:31-dimethoxy4:41-diamino6:61-dimethyl1: 11-azobenzene 4:1
1-diaminofluoranthene 3:6:31:61tetrachloro4:41-diaminodiphenylmethane
2:2'-dichloro4:41-diaminodiphenylmethane 3:8-diamino-pyrene
4:41-diamino1:11-azobenzene 4:41-diaminodiphenyl-urea
4:41-dianiinodfiphenylsulphone greenish yellow yellow ruby scarlet
orange scarlet yellowish brown yellowish scarlet reddish brown bluish
red yellowish orange red brown scarlet scarlet scarlet
Li2:8-diaifino-chxysene yel ws br n to F i i t z 780,031
yellowishbrown 780,031 9 Iv Colour obtained by rolling the I 1I
pigment into Diazo Coupling ill polyvinyl chloride Components
Components Diamines foils.
1-aminobenzene2-carboxylic acid methyl ester
1-aminobenzene-2carboxylic acid phenyl ester
1-anminobenzene2-carboxylic acid methyl ester S
2-aminonaphthalene3-carboxylic acid ethyl ester
1-aminobenzene2-carboxylic acid methyl ester
4-chloro-1-ammnobenzene-2-carboxylic acid methyl ester
-oxynaphthalene-carboxylic acid 4.
1.
3 4 d 2-oxycarbazole3-carboxylic acid oxycarboxylic acid of the
formula 3-oxydiphenyleneoxide-2-carboxylic acid
3-acetoacetylamino-4-chlorobenzene-l-carboxylic acid
2-oxynaphthalene3-carboxylic acid
3-acetoacetylamino4-methoxybenzene1-carboxylic acid -carboxylic henyl
ester :4'-diamino-diphenyl :3'-dichloro:41-diaminoiphenyl
1:4-diamino-benzene 4:41-diaminodiphenyl 1-methy-2:4diaminobenzene
4:41-diwmino-diphenyl 1:4-diainino-benzene
3:31-dichloro4:41-diamino-diphenyl 4:41-diwminodiphenylether
3:31-dichloro4:4'-diaminodiphenyl 1:4-diamino-benzene
3:3'-dichloro4:41-diamino-diphenyl 4:41-diamino-diphenyl
3:31-dichloro4:41-diamino diphenyl eddish orange scarlet scarlet
maroon brown brown bordeaux bordeaux brown brown yellow yellow red red
yellow 2 [7 1.
r 780,031 6 f EXAMPLE 6.
73.7 parts of the acid chloride of the dyestuff from diazotised
1-aminobenzene-2carboxylic acid methyl ester and
2-oxynaphthalene-3-carboxylic acid, prepared as described in Example
1, are introduced into 2000 parts of dry chlorobenzene and 20 parts of
pyridine. 13.26 parts of 2:4: 4-triaminodiphenyl are added to the
mixture, and the whole is heated at the boil while stirring for about

13. 24 hours. When the condensation ceases, the pigment formed is filtered
off while hot, washed with warm chlorobenzene then with hot alcohol
and dried. The resulting trisazodyestuff of the formula O-C-CH
HO.NHCONNH-GC OH o=C- CH3 MNX-j OH N= 1 O=C-.OCH3 (N=N-0 is a scarlet
pigment which is sparingly soluble to insoluble in the usual solvents
and, when incorporated by rolling into polyvinyl chloride foils,
yields strong bright yellowish scarlet tints of good fastness to
migration and light.
The pigment dissolves in concentrated sulphuric acid with a red
coloration.
EXAMPLE 7.
40.3 parts of the acid chloride of the dyestuff from diazotised
4-chloro-1-aminobenzene-2-carboxylic acid methyl ester and
2oxynaphthalene-3-carboxylic acid, prepared as described in Example 3,
and 43.75 parts of the acid chloride of the dyestuff from diazotised
4: 6 - dichloro - 1 - aminobenzene - 2carboxylic acid methyl ester and
2-oxynaphthalene-3-carboxylic acid, prepared as described in Example
4, are introduced into 2000, parts of dry chlorobenzene and 20 parts
of pyridine. 10.8 parts of 1: 4-diaminobenzene are added to the
mixture, and the whole is stirred at the boil for about 24 hours. When
condensation has ceased, the pigment formed is filtered off while hot,
washed with warm chlorobenzene, then with hot alcohol and dried. The
resulting mixture of disazo-dyestuffs is a red-brown pigment which is
sparingly soluble to insoluble in the usual solvents and, when
incorporated by rolling into polyvinyl chloride foils, yields strong
brown-orange tints of good fastness to migration and light. The
pigment dissolves in concentrated sulphuric acid with a reddish violet
coloration.
EXAMPLE 8.
34.5 parts of 1-amino-2-nitro-4-chlorobenzene are diazotised in the
usual way and the diazo solution is run into a finely divided
suspension of 39 parts of 5-ethoxy-1-aminobenzene-2-carboxylic acid
methyl ester in aqueous methyl alcohol below 100 C. in the presence of
sodium acetate. When coupling is complete, the monoazo dyestuff is
filtered off and washed with water; it is then stirred in parts of
water and 212 parts of a solution containing sulphuric acid and 30%
naphthalene-l-sulphonic acid. The mixture is diazotised at room
temperature with 13.8 parts of sodium nitrite in 200 parts of water
and stirred overnight, then coupled on to a solution of 37.6 parts of
2-oxynaphthalene-3carboxylic acid and 50 parts of soda ash in 500
parts of water. When coupling is complete, the mixture is acidified to
Congo with 30% hydrochloric acid and stirred for a further period of 2
hours. The disazo dyestuff of the formula COOCH3 OH COOHNO, OC2H5 is
isolated and dried in the usual manner.

14. 57.7 parts of this disazo dyestuff are converted into the acid
chloride by treatment with 10 parts of thionyl chloride in 300 parts
of dry chlorobenzene at the boil. The acid chloride crystallises after
cooling; it is filtered off, washed with dry chlorobenzene and dried.
59.6 parts of the acid chloride so obtained are introduced into 1000
parts of dry chlorobenzene and 10 parts of pyridine. 9.2 parts of 4:
4-diaminodiphenyl are added to the mixture and the whole is boiled,
while stirring, until condensation ceases. The pigment formed is
filtered off, washed with warm chlorobenzene and hot alcohol, then
dried.
The resulting tetrakisazo dyestuff of the formula 780,031 780,031
O=C-OCH3 o CO. M,-1N3----NH.OC OH Ct-CJ7-N1=N-'(7i>N-= g1$ NN2 N=N}CL
_u45 2Y is a dark red pigment which is sparingly soluble to insoluble
in the usual solvents and, when incorporated by rolling into polyvinyl
chloride foils, yields strong reddish brown tints of very good
fastness to light. The pigment dissolves in concentrated sulphuric
acid with a greenish blue coloration.
EXAMPLE 9.
65 parts of polyvinyl chloride, 35 parts of dioctylphthalate and 1
part of the dyestuff obtained as described in Example 1 are stirred
together, and then rolled to and fro in a 2roller calender for 7
minutes at 140 C.
There is obtained a reddish brown coloured foil of which the tint is
very fast to light and dyestuff migration.
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* Last updated: 08.04.2015
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* 5.8.23.4; 93p