The Manufacture of New Colouring Matters.
Year: 1891

page_text: Date of Application, 28th Dec., 1891
Complete Specification Left. 24th Sept., 1892-Accepted, 29th Oct., 1892
PROVISIONAL SPECIFICATION.
The Manufacture of New Colouring Matters.
I, BENJAMIN WILLCOX of 47 Lincoln's 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 the Farbenfabriken vormals Friedrich
Bayer & Cie. of Elberfeld in the Empire of Germany) to be as follows :—
By nitrating naphthalene beta-monosulpho-acid and reducing the mixture of
mononitro derivatives so formed Clève has obtained three new alpha naphthylamine
beta-mono-sulpho-acids of the following compositions:
These acids (which are described in the Bulletin de la Societe Chimique
Volume 26, page 447 and Volume 29 page 415 and in the Berichte der Deutschen
Chemischen Gesellschaft Volume 19 page 2181, and Volume 21 pages 3260
and 3276) have hitherto not been employed for the production of dye-stuffs.
My foreign correspondents have found that the aforesaid three alpha-naphthyl-
amine-beta-monosulpho acids are of high value especially as the tetrazo dyestuffs
obtained by them are superior to the analogous products resulting from the
employment of the other naphthylamine sulpho acids as components. Whilst the
latter colouring matters when fixed on cotton fibre can not be directly diazotised
the new dye stuffs derived from the aforesaid three alpha naphthylamine-beta-
monosulpho acids (Clève) after having been diazotised on the fibre by combining
the resulting diazo derivatives directly with an amine, a phenol, amido phenol,
sulpho or carboxylic acid thereof yield new and valuable dyes of very great
fastness against the action of light, fulling and soaping.
For the production of tetrazo colouring-matters the following tetrazo com-
pounds can be employed with good results, i.:-tetrazo-diphenyl; tetrazo-phenyl-
tolyle, tetrazo-ortho-ditolyle, tetrazo-monomethoxydiphenyle; tetrazomonoethoxy-
diphenyle tetrazomonomethoxyphenyletolyle; tetrazo-monoethoxyphenyletolyle,
tetrazoortho diphenoldimethylether; tetrazoorthodiphenoldiethylether; tetrazo-
diphenoxylacetic acid; tetrazo phenylene, tetrazonaphthalene, (a, a3), tetrazo
fluorene, tetrazo stilbene, tetrazo diphenylene oxide; tetrazo ditoluylene oxide;
tetrazo diphenyle sulphone tetrazoditolyle sulphone and the sulpho or carboxylic
acids thereof.
A very great number of dyestuffs are obtainable by means of the three alpha
naphthylamine beta monosulpho acids (Clève) as one molecular proportion of the
aforesaid tetrazo compounds may be combined either with two molecular pro-
portions of Cleve's alpha naphthylamine-beta-mono-sulpho-acids when so called
symmetrical dye-stuffs are formed; or with one molecular proportion of Clève's
acids and one molecular proportion of an amine, a phenol, amido-phenol or sulpho
or carboxylic acids thereof, when so called mixed tetrazo dye stuffs are formed
which may also be obtained inversely viz. by first combining in equal molecular
A

page_text: proportions the aforesaid tetrazo compounds and an amine, a phenol, amido-phenol
or a sulpho or carboxylic acid thereof and subsequently reacting with one
molecular proportion of Clève's acids on the resulting intermediate products.
Instead of employing the three alpha naphthylamine beta mono sulpho acids in a
separated form a mixture of them may also be used.
The colouring-matters which are obtained from benzidine methylbenzidine and
orthotolidine by the combination of their tetrazo compounds with two molecular
proportions of one of the said alpha-naphthylamine-beta-mono-sulpho-acids
(Clève), with two molecular proportions of two different Clève's acids or with the
corresponding quantity of the mixture of these three acids, produce on unmordanted
cotton a bluish red colour in alkaline soap-baths.
The following are examples for the production of these symmetrical tetrazo
colouring-matters.
TETRAZO DYE-STUFF FROM ONE MOLECULAR PROPORTION OF TETRAZO)-
DITOLYLE-CHLORIDE AND TWO MOLECULAR PROPORTIONS OF ALPHA
NAPHTHYLAMINE-BETA-MONO SULPHO ACID (CLEVE'S B-ACID).
The tetrazo solution prepared by diazotising 31 parts, by weight, of ortho
tolidine sulphate by means of 14 parts, by weight, of sodium nitrite is allowed to
flow into a cold watery solution of 49 parts, by weight of the sodium salt of alpha
naphthylamine-beta mono sulpho-acid (Clève's B-acid) and of 100 parts by weight
of sodium acetate. The formation of the dye-stuff is complete after standing for
some days at ordinary temperature or after about 24 hours when the mixture is
slowly heated to the boiling point. On neutralizing the free acetic acid by the
addition of sodium carbonate or soda-lye the difficultly soluble dye stuff formed
separates. By filtering off, pressing and drying the latter may be isolated in the
It produces on unmordanted cotton in alkaline soap-baths a
well known manner.
bluish-red colour.
In an analogous manner the mixed dyestuffs are obtained by combining equal
molecular proportions of the alpha-naphthylamine-beta-mono-sulpho-acids and one
of the above enumerated tetrazo compounds; tetrazo diphenyl, tetrazo phenyltolyle
or tetrazoorthoditolyle, by subsequently reacting with one molecular proportion
of an amine, a phenol, amidophenol sulpho or carboxylic acid thereof on the
resulting intermediate products. Of course, the same colouring-matters can be
obtained inversely when the last named three tetrazo compounds are combined
at first in equal molecular proportion with an amine, a phenol, amido phenol or
sulpho or carboxylic acid thereof and the intermediate products resulting are
allowed to react on the alpha naphthylamine beta monosulpho acids (Clève)
likewise in molecular proportions.
The obtainment of these mixed products may be illustrated by the following
MIXED COLOURING-MATTER OBTAINED BY THE
COMBINATION
OF EQUAL
MOLECULAR PROPORTIONS OF TETRAZO-DIPHENYLE-CHLORIDE ALPHA-
NAPHTHYLAMINE-BETA-MONO-SULPHO ACID (CLEVE'S Y-ACID) AND ALPHA-
NAPHTHYLAMINE.
184 parts by weight, of benzidine (or of one of its salts) after adding hydro-
chloric acid are diazotised by means of a watery solution of 14 parts, by weight,
of sodium nitrite and the resulting tetrazo solution is allowed to flow into a solution
of 24-5 parts, by weight, of the sodium salt of the alpbanaphthylamine beta mono

page_text: OF
DYE-STUFF OBTAINED FROM ONE MOLECULAR PROPORTION OF TETRAZOMONO-
METHOXYPHENYLTOLYLE CHLORIDE, AND TWO MOLECULAR PROPORTIONS
ALPHANAPHTHYLAMINE-BETA-MONOSULPHO-ACID (CLEVE'S B-ACID).
A watery solution of tetrazomonomethoxyphenyltolyle chloride obtained by
diazotising 228 parts, by weight, of monomethoxymethylbenzidine in the presence
of hydrochloric acid by means of 14 parts, by weight, of sodium uitrite are slowly
added to a solution in water of 49 parts, by weight of the sodium salt of the
alphanaphthylamine betamonosulpho acid (Cleve's B-acid) and 100 parts by weight
of sodium acetate. The formation of the dyestuff is complete after standing for
some days at ordinary temperature, or when after about 24 hours the mixture is
slowly heated to the boiling point. Then the free acetic acid is neutralized by the
addition of sodium carbonate or soda-lye to the mixture and the difficultly soluble
dye-stuff is filtered off, pressed and dried. It dyes unmordanted cotton in alkaline
soap baths a bluish-red colour.

page_text: MIXED COLOURING-MATTER OBTAINED FROM ONE MOLECULAR PROPORTION OF
TETRAZO-ORTHO-DIMETHYLDIPHENOL ETHER, ONE MOLECULAR PROPOR-
TION OF ALPHANAPHTHYLAMINE-BETA-MONOSULPHO-ACID (CLEVE'S
8-ACID) AND ONE MOLECULAR PROPORTION OF ALPHANAPHTHYLAMINE.
34.2 parts, by weight, of dianisidine sulphate are diazotised in the presence of
muriatic acid by adding a watery solution of 14 parts, by weight, of sodium nitrite
and the tetrazo solution formed is added to a solution of 24.5 parts, by weight, of
alpha-naphthylamine-beta-mono-sulpo-acid (Clève's d-acid) and about 50 parts by
weight of sodium acetate. The resulting intermediate product (which is almost
insoluble in water) is filtered off and introduced into a solution of 143 parts, by
weight of alphanaphthylamine in a small excess of diluted hydrochloric acid.
After about 24 hours the liquid is slowly heated to the boiling point, then
neutralized by adding sodium carbonate or soda-lye and the dye-stuff is filtered
off, pressed and dried. It produces on unmordanted cotton in alkaline soap baths
a bluish-red colour.
Whilst the symmetrical colouring-matters obtained by the combination of one
molecular proportion of the tetrazo chlorides of monomethoxydiphenyle, mono-
ethoxydiphenyle monomethoxyphenytolyle, monoethoxyphenyl tolyle diphenol-
dimethylether and diphenoldiethylether with two molecular proportions of Clève's
alpha.naphthylamine beta mono sulpho acids in general dye unmordanted cotton in
alkaline soap-baths from bluish-red to reddish-violet colours the shades produced
by means of the mixed tetrazo dye-stuffs derived from the aforesaid tetrazo com-
pounds in combination with one molecular proportion of Clève's alpha naphthyl-
amine-beta-mono-sulpho acids, and one molecular proportion of an amine, a phenol,
amido phenol or sulpho or carboxylic acid thereof (or inversely) are of a greater
variety.
When the so-called intermediate products resulting from the combination of
equal molecular proportions of one of the last named tetrazo compounds and of
Clève's alphanaphthylaminebetamonosulpho acids are allowed to react on the
usual dye-stuff components the following shades are produced, a yellowish-red to
red by means of phenol or its sulpho and carboxylic acids; a reddish-violet. to
violet with naphthol; a violet to blue with naphtholsulpho acids; a violet with
dihydroxynaphthalenes: and from bluish-violet to blue, with the dihydroxy-
naphthalenes and from bluish-red to violet with aniline, its homologues naphthyl-
amines and the sulpho acids thereof; and a bluish-violet with amidonaphthols and
sulpho acids thereof. The same mixed dye-stuff's of course are inversely obtained
when the aforesaid tetrazo-compounds are at first combined in equal molecular
proportions with an amine, a phenol, amido phenol, or sulpho or carboxylic acid
thereof and the resulting intermediate products are then allowed to react with
Clève's alphanaphthylaminebetamonosulpho acids, likewise in molecular
proportions.

page_text: The symmetrical dyestuffs obtained as hereinbefore described (by combining one
molecular proportion of a tetrazo compound and two molecular proportions of
Chève's alphanaphthylamine beta mono sulpho acids containing still two free amido
groups and the mixed dyestuffs resulting from one molecular proportion of a tetrazo
compound one molecular proportion of Clève's acids and one molecular proportion of
an amine a phenol, amido phenol, sulpho or carboxylic acid thereof and which contain
either one or two free amido groups) can be converted into new colouring matters
by further diazotising them and subsequently combining the resulting products
with two molecular proportions of an amine, a phenol, amidophenol sulpho or
carboxylic acid thereof employing either the same or two different components.
The mixed dyestuffs resulting inversely by the combination of one molecular pro-
portion of a tetrazo compound firstly with one molecular proportion of an amine, a
phenol, amidophenol, sulpho or carboxylic acid thereof and then with one molecular
proportion of Clève's naphthylamine sulpho acids likewise can be changed into new
colouring matters as they may, after having been diazotised be combined with one
or two molecular proportions of the known dyestuffs components, in the latter case
employing either the same or different components.

page_text: The number of these dyestuffs is, of course very great and they are in general
produced in a similar manner as those which are obtained according to the Speci-
fication of letters Patent No. 16484 dated 13th November 1887.
In order to explain the method for the production of these new colouring matters
the following example is given.
RESULTING AS DESCRIBED IN THE FOREGOING FIRST EXAMPLE AND
COMBINING THE FORMED PRODUCT WITH TWO MOLECULAR PROPORTIONS
OF ALPHA NAPHTHYLAMINE BETAMONOSULPHO ACID (CLEVE'S B-ACID).
724 parts by weight, of the dyestuff which is obtained as described in the fore-
going first example and possesses the following formula:
CH₂
CH-N=N-CH
N H₂
\SO, Na
SO, Na
CH, N=N-C₁₁H¸‹
NH
CH₂
are suspended in water and after adding a watery solution of 14 parts, by weight
of sodium nitrite the resulting mixture is acidulated by adding slowly, and on
cooling by ice, such a quantity of hydrochloric acid as is necessary for producing a
moderately acid reaction. After about 12 hours the mixture formed is allowed to
flow into a cold watery solution of 49 parts by weight, of the sodium salt of the
alphanaphthylamine beta monosulpho acid (Clève's BB-acid) and of about 100 parts
by weight of sodium acetate. After standing for some days the mixture is slowly
heated to from about 60 to 70 degrees centigrade and maintained for a short time
at this temperature in order to complete the reaction. After adding sodium
carbonate or soda-lye to the acetic acid solution the dyestuff' formed is salted out
filtered, pressed and dried. It dyes unmordanted cotton in an alkaline soap-bath a
deep black with bluish hue.
According to the process described in the last example the analogous products
derived either from the symmetrical or from the mixed dyestuffs are also
obtainable.
VI.
New and valuable dyestuffs have further been prepared by my foreign corre-
spondents by combining one molecular proportion of the tetrazo compounds
enumerated in the first part of this Specification with one molecular proportion of
alpha naphthylamine beta mono sulpho acid (Clève) by rediazotizing the intermediate
products formed and by combining the resulting compounds with two molecular
proportions of the known dyestuff components; amines phenols, amidophenols or
their sulpho or carboxylic acids employing either the same component or two
different ones. The naphthols, dihydroxynaphthalenes, amido naphthols, sulpho
acids thereof and the alpha naphthylaminebetamonosulpho acids (Clève) employed
as components yield good results.
The following is given as an example for the production of these new hexaazo
dye-stuff's.

page_text: My foreign correspondents have found that the alpha naphthylamine beta mono
sulpho acids (Clève) can be employed advantageously for the production of new
disazo colouring matters suitable for dyeing wool black in acid baths by combining
with the known dyestuff components amines phenols amido phenols or the sulpho
and carboxylic acids thereof most preferably with naphthols dihydroxynaphthalines
amido naphthols and the sulpho acids thereof the diazo compounds of those azo
bodies which are formed from aniline toluidine xylidine alpha or beta naphthyl-
amine amidonaphthols amido naphthol ethers and the sulpho and carboxylic acids
thereof by diazotizing them and subsequently combining the resulting diazo
products with Clève's alphanaphthylamine beta mono sulpho acids.
The process for the production of these new disazo colouring matters may be
conducted in the known manner vizt., by diazotizing aniline toluidine and the like
combining the diazo derivatives so obtained with alphanaphthylamine beta mono
sulpho acid (Clève) rediazotizing the amido azo compounds formed and reacting
with the resulting diazo products on the said dye stuff components colouring matters
being produced which are similar to those described in the Specification of Letters
Patent No. 3397 dated 4th March 1890.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents.
COMPLETE SPECIFICATION.
The Manufacture of New Colouring Matters.
I BENJAMIN WILLCOX of 47 Lincoln's 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. Friedr. Bayer & Co.
of Elberfeld in the Empire of Germany) and in what manner the same is to be

page_text: performed to be particularly described and ascertained in and by the following
statement :-
By either nitrating naphthalene-beta-monosulpho-acid or sulphonating alpha
nitro-naphthalene, then reducing the resulting mixtures of mono-nitro derivatives,
and isolating the isomeric amido acids, Clève has obtained the three alpha-naph-
thylamine beta-mono-sulpho acids represented by the following formulæ :-
37
These acids (which are described in the "Bulletin de la Societé Chimique,”
volume 26, page 447 and volume 29-page 415 and in the "Berichte der Deutschen
Chemischen Gesellschaft," volume 19, page 2181, and volume 21 pages 3260
and 3276) have not hitherto been used in practice for the production of dye-
stuffs.
My foreign correspondents have found that of the aforesaid alpha-naphthylamine-
mono-sulpho acids the beta and delta acids are of high value more particularly
because the tetrazo dye-stuffs which they afford are superior to the analogous
products prepared from other alpha naphthylamine sulpho acids. Whilst the
colouring matters derived from the latter, cannot, when fixed on cotton fibre, be
directly diazotised, the new dye-stuffs derived from the aforesaid alpha-naphthyl-
amine-beta-mono-sulpho-acids to wit, Clève's beta acid and delta acid yield new
and variable dyes of very great fastness when they are diazotised on the fibre and
the resulting diazo derivatives are subsequently combined with an amine, a phenol,
an amidophenol, or a sulpho or carboxylic acid thereof.
The said dye-stuffs may also be prepared in the usual manner, and are of high
value, as they produce shades of great intensity and fastness on unmordanted
cotton.
To prepare these substantive dye-stuffs my foreign correspondents employ either
the products obtained by combining one molecular proportion of a tetrazo salt
either with two molecular proportions of Clève's beta or delta acid or with one
molecular proportion of the one, and one molecular proportion of the other, of these
two Clève alpha-naphthylamine-beta-mono-sulpho acids or the products resulting
from the combination of equal molecular proportions of tetrazo salts, Clève's beta
or delta acid and the known dye-stuff components viz. :-amines, phenols, amido-
phenols, amido-phenolethers or their sulpho or carboxylic acids.
For the production of such colouring-matters the following tetrazo compounds
can be employed viz. :-tetrazo-diphenyl, tetrazo-phenyltolyl, tetrazo-ortho-ditolyl,
tetrazo-mono-methoxydiphenyl, tetrazo-monoethoxydiphenyl, tetrazo-monometh-
oxyphenyltolyl, tetrazo-monoethoxyphenyltolyl, tetrazo-ortho-diphenoldimethyl-
ether, tetrazo-ortho-diphenol-diethylether, tetrazo-diphenoxyl acetic acid, tetrazo
phenylene, tetrazo-naphthalene (a, as), tetrazo-fluorene, tetrazo-stilbene, tetrazo-
diphenylene oxide, tetrazo, ditoluylene oxide, tetrazo diphenyl-sulphone, tetrazo-
ditolyl-sulphone and the sulpho or carboxylic acids thereof.
The symmetrical dye-stuffs containing two free amido groups obtained by
combining one molecular proportion of a tetrazo compound with two molecular
proportions of Clève's alpha-naphthylamine-beta-mono-sulpho acid, delta or beta,
and the mixed dye-stuffs formed from one molecular proportion of a tetraz com-
pound, one molecular proportion of Clève's beta or delta acid, and one molecular
proportion of an amine, a phenol, an amido phenol, or a sulpho or carboxylic ad
thereof and which contain either one, or two, free amido groups, can be converted

page_text: into new colouring-matters by further diazotizing them and subsequently combining
the resulting diazo-compounds with one molecular proportion or two molecular
proportions of an amine, a phenol, an amidophenol, or a sulpho or carboxylic acid
thereof, employing, in the latter case, either the same, or two different, components.
The mixed dye-stuffs formed inversely by the combination of one molecular pro-
portion of a tetrazo compound first with one molecular proportion of an amine, a
phenol, an amidophenol, or a sulpho or carboxylic acid thereof, and then with one
molecular proportion of Clève's beta or delta naphthylamine sulpho acid can
likewise be changed into new colouring-matters as they may be diazotised and the
resulting diazo compound may be combined with one molecular proportion or two
molecular proportions of the known dye-stuff components, in the latter case
employing either the same, or two different, components. In this manner colouring
matters result, containing either three or four azo groups (-N-N-) which
therefore will be briefly termed trisazo- or tetrakis-azo dye-stuffs.
The number of these dye-stuffs is, of course, very great, and they are, in general,
produced in manner similar to that in which those described in the Specification of
Letters Patent No. 16484 dated 13th November 1887 are obtained.
In order to explain the method of producing these new colouring-matters the
In all the examples the parts are by weight.)
CH₁
are suspended in water and a solution in water of 14 parts of sodium nitrite having
been added and the mixture cooled by ice, such a quantity of hydrochloric acid as
is necessary to produce a moderately acid reaction is slowly added. After about
12 hours the mixture is allowed to flow into a cold solution in water of 49 parts, of
the sodium salt of alpha-naphthyl-amine-alpha-mono-sulpho acid (naphthionic acid)
together with about 100 parts, of sodium acetate. After standing for some days
the mixture is slowly heated to from 60 to 70 degrees centigrade and is maintained
at this temperature, in order to complete the action. Then after adding sodium
carbonate or soda-lye to the acetic acid solution, the dye-stuff, which has been
formed, is salted out, filtered, pressed, and dried. It dyes unmordanted cotton in
an alkaline soap bath a deep black of a bluish hue.
The following example is given in illustration of the method of producing dye-
stuff's by combining a tetrazo salt with two molecular proportions of Clève's alpha-
naphthylamine-mono-sulpho acid beta or delta by rediazotising the diamido
products thus obtained, and coupling the resulting tetrazo compounds with one
molecular proportion of one, and one molecular proportion of another, dye-stuff
component
B

page_text: SECOND EXAMPLE.
DYE-STUFF OBTAINED BY COMBINING THE TETRAZO-CHLORIDE OF ORTHO-
DIAMIDO-DIPHENOL-DIMETHYL-ETHER WITH TWO MOLECULAR PRO-
ACID
PORTIONS OF CLEVE'S ALPHA-NAPHTHYLAMINE-MONO-SULPHO
(BETA) THEN REDIAZOTISING THE DIAMIDO PRODUCT AND COUPLING
FIRST WITH ONE MOLECULAR PROPORTION OF ALPHA-NAPHTHYLAMINE-
ALPHA-MONO-SULPHO ACID (1.4) AND THEN WITH ONE MOLECULAR PRO-
PORTION OF ALPHA-NAPHTHOL-ALPHA-MONO-SULPHO ACID (1.4).
The tetrazo solution obtained from 31.7 parts of ortho-diamido diphenoldimethyl-
ether dissolved in water by means of 14 parts of sodium nitrite and the necessary
quantity of hydrochloric acid is allowed to flow into a solution in water of 49 parts
of the sodium salt of Clève's alpha-naphthylamine-mono-sulpho acid (beta).
product is a diamido-tetrazo compound possessing the following formula ·
The
OCH
SO₂H
When its formation is completed, a concentrated solution in water of 14 parts of
sodium nitrite is added and subsequently a slight excess of hydrochloric acid is
slowly run in. The diazotising being completed, a concentrated solution in water
of 24.5 parts of the sodium salt of alpha-naphthylamine-alpha-mono-sulpho-acid (1.4)
is introduced together with 50 parts of sodium acetate. As soon as the combination
is finished, a solution in water of 246 parts of the sodium salt of alpha-naphthol-
alpha-mono-sulpho-acid (1-4) is allowed to flow into the mixture care being taken
to maintain it alkaline by adding sodium carbonate during the operation. After
standing some days the mixture is heated for a short time at about 60 degrees
centigrade, and the dye-stuff is then isolated by salting out, filtering off, pressing,
and drying.
It produces on unmordanted cotton in an alkaline soap bath, a black with a
bluish hue. Following the processes described in the foregoing two examples
analogous products may be obtained either by employing in place of tetrazo-
ditolylchloride, or tetrazo-ortho-diphenol-ether, other tetrazo compounds, or by
replacing Clève's alpha-naphthylamine-mono-sulpho acid (beta) by the isomeric
delta acid or by using one molecular proportion of the one, and one molecular
proportion of the other of these two acids, or a mixture of them, or by starting
from such intermediate products as result on combining a tetrazo salt with one
molecular proportion of Clève's alpha-naphthylamine-mono-sulpho acid (beta or
delta) and one molecular proportion of another component (an amine, phenol,
amidophenol, amidophenol-ether, or a sulpho, or carboxylic acid thereof) or
inversely on coupling a tetrazo salt first with one of the said components and then
with one molecular proportion of Clève's beta or delta acid. The alpha-naphthyl-
amine-alpha-mono-sulpho acid (1-4) and alpha-naphthol-alpha-mono-sulpho acid
(14) employed in the foregoing two examples as final components can be replaced
by other naphthylamine or naphthol-sulpho acids or in general by amines, phenols,
amido phenols, amidophenolethers, or sulpho or carboxylic acids thereof.
Of course the production of such trisazo and tetrakisazo-dye-stuffs can be effected
in other ways to wit by means of all the methods which are generally in use for the
production of analogous colouring-matters.
The shades produced by these tris-azo and tetrakisazo colouring-matters are
generally from greenish-black, to bluish-black, and pure black.

page_text: New and valuable dye-stuffs have also been prepared by my foreign corre-
spondents by combining one molecular proportion of the tetrazo compounds above
enumerated with one molecular proportion of Clève's alpha naphthylamine-mono-
sulpho-acid (delta or beta) rediazotising the intermediate products thus formed and
combining the resulting diazo compounds with two molecular proportions of the
known dye-stuff components: amines, phenols, amidophenols amidophenolethers or
their sulpho, or carboxylic acids; employing either the same component, or two
different components. The naphthols, dihydroxy naphthalenes, amidonaphthols, or
sulpho acids thereof employed as components yield the best results.
The following are given as examples of the production of these new azo dye-
140
DYE-STUFF
BY
THIRD EXAMPLE.
DIAZOTISING
THE
INTERMEDIATE
PRODUCT
OBTAINED
RESULTING FROM THE COMBINATION OF ONE MOLECULAR PROPORTION
. OF TETRAZO-DIPHENYL-CHLORIDE WITH ONE MOLECULAR PROPORTION OF
ALPHA-NAPHTHYLAMINE-BETA-MONO-SULPHO ACID (CLEVE'S BETA ACID)
AND COUPLING THE TETRAZO-CHLORIDE SO FORMED WITH TWO MOLE-
CULAR PROPORTIONS OF 18 DIHYDROXY-NAPHTHALENE-ALPHA-MONO-
SULPHO ACID.
The solution in water of tetrazodiphenyl chloride obtained by diazotising
184 parts of benzidine (or the corresponding quantity of one of its salts) is allowed
to flow into a cold solution of 24.5 parts of the sodium salt of alpha-naphthylamine-
beta-monosulpho-acid (Clève's beta-acid) and of about 50 parts of sodium acetate.
When the formation of the intermediate product is completed, it is directly
diazotised by adding to the cool mixture a solution in water of 7 parts of sodium
nitrite and the necessary quantity of hydrochloric acid. As soon as the diazotising
is finished, the mixture is introduced into a solution in water of 52.4 parts of
1.8 dihydroxy-naphthalene-mono-sulphonate of sodium and about 100 parts of
sodium carbonate. After the mixture has stood for some hours the formation of
the dye-stuff is finished, and it is salted out, filtered off pressed and dried.
unmordanted cotton in an alkaline soap-bath a bluish-black,
It dyes
COLOURING-MATTER OBTAINED BY COMBINING ONE MOLECULAR PROPORTION
OF TETRAZO-ORTHO-DIPHENOL-DIMETHYL-ETHER WITH ONE MOLECULAR
PROPORTION
OF CLEVE'S ALPHA-NAPHTHYLAMINE-MONO-SULPHO ACID
(BETA) BY REDIAZOTISING THE INTERMEDIATE PRODUCT AND COUPLING
1-8-DIHYDROXY-
WITH ONE MOLECULAR PROPORTION OF BETA-NAPHTHOL-MONO-SULPHO
ACID F.
ONE MOLECULAR PROPORTION
NAPHTHALENE-ALPHA-MONO-SULPHO ACID.
AND
OF
34-2 parts of dianisidine sulphate are converted in the usual manner into the
tetrazo-compound; and the solution of the latter is allowed to flow into a solution
in water of 245 parts of the sodium salt of Clève's alpha-naphthylamine-mono-
When the combination
sulpho acid (beta) and about 50 parts of sodium acetate.
is completed, a concentrated solution in water of 7 parts of sodium nitrite is added
and then hydrochloric acid is slowly run into the liquid mixture until it acquires a
permanent acid reaction. The diazotising being finished, a solution in water of
246 parts of the sodium salt of beta-naphthol-mono-sulpho acid F (beta-naphthol-
delta-mono-sulpho acid 2.7) is added and, when the combination is complete, a
solution in water of 26-2 parts of the sodium salt of 18 dihydroxy-naphthalene-
alpha-mono-sulpho acid is introduced together with about 50 parts of sodium

page_text: acetate. After some days the mixture is heated to about 60 degrees centigrade
and subsequently the dye-stuff is isolated by rendering the cooled liquid alkaline,
salting out, filtering off, pressing, and drying.
This colouring-matter dyes unmordanted cotton black with a blueish tinge in an
alkaline soap bath.
In a manner analogous to that described in the foregoing third and fourth
examples, the other dye-stuffs are obtained, either by employing other tetrazo
salts in place of tetrazo-diphenyl-chloride or tetrazo-ortho-diphenol-ether-chloride,
or by coupling the tetrazo compounds with Clève's delta-acid, or a mixture of beta
and delta acid instead of the isomeric beta acid employed in the said two examples
or by replacing the 18 dihydroxy-naphthalene-alpha-mono-sulpho acid or beta-
naphthol-mono-sulpho acid F by other dihydroxy-naphthalene-sulpho acids or
naphthol-sulpho acids or in general by phenols, amines, amidophenols, or amido-
phenol-ethers to wit all those products which can be used as dye-stuff components.
The shades produced by these new azo dye-stuffs are, from blueish-black, to
deep, and pure, black.
My foreign correspondents have found that Clève's alpha-naphthylamine-mono-
sulpho acids (beta and delta) can be advantageously employed for the production
of new disazo colouring-matters (suitable for dyeing wool black in an acid bath)
by combining with the known dye-stuff components (viz. amines, phenols, amido-
phenols or the sulpho and carboxylic acids thereof, preferably with naphthols,
dihydroxy-naphthalenes, amido-naphthols and the sulpho acids thereof), the diazo
compounds of those azo bodies which are formed from aniline, toluidine, xylidine,
alpha or beta naphthylamine, amido-naphthols, amido-naphthol-ethers and the
sulpho and carboxylic acids thereof, by diazotising them and subsequently
combining the resulting diazo products with Clève's alpha-naphthylamine-mono-
sulpho acid (beta or delta).
The process for the production of these new disazo colouring-matters may be
conducted in the known manner viz. by diazotising aniline, toluidine, and the like,
combining the diazoderivatives with the said alpha-naphthylamine-mono-sulpho
acids (beta or delta) rediazotising the resulting amido-azo compounds and acting
with the diazo products thus obtained on the said dye-stuff components, colouring
matters being produced which are similar to those described in the Specification
of Letters Patent No. 3397 dated 4th March 1890.
The following example is given in order to illustrate the production of the said
disazo dye-stuffs by means of Clève's alpha-naphthylamine-mono-sulpho acid (beta
or delta
DERIVATIVE
COLOURING-MATTER OBTAINED BY COMBINING, IN EQUAL MOLECULAR PRO-
PORTIONS, DIAZOTISED ANILINE WITH CLEVE'S ALPHA-NAPHTHYLAMINE-
MONO-SULPHO ACID (BETA) REDIAZOTISING THE AMIDO-AZO COMPOUND
THUS PRODUCED, AND COUPLING THE RESULTING DIAZO
WITH 18 DIHYDROXY-NAPHTHALENE-ALPHA-MONO-SULPHO-ACID.
The solution of diazo benzene chloride, obtained from 9.3 parts of aniline in
hydrochloric acid solution by means of 7 parts of sodium nitrite, is allowed
to flow into a solution in water of 24.5 parts of the sodium salt of Clève's
alpha-naphthylamine-mono-sulpho acid (beta) and about 50 parts of sodium
acetate. When the combination is completed, the resulting amido-azo
compound is diazotised by means of 7 parts of sodium nitrite, and the necessary
quantity of hydrochloric acid. The diazo salt thus obtained is then combined
with 262 parts of the sodium salt of 1.8 dihydroxy-naphthalene-alpha-
mono-sulpho acid in aqueous solution and with the addition of about 50 parts
of sodium acetate. This combination being finished, the mixture is rendered

page_text: alkaline and the dye-stuff, is isolated by salting out, filtering off, pressing and
drying. It possesses the following composition :
The shades produced by this dye on unmordanted wool in an acid bath are blueish-
black, whilst those on wool mordanted with chromium salts are greenish-black.
This product can also be employed for printing purposes as when used in printing
it at once yields an intense pure black.
Other disazo dye-stuffs may be produced in a manner analogous to that described
in the foregoing fifth example either by replacing aniline by toluidine or analogues
thereof, by naphthylamine or generally by amines, amidophenols, amidophenolethers
or sulpho or carboxylic acids thereof, or by employing in place of Clève's beta
acid the isomeric delta acid as middle component or by using in place of
18 dihydroxy-naphthalene-alpha-mono-sulpho acid as last components other
dihydroxy-naphthalene-sulpho-acids, or generally amines, phenols, amidophenols,
amido-phenol-ethers, or sulpho or carboxylic acids thereof.
The last named colouring matters are especially suitable for dyeing wool in an
acid bath and some amongst them can also be employed for printing purposes.
The shades produced by them are in general from bluish-black to greenish-black
and pure black.
In the aforesaid examples directions are given for obtaining these dye-stuffs by
means of Clève's alpha-naphthylamine-mono-sulpho acid (beta or delta) as the best
means with which my foreign correspondents are acquainted for carrying this
invention into effect but I do not limit myself to the ways therein described.
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 manufacture or production of new substantive trisazo and tetrakisazo
dye-stuffs by combining one molecular proportion of a tetrazo salt with two
molecular proportions of Clève's alpha-naphthylamine-mono-sulpho-acid (beta or
delta) or with one molecular proportion of the one, and one molecular proportion
of the other, of these two acids, or with two molecular proportions of a mixture
of these two acids, or with one molecular proportion of one of these two acids,
and one molecular proportion of another dye-stuff component, (amine, phenol,
amidophenol, amidophenolether of the benzene, or naphthalene, series or sulpho
and carboxylic acid thereof) or first with one molecular proportion of these latter
dye-stuff components and then with one molecular proportion of Clève's beta or
delta acid, by subsequently diazotising the symmetrical, or mixed, products thus
obtained, and combining the resulting compounds with one, or two, molecular
proportions of an amine, a phenol, an amidophenol, an amidophenolether, or a
sulpho or carboxylic acid thereof, employing in the latter case either the same
component, or two different components.
2. The manufacture of new substantive trisazo dye-stuffs by combining one
molecular proportion of a tetrazo salt with one molecular proportion of Clève's
alpha-naphthylamine-mono-sulpho acid (beta or delta) further diazotising the
resulting intermediate products and coupling the compounds thus formed, with two
molecular proportions of an amine, a phenol, an amido-phenol, an amidophenol-
ether of the benzene or naphthalene series, or a sulpho or carboxylic acid thereof,
employing either the same product, or two different components.
3. The process for producing new disazo colouring matters (capable of dyeing
wool in an acid bath) by combining the diazo derivatives of aniline, toluidine,

page_text: xylidine, alpha-naphthylamine, beta-naphthylamine, amido-naphthol, amido-naphthol-
ether, or sulpho or carboxylic acids thereof, including the three alpha-naphthyl-
aminebeta mono sulpho acids (beta, alpha or delta of Clève) with Clère's alpha-
naphthylamine-mono-sulpho acid (beta or delta), rediazotising the amido-azo-
products so formed and coupling the diazo products with an aminc, a phenol, an
amidophenol, an amidophenolether of the benzene or naphthalene series, or a sulpho
or carboxylic acid thereof.
4. As new articles of manufacture the new dye-stuffs hereinbefore defined.
Dated this 24th day of September 1892.
B. WILLCOX.

page_text: Date of Application, 28th Dec., 1891
Complete Specification Left, 19th Sept., 1892-Accepted, 22nd Oct., 1892
PROVISIONAL SPECIFICATION.
Improvements in the Production of Azo Colours on Fibre.
I BENJAMIN WILLCOX of 47 Lincolns Ion 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 vormals Friedrich Bayer
& Co. of Elberfeld in the Empire of Germany to be as follows :-
It is known that certain substantive dyes containing one free amido group when
fixed on fibre in the usual manner possess the property of being diazotable by
means of nitrous acid diazo compounds resulting which owing to their insolubility
remain on fibre and can directly be combined with amines, phenols, amidophenols
or sulpho- or carboxylic acids thereof. For example cotton which has been dyed
a yellow by primuline acquires after treating with nitrous acid and subsequently
with an alkaline solution of beta naphthol a beautiful red colour fast against
washing.
My foreign correspondents have described in the Specification of Letters
Patent No. 8530 dated 2nd July 1890 that black azo colours may be produced,
likewise, on fibre by subjecting to the same process cotton previously dyed with
colouring-matters obtained by combining the tetrazo compounds of benzidine,
tolidine, dianisidine, or diamidostilbene with amido-naphthol-mono-sulpho-acid-G
and they have further discovered that in the last named process the amido-naphthol-
mono-sulpho-acid-G may advantageously be replaced by the 1-8-amido_naphtol-
beta-disulpho acid as described in the Specification of Letters Patent No. 9636
dated 6th June 1891.
It has not been hitherto known that also dyes obtained from tetrazo compounds
and naphthylamine monosulpho acids could be employed in the said process.
Whilst the alpha-naphthylamine-mono-sulpho acids 1.4, 1.5 and 1.8 which are
usually employed in practice, cannot be used for such purposes as my foreigu
correspondents have found but they have discovered that alpha naphthylamine
beta monosulpho acids yield good results as the tetrazo dyestuff's obtained with the
aid of them after having been fixed on fibre are capable of being diazotised and
subsequently combined with amines phenols, amidophenols or sulpho and carboxylic
acids thereof. Amongst the alphanaphthylamine-beta-mono-sulpho acids which
are known and correspond with the formula:
the three last have been obtained by Clève by nitrating naphthalene-beta-mono-
sulpho acid or by sulphonating alpha nitro naphthalene and reducing the mixture
of mono-nitro-derivatives so formed. These three acids especially when combined
with the tetrazo compounds of benzidine, its homologues and analogues yield
valuable dyestuffs which have been described in the Specification of my application
for Letters Patent No. 22641 dated 28th December 1891. My foreign corre-
spondents have now found that the tetrazo dyestuff's obtained by the employment
of the said three alpha naphthylamine-beta-mono-sulpho-acids of Clève possess a
high technical value as they are capable of being further diazotised when fixed on
fibre and as the resulting diazo or tetrazo chlorides (which owing to their insolubility
remain fixed on fibre) can directly be combined with the known dye-stuff components

page_text: (amines, phenols amidophenols or sulpho or carboxylic acids thereof) shades can be
produced in this manner which possess high intensity and beauty and very great
fastness against the action of light, washing soaping and fulling. This peculiar
property seems to be caused by the mutual position of the amido- and sulpho- group
in the alphanaphthylamine-beta-monosulpho-acids (Clève) which contain the amido
group in alpha and the sulpho group in beta position. The fourth of the isomeric
alpha-naphthylamine-beta-monosulpho-acids the alpha, beta, or 1-2-naphthylamine-
beta-monosulpho acid, is, my foreign correspondents have found, less adapted for
such purposes.
The variety of shades which can be obtained by means of this process is very
great as the tetrazo dye-stuffs resulting from one molecular proportion of a tetrazo
compound and two molecular proportions of one of Clèves naphthylamine-sulpho-
acids or the corresponding quantity of a mixture of them or the mixed dye-stuffs
obtainable as described in the Specification of application for Letters Patent
No. 22641" can be diazotised after having been fixed on cotton and likewise be
directly combined on the fibre with the known dye-stuff' components.
In order to illustrate this method for producing azo colours on the fibre the
following example is given the parts being by weight.
About 10 parts of unmordanted cotton are dyed by immersion, for say one hour,
in a boiling solution prepared by dissolving 0.5 of a part of the dye-stuff obtained
from tetrazo diphenoldimethylether and two molecular proportions of alphanaphthyl-
amine-beta-mono-sulpho acid (Clève's beta acid) in 250 parts of hot water and
adding one part of common salt after which the cotton is carefully rinsed. The
cotton which is now dyed bluish-red is then placed in a solution of 0.3 of a part of
sodium nitrite in 250 parts of cold water acidulated with 0.9 of a part of hydro-
chloric acid (20° Baumé) and well agitated therein.
When the diazotising is finished the cotton is rinsed with cold water and then is
placed in an alkaline solution of 0-4 of a part of the sodium salt of betanaphthol.
The cotton gradually acquires a bluish-black colour which is fast against the action
of light, washing soaping and fulling.
The colours thus produced are of the same brightness beauty and fastness as
those which are obtained when the cotton is dyed at first with the colouring-matters
resulting by the combination of tetrazo compounds either with amido-naphthol-
monosulpho-acid G or with 1.8-amidonaphthol-disulpho-acids employing both
the symmetrical and the mixed dye-stuffs obtained in this manner, and when these
colours are further diazotised on the fibre and directly combined with known
dye-stuff components as described in the Specifications of Letters Patents No. 8530
of 1890 and No. 9636 of 1891.
The best shades are obtained by employing betanaphthol and the dye-stuffs
described under the heads I-IV in the Specification of application for Letters
Patent No. 22641" yield violet to blue and black colours when diazotised on fibre
and combined with beta-naphthol.
When the beta-naphthol is replaced by alpha-naphthol, phenol, resorcine or
sulpho or carboxylic acids thereof or by dihydroxynaphthalines or their sulpho
acids or by amines or sulpho or carboxylic acids thereof a great variety of excellent
colours (from violet to blue and pure black) are produced.
Dated this 22nd day of January 1892.

page_text: · COMPLETE SPECIFICATION.
Improvements in the Production of Azo Colours on Fibre.
I 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 com-
municated to me from abroad by Farbenfabriken vormals 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:-
It is known that certain substantive dyes containing a free amido group possess
when fixed on fibre in the usual manner the property of being diazotisable by
means of nitrous acid and that the resulting diazo compounds which, owing to their
insolubility, remain on the fibre can be directly combined with amines, phenols,
amidophenols or sulpho- or carboxylic acids thereof. For example cotton which
has been dyed yellow by primuline acquires, after treatment with nitrous acid
and subsequently with an alkaline solution of beta naphthol, a beautiful red colour
which withstands washing.
Moreover my foreign correspondents have described in the Specification of
Letters Patent No. 8530 dated 2nd July 1890 the production of black azo colours
on fibre in like manner by subjecting to the aforementioned processes cotton dyed
with colouring matters obtained by combining the tetrazo compounds of benzidine,
tolidine, dianisidine, or diamido-stilbene, with amido-naphthol-mono-sulpho-acid-G
and they have further discovered that, in the last named process, the amido-
naphthol-mono-sulpho-acid-G may be advantageously replaced by the 18 amido-
naphthol-beta-disulpho acid as described in the Specification of Letters Patent
No. 9636 dated 6th June 1891.
It has not been hitherto known that dyes obtained from tetrazo compounds and
naphthylamine monosulpho acids could also be employed in the said process.
My foreign correspondents have found that the alpha-naphthylamine-alpha-mono-
sulpho-acids 14, 1.5 and 1-8, which are usually employed in practice, cannot be
used for such purposes, but they have discovered that certain alpha-naphthylamine-
beta-mono-sulpho acids yield good results as the tetrazo dye-stuffs obtained with
their aid when fixed on fibre, may be diazotised and subsequently combined with
amines, phenols, amidophenols, or sulpho and carboxylic acids thereof. Of the
known alphanaphthylamine-beta-mono-sulpho-acids represented by the formula:
acid.
mono-sulpho-acid y. mono-sulpho-acid 5. mono-suipno-acid d.
the three last have been obtained by Clève by nitrating naphthalene-beta-mono-
sulpho-acid, or by sulphonating alpha-nitro-naphthalene, reducing the mixture of
mono-nitro derivatives so formed and isolating the isomeric amido-sulpho-acids.
These three acids yield tetrazo dyes when combined with the tetrazo compounds of
benzidine, its homologues and analogues in the known manner. My foreign corre-
spondents have now found that the tetrazo dye-stuffs obtained by the employment
of Clève's alpha-naphthylamine mono-sulpho acids (beta- and delta-) possess a high
technical value as they may be further diazotised, when fixed on the fibre, and as
the resulting diazo or tetrazo chlorides (which owing to their insolubility remain

page_text: fixed on the fibre) can be directly combined with the known dye-stuff components
(amines, phenols, amidophenols or sulpho or carboxylic acids thereof) and thus
shades can be produced of high intensity and great fastness.
The dye-stuffs thus produced on the fibre contain either three or four azo
groups N=N-) and will therefore for the sake of brevity be called trisazo
colouring-matters or tetrakisazo colouring-matters.
The variety of shades which can be obtained by means of this process, is very
great as the tetrazo dye-stuffs resulting from the use of one molecular proportion
of a tetrazo compound and two molecular proportions of Clève's alpha-naphthyl-
amine-mono-sulpho-acids (beta or delta) or the corresponding quantity of a mixture
thereof or the mixed dye-stuffs can be diazotised when fixed on cotton and the
resulting diazo compounds while on the fibre can then be directly combined with
the known dye-stuff components.
By the expression "mixed dye-stuffs" my foreign correspondents mean those
colouring-matters which can be produced by the combination of one molecular
proportion of a tetrazo salt, with one molecular proportion of the one and one
molecular proportion of the other of the said two acids or those products formed by
acting with one molecular proportion of a tetrazo salt on one molecular proportion
of Clève's beta or delta acid and one molecular proportion of an amine, a phenol,
amido phenol, amidophenolether of the benzene or naphthalene series, a sulpho or
carboxylic acid thereof or inversely by coupling a tetrazo salt, first with an amine,
phenol, amidophenol, amidophenolether, or sulpho or carboxylic acid thereof and
then with Clève's beta or delta acid in equal molecular proportions.
In order to illustrate this method for producing azo colours on the fibre the
following example is given, the parts being by weight.
PRODUCTION OF A BLUEISH-BLACK.
About ten parts of unmordanted cotton are dyed by immersion for say one hour
in a boiling solution prepared by dissolving 0.5 of a part of the dye-stuff obtained
from tetrazo ortho diphenol-dimethyl-ether and two molecular proportions of alpha-
naphthylamine beta-mono-sulpho-acid (Clève's beta acid) in 250 parts of hot
water and adding one part of common salt, after which dyeing the cotton is
carefully rinsed. The cotton, which is now dyed blueish-red, is then placed in a
solution of 0.3 of a part of sodium nitrite in 250 parts of cold water acidulated
with 0.9 of a part of hydrochloric acid (20° Baumé) and well agitated therein.
When the diazotising is finished the cotton is rinsed in cold water and is then
placed in an alkaline solution of 04 of a part of the sodium salt of betanaphthol.
The cotton gradually acquires a fast blueish-black colour.
The dye-stuff employed in the foregoing example can be replaced by the analogous
products prepared from other tetrazo salts or by means of Clève's delta acid, with
the exception however of the dye-stuff from tetrazo-diphenyl-chloride and Clève's
heta acid, as my foreign correspondents have found that this dye-stuff is insoluble.
By employing the aforesaid colouring-matters red or blueish-red shades are produced
on unmordanted cotton, whilst by further diazotising them on the fibre and
coupling for instance with betanaphthol bluer and blueish-black shades are
obtained.
Of course a greater difference in shade results on replacing the symmetrical dye-
stuffs by the aforementioned mixed products, diazotising these on the fibre and
subsequently coupling with beta naphthol or the like. The mixed dye-stuff's
derived from tetrazo-diphenyl produce the reddest shades, the colour gradually
becoming bluer or greener when colouring-matters obtained from diamines of a
greater molecular weight, or from alkylhydroxydiamines are subjected to such a
treatment on the fibre. The tetrazostilbene dye-stuffs generally yield shades
similar to those obtained by means of the products from benzidine.
The colours thus produced are of the same fastness as those which are obtained
when the cotton is first dyed with the colouring-matters resulting from the com-

page_text: bination of tetrazo compounds either with amidonaphthol mono sulpho acid G or
with 18 amidonaphthol-beta-disulpho acid, employing both the symmetrical and
the mixed dye-stuffs obtained in this manner, and when these colours are further
diazotised on the fibre and directly combined with known dye-stuff components as
described in the Specifications of Letters Patent No. 8530 of 1890 and No. 9636
of 1891.
The best shades are obtained by employing beta-naphthol and combining it with
diazo or tetrazo-compounds on the fibre.
When the beta-naphthol is replaced by alpha-naphthol, phenol, resorcinol, or
sulpho, or carboxylic, acids thereof, by di-hydroxynaphthalenes, or their sulpho
acids, or in general by amines, phenols, or sulpho, or carboxylic, acids thereof, a
great variety of colours (from violet to blue and black) is produced.
Amines, certain dihydroxynaphthalenes and sulpho acids thereof are most
profitably coupled in a solution made moderately acid by acetic acid and in
presence of sodium acetate. Somewhat redder shades result from the employment
of phenol, cresol, resorcinol, or alpha-naphthol whilst alpha-amido-naphthol-ether
or di-hydroxy-naphthalenes in general yield shades more inclined to blue or green
and metaphenylene diamine and toluylene diamine produce much darker shades
than does beta naphthol.
If sulpho or carboxylic acids of these amines or phenol, used as last components,
are combined with the diazo or tetrazo compounds on the fibre similar shades are
produced but these do not withstand washing so well.
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 trisazo- or tetrakisazo colouring-matters on fibre by first
dyeing unmordanted cotton with the dye-stuffs which result from the combination
of one molecular proportion of tetrazo salt with two molecular proportions of
Clève's alpha naphthylamine monosulpho acid (beta or delta) or a mixture of them
or with one inolecular proportion of the one, and one molecular proportion of the
other, of these two acids, or with one molecular proportion of the latter two acids,
and one molecular proportion of the known dye-stuff components (amine, phenol,
amidophenol, amidophenol ether of the benzene or naphthalene series, or a sulpho
or carboxylic acid thereof) or inversely first with one molecular proportion of
these last-named dye-stuff components and then with one molecular proportion of
Clève's alpha naphthylamine mono sulpho acid [beta or delta] (the use of the dye-
stuff from tetrazodiphenylchloride and Clève's alpha naphthylamine mono sulpho
acid [beta] is hereby disclaimed), by further diazotising these colouring-matters on
the fibre and coupling the resulting diazo or tetrazo products, also whilst on the
fibre, with amines, phenols, amidophenols, amidophenolethers of the benzene or
naphthalene series, sulpho or carboxylic acids thereof, effecting the latter two
processes (viz. diazotation and combination) by treating cotton, previously dyed,
first in a bath of moderately acidulated sodium nitrite and then in moderately acid
or alkaline baths of amines, phenols, amidophenols, amidophenolethers of the benzene
or naphthalene series, or a sulpho or carboxylic acid thereof.
2. Cotton fibres or textures dyed in the manner hereinbefore described or by any
other process producing a like result.
Did J
1000
J. H. JOHNSON & Co.,
Agents.