Improvements in the Manufacture or Production of Azo Colouring Matters.
Year: 1891

page_text: Date of Application, 7th Apr., 1891
Complete Specification Left, 20th Jan., 1892-Accepted, 20th Feb., 1892
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture or Production of Azo Colouring
Matters.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which invention has
been communicated to me from abroad by Farbenfabriken vormals Friedrich
Bayer and Company of Elberfeld in the Empire of Germany to be as follows:-
:-
In the Specification of Letters Patent No. 13665 granted to me and dated
29 August 1889 a description is given of a dihydroxy-naphthalin-mono-sulpho-acid
obtained from the alpha-naphthol-disulpho-acid-S described in the Specification of
the German Patent No. 40571 by melting with alkalies and this my foreign corre-
spondents have discovered is a derivative of 1.8 dihydroxy-naphthalin.
The dihydroxy-naphthalin-disulpho-acids described in the Specification of Letters
Patent No. 3397 granted to me and dated 4th March 1890 and of my application
for Patent No. 13443 of 1890 have likewise been found to be sulpho-acids of the
18 dihydroxy-naphthalin and are hereinafter referred to simply as 1.8 dihy-
droxy-naphthalin-alpha-lisulpho-acid (Patent No. 339700) and as 1.8 dihydroxy-.
naphthalin beta disulpho acid (application for Patent No. 134430).
The new sulpho acids (amido-napthol mono and di-sulpho-acids) further
described in the Specification of my application for Patent No. 13443" also have
two substitutes videlirit the hydroxyl- and amido-groups in the para position and
may therefor be regarded as sulpho-acids of the 18 amido-naphthol.
The azo colouring matters of all these acids are of great technical importance
and are in part described in the hereinbefore mentioned Specifications, and also in
the Specification of Letters Patent No. 18517 granted to me and dated
19 November 1889.
In practising the invention protected by this Patent my foreign correspondents
have now discovered that the following amines are likewise capable of being
employed with advantage for obtaining azo colouring matters from these sulpho
acids of the 18 dihydroxy-naphthalin and 1-8 amido-naphthol (the combinations.
which have already been made public in the said former Specifications being of
course not included in the present application) ridelicit.
1. Those amido-phenols and amido-cresols and their substitution products which
contain the amido- and hidroxyl-groups not in the ortho-positions.
II. All the amido-phenol ethers, amido cresol ethers and amido-naphthol ethers
of which anisidine and cresidine have been already mentioned in the Specification
of Patent No. 18517 and the sulpho acids thereof.
III. Nitraniline, amido-azo-benzene, and the homologues and sulpho-acids
thereof.
IV. Amido-napthols, amido-dihydroxy naphthalin-ether and
acids.
their sulpho-
V. Amide-benzoic acids, amido-hydroxy-benzoic acids, amido-cresotinic-acids,
amido-phthalic acids, amido-anisic acids, and their sulpho acids.
VI. Phenylene-diamine, toluylene-diamine and naphthylene-diamine substituted
in the amido rest or residue (alkylised, phenylised, benzylised etcetera) and their
sulpho acids.
VII. With the object of producing simple azo colouring matters;-benzidine,
tolidine, diamido-diphenol-ether, diamido-stilbene, diamido-carbazol, para- and meta-
phenylene, diamine, toluylen-diamine and their sulpho-acids and similar para-

page_text: diamines so far as they are capable of being partially diazotised with the aid if
required of their monacetyl combinations.
VIII. Those amido-azo bodies which result from the coupling with alpha-
naphthylamine or alpha-amido-naphthol-ether of the diazo derivatives of amido-
benzoic acids, amido-hydroxy-benzoic acids amido-cresotinic acids, amido phthalic
acids amido-anisic acids, amido-phenols, amido-cresols, amido-naphthols, amido-
phenol ethers, amido-cresol ethers, amido-naphthol ethers and their sulpho acids
alpha and beta-naphthylamine-trisulpho-acids and of sulpho-acids of the phenylene
diamine toluylene diamine substituted in an amido group.
Y
IX. With the object of producing disazo colouring matters; diamido-diphenoxyl-
acetic acid, meta- and para-phenylene-diamine, toluylene-diamine and their sulpho
acids which can be directly employed in the form of their tetrazo compounds.
The production of these colouring matters is effected by causing the diazo
compounds of the selected amine to act upon a solution (mixed with sodium acetate)
of the selected sulpho acid of the 18 dihydroxy naphthalin or amido-naphthol.
It is advantageous to employ the solutions not in a highly diluted condition. The
following are given as examples of the manner of conducting the operations
according to the present invention the parts being by weight.
1. Colouring matter from para-amido-phenol and 18 dihydroxy-naphthalin-
beta-disulpho-acid.
I part of para-amido-phenol is diazotised in the usual way with a solution of
0-7 parts of sodium nitrite and the diazo compound is introduced into a solution
(mixed with an excess of sodium acetate) of 4 parts of 1.8 dioxy-naphthalin-beta-
disulpho acid salt of sodium.
After standing for about twenty four hours heat is applied and after adding
common salt the colouring matter is filtered off and pressed. This product in an
acid bath dyes wool a beautiful clear violet. From reddish violet to pure violet
colours are thus obtained from the amido-phenols, amido-cresols, uitramido-phenols
and cresols or the sulpho-acids of these substances with 18 dihydroxy-naphthalin
mono-sulpho acid or 18 dihydroxy-naphthalin alpha-disulpho acid the 1-8
dihydroxy-naphthalin beta-disulpho acid yielding products of a somewhat redder
tinge.
II. By employing in the process according to the preceding example in place of
the amido-phenol for example phenetidine or its sulpho-acids or other amido-phenol
ethers or in place of the 18 dihydroxy-naphthalin beta disulpho acid, the other
sulpho acids hereinbefore specified dyes are obtained capable of colouring wool a
fuchsine red.
III. The colouring matters obtained from the diazo derivatives of nitranilin and
its homologues with 18 dihydroxy-naphthalin-disulpho acid produce red colours
upon unprepared wool and violet-black upon chrome mordanted wool. The azo
colouring matters produced with amido-azo-benzene amido-azo-toluol and amido-
azo-xylol or their sulpho-acids and the sulpho acids of 18 dihydroxy-naphthalin
or amido-naphthols dye wool from reddish-violet to violet and blue.
IV. The amido-naphthols, amido-dihydroxy-naphthalin-ethers and their sulpho-
acids afford from violet to blue colouring matters.
V. With the employment of the amido-carboxy acids hereinbefore specified
under head V from red to blue-red colouring matters are obtained which can be
employed with great advantage in dyeing wool previously mordanted with
chromium salts and the like almost black tones or shades being obtained by these
means. These dyes are prepared in the manner described in the preceding
examples.
VI. and VII. These amido compounds contain along with the free amido group
at least one more amido group which is either likewise free or acetilysed or
substituted by any alkyl groups such as methyl, ethyl, benzyl or phenyl, single or
double, similar or dissimilar. The substituted phenyl or benzyl groups may be
sulphurized or the hydro-carbon neucleus itself may be modified by the introduction
of sulpho or carboxyl groups.

page_text: The mono-diazo combinations of these amines produce in combination with the
sulpho acids of the 18 dihydroxy-naphthalin or 18 amido-naphthol, from
reddish-violet to blue dyes of remarkable clearness and colouring power.
It is found as a general rule that those colouring matters which contain the basic
group in the para position to the azo group are violet to blue but those of the meta
series are from red to violet. With an increased number of the acid groups such
as sulpho and carboxyl groups in the dyestuffs molecule the colour tends to acquire
a more violet, blue-red, or yellow-red shade.
With regard to the solubility it is to be observed that the colouring matters
obtained from pure basic diazo compounds whose basic groups consist either of a
free amido-group or of an amido-group substituted by single or double fatty alkyls
and the sulpho acids hereinbefore referred to of 1.8 dihydroxy-naphthalin or
amido-naphthol are readily soluble in cold water when in the form of their soda
salts but on the other hand the substitution of one or both hydramides by phenyl
or benzyl renders the product difficult of solution. The solubility is of course
increased by the introduction of more than one sulpho group into the dye stuff
molecule on either side of the azo group either in the neucleus or in the substituted
atom groups.
In all cases the coupling is conducted in an acetic acid solution.
The following are given as examples of the manner of conducting the process the
parts being by weight.
Colouring matter from mono acetyl-meta-toluylene-diamine and 1.8 dihydroxy-
naphthalin-alpha-mono-sulpho acid.
8.5 parts of mono-acetyl-meta-toluylene-diamine (Berichte XV. 2831) are
dissolved without heat in 40 parts of water and 11 parts of concentrated
(33 per cent.) hydrochloric acid and diazotised by pouring in a 10 per cent. solution
of 35 parts of sodium nitrite the materials being cooled with ice during this
operation.
This solution is caused to run slowly into a cooled solution of 12 parts of
1.8 dihydroxy-naphthalin-alpha-mono-sulpho acid in 25 parts of water and 14 parts
of sodium acetate.
The dark brown precipitate which forms is after standing for a considerable
time dissolved by the addition of 14 parts of 30 per cent. soda lye and the orange-
red solution obtained is slowly heated to boiling. Splitting off of the acetyl
group then takes place. By neutralising with diluted hydrochloric acid and finally
with acetic acid the colouring matter is almost completely precipitated on cooling
in the form of a dark coloured deposit which being filtered off pressed and dried
presents the appearance of a brown powder with greenish metallic lustre. The
colouring matter thus obtained dissolves readily in water with a red colour and dyes
wool red in a weak sulphuric acid bath.
Colouring matter from amido-ethyl-benzyl-aniline-sulpho acid and 18 dihy-
droxy-naphthalin-alpha-mono-sulpho-acid.
178 parts of the nitroso-ethyl-benzyl-aniline-sulpho acid are dissolved in 40 parts
of hot water, mixed with 20 parts of concentrated (33 per cent.) hydrochloric acid
and reduced at a temperature of about 60 degrees Centigrade by gradually adding
zinc powder. When the colour of the solution has changed from yellow to a fainf
green it is filtered and the undecomposed zinc powder washed out. The solution
being cooled to about 50 degrees Centigrade is then diazotised with a watery
solution of 35 parts of sodium nitrite. The liquid acquires under this treatment a
green colour which subsequently changes to yellow. This liquid shows at first no
reaction when mixed with a solution of 12 parts of 18 dihydroxy-naphthalin-
alpha-mono sulpho acid in 25 parts of water and 20 parts of acetate of soda but the
longer the mass is left standing at atmospheric temperature the more the original
dark green colour of the solution tends to change to blue. After about 3 hours
the colouring matter begins to separate in the form of small metallic lustrous
crystals visible on the surface. After about 12 hours the action is completed.
The colouring matter is filtered off pressed and dried. It forms a powder composed
of minute or microscopic crystals of a bronze lustre dissolving readily in water with

page_text: a splendid blue colour and dyes wool uniformly and equally a bright blue in a
sulphuric acid bath.
Colouring matter from one molecular proportion of benzidine and one molecular
proportion of 18 dihydroxy-naphthalin alpha-mono-sulpho acid.
92 parts of benzidine in the form of the neutral hydrochloric acid salt are
converted according to the process described in the Specification accompanying
the application for a German Patent B38573 dated 2nd May 1888 into the com-
bination according to the equation NH, C, H, C, H, N=NCI and this product
is introduced into a solution of 12 parts of 1.8 dihydroxy-naphthalin-alpha-mono-
sulpho acid in 25 parts of water. On mixing with acetate of soda a dark precipitate
is formed which is almost insoluble in cold water, but is more readily soluble in cold
water containing acetic acid, and dissolving without difficulty in hot water with a
red violet colour. It dyes wool violet in a weak sulphuric acid bath.
Colouring matter from para-amido-phenylamine-sulpho acid. and 1·8 dihydroxy-
naphthalin-alpha-mono-sulpho acid.
92 parts of para-amido-diphenylamine are introduced into 50 parts of 20 per
cent. fuming sulphuric acid the temperature being maintained below 50 degrees
Centigrade. When this operation is concluded the melt is allowed to stand for
about 24 hours at a temperature of from about 25 to 30 degrees Centigrade. When
poured out on to ice almost the whole goes into solution. The dissolved matter as
well as the small quantity of precipitate dissolve readily in ammonia. After
filtering the greater part of the sulphuric acid in the filtrate is neutralised with
soda lye then largely diluted with water cooled and the amido-diphenylamine-
sulpho acid formed is diazotised with 34 parts of nitrite. When the yellow
solution thus obtained is allowed to act upon 12 parts of 1.8 dihydroxy-naphthalin-
alpha-mono-sulpho acid there is formed, in the presence of acetate of soda, an
extremely easily soluble red-violet colouring matter which can be isolated by salting
out with common salt. It forms a black powder.
VIII. The disazo colouring matters obtained from amido-phenols, amido-
naphthols their ethers and sulpho acids, from alpha- and beta-naphthylamine-
trisulpho acids, from amido-carboxy acids, amido-sulpho-carboxy acids from amido-
mono- and di-benzyl-anilin-sulpho acid, from amido-alkyl-benzyl-anilin-sulpho acid,
from amido-diphenylamine-sulpho acids and the like, by coupling their diazo
compounds with alpha-naphthylamine or alpha-amido-naphthol-ether, further
diazotising the product and combining it with the sulpho acids of the 1-8 dily-
droxy-naphthaline or 1:8 amido-naphthol, produce upon wool violet-black and
from blue-black to blue-green colours. The following is given as an example of
the method of conducting the process.
2-4 parts of gamma-amido-naphthol-mono-sulpho acid are diazotised in the usual
way with a solution of 0.7 parts of sodium nitrite and the diazo compound formed
.is introduced into a solution of 18 parts of alpha-naphthylamine-hydrochlorate.
After standing for a considerable period and heating the amido-azo colouring
matter formed is filtered off dissolved in diluted soda lye, mixed with a solution
of 0.8 parts of sodium nitrite and gradually acidulated with hydrochloric acid.
After standing for about 24 hours the diazo compound formed is introduced into a
solution of 25 parts of 1-8 dihydroxy-naphthalin-mono-sulpho acid mixed with an
excess of acetate of soda and allowed to stand for some time. The materials are
then heated and filtered after adding common salt.
IX. The production of the colouring matter obtained from para-diamido-
diphenoxyl-acetic acid

page_text: is effected by taking 19 parts by weight of the soda salt of this acid and dissolving
them in cold water with the addition of parts of concentrated hydrochloric acid,
diazotising with 07 parts of sodium nitrite and introducing the product into a
solution of the calculated quantity of the soda salt of the corresponding sulpho acid
mixed with the sodium acetate, the formation of the colouring matter commences
immediately and is after standing for a considerable time completed by heating the
materials and rendering them alkaline.
The colouring matters thus obtained dye from blue to green-blue on unmordanted
cotton. Mixed azo colouring matters can also be obtained from the diamido-
diphenoxyl-acetic acid by combining one molecular proportion of their tetrazo
compound first with one molecular proportion of a 18 dihydroxy-naphthalin-
sulpho acid or a 18 amido-naphthol-sulpho acid and combining the intermediate
product formed with one molecular proportion of an amine or a phenol. If
preferred the intermediate product can be formed in the first place from one mole-
cular proportion of the tetrazo compound with one molecular proportion of an amine
or a phenol and be caused to react upon the sulpho acid of the 18 dihydroxy-
naphthalin or amido-naphthol.
The tetrazo combinations of the meta- and para-phenylene-diamine and of the
toluylene-diamine and their sulpho acids produce, when combined with the sulpho
acids of 18 dihydroxy-naphthalene or 18 amido-naphthol, from red to violet and
blue azo colouring matters.
All these products are remarkable for their great clearness, colouring power and
fastness against the action of light and of acids and alkalies.
Owing to the facility with which the telrozo body is decomposed the same object
can be better attained by first diazotising the mono-acetyl combination of the
diamine selected then acting on one molecular proportion of the acid specified and,
after splitting off the acetyl group, combining the colouring matter (after rediazo-
tising) with a second molecular proportion of a dioxy-naphthalin sulpho acid.
In this way it is also possible to obtain a very great variety of mixed disazo
colouring matters when after the second diazotising one of the known mono-or-
poly-sulpho acids of naphthol, dioxy-naphthalin or naphthylamine is caused to enter
in reaction.
All these colouring matters dye wool in a sulphuric acid bath with colours that
are fast against the action of acids and alkalies.
The process for the production of this azo colouring matter is illustrated by the
following example-
Colouring matter from para-phenylene-diamine and 18 dihydroxy-naphthalin-
alpha-mono-sulpho acid.
54 parts of para-phenylene-diamine are converted into the tetrazo combination
according to the directions given by Griess and the solution obtained is quickly
poured (whilst the temperature is kept as low as possible by the application of ice)
into a highly diluted solution (mixed with an excess of soda lye) of 24 parts
of 18 dihydroxy-naphthalin-alpha-mono-sulpho acid. From the blue solution
when neutralised with hydrochloric acid and mixed with salt, the colouring matter
can be precipitated in the form of dark black-blue flakes readily soluble in water
and which form a bronze lustrous powder when separated by filtration and dried.
This product represents the soda salt of a disulpho acid which is readily soluble in
water even when it contains sulphuric acid. The dye colours wool a blue-violet in
a sulphuric acid bath.
Colouring matter from mono-acetyl-meta-phenylen-diamine-azo-dihydroxy-naph-
thalin-alpha-mono-sulpho acid and 18 dihydroxy-naphthalin-beta-disulpho acid.
The colouring matter obtained from 3 parts by weight of mono-acetyl-meta-
phenylen-diamine- and 4-8 parts of 18 dihydroxy-naphthalin-alpha-mono-sulpho
acid according to the process hereinbefore described under head VII. is diazotised
with 14 parts of sodium nitrite after splitting off the acetyl group by diluted
alkaline lye or diluted sulphuric acid and united with a watery solution of 64 parts
of 18 dihydroxy-naphthalin-beta-di-sulpho acid.

page_text: On gradually adding acetate of soda and common salt the blue disazo colouring
matter separates in the form of dark flakes readily soluble in water.
Dated the 7th day of April 1891..
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture or Production of Azo Colouring
Matters.
1 BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which has been
communicated to me from abroad by Farbenfabriken vorm. Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany and in what manner the same is to be
performed to be particularly described and ascertained in. and by the following
statement :-
In the Specification of Letters Patent No. 13665 granted to me and dated
29th August 1889 a dihydroxy-naphthalene-mono-sulpho-acid is described which is
obtained from the alpha-naphthol-disulpho-acid S described in the Specification of
the German Patent No. 40571 by fusing the said acid with alkalies and which my
foreign correspondents have discovered is a 1.8-dihydroxynaphthalene alpha-mono-
sulpho acid.
The dihydroxy-naphthalene disulpho acid described in the Specification of
Letters Patent No. 3397 dated 4th March 1890 has also been found to be a sulpho
acid of the 18-dihydroxy-naphthalene and is hereinafter briefly called 1.8
dihydroxy-naphthalene alpha-disulpho acid.
The new sulpho acids (amidonaphthol-mono- and disulpho acids) further described
in the Specification of Letters Patent No. 13443 granted to me and dated 26th
August 1890 also have two groups iz. the hydroxyl- and amido-groups in the 1.8-
or peri position and may therefore be termed 1.8-amidonaphthol mono and disulpho
acid.
The azo colouring-matters derived from all these acids are of great technical
importance and are described partly in the herein before mentioned Specifications
and partly in the Specification of Letters Patent No. 18517 granted to me and
dated 19th November 1889.
In addition to the last named inventions my foreign correspondents have now
discovered that the following amines are also capable of being employed with
advantage for obtaining azo colouring-matters from these. sulpho acids of the
18-dihydroxy-naphthalene and 1-8-amidonaphthol, (the combinations which have
already been published in the said former Specifications being however of course
excluded from the present application).
1. Those amidophenols and amidocresols and their substitution products which
contain the amido- and hydroxyl groups in positions other than the ortho-
positions.
11. All the amidophenol ethers, amidocresol ethers and amidonaphthol ethers and
the sulpho acids thereof (with the exception of anisidine and cresidine as they
have been already mentioned in the Specification of the aforesaid Patent No. 18517
of 1889).
III. Nitraniline, amidoazobenzene, the homologues and sulpho acids thereof.
IV. Amidonaphthols, amidodihydroxy-naphthalene-ethers and their sulpho acids.
V. Amidobenzoic acids, amidohydroxy-benzoic acids, amidocresotinic acids,
amido-phthalic acids, amidoanisic acids and their sulpho acids.
VI. Phenylenediamine, toluylenediamine and naphthylene-diamine (substituted
in one of the amido groups by alkyl, phenyl or benzyl groups) and the sulpho acids
thereof.
VII. Those amidoazo compounds which are formed by coupling with alpha-

page_text: naphthylamine or alpha-amidonaphtholether the diazo derivatives of the following
compounds amidobenzoic acids, amidohydroxy-benzoic acids, amidocresotinic
acids, amidophthalic acids, amidoanisic acids, amidophenols, amidocresols, amido-
naphthols, amidophenol-ethers, amidocresol-ethers, amidonaphtholethers and their
sulpho acids, alpha- and beta-naphthyl-aminetrisulpho acids, or sulpho acids of
phenylene diamine and toluylene diamine substituted in one of the amido groups.
The production of these colouring matters is in general carried out by causing the
diazo compounds of the above named amines to act in equal molecular proportions
on a solution of the 18-dihydroxy-naphthalene or 18-amidonaphthol sulpho acid
in the presence of sodium acetate in excess. It is not advantageous to employ
too dilute solutions. The following are examples of the method of producing
these new colouring-matters the parts being by weight.
COLOURING-MATTER FROM P-AMIDOPHENOL AND 1.8 DIHYDROXY-NAPHTHA-
LENE-a-DISULPHO ACID IN EQUAL MOLECULAR PROPORTIONS.
11 parts of para-amidophenol are diazotised in the known manner by means of
a solution in water of 07 parts of sodium nitrite and the resulting solution of
the diazo compound is introduced into a solution, containing 4 parts of 1-8-dihy-
droxy-naphthalene-a-disulfonate of sodium and about 8 parts of sodium acetate.
After about 24 hours the liquid is gently heated and the colouring matter is
subsequently precipitated from the cool solution by the addition of salt. The
precipitate is filtered off and pressed. The product thus obtained is represented
by the formula
-
and in an acid bath dyes wool a beautiful clear violet.
Dyes varying from reddish-violet to pure violet in colour are obtained by com-
bining in like manner the amidophenols, amidocresols, nitramido-phenols and
cresols or the sulpho acids of these substances with 18-dihydroxy-naphthalene-
mono sulpho acid or 1·8-dihydroxy-naphthalene-a-disulpho acid.
Dyes are obtained which are capable of colouring wool a magenta red if in
place of the amido phenol of the preceding example aetherphenetidine for instance
or a sulpho acid thereof or an ainidophenolether or in place of the dihydroxy-
naphthalene-a-disulpho acid the other sulpho acids hereinbefore specified are
employed.
The colouring matters obtained by the action of the diazo derivatives of nitraniline
or its homologues on 18-dihydroxy-naphthalene-a-disulpho acid produce red colours
on unmordanted wool and violet-black shades ou wool mordanted with chromium
salts. The azo colouring-matters derived from amidoazobenzene, amidoazotoluene,
amidoazoxylene or their sulpho acids and the sulpho acids of 1.8-dihydroxy-.

page_text: previously mordanted with chromium salts, black shades are obtained by employing
the following amidocarboxy acids .:-amidobenzoic acids, amidohydroxybenzoic
acids, amidocresotinic acids, amidophthalic acids, amidoanisic acids and their sulpho
acids as hereinbefore specified. These dyes are prepared in the same manner as
that described in the example previously given.
VI.
The diazo combinations of the following diamines viz. phenylendiamine, toluy-
lenediamine, and naphthylenediamine (substituted in one of the amido groups by
alkyl, phenyl or benzyl, groups) and the sulpho acids thereof produce when com-
bined with the sulpho acids of the 1-8-dihydroxy-naphthalene or 1-8-amidonaphthol
from reddish-violet to blue dyes of remarkable clearness and colouring power.
My foreign correspondents have recognised as a general rule that the colouring-
matters which contain the basic group in the para position to the azo group
produce violet to blue and that those of the meta series yield from red to violet
shades and that the shades produced approach more nearly to violet, blue-red or
yellow-red according to the number of acid groups (sulpho and carboxyl groups)
introduced into the dye-stuff molecules.
With regard to solubility the colouring-matters, obtained in the form of sodium
salt from the sulpho acids of 18-dihydroxynaphthalene or 1.8-amidonaphthol, and
pure basic diazo compounds in which the basic groups consist either of a simple
amido group, or of an amido group into which either one or two fatty alkyls have
been introduced are readily soluble even in cold water whilst on the other hand
when one or both hydrogen atoms in the amido group have been displaced by
phenyl or benzyl the resulting products dissolve with difficulty in water.
solubility as a rule is, increased if more than one sulpho group be introduced into
the dye-stuff molecule whatever position it may occupy.
The
In all cases the coupling is most practically conducted in an acetic acid solution.
The following are given as examples of the manner of conducting the process the
parts being by weight.
COLOURING - MATTER FROM
DIETHYL-META-TOLUYLENE DIAMINE AND
1.8-DIHYDROXY-NAPHTHALENE-a-MONOSULPHO ACID.
8.9 parts of diethyl-m-toluylene-diamine having been dissolved without heating
in 11 parts of concentrated hydrochloric acid of 33 per cent. diluted with 40 parts
of water, the solution is diazotised by the addition of a solution of 3.5 parts of
sodium nitrite in 31-5 parts of water the liquid being kept cool with ice during this
operation. The resulting diazo solution is caused to run slowly into a cooled
solution of 131 parts of 18-dihydroxy-naphthalene-a-monosulphonate of sodium
and 26 parts of sodium acetate in 25 parts of water. On adding sodium carbonate
the dye-stuff separates as a dark coloured deposit which when filtered off' pressed

page_text: and dried, forms a brown powder having a greenish metallic lustre. The colouring
matter thus obtained is represented by the formula.
COLOURING-MATTER FROM AMIDOETHYLBENZYLANILINE SULPHO ACID AND
18-DIHYDROXY-NAPHTHALENE-a-MONOSULPHO ACID.
160 parts of the nitrosoethylbenzylaniline sulpho acid are dissolved in 40 parts
of hot water, mixed with 20 parts of concentrated hydrochloric acid (33 per cent.)
and reduced at a temperature of about 60 degrees Centigrade by gradually adding
zinc powder. When the colour of the solution has changed from yellow to a faint
green it is filtered and the unattached zinc powder is washed. The solution having
been cooled to about 50 degrees Centigrade is then diazotised with a solution in
water of 35 parts of sodium nitrite. The liquid at first assumes a green colour
which subsequently changes to yellow. This yellow solution is at first without
action when added to a solution of 131 parts of 18-dihydroxy-naphthalene-a-
monosulphonate of sodium and about 26 parts of sodium acetate in 25 parts of
water but the longer the mixture is allowed to stand at ordinary temperatures the
more the original dark green colour of the solution changes into blue. After about
3 hours the colouring-matter begins to separate in the form of small metallic
lustrous crystals and after about 12 hours the action is completed. The colouring
matter is filtered off, pressed and dried. It forms a powder composed of minute or
microscopic crystals exhibiting a bronze like lustre which dissolve readily in water
affording a splendid blue coloured solution and dyes wool in a sulphuric acid bath a
very uniform and bright blue.
COLOURING-MATTER FROM I-AMIDODIPHENYLAMINE SULPHO ACID AND
1.8-DIHYDROXY-NAPHTHALENE-a-MONOSULPHO ACID.
92 parts of para-amidodiphenylamine are introduced into 50 parts of fuming
sulphuric acid containing 20 per cent. of anhydride the temperature being
maintained below 50 degrees Centigrade and the resulting mixture is allowed to
stand for about 24 hours at a temperature of from about 25 to 30 degrees
Centigrade. When it is poured on to ice almost the whole dissolves. The solution
having been filtered off the greater part of the sulphuric acid in the liquid is
neutralised with soda lye, the solution is then largely diluted with water and then
cooled. The amidodiphenylamine sulpho acid dissolved in the liquid is now
When the yellow
diazotised with 3.5 parts of sodium nitrite in the usual manner.
solution thus obtained is allowed to act upon 13.1 parts of the sodium salt of
1-8-dihydroxy naphthalene-a-monosulpho acid, in the presence of sodium acetate
a very soluble red-violet colouring-matter is formed which can be isolated by
salting out with common salt. It forms a black powder and dyes unmordanted
wool a bluish-violet colour.

page_text: The diazo colouring-matters obtained from amidophenols, amidonaphthols, their
ethers and sulpho acids, a- and ẞ naphthylamine-trisulpho acids, amidocarboxy acids,
amidosulphocarboxy acids, amidomonobenzyl and dibenzylaniline sulpho acids,
amidoalkylbenzylaniline sulpho acid, amidodiphenylamine sulpho acids and the like,
by coupling their diazo compounds with a-naphthylamine or a-amidonaphtholether
then diazotising the product and combining it with the sulpho acids of the
18-dihydroxy-naphthalene or 18-amido-naphthol, produce on wool voilet black
and from blue black to blue green shades. The following is given as an example
of the method of conducting the
process.
DYE-STUFF
OBTAINED
FROM
a-NAPIITHYLAMINE AND
ACID.
GAMMA-AMIDO-NAPHTHOLMONOSULPHO-ACID,
1.8-DIHYDROXY-a-NAPHTHALENE
MONOSULPHO
24 parts of gammaamidonaphthol monosulpho acid are diazotised in the usual
way with a solution of 0.7 parts of sodium nitrite and the resulting diazo
compound is introduced into a solution of 1-8 parts of a-naphthylamine hydro-
chloride. After standing for several hours the solution is moderately heated and
the resulting amidoazo colouring matter is filtered off. It is then dissolved in
diluted soda lye, mixed with a solution in water of 0.7 parts of sodium nitrite and
the liquid is gradually acidulated with hydrochloric acid. After about 24 hours
the resulting diazo compound is filtered off and introduced into a solution of
26 parts of 18-dihydroxy-naphthalene-monosulphonate of sodium and 5 parts of
sodium acetate and after some time the liquid is moderately heated.
The resulting dye stuff is separated by the addition of common salt filtered off
pressed and dried. It produces on unmordanted wool a bluish black colour.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The production of new azo colouring matters by combining in equal molecular
proportions one of the following acids.
18 dihydroxynaphthalene-a-monosulpho acid (described in the Specification of
Letters Patent No. 13665 dated August 29th 1889).
18-dihydroxynaphthalene-a-disulpho acid (described in the Specification of
Letters Patent No. 3397 dated March 4th 1890).
18 amidonaphthol monosulpho acid) (described in the Specification of Letters
18 amidonaphthol disulpho acid Patent No. 13443 dated August 26th 1890)
with the diazo derivatives of the hereinafter named amido compounds viz.
a Amidophenols, amidocresols and their sulpho acids containing the amido and
hydroxyl group relately in the meta or para position.
Amidophenolethers, amidocresolethers, amidonaphtholethers and the sulpho
acids of these products with the exception of anisidine and cresidine. the
employment of which is already described in the Specification of Letters
Patent No. 18517 of 1890.
c Nitraniline and amido-azobenzene and the homologues and sulpho acids
thereof.
d Amidonaphthols and amidodihydroxynaphthalenes and their sulpho acids.
e Amidobenzoic acids, amidohydroxybenzoic acids, amido cresotinic acids,
amidophthalic acids and amido anisic acids and the sulpho acids thereof.
Phenylene diamines, toluylene diamines and naphthylene diamines containing
in one of the amido groups fatty alkyl groups phenyl, benzyl or the like,

page_text: Those amido azo compounds which are obtained by combining in equal
molecular proportions alpha naphthylamine or alpha amidonaphtholether
with diazotised amidobenzoic acids, amido-hydroxybenzoic acids amido
cresotinic acids amidophthalic acids, amido anisic acids, amidophenols,
amidocresols, amidonaphthols, amido-phenolethers, amidonaphthol ethers and
their sulpho acids, alpha- and betanaphthylamine trisulpho acids and the
sulpho acids of phenylene diamine and toluylene diamine substituted in one
of the two amido groups.
As new products of manufacture the colouring-matters of the preceding
ming clause.
Dated this 20th day of January 1892.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.