Improvements in the Manufacture of Dye-stuffs.
Year: 1892

page_text: Date of Application, 20th Aug., 1892
Complete Specification Left, 23rd May, 1893-Accepted, 5th Aug., 1893
INUYIRIONAL РІДАЛІСА Пом.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
Improvements in the Manufacture of Dye-stuffs.
I HENRY EDWARD NEWTON of the Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
:-
My foreign correspondents have described in the Specification of the British
Patent granted to Benjamin Willcox, No. 13235, dated August 22nd 1890, valuable
dye-stuffs which are obtained by combining the tetrazo salts of diamines (substituted
or not substituted) with one molecular proportion of salicylic acid, or analogous
oxycarbonic acids, and one molecular proportion of alphanaphthylamine, or alpha-
amidonaphtholether, or inversely, by coupling the said tetrazo salts at first with
one molecular proportion of alphanaphthylamine, or alpha amido naphtholether,
and then with one molecular proportion of salicylic acid, or analogous hydroxy-
carbonic acids, and by subsequently diazotising the amido tetrazo products thus
obtained, and coupling the diazo salts resulting, with one molecular proportion of
an amine, a phenol, or sulpho acid thereof.
Analogous dye-stuffs have been produced by my foreign correspondents
as described in the Specification of the British Patent granted to the said
B. Willcox No. 3439, dated February 25th 1891, viz., such products as possess the
advantage of a greater solubility compared with those of the Patent No. 13235*,
and are obtained either by treating with sulphurising agents those colours of the
last named Patent which are derived from diamines containing no sulpho groups, or
by sulphurising the intermediate products obtained by coupling the tetrazo salt of
a diamine not containing a sulpho group, with molecular proportions of salicylic
acid, or analogous hydroxycarbonic acid, and alphanaphthylamine, or amidonaph-
tholether, and by subsequently combining the amidotetrazo compounds, sulphurised
after having been diazotised with one molecular proportion of one of the known
dye-stuff components, and likewise such mixed colouring matters as result by the
combination of tetrazo salts with one molecular proportion of alphanaphthylamine,
or alpha amidonaphtholether, and one molecular proportion of a phenol, naphthol,
dihydroxynaphthalene, an amine, amidonaphthol, or sulpho acid thereof, by further
diazotising these intermediate products containing one or two free amido groups,
and coupling with one or two molecular proportions of the known dye-stuff
components.
In order to obtain dye stuffs soluble with greater ease, the intermediate products
obtained in the latter case, and derived from diamines containing no sulpho groups,
or the complete dye stuffs, can be treated with sulphurising agents.
My foreign correspondents have now found that in place of alphanaphthylamine,
or alpha amidonaphtholether employed as second components, as described in the
Specifications of the aforesaid two British Patents, the following compounds can be
used with the same, or a better. result, viz.: amidonaphthol, amidonaphtholsulpho

page_text: acids, amidonaphtholether sulpho acids, amidonaphthoxylacetic acids, and amido-
naphthoxylacetic sulpho acids.
If amidonaphthols, or amidonaphthoxylacetic acids, be employed as components,
the complete dye-stuffs derived from diamines containing no sulpho groups, or the
amidotetrazo products first produced, are advantageously treated with sulphurising
agents, the sulpho derivatives obtained in the latter case being further diazotised,
and combined with dye-stuff components. The method of sulphurising is effected
in the same manner as described in the Specification of the Letters Patent
No. 3439º¹.
Colouring-matters are thus produced which are capable of dyeing unmordanted
cotton, not only in an alkaline soap bath, but also are capable of dye cotton in
neutral baths, with the addition of common salt.
The tetrazo compounds of the following diamines can be employed: benzidine,
orthotolidine, paradiamidophenyl orthotolyl, paradiamido ortho monoalkyloxy-
diphenyl, paradiamido ortho monoalkyl oxyphenyl ortho tolyl, paradiamido ortho
diphenolether, paradiamidoazo benzene, paradiamido azo toluene, paradiamido-
azoxylene, and the azoxy derivatives of the latter three azo products, para amido-
benzene azo para toluidine, paraamido benzene azo paratoluidine, para amido benzene
azo paraxylidine, amidobenzene azo alpha amido naphthalene and the oxyethers
(alkylhydroxy derivatives) thereof, diamido naphthalene, diamido stilbene, diamido-
fluorene, diamidocarbazol, diamidodiphenic acid, diamidodiphenoxy acetic acid,
diamidodiphenylene ketoxime, and analogues thereof, paradiamidophenylenoxide,
paradiamidotoluylene oxide, paraphenylene diamine, toluylendiamine, and analogous
diamines, the sulpho derivatives of the said diamines, including sulpho acids,
sulphones, and sulpho acids, for example, benzidine monosulpho acid, benzidine
disulpho acid, benzidine sulphone mono- or disulpho acid, tolidine mono and
tolidine disulpho acid, diamido stilbenedisulpho acid.
In order to illustrate the method of producing these new dye stuffs, which in
general is carried out in the same manner as described in the aforesaid Letters
Patent No. 13235 and 3439", the following example is given, the parts being by
weight:
DYE-STUFF
OF
OF
OBTAINED BY COMBINING ONE MOLECULAR PROPORTION
TETRAZODIPHENYLCHLORIDE WITH ONE MOLECULAR PROPORTION
SALICYLIO ACID AND ONE MOLECULAR PROPORTION OF 1.5-AMIDO-
NAPHTHOL, BY FURTHER DIAZOTISING AND COUPLING THE DIAZO PRODUCT
WITH ONE MOLECULAR PROPORTION OF 1.8 DIHYDROXYNAPHTHALENE
ALPHA MONOSULPHO ACID.
18-4 parts of benzidine are, in the usual manner, transformed in muriatic solution
into tetrazodiphenyl chloride, by means of 14 parts of sodium nitrite, and the
tetrazo solution thus obtained is allowed to flow into a solution, in water, of 13.8
parts of salicylic acid, with the addition of a little excess of sodium carbonate.
When the formation of the intermediate product is completed, the hydrochloric
watery solution of 15.9 parts of 15 amido naphthol is added (whilst stirring).
After several hours, the mixture is heated for a short time at about 90 degrees
centigrade, in order to complete the production of the amidotetrazo compound.
The latter is filtered off, mixed with water, and after adding a concentrated solution
(in water) of 7 parts of sodium nitrite, hydrochloric acid is slowly added, until the
liquid exhibits a lasting acid reaction. The diazo product thus formed, within
about 24 hours, is filtered off, and introduced into a watery solution. prepared by
dissolving 26-2 parts of the sodium salt of 1.8 dihydroxynaphthalene alpha mono-
sulpho acid, and of about 50 parts of sodium acetate. After about 24 hours, the
combination is finished. Alkali is added, and the dye stuff then is isolated in the

page_text: usual manner, by salting out, filtering off, pressing, and drying. Its composition
corresponds with the following formula :-
It produces, ou unmordanted cotton, in an alkaline soap bath, green shades.
The method for producing these coloring matters is not restricted to that of the
foregoing example. They can be produced in other ways, in general by means
of all those processes usually employed for the manufacture of tetrazo dye stuffs.
The same result, for example, is obtained by coupling tetrazodiphenylchloride
at first with 1-5 amidonaphthol, and then with salicylic acid, by further diazotising
and combining with 1.8 dihydroxynaphthalene alpha mono sulpho acid.
In place of 15 amidonaphthol used in the aforegoing example, the isomeric
amidonaphthols, amidonaphtholsulpho acids, amidonaphtholethersulpho acids,
amidonaphthoxylacetic acids, amidonaphthoxylacetic sulpho acids, or analogous
components, being capable of reacting with tetrazochlorides, and of being further
diazotised, when combined with tetrazo salts, can be employed.
In an analogous manner, the other dye stuffs are produced, viz.: by employing, in
place of tetrazodiphenylchloride, the tetrazo salts of the analogous diamines above
mentioned (substituted or not substituted), or by replacing the salicylic acid by
other aromatic hydroxycarbonic acids, or by amines, phenols, amidophenols,
amidophenolethers of the benzene or naphthalene series, sulpho or carboxylic acids
of these components, amidonaphthoxyacetic acids, or amidonaphthoxyaceticsulpho
acids, or by employing, in place of 18 dihydroxynaphthalene, alpha monosulpho
acid, as described in the preceding example, 1.8 dihydroxynaphthalene alpha disulpho
acid, 18 dihydroxynaphthalene beta disulpho acid, naphtholsulpho acid, amido-
naphtholsulpho acid, or, generally, an amine, à phenol, an amidophenol, amidophenol-
ether of the benzene or naphthalene series, a sulpho or carboxylic acid of these
components.
If amidonaphtholsulpho acids be employed as second or as last components,
different products in general are obtained, according as these acids are allowed to
react on diazo or tetražo salts in either acid or alkaline solution.
In case the complete dye stuffs be not capable of general employment, on
account of their slight solubility, they are advantageously converted into such as
are soluble with greater ease, and therefore generally can be used, say, for
dyeing cotton in alkaline and neutral baths, by subsequently treating them in a
perfectly dry state with sulphurising agents, for example, with fuming sulphuric
acid, substantially as described in the Specification of the said English Letters
Patent No. 3439°1
Analogous dye-stuffs, possessing similar dyeing properties as the last obtained
products, results by combining tetrazo salts with one molecular proportion of
an aromatic hydroxycarbonic acid, or generally, of an amine, a phenol, amido-
phenol, amidophenolether of the benzene or naphthalene series, a sulpho or
carboxylic acid of these components, and with one inolecular proportion of amido-
naphthol, or amidonaphtholxylacetic acid, by further diazotising the sulpho products
thus obtained, and coupling with the known dye stuff components.
The coloring matters derived from paraphenylene diamine, naphthylendiamine,
or analogous diamines, are advantageously produced by diazotising the monoacetyl-
derivatives thereof, coupling with salicylic acid, cresolcarbonic acid, or, generally,

page_text: an amine, a phenol, amidophenol, amidophenolether of the benzene or naphthalene
series, a sulpho or carboxylic acid of these components, amidonaphthoxyacetic acid,
or amidonaphthoxyaceticsulpho acid, splitting off the acetyl group, further
diazotising, combining with amidonaphthol, amidonaphtholether, amidonaphthol-
sulpho acid, amidonaphtholethersulpho acid, amidonaphthoxyacetic acid, amido-
naphthoxyacetic sulpho acid, rediazotising; and coupling with the known dyestuff
components, viz.: amines, phenols, amidophenols, amidophenolethers of the benzene
or naphthalene series, the sulpho or carboxylic acid thereof, including amido-
naphthoxylacetic acids and amidonaphthoxylaceticsulpho acids.
In order to obtain these dye stuffs, the same method can be employed which my
foreign correspondents have described for the production of analogous dye stuffs in
the Specification of the English Letters Patent No. 16484 dated November 30th
1887, granted to James Yate Johnson.
are
Amongst the dye stuffs herein before defined, those coloring matters
especially of high value which contain, as middle compounds, on the one hand,
amidonaphthol, amidonaphtholether, amidonaphtholsulpho acid, amidonaphthol-
ethersulpho acid, amidonaphthoxylacetic acid, amidonaphthoxylaceticsulpho
acid; on the other hand, salicylic acid or anologous hydroxycarbonic acids, and,
as last components, dihydroxynaphthalenesulpho acids, or amidonaphtholsulpho
acids.
The shades produced by the last named dye stuffs on cotton unmordanted,
are from green to greenish black, and remarkable for their fastness to the action of
alkalies.
My foreign correspondents have further found, that valuable analogous dye-stuffs
are obtained by combining certain 18 dihydroxynaphthalene sulpho acids, or
amidonaphtholsulpho acids, with those tetrazo compounds which result by the
combination of one molecular proportion of a tetrazo salt, with one molecular
proportion, or two molecular proportions, of amidonaphtholether sulpho acid,
amidonaphthoxyacetic acid, amidonaphthoxyaceticsulpho acid, and by further
diazotising the resulting intermediate products containing one or two free amido
groups.
These new dye stuffs, in general, are produced by allowing a tetrazo salt, derived
from the diamines above enumerated, to react with one or two molecular
proportions of amidonaphtholethersulpho acid, amidonaphthoxyacetic acid, or
amidonapthoxyaceticsulpho acid, in neutral, moderately-acid, or alkaline solution,
by further diazotising the so formed intermediate products, and combining the
tetrazo compounds thus obtained, with two molecular proportions of 1.8 di-
hydroxynaphthalene alpha mono sulpho acid, 1.8 dihydroxynaphthalene alpha
disulpho acid, 18 dihydroxynaphthalenebeta disulpho acid, or amidonaphthol-
sulpho acids.
In order to illustrate the method of producing these new coloring matters, the
following examples are given. The parts are by weight.
COLORING MATTER OBTAINED BY COMBINING ONE MOLECULAR PROPORTION
OF TETRAZO-DIPHENYLCHLORIDE, WITH ONE MOLECULAR PROPORTION OF
ALPHAAMIDOBETANAPHTHOLETHERBETAMONOSULPHO ACID, BY FURTHER
DIAZOTISING THE SO FORMED INTERMEDIATE PRODUCT, AND COUPLING
WITH TWO MOLECULAR PROPORTIONS OF 1.8 DIHYDROXYNAPHTHALENE-
ALPHA DISULPHO ACID.
The solution of tetrazodiphenylchloride obtained in the usual manner, by means
of 18.4 parts of benzidene in hydrochloric solution, is allowed to flow into a
moderately acetic acid or alkaline solution of 26-7 parts of alphaamidobeta-
naphtholetherbetamonosulpho acid, obtained from hetanaphtholbeta monosulpho
acid (26), by ethylising, nitrating, and reducing. After heating. for several days

page_text: at about 50 degrees centigrade, and then for a short time at 90 degrees centigrade,
soda lye is added (in case the combination be effected in acid solution), and the
intermediate product is filtered off, after adding common salt.
It is mixed with a
concentrated solution (in water) of 7 parts of sodium nitrite, and hydrochloric acid
is slowly added, till the liquid shews a lasting acid reaction. After about 24 hours,
the tetrazo compound is filtered off, and introduced into a solution, in water,
of 72.8 parts of 18 dihydroxynaphthalene alpha disulphonate of sodium, and
140 parts of sodium acetate. In order to complete the reaction, the mixture is
heated to 90 degrees centigrade, and after rendering alkaline, the dye stuff is isolated
in the known manner, viz., by filtering off, pressing, and drying. It possesses the
Call fremule
and produces, on unmordanted cotton, green shades.
In an analogous manner, those coloring matters are prepared which contain, as
last component, either the 18 dihydroxynaphthalenebetadisulpho acid, or
18 dihydroxynaphthalenealphamonosulpho acid, instead of 1-8 dihydroxynaphtha-
lene alphadisulpho acid of the foregoing second example. The said 1.8 dihydroxy-
naphthalenesulpho acids advantageously are coupled in moderately acetic acid
solution. On replacing these latter acids by amidonaphtholsulpho acids, the
combination can be effected either in moderately acid or alkaline solution, different.
coloring matters of course being thus produced.
The method illustrated in the preceding second example, can likewise be
employed for producing dye stuffs by means of the isomeric or analogous amido-
naphtholethersulpho acids, or amidonaphthoxyacetic acids, or amidonaphthoxy-
aceticsulpbo acids.
DYESTUFF RESULTING FROM THE COMBINATION OF ONE MOLECULAR PRO-
PORTION OF TETRAZO DIPHENYLCHLORIDE WITH TWO
PROPORTIONS
MOLECULAR
OF ALPHAAMIDOBETANAPHTHOLETHERBETAMONOSULPHO
ACID, BY REDIAZOTISING AND COUPLING THE SO FORMED TETRAZO SALT
WITH TWO MOLECULAR PROPORTIONS OF 1.8 DIHYDROXYNAPHTHALENE-
ALPHAMONOSULPHO ACID.
184 parts of benzidine are converted by means of 14 parts of sodium nitrite, in
hydrochloric acid solution, into tetrazodiphenylchloride, & the solution of the latter
is allowed to flow into a moderately acetic or alkaline solution of 53.4 parts of
alphaamidobetanaphtholetherbetamonosulpho acid. After heating for several days
at 50 degrees, & then for a short time at 90 degrees centigrade, the mixture is
rendered alkaline (if the combination be effected in acid solution), & the inter-
mediate product is salted out, filtered off, & pressed. After mixing the latter with

page_text: a concentrated watery solution of 14 parts of sodium nitrite, it is tetrazotised by
slowly alding hydrochloric acid slightly in excess. The tetrazo-chloride, after
about 24 hours, is filtered off, & introduced into a solution obtained by dissolving
524 parts of 18 dihydroxynaphthalenealphamonosulphonate of sodium, &
100 parts of sodium acetate. The mixture is heated for a short time at 5
90 degrees centigrade, in order to complete the reaction, and the dye stuff thus
produced is filtered off, pressed, & dried. Its composition corresponds to the
following formula :—
OC,H
The shades produced on unmordanted cotton are pure green.
SO,Na.
If, in the foregoing last example, on the one hand, benzidine be replaced by the
analogous diamines above enumerated, or alphaamidobetanaphtholetherbetamono-
sulpho acid by the isomeric or analogous amidonaphtholethersulpho acids by
amidonaphthoxyacetic acids or amidonaphthoxyacetic sulpho acids, or, if, in place
of 18 dihydroxynaphthalenealphamonosulpho acid, the aforesaid other 1-8 dihydroxy-
naphthalenemonosulpho acids, or amidonaphthol monosulpho acid G, 1.8 amido-
naphtholbetadisulpho acid, or other amidonaphtholsulpho acids are employed, the
analogous dye stuffs are produced in the same or similar manner.
By means of the same process, mixed dye stuffs likewise can be obtained, either
by combining the tetrazo compounds of the above named diamines at first with
one molecular proportion of one amidonaphtholethersulpho acid, and then with one
molecular proportion of another amidonaphtholethersulpho acid, amidonaphthoxy-
acetic acid, amidonaphthoxyaceticsulpho acid, or inversely, by further diazotising
and coupling with two molecular proportions of 1-8 dihydroxynaphthalenesulpho
acid or amidonaphtholsulpho acid.
The shades produced on unmordanted cotton by these dye stuffs obtained from
amidonaphtholethersulpho acid, amidonaphthoxyacetic acid, or amidonaphthoxy-
aceticsulpho acid, in general, are from green to greenish black, and likewise
remarkable for their "fastness" against the action of light and soap.
As hereinbefore mentioned, valuable dye stuffs result by combining one
molecular proportion of a tetrazo salt with one molecular proportion of an
oxycarbonic acid, or another component, and with one molecular proportion of an
amido compound, further diazotising, and coupling with certain dye stuff
components.
My foreign correspondents have now found, that analogous dye stuffs likewise
of technical value can be obtained by producing so-called intermediate products
from one molecular proportion of a tetrazo salt and one molecular proportion of
an oxycarbonic acid, or another dye stuff component, and combining them with
one molecular proportion of azo products, resulting from the combination of the
diazo compounds of amines, or substituted amines, with certain phenols, naphthols,
dihydroxynaphthalenes, amidonaphthols, sulpho or carboxylic acids thereof, or
analogous products.
The method of producing these dye stuffs, in general, consists in preparing azo
compounds by coupling the diazo derivatives of amines, or substituted amines, for
example, nitramines, amido phenols, amidophenolethers of the benzene or naphtha-

page_text: lene series, sulpho or carboxylic acids thereof, likewise the diazo derivatives of
the so called thio condensation products of paratoluidine, metaxylidine pseudo-
cumidine, or sulpho acids of these condensation products, with certain phenols,
naphthols, dihydroxynaphthalenes, amidonaphthols, sulpho or carboxylic acids
thereof, and in combining the so-formed azo products with those intermediate
compounds obtained by combining equi-molecular proportions of tetrazo salts, and
amines, phenols, amidophenols, amidophenolethers of the benzene or naphthalene
series, sulpho and carboxylic acids of these components.
In this process, the following components can be used; first, the tetrazo-
compounds derived from benzidine and the other diamines above mentioned;
secondly, as components in second place, viz.: salicylic acid, orthohydroxypara-
toluylic acid, orthohydroxymetatoluylic acid, phenol, resorcinol, alpha or beta
naphthol, dihydroxynaphthalene (15, 16, 18, 26, or 2-7), alphanaphtholalphamono
sulpho acid (14, 15, 18) alphanaphtholdisulpho acid S, alpha naphthol epsilon
disulpho acid described in the German Patent No. 45776, alpha naphtholdisulpho
acid of the German Patent No. 38281, betanaphthol alphamono sulpho acid,
betanaphtholbeta monosulpho acid, betanaphthol gamma monosulpho acid, beta-
naphthol deltamonosulpho acid, betanaphtholdisulpho acid R and G, 1.8 dihydroxy-
naphthalene alphamonosulpho acid, 18 dihydroxynaphthalenealpha disulpho acid,
18 dihydroxynaphthalene beta disulpho acid, and likewise amido phenols, amido
phenolethers, amines, phenols of the benzene or naphthalene series, sulpho and
carboxylic acids thereof, and such other analogues as are not above enumerated.
Amongst the azo products, those, for example, are employed which result by the
combination of diazotised aniline, ortho and paratoluidine, ortho, meta, and paraxy-
lidine, cumidine, sulfanilic acid, paratoluidine monosulpho acid, metaxylidine mono
sulpho acid, cumidine monosulpho acid, anisidine, phenctidine, cresidine, metanitro-
aniline, paranitroaniline, nitro paratoludine, nitroanisidine, nitrophenetidine, amido-
azobenzene, amidoazotoluene, amidoazoxylene, sulpho acids of the last named three
amido azo compounds, alphanaphthylamine, alphanaphthylamine alphamonosulpho
acid (14, 15, 18),alphanaphthylamine orthomonosulpho acid described in the German
Patent No. 56563, alphanaphthylamine betamonosulpho acids of Clève (ẞ, y and 8),
betanaphthylamine, betanaphthylaminealphamonosulpho acid, betanaphthylamine
betamonosulpho acid, betanaphthylamine gammamonosulpho acid, betanaphthyl-
amine deltamonosulpho acid, betanaphthylaminedisulpho acid R and G, alpha-
amidoalphanaphthol, alphaamidobetanaphthol, orthoamidophenol ether, paraamido-
phenolether, alpha amido alpha naphtholether, alphaamido betanaphtholether,
alphaamido betanaphtholetherbetamonosulpho, and alpha amido betanaphtholether-
deltamonosulpho acid (which result from betanaphtholbeta monosulpho acid
26 or 2-7 by alkylising, nitrating, and reducing), amidonaphtholmonosulpho acid G,
1.8 amidonaphtholbetadisulpho acid, dehydrothioparatoluidine, primuline base,
dehydrothiometaxylidine, dehydrothiopseudocumidine, primuline, dehydrothio-
paratoluidine sulpho acid, dehydrothiometaxylidine sulpho acid, or dehydrothio-
pseudocumidine sulpho acid, with one of the following compounds alpha naphthol,
alphanaphthol alphamonosulpho acid S, 1.8 dihydroxyuaphthalene, 18 amido-
naphthol, dihydroxynaphthalenemonosulpho acid G, 1.8 dihydroxynaphthalene
alphamonosulpho acid, 1-8 dihydroxynaphthalene alphadisulpho acid, 1-8 dihydroxy-
naphthalene beta disulpho acid, amidonaphtholmorosulpho acid G, or 1.8 amido-
naphthol betadisulpho acid, 1·3.5-dihydroxybenzoic acid.
All these components have been enumerated, in order to illustrate the nature of
this invention, but the employment is not restricted thereto, for other products can
likewise be used, i.e., monoazo dye stuffs can be employed, not only derived from
the aforesaid diazotised amines and substituted amines, but also, in general, from
diazotised amines, amidophenols amidophenolethers of the benzene and naphthalene
series, substitution products thereof, especially sulpho and carboxylic acids thereof.
The method for producing these coloring matters is illustrated by the following
example. The parts are by weight.

page_text: FOURTH EXAMPLE.
OF
DYE STUFF OBTAINED BY COMBINING ONE MOLECULAR PROPORTION
TETRAZODIPHENYL CHLORIDE, ONE MOLECULAR PROPORTION OF SALICYLIC
ACID, AND ONE MOLECULAR PROPORTION OF THE AZO COMPOUND FROM
EQUIMOLECULAR PROPORTIONS OF DIAZOTISED BETANAPHTHYLAMINE
BETAMONOSULPHO ACID, AND 1.8 DIHYDROXYNAPHTHALENE BETADISULPHO
of
ACID.
The solution of tetrazodiphenylchloride obtained in usual manner from 18.4
parts of benzidine, by means of 14 parts of sodium nitrite, is allowed to flow into a
solution prepared by dissolving 13-8 parts of salicylic acid in about 500 litres of
water, with the addition of sodium carbonate in excess. After some time, the
formed intermediate product separates as a reddish-brown precipitate. 22.3 parts
betanaphthylaminebetamonosulpho acid are diazotised by means of 7 parts of
sodium nitrite in hydrochloric solution, and the resulting diazo compound is made
to act on 364 parts of 1.8 dihydroxynaphthalenebetadisulphonate of sodium in
acetic acid solution. In order to complete this latter combination, the mixture,
after about 12 hours, is heated at 60 degrees centigrade, and after being rendered
alkaline, the simple azo dye thus formed is filtered off. The resulting pasty mass
is directly added to the above intermediate product from tetrazodiphenyl and
salicylic acid, and soda lye is then introduced, until the whole has dissolved. After
about 12 hours the combination is complete, and the dye stuff is isolated by salting
out, filtering off, pressing, and drying. It dyes unmordanted cotton, in an alkaline
soap bath, a pure green.
In an analogous manner, the corresponding coloring matters are produced by
employing, either in place of tetrazodiphenylchloride, the tetrazo salts of the other
diamines above mentioned, or, in place of salicylic acid, analogous hydroxycarbonic
acids, or other dye stuff components, or by replacing the azo product employed in the
foregoing fourth example by other azo compounds, substantially as above described.
The shades produced by these coloring matters on unmordanted cotton, in general,
are from green, greenish black, to bluish black, and of a considerable "fastness
and intensity.
"
The dye stuffs hereinbefore defined in general result by combining one molecule
of a tetrazo salt with one or two molecules of the above named components, further
diazotising, and coupling the so-formed intermediate substances with one or two
molecules of the products above mentioned. If two molecules be combined with the
original tetrazochloride, either two molecules of the same compound, or of two
different substances, can be employed as so-called middle components, and likewise, if
two molecules be used as last components, either two molecules of the same product,
or one molecule of the one and one molecule of another substance, can be employed.
Of course my foreign correspondents understand by "molecule" the quantity of the
different components which corresponds to the molecular weight, and usually is
termed "molecular proportion."
Dated this 20th day of August 1892.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Dye-stuffs.
I, HENRY EDWARD NEWTON of the Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be 50
particularly described and ascertained in and by the following statement :-
My foreign correspondents have described in the Specification of the British

page_text: Patent granted to Benjamin Willcox, No. 13235, dated August 22nd 1890, valuable
dyestuffs, which are obtained by combining the tetrazo salts of diamines (substituted
or not substituted) with one molecular proportion of salicylic acid, or analogous
hydroxycarboxylic acids, and one molecular proportion of alphanaphthylamine, or
alphaamidonaphtholether, or, inversely, by coupling the said tetrazo salts at first
with one molecular proportion of alphanaphthylamine or alphaamidonaphtholether,
and then with one molecular proportion of salicylic acid, or analogous hydroxy-
carboxylic acids, and by subsequently diazotising the amidotetrazo products thus
obtained, and coupling the resulting diazo salts with one molecular proportion of an
amine, a phenol, or sulpho acid thereof.
Analogous dyestuffs have been produced by my foreign correspondents as
described in the Specification of the British Patent granted to the said Benjamin
Willcox, No. 3439, dated February 25th 1891, viz., such products as possess the
advantage of a greater solubility compared with those of the Patent No. 13,235,
and are obtained either by treating with sulphonating agents those colors of
the last named Patent which are derived from diamines destitute of sulpho groups,
or by sulphonating the intermediate products obtained by coupling the tetrazo salt
of a diamine (not containing a sulpho group) with molecular proportions of salicylic
acid or analogous hydroxycarboxylic acids, and alphanaphthylamine, or amido-
naphtholether, and by subsequently diazotising the sulphonated amidotetrazo
compounds, and combining them with one molecular proportion of one of the known
dye-stuff components, and likewise such mixed colouring matters as result from the
combination of tetrazo salts with one molecular proportion of alphanaphthylamine
or alphaamidonaphtholether, and one molecular proportion of a phenol, naphthol,
dihydroxynaphthalene, an amine, amidonaphthol, or sulpho or carboxylic acid
thereof, further diazotising these intermediate products containing one or two free
amido groups, and coupling with one or two molecular proportions of the known
dye-stuff components.
In order to obtain more soluble dye-stuffs, the before mentioned intermediate
products derived from diamines destitute of sulpho groups, or the complete
dyestuffs, can be treated with sulphonating agents.
My foreign correspondents have now found that the same or a better result is
obtained, if, in place of alphanaphthylamine or alphaamidonaphtholether employed
as second components, as described in the Specifications of the aforesaid two British
Patents, the following compounds be used, viz.: amidonaphthol, amidonaphtholsulpho
acids, amidonaphthol ether sulpho acids, amidonaphthoxyacetic acids, and amido-
naphthoxyacetic sulpho acids.
If amidonaphthols or amidonaphthoxyacetic acids be employed as components,
the complete dye stuffs derived from diamines destitute of sulpho groups, or the
amido tetrazo products which are at first produced, are advantageously treated with
sulphonating agents, the sulpho derivatives obtained in the latter case being further
diazotised and combined with dye stuff components. The sulphonation is effected
in the manner described in the Specification of the Letters Patent No. 3439".
Colouring matters are thus produced which will not only dye unmordanted cotton
in an alkaline soap bath, but also in a neutral bath containing common salt.
The tetrazo compounds of the following diamines can be employed: benzidine,
orthotolidine, paradiamidophenylorthotolyl, paradiamidoorthomonoalkyloxydi-
phenyl, paradiamidoorthomonoalkyloxyphenylorthotolyl, paradiamidoorthodiphenol-
ether, paradiamidoazobenzene, paradiamidoazotoluene, paradiamidoazoxylene, and
the azoxy derivatives of the latter three azo products, paraamidobenzeneazo
paratoluidine, paraamidobenzeneazoparaxylidine, amido benzene azoalphaamido
naphthalene, and the oxy-ethers (alkylhydroxy derivatives) thereof, diamido-
naphthalene, diamido stilbene, diamido fluorene, diamido carbazol, diamido diphenic
acid, diamido diphenoxyacetic acid, diamidodiphenyleneketoxime, and analogues
thereof, paradiamidodiphenyleneoxide, paradiamido-ditoluylene oxide, para-
phenylenediamine, toluylenediamine, and analogous diamines, the sulpho derivatives
of the said diamines, including sulpho acids, sulphones, and sulphone sulpho acids,
B

page_text: for example, benzidinemono sulpho acid, benzidine disulpho acid, benzidine sulphone-
mono- or disulpho acid, tolidinemono- and tolidine disulpho acid, diamido stilbene
disulpho acid.
In order to illustrate the method of producing these new dye stuffs, which in
general is carried out in the same manner as described in the Letters Patent
No. 13235 and 3439, the following example is given, the parts being by weight.
DYE-STUFF
FIRST EXAMPLE.
OBTAINED BY COMBINING ONE MOLECULAR PROPORTION OF
TETRAZO DIPHENYL-CHLORIDE WITH ONE MOLECULAR PROPORTION OF
SALICYLIC ACID, AND ONE MOLECULAR PROPORTION OF 15 AMIDO-
NAPHTHOL, BY FURTHER DIAZOTISING AND COUPLING THE DIAZO
PRODUCT WITH ONE MOLECULAR PROPORTION OF 1.8 DIHYDROXY-
NAPHTHALENE ALPHAMONO. SULPHO ACID.
184 parts of benzidine are converted in the usual manner into tetrazodiphenyl-
chloride, and the tetrazo solution is allowed to flow into a solution in water of
13-8 parts of salicylic acid, together with a slight excess of sodium carbonate.
When the formation of the intermediate product is completed, a solution in water
and hydrochloric acid, of 15.9 parts of 1.5 amidonaphthol is added, the mixture
being stirred the while. After several hours, the mixture is heated during a short
time at about 90 degrees centigrade, in order. to complete the production of the
amido tetrazo compound. The latter is filtered off, mixed with water, and a
concentrated solution (in water) of 7 parts of sodium nitrite; hydrochloric acid is
then slowly added until the liquid is acid. The formation of the diazo product is
complete within about 24 hours. It is filtered off, and introduced into a solution
prepared by dissolving in water 26.2 parts of the sodium salt of 1.8 dihydroxy-
naphthalene alphamonosulpho acid, about 50 parts of sodium acetate, and a small
quantity of acetic acid. After about 24 hours the combination is finished: The
resulting mixture is heated at about 60 degrees centigrade for some time, and is.
then cooled and rendered alkaline by means of sodium carbonate.
The dyestuff is isolated in the usual manner. by salting out, filtering off, pressing,
and drying.
Its composition is represented by the following formula :—
It produces green shades on unmordanted cotton in an alkaline soap bath.
The method of producing these colouring matters is not restricted to that described. 3
in the foregoing example. They can be obtained in other ways, in. general by
means of all the processes usually employed.in manufacturing analogous or similar
tetrazo dyestuffs.
The same result, for example, is obtained, by coupling tetrazodiphenylchloride at.
first with 15 amidonaphthol, and.. then with salicylic acid, by further diazotising,, 40
and combining the resulting product with 1.8 dihydroxynaphthalene alpha mono-.
sulpho acid.

page_text: The 15 amidonaphthol employed in the above example, can also be coupled in
moderately alkaline or neutral solution.
In place of 15 amidonaphthol used in the aforegoing example, the isomeric
amidonaphthols, amidonaphtholsulpho acids, amidonaphtholether sulpho acids,
amidonaphthoxyacetic acids, or amidonaphthoxyacetic sulpho acids can be employed
as middle components.
Other dye stuffs are produced in an analogous manner, viz., by employing, in
place of tetrazo diphenylchloride, the tetrazo salts of the above mentioned
analogous diamines, substituted or not substituted, or by replacing the salicylic
acid by other aromatic hydrocarboxylic acids, or by employing, in place of
1.8 dihydroxynaphthalene alphamonosulpho acid, as described in the preceding
example, 18 dihydroxynaphthalenedisulpho acid, 1.8 didydroxynaphthalene beta
disulpho acid, naphtholsulpho acid, amido naphthoisulpho acid, or generally an
amine, a diamine, a phenol, an amidophenol, amidophenolether of the benzene or
naphthalene series, or a sulpho or carboxylic acid of these components.
If amidonaphtholsulpho acids be employed as middle or as last components,
different products in general are obtained, according as these acids are allowed to
act on diazo or tetrazo salts, either in acid or in alkaline solution.
In case the complete dye stuffs are not suitable for general use, on account of
their slight solubility, they are advantageously converted into such as are more
readily soluble, and which therefore can be generally used, say, for dyeing cotton
directly in an alkaline soap bath, and also in neutral baths in presence of common
salt, by subsequently treating them in a dry state with sulphonating agents, for
example, with fuming sulphuric acid, substantially as described in the Specification
of the said English Letters Patent No. 3439º¹.
Analogous dyestuffs, possessing dyeing properties similar to those of the last
obtained products, result on combining tetrazo salts of diamines (destitute of sulpho
groups) with one molecular proportion of an aromatic hydroxycarboxylic acid, and
with one molecular proportion of amidonaphthol or amidonaphthoxyacetic acid, by
sulphonating the thus formed intermediate products, further diazotising the sulpho
products thus obtained, and coupling them with the known dye-stuff components.
The colouring matters derived from paraphenylene diamine, naphthylenediamine,
or analogous diamines, are advantageously produced by diazotising the monoacetyl
derivatives thereof, coupling the diazo products with salicylic acid or cresol-
carboxylic acid, splitting off the acetyl group, further diazotising, combining the
diazo compounds so formed with amidonaphthol, amidonaphtholether, amido-
naphtholsulpho acid, amidonaphtholethersulpho acid, amidonaphthoxyacetic
acid, amidonaphthoxyacetic sulpho acid, rediazotising, and coupling the
diazo products thus obtained with the known dyestuff components, riz., amines,
diamines, phenols, amidophenols, amidonaphtholethers of the benzene or naphtha-
lene series, the sulpho or carboxylic acids thereof, including amidonaphthoxyacetic
acids, and amidonaphthoxyacetic sulpho acids. In order to obtain these dye stuffs,
the method can be employed which my foreign correspondents have described for
the production of analogous dye stuffs in the Specification of the English Letters
Patent No. 16484, dated November 30th 1887, granted to James Yate Johnson.
Amongst the dye-stuffs hereinbefore defined, those colouring matters are especially
of high value, which contain, as middle components, on the one hand, amido-
naphthol, amidonaphtholether, amidonaphthol sulpho acid, amidonaphtholether
sulpho acid, amidonaphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid, and,
on the other hand, salicylic acid, or analogous hydroxy carboxylic acids, and, as
last components, dihydroxynaphthalenesulpho acids, or amidonaphtholsulpho acids.
The shades produced by the last named dyestuffs on unmordanted cotton, are in
" in
general from green to greenish black, and remarkable for their "fastness
presence of alkalies.
My foreign correspondents have further found, that valuable analogous dyestuffs
are obtained by combining certain 1-8 dihydroxynaphthalene sulpho acids, or
amidonaphtholsulpho acids, with those tetrazo compounds which are formed by

page_text: combining one molecular proportion of a tetrazo salt, with either one molecular
proportion or two molecular proportions of amidonaphtholether sulpho acid,
amidonaphthoxyacetic acid, amidonaphthoxyaceticsulpho acid, and further diazo-
tising the resulting intermediate products, containing either one or two free
amido groups.
These new dye stuffs, in general, are produced by allowing the tetrazo salts
derived from the diamines above enumerated, to act on either one or two molecular
proportions (employing in the latter case either one or two different compounds) of
amidonaphtholether sulpho acid, amidonaphthoxyacetic acid, or amidonaphthoxy-
acetic sulpho acid, in neutral, moderately acid, or alkaline solution, by further
.diazotising the products so formed; in case they are true amido azo compounds
which can be further diazotised, and combining the tetrazo compounds thus
obtained with two molecular proportions of 1.8 dihydroxynaphthalene alphamono
sulpho acid 1.8 dihydroxynaphthalene alphadisulpho acid, 1-8 dihydroxynaph-
thalene beta disulpho acid, or amidonaphtholsulpho acids (employing either one or
two of these components).
In order to illustrate the method of producing these new coloring matters, the
following examples are given. The parts are by weight.
COLOURING MATTER OBTAINED BY COMBINING ONE MOLECULAR PROPORTION
OF TETRAZODIPHENYLCHLORIDE, WITH ONE MOLECULAR PROPORTION OF
ALPHAAMIDOBETANAPHTHOLETHER BETAMONOSULPHO ACID, FURTHER
DIAZOTISING THE RESULTING INTERMEDIATE PRODUCT, AND COUPLING
WITH TWO MOLECULAR PROPORTIONS OF 1.8 DIHYDROXYNAPHTHALENE
ALPHA DISULPHO ACID.
The solution of tetrazodiphenylchloride obtained in the usual manner from
184 parts of benzidine, is allowed to flow into a moderately acetic acid or alkaline
solution of 26.7 parts of alphaamido betanaphtholetherbetamonosulpho acid,
obtainable from beta naphtholbetamónosulpho acid (26), by ethylating, nitrating,
and reducing. At the end of about 12 hours, the formation of the intermediate
product is finished. It is mixed with a concentrated solution (in water) of 7 parts
of sodium nitrite, and hydrochloric acid is slowly added till the liquid is acid.
After about 24 hours, the tetrazo compound is filtered off, and introduced into a
solution, in water, of 72-8 parts of 1.8 dihydroxynaphthalene alpha disulphonate
of sodium, and 140 parts of sodium acetate, adding a small quantity of acetic acid.
In order to complete the action, the mixture (after 24 hours standing) is heated at
90 degrees centigrade, and is then rendered alkaline by means of sodium carbonate,
and the dye stuff is isolated in the known manner, viz., by filtering off, pressing, and
drying. It possesses the following formula:-

page_text: The coloring matters containing, as last component; either the 1.8 dihydroxy-
naphthalene betadisulpho acid, or 1.8 dihydroxynaphthalene alphamonosulpho
acid, instead of 1-8 dihydroxynaphthalene alpha disulpho acid, employed in the
aforegoing second example, are prepared in an analogous manner. The said
1.8 dihydroxynaphthalene sulpho acids are advantageously coupled in a solution
made moderately acid by adding acetic acid. If, instead of these latter acids,
amidonaphtholsulpho acids be used, the combination can be effected either in
moderately acid or alkaline solution, different colouring matters of course being
thus produced.
The method illustrated in the preceding second example can also be employed in
producing dyestuffs from the isomeric analogous amidonaphtholethersulpho acids,
or amidonaphthoxyacetic acids, or amidonaphthoxyacetic sulpho acids.
MOLECULAR
DYE-STUFF RESULTING FROM THE COMBINATION OF ONE MOLECULAR PRO-
PORTION OF TETRAZO DIPHENYLCHLORIDE, WITH TWO
PROPORTIONS OF ALPHAAMIDO BETA NAPHTHOLETHERBETAMONOSULPHO
ACID, BY REDIAZOTISING, AND COUPLING THE TETRAZO, SALT SO FORMED
WITH TWO MOLECULAR PROPORTIONS OF 1.8 DIHYDROXYNAPHTHALENE-
ALPHAMONOSULPHO ACID.
184 parts of benzidine are converted into tetrazo diphenylchloride, and the
solution of the latter is allowed to flow into a moderately acetic or alkaline solution
of 534 parts of alphaamidobetanaphtholether betamnono sulpho acid. After heating
for several days at 50 degrees, and then for a short time at 90 degrees centigrade,
the mixture is rendered alkaline (if the combination be effected in acid solution),
and the intermediate product is salted out, filtered off, and pressed. After mixing
the latter with a concentrated watery solution of 14 parts of sodium nitrite, it is
tetrazotised by slowly adding hydrochloric acid slightly in excess. At the end of
about 24 hours, the tetrazochloride is filtered off, and introduced into a solution
obtained by dissolving 52.4 parts of 18 dihydroxynaphthalene alpha mono
sulphonate of sodium and 100 parts of sodium acetate, together with a small
quantity of acetic acid. The mixture is heated for a short time at 90 degrees
centigrade, in order to complete the action, and is then rendered alkaline by means
of sodium carbonate; the dye stuff thus produced is filtered off, pressed, and dried.
Its composition is represented by the following formula :-
The shades produced on unmordanted cotton are pure green.
If, in the foregoing last example, instead of benzidine, the analogous diamines
above enumerated, or instead of alphaamidobetanaphtholetherbetamono sulpho acid,
the isomeric or analogous amido naphthol ether sulpho acids, amidonaphthoxyacetic

page_text: acids, or amidonaphthoxyacetic sulpho acids, are used, or if, in place of 1.8 dihy-
droxynaphthalene, alpha mono sulpho acid, other 18 dihydroxynaphthalene sulpho
acids, or 18 amidonaphthol sulpho acids (such as 1.8 amidonaphthol beta disulpho
acid or the like) are employed, analogous dye-stuffs are produced in the same or
a similar manner.
By means of the process described in the last example, mixed dye stuffs can also
he obtained, either by combining the tetrazo compounds of the above named
diamines, first with one molecular proportion of an amidonaphtholether sulpho acid,
and then with one molecular proportion of another amidonaphtholether sulpho acid
or amidonaphthoxyacetic acid, amidonaphthoxyacetic sulpho acid, or inversely, by
further diazotising the resulting products, and coupling them with two molecular
proportions of 18 dihydroxynaphthalenesulpho acid, or amido naphtholsulpho acid
(employing either one or two different compounds).
"
The shades produced on unmordanted cotton by these dyestuffs obtained from
amidonaphtholethersulpho acid, amidonaphthoxyacetic acid, or amidonaphthoxy-
acetic sulpho acid, in general are from blue, green, to greenish-black, and are
likewise remarkable for their "fastness on exposure to the action of light and soap.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed (as communicated to me
from abroad), 1 declare that what I claim is :-
1. The process for producing dye stuffs which consists in first producing. so called
intermediate products, either by combining one molecular proportion of the tetrazo
derivatives of paradiamines with one molecular proportion of salicylic acid, ortho,
meta, or paracresolcarboxylic acid, and then with one molecular proportion of amido-
naphthol, amidonaphtholsulpho acid, amidonaphthol ethersulpho acid, amido-
naphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid, or inversely, in pro-
ducing the above intermediate products by combining one molecular proportion of
the tetrazo derivatives of paradiamines, first with one molecular proportion of
amidonaphthol, amidonaphtholsulpho acid, amidonaphtholethersulpho acid, amido-
naphthoxyacetic acid, or amidonaphthoxyaceticsulpho acid, and then with one mole-
cular proportion of salicylic acid, orthocresol carboxylic acid, metacresolcarboxylic
or paracresolcarboxylic acid, further diazotising the intermediate products thus.
formed (in case they are true amido azo compounds, and can be diazotised), com-
bining the resulting products with one molecular proportion of the known dye-stuff
components (such as amines, diamines, phenols, amidophenols, amidophenol ethers
of the benzene or naphthalene series, sulpho or carboxylic acids thereof), and
subsequently, if desirable, treating the products thus formed, with fuming sulphuric
acid or other sulphonating agents.
2. The production of colouring matters by treating with fuming sulphuric acid,
or other sulphonating agents, the so-called "intermediate products" obtainable by
means of the process described in the foregoing first claim, diazotising the sulpho
derivatives so formed (in case they are true amidoazo products, and can be further
diazotised), and coupling the resulting diazo compounds with one molecular pro-
portion of the known dye stuff components (such as amines, diamines, phenols,
amidophenols, amido phenolethers of the benzene or naphthalene series, sulpho or
carboxylic acids thereof, including sulpho acids of dihydroxynaphthalene and
amidonaphthol)..
3. The manufacture of dyestuffs by combining one molecular proportion of the
tetrazo derivatives of diamines, with one or two molecular proportions (employing,
in the latter case, either one or two different compounds) of amidonaphtholether
sulpho acid, amidonaphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid,
rediazotising the intermediate products or dyestuffs thus formed (excluding those
which are not true amidoazo products, which can be diazotised), and coupling
the resulting products with two molecular proportions of sulpho acids of 1.8 dihy-
droxynaphthalene, or 1-8 amido naphthol, employing either one or two of these
components, or one of these components and any other dyestuff component. (The

page_text: colouring matters described in the Letters Patent No. 7067, dated 27th April 1889,
and No. 14416, dated 12th September 1890, are disclaimed.)
amido-
4. The production of coloring matters by coupling the diazo derivatives of
acetylated diamines (such as mono acetyl, phenylene diamine, mono acetylnaphthy-
lene diamine, or the like) with one molecular proportion of salicylic acid, ortho-
cresol carboxylic acid, meta cresol carboxylic acid, or para cresol carboxylic acid,
splitting off the acetyl group, rediazotising the amido azo products thus formed,
coupling the resulting diazo compounds with amidonaphthol, amidonaphtholsulpho
acid, amidonaphtholethersulpho acid, amidonaphthoxyacetic acid, or
naphthoxyacetic sulpho acid, again diazotising the products thus formed
(excluding those which are not true amido azo compounds, which can be diazotised),
and combining the diazo compounds thus produced, with one molecular proportion
of the known dye-stuff components, viz., amines, diamines phenols, amidophenols,
amidophenolethers of the benzene or naphthalene series, sulpho or carboxylic
acids thereof, including sulpho acids of dihydroxynaphthalene and amidonaphthol.
5. As new manufactures, the new dye-stuffs obtainable by means of the
processes herein before described, or by any other way producing the same result.
Dated this 23rd day of May 1893.
NEWTON & SON,
Agents for the Applicant.