The Manufacture or Production of Amidonaphtholsulpho Acids and Colouring Matters therefrom.
Year: 1893

page_text: Date of Application, 10th Aug., 1893
Complete Specification Left, 10th May, 1894-Accepted, 23rd June, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Amidonaphtholsulpho Acids and
Colouring Matters therefrom.
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 :-
1
disulpho
My foreign correspondents have found that the a naphthylamine as a
acid, and a naphthylamine B, a disulpho acid, when melted with alkalies, are
converted into amidonaphtholsulpho acids, the sulpho group in the position peri
(so-called) to the amido group being replaced by the hydroxylic group,
απ amido a naphthol a, monosulpho acid and a, amido a naphthol B, monosulpho
acid being thus formed, which possess the compositions represented by the following
formulæ respectively :-
:-
PRODUCTION OF a₁ AMIDO
as
NAPHTHOL α3
MONOSULPHO
100 parts of a naphthylamine a, a, disulphonate of sodium are mixed with
250 parts of potash lye (containing 75 per cent. of pure potassium hydroxide).
The mixture is heated, taking care that the temperature does not rise above
from 150 to 160 degrees centigrade, whilst the melting takes place, which, at the
said temperature, proceeds without applying further heat. The resulting mass is
dissolved in water, and the solution thus obtained is rendered neutral by adding
400 parts of muriatic acid (at 20 degrees Baumé), the new a₁ a amidonaphthol
a, monosulpho acid then separating as a heavy precipitate, which is filtered off and
carefully washed with cold water.
The amido naphtholsulpho acid thus obtained possesses the said composition,
my foreign correspondents having proved that it is converted by heating with

page_text: dilute alkalies into the a₁ α dihydroxyna phthalene a, mono acid possessing the
following formula:
:-
If, in the above example, the isomeric a₁ naphthylamine ẞ, a disulpho acid is
employed in place of a₁ naphthylamine a, a, disulpho acid, the melting process
proceeds in an analogous manner, viz., the sulpho group contained therein in the
position peri to the amido group being replaced by the hydroxylic group.
The last named new a, naphthylamine ẞs a disulpho acid can be obtained by
sulphonating acetylated a naphthylamine a monosulpho acid, splitting of the
acetyl group, and separating the a₁ naphthylamine ẞ, a disulpho acid from the
isomeric a, naphthylamine a, a disulpho acid which is produced in the same
process. The latter separation can profitably be effected by utilizing the varying
degrees of solubility in water of the salts of these two acids.
The production of the said a, naphthylamine ẞ, a, disulpho acid is illustrated
by the following example. The parts are by weight.
PRODUCTION OF a₁ NAPHTHYLAMINE B
a↓
DISULPHO ACID.
10 parts of a, naphthylamine a monosulpho acid are mixed with 60 parts of
glacial acetic acid, 12 parts of acetic anhydride, and 6 parts of sodium acetate.
The mixture is boiled during 8 hours. After cooling to about 40 degrees
centigrade, 6.6 litres (in case the parts are kilos. by weight) of technical muriatic
acid are added. The acetylated compound separates, on cooling, in the form of
white needles. 10 parts of the acetylated a naphthylamine a monosulpho acid
are introduced into 50 parts of fuming sulphuric acid (containing 25 per cent. of
anhydride). The whole mass is then allowed to stand at ordinary temperature
during from one to two days. It is poured on ice, and the liquid thus obtained is
mixed with such a quantity of water that the whole volume is 300 litres (in case
the parts mentioned are kilos. by weight). The solution so formed is boiled during
from 3 to 4 hours, the acetyl group being thus separated. In order to remove
the sulphuric acid, lime water is added until the liquid shows an alkaline reaction.
The calcium sulphate precipitated is filtered off, and the filtrate is mixed with
sodium carbonate. After filtering off the calcium carbonate, the resulting filtrate
is evaporated, until a skin is formed on the surface of the hot liquid. The latter
is allowed to cool and stand for 24 hours. During this time, a salt will have
separated in the form of crusts. It is filtered off from the liquid which contains
another salt. The former salt is chemically the pure sodium salt of a naphthyl-
amine as a disulpho acid S., which is perfectly separated. The filtrate is
acidulated, and then allowed to stand for 24 hours. A salt then crystallises out in
the form of white needles, which collect in the form of balls. The separation of
the same takes place slowly but is nearly perfect, as only a trace thereof is
obtained on salting out the mother liquid. The last named salt contained in
the aforesaid filtrate is the acid sodium salt of the new a₁ naphthylamine
Ba disulpho acid.

page_text: My foreign correspondents have proved the composition thereof in the following
manner-If the amido group contained therein is replaced by hydrogen by
means of the so-called hydrazine method, a naphthalene disulpho acid is obtained,
which my foreign correspondents have, by treatment with phosphorus penta-
chloride, converted into the corresponding naphthalene disulpho chloride. The
latter melts at 138 degrees centigrade, and also, in its chemical properties, is found to
be identical with the naphthalene disulpho chloride first prepared by Armstrong &
Wynne (see Abstracts of the Proceedings of the Chemical Society No. 77 (1890),
page 11), and having the following formula :-
-
As the a, naphthylamine a monosulpho acid was employed as initial product
for preparing the new naphthylamine disulpho acid, the latter must have the
composition represented by the following formula :—
10 parts of a naphthylamine ẞ, a disulpho acid (employed as acid sodium salt)
are mixed with 20 parts of potash lye (containing 50 per cent. of potassium
hydroxide). The mixture is heated during 6 hours at from 180 to 190 degrees
centigrade in a closed vessel capable of withstanding pressure, and provided with
a stirring apparatus. The temperature is then raised to 200 degrees centigrade,
and kept thereat for 2 hours. After cooling, 200 litres (in case the parts are kilos.
by weight) of technical muriatic acid are added. The new a₁. amido a naphthol
6 monosulpho acid crystallises out in minute white needles. When combined with
diazo compounds, it yields dye stuffs. It differs by its properties and reactions from
all isomeric acids known up to the present time.
My foreign correspondents do not limit themselves to the directions above given
for the production of the new amido naphtholsulpho acids. The particulars above
mentioned can be varied. For instance, in place of the free naphthylamine sulpho
acids, the salts thereof can be melted; the potash lye can be replaced by soda İye,
or mixtures of potash lye and soda lye; the strength of alkali lye employed
can vary, within certain limits; the temperature applied can be raised or lowered
i

page_text: and, by reason thereof, the time of reaction may be shortened or extended. Such
modifications do not alter the nature of this part of the present invention.
My foreign correspondents have further found, that the above two amido
naphtholmonosulpho acids can be profitably employed for the production of
dye-stuff's herein defined.
The researches of my foreign correspondents have shown that new disazo coloring
matters can be obtained, if either of the said two acids is allowed to act on the
tetrazo compounds of "benzidine, its analogues or homologues." The dye-stuffs
thus obtainable are distinguishable by the beauty and intensity of the shades
produced therewith.
By "benzidine, its analogues or homologues," the following substances, for
example, are meant, viz., Benzidine, tolidine. diamido phenyl tolyl, diamidodiphenol-
ether, diamidoalkylhydroxydiphenyl, diamido alkylhydroxy phenyl tolyl, diamido
azobenzene, diamido azotoluene, diamido azoxylene, diamido azoxybenzene, diamido
azoxytoluene, diamidostilbene, diamidofluorene, diamidonaphthalene, diamidocar-
bazol, diamidodiphenylene oxide, diamidoditoluylene oxide, paraphenylene diamine,
paratoluylene diamine, benzidine sulphone, tolidine sulphone, diamidophenyltolyl
sulphone, diamidodiphenoxyacetic acid, diamidodiphenylene ketoxine, diamido-
phenylbenzimidazols, amidobenzeneazo alphanaphthylamine, amidotoluene azoalpha-
naphthylamine, amidoxyleneazoalphanaphthylamine, amidobenzene (amidotoluene
or amidoxylene)- azoparaxylidine, amidobenzene (amidotoluene or amidoxylene)
azometa (or azo ortho) amido paracresolether, amidobenzene- (amidotoluene or
amidoxylene-) azobetaalkyloxyalpha naphthylamine, the sulpho or carboxylic acids
thereof.
Similar diamines, or substitution derivatives thereof, which can be converted into
tetrazo salts, either directly or by means of the monoacetyl compounds, also can
be used. In place of the monoacetylated diamines, the corresponding mononitro
amines can be employed; in the latter case, the resulting nitro azo products must
be reduced, diazotised again, and combined with dye stuff components, whilst in
the employment of monoacetylated diamines, the first produced monoacetylamidoazo
derivatives must be treated in a suitable manner (for separating the acetyl group),
diazotised again, and combined with the respective dye-stuff components, or the
above new amidonaphtholmonosulpho acids.
The combination of the above tetrazo compounds with the said amidonaphthol
monosulpho acids, can be effected in an alkaline or a moderately acid solution.
The process for producing these new coloring matters, in general, is analogous
to that which my foreign correspondents have described for the production of
analogous dye-stuffs from other amidonaphtholsulpho acids in the 'Specification
of Letters Patent No. 13443 of 1890.
In order to illustrate this process, the following example is given, the parts being
by weight
COLORING MATTER FROM ONE MOLECULAR
TWO MOLECULAR PROPORTIONS OF α
SULPHO ACID.
PROPORTION OF TOLIDINE AND
AMIDO NAPHTHOL-a,-MONO
a
21.2 parts of tolidine are converted into the tetrazo compound in the usual
manner. The resulting tetrazo solution is allowed to flow into an icy-cold solution of
50 parts of aι a amido naphthol a, monosulpho acid, rendered alkaline by means
of sodium carbonate. The formation of the dye stuff, which instantly begins, is
complete after about 24 hours. The coloring matter is isolated in the usual way,
pressed, and dried. It produces greenish-blue shades on unmordanted cotton.
As above mentioned, the said a₁ a amido naphthol a, mono sulpho acid can also
be employed for the production of so-called mixed dye stuffs. The manufacture
of the latter is illustrated by the following example. The parts are by weight.

page_text: DYE
STUFF FROM DIANISIDINE a₁ NAPHTHOL a, MONOSULPHO
a a AMIDO-NAPHTHOL az MONOSULPHO ACID.
ACID AND
A solution of tetrazo diphenolether obtained in the known manner from 24°4 parts
of dianisidine, is introduced into a solution prepared by dissolving 24.6 parts of
the a naphthol a, monosulphonate of sodium, and 30 parts of sodium acetate, the
solution being kept at from 0 to 5 degrees centigrade. The formation of the
intermediate product being finished, an icy-cold solution in water of 24 parts of
a a amido naphthol a mono-sulpho acid, rendered alkaline by means of sodium
carbonate, is added. The formation of the mixed dye-stuff begins immediately,
and may
be profitably completed by heating.
The coloring matter isolated in the usual way produces blue shades on
unmordanted cotton.
Dye-stuffs analogous to those described in the foregoing fourth and fifth
examples are obtained, if, in these examples, the tetrazo compounds of tolidine and
dianisidine, are replaced by the corresponding quantities of other of the tetrazo
compounds hereinbefore defined, or if, in the preceding fifth example, a, naphthol
a, monosulpho acid is replaced by any other naphtholsulpho acid, or a phenol,
amine, diamine, amidophenol, amidophenolether of the benzene or naphthalene
series, or a sulpho or carboxylic acid thereof.
Of course the production of the mixed dye-stuffs can also be effected inversely,
viz., by combining the tetrazo compound first with the said a₁ a-amidonaphthol-
a-mono sulpho acid, and then with another dye-stuff component.
COLORING MATTER FROM ONE MOLECULAR PROPORTION OF TOLIDINE, AND
TWO MOLECULAR PROPORTIONS OF a₁ a AMIDO-NAPHTHOL ẞ MONO-
SULPHO ACID.
A solution of tetrazoditolyl prepared from 21-2 parts of tolidine, is allowed to
flow into a solution prepared by dissolving 50 parts of a₁ a, amidonaphthol ẞ, mono-
sulpho acid, the latter solution being rendered alkaline by means of sodium
carbonate, and cooled by means of ice. The formation of the dye-stuff begins
instantly, and is finished after about 24 hours. The coloring matter is isolated in
the usual manner, and pressed and dried. It yields blue shades on unmordanted
cotton.
DYE STUFF FROM BENZIDINE a₁ NAPHTHOL a, MONO SULPHO ACID
α₁ α AMIDO NAPHTHOL ẞ MONO SULPHO ACID.
AND
18.4 parts of benzidine are converted into the tetrazo compound in the usual
manner, and the tetrazo solution thus obtained is allowed to flow into a watery
solution prepared by dissolving 24.6 parts of the a, naphthol a, monosulphonate of
sodium, and 30 parts of sodium acetate. When the formation of the intermediate
product is complete, a carefully cooled solution of 24 parts of a₁ a amido-
naphthol B, monosulpho acid is added. The production of the mixed dye-stuff
instantly begins, and is completed by heating. The coloring matter is isolated
in the usual manner, and pressed and dried. It produces blue shades on unmordanted
cotton.

page_text: Its composition is represented by the following formula :—
Dye-stuffs analogous to those described in the foregoing sixth and seventh
-examples result, if the tetrazo products of tolidine or benzidine respectively are
replaced by the equivalent quantities of other tetrazo derivatives, or if, in the
-seventh example, a naphthol a monosulpho acid is replaced by another naphthol
sulpho acid, or a phenol, an amine, diamine, amidophenol, amidophenolether of the
benzene or naphthalene series, or a sulpho or carboxylic acid thereof.
The production of these mixed coloring matters may also be effected inversely,
riz., by combining the tetrazo salts first with a₁ a, amido naphthol ẞ, monosulpho
acid, and then with another dye-stuff component.
By means of the processes illustrated by the above examples four, five, six, and
seven, dye-stuffs result which in general yield reddish brown, brown, violet, bluish
violet, blue, or greenish-blue shades, which are remarkable for their fastness against
the action of alkalies. The coloring matters, when fixed on the fibre, can be
rediazotised, and then combined with phenols, amines, diamines, amidophenols,
amidophenolethers of the benzene or naphthalene series, or sulpho or carboxylic
acids of these components,-shades being thus produced which vary from brown to
grey and black, and withstand the action of fulling.
My foreign correspondents have ascertained that the above two amidonaphthol
monosulpho acids can also profitably be employed for the production of valuable
so-called tris and tetrakis azo dye-stuffs which result if tetrazo derivatives of
diamines are first combined with one or two molecular proportions of an "amine or
substituted amine," and the resulting intermediate products, after being rediazotised,
are combined with two molecular proportions of one of the above two amidonaph-
tholmono sulpho acids, or with one molecular proportion of one of these amido-
naphthol sulpho acids, and one molecular proportion of another dye stuff component,
or inversely, first with one molecular proportion of a dye-stuff component,
and then with one molecular proportion of one of the said amidonaphtholmonosulpho
.acids.
"
My foreign correspondents mean by the expression "amine or substituted amine'
which can be employed as middle components, all those amido compounds which,
when combined with diazo products, yield amidoazo products further diazotisable,
viz., Aniline, toluidine, xylidine, cresidine, the analogues, homologues, or substitution
products thereof, alphanaphthylamine, amidonaphthols, amidonaphtholethers,
alphanaphthylamine betamonosulpho acids (Clève's beta and delta acid), the
amidonaphtholsulpho acids hitherto known (including the two a₁ a. amidonaph-
tholmonosulpho acids hereinbefore described), amidonaphtholether sulpho acids,
amidonaphthoxyacetic acids, amidonaphthoxyacetic sulpho acids, or the like.
If the tetrazo salts of diamines are combined with one molecular proportion of
one of the said "amines or substituted amines," intermediate products result which
contain a free diazo group, and after being again diazotised, can be combined with
two molecular proportions of either of the above two new amidonaphtholmonosulpho
-acids, or with one molecular proportion of the one, and one molecular proportion of
the other of these two acids, or with one molecular proportion of one of these two

page_text: acids, and one molecular proportion of another dye-stuff component (viz., amine,.
diamine, phenol, amidophenol, amidophenolether of the benzene or naphthalene
series, a sulpho or carboxylic acid thereof), or inversely, first with one molecular
proportion of such a dye-stuff component, and then with one molecular proportion
of one of the above a, a, amidonaphtholsulpho acids. Coloring matters result in
this manner which contain three times the azo group (- N = N-) and briefly
are termed trisazo dye-stuffs. If the said two a, a, amidonaphtholsulpho acids are
employed as middle components, other dye-stuff components can be used as last-
components.
The following example will serve to illustrate the production of these trisazo-
PROPORTIONS OF α, a₁ AMIDONAPHTHOL α3 MONO SULPHO ACID.
The tetrazo solution prepared from 21-2 parts of tolidine (or the corresponding
quantity of a tolidine salt), is allowed to flow slowly into a cold solution of
24-5 parts of the sodium salt of Clève's alpha naphthylamine beta mono.
sulpho acid (delta), and 50 parts of sodium acetate. In this manner, a so-called
intermediate product is formed which possesses either of the following formulæ :-
CH,
SO,H
CH-N=N- CH –NH,
-
C.H. NN - CI
CH,
or,
CH,
-
CH. NN - C₂H, – NH,
1
C.H. NN-
-
CH,
So,
When the formation of the intermediate product is completed, the latter is
rediazotised by mixing the liquid with a solution in water of 7 parts of sodium
nitrite, and subsequently adding muriatic acid, until the liquid shows a moderately
lasting acid reaction. The diazotisation being finished, a solution prepared by
dissolving 25 parts of sodium carbonate and 48 parts of a, a amidonaphthol
as monosulpho acid is added. The formation of the dye-stuff is finished after a few
hours. The new dye stuff is isolated in the usual manner by salting out, filtering
off, pressing, and drying. It produces bluish-black shades on unmordanted cotton.
Its composition is represented by the following formula :-
-

page_text: A coloring matter analogous to that described in the preceding eighth example.
is obtained if, in place of a, a, amidonaphthol as monosulpho acid, the isomeric
a, a amidonaphthol 3 monosulpho acid is used. The alphanaphthylamine beta
monosulpho acid (Clève's delta acid) can be replaced by the isomeric beta acid, or
by the equivalent quantities of alpha naphthylamine, amidonaphthols, amido-
naphtholether, amidonaphthol sulpho acid (including the above two a amido-
naphtholmonosulpho acids), amidonaphtholethersulpho acid, amidonaphthoxyacetic
acid, amidonaphthoxyacetic sulpho acid, aniline, toluidine, xylidine, cresidine, or,
in general, by such amido compounds as, when combined with diazo derivatives,
yield amidoazo products further diazotisable, and which are briefly termed herein-
before "amines or substituted amines." The amidonaphtholsulpho acids employed
as middle components, can be coupled either in an alkaline or acid solution. Of
course the intermediate products further diazotised can be coupled with one
molecular proportion of the one and one molecular proportion of the other of
these two amidonaphthol monosulpho acids (in any order), or with one molecular
proportion of the one of these two amidonaphthelmonosulpho acids and one
molecular proportion of another dye-stuff component, or inversely, first with one
molecular proportion of such a dye-stuff component and then with one molecular
proportion of one of the said two amidonaphtholmonosulpho acids. The process
can also be carried out in an analogous manner if, in place of tolidine, other
diamines or substituted diamines are employed. If the aforesaid two a₁ a amido-
naphtholsulpho acids are employed as middle components, other dye-stuff components
can be used as last components.
The coloring matters thus obtainable yield from bluish black to pure black
shades on unmordanted cotton, when the amido naphtholsulpho acids are coupled
in alkaline solution, whilst the products resulting in acid solution in general yield
violet shades.
Analogous dye stuffs (likewise trisazo dye stuffs) result, if one molecular pro-
portion of a tetrazo compound is first combined with one molecular proportion of a
phenol, naphthol, dihydroxynaphthalene, a sulpho or carboxylic acid thereof; if
the resulting intermediate products are then combined with one molecular pro-
portion of an "amine or substituted amine" (including the above two a₁ a amido-
naphthol monosulpho acids); and if the products thus formed (after further
diazotising) are coupled with one molecular proportion of one of the above
new a₁ a amido-naphtholmonosulpho acids (in alkaline or acid solution). Inversely,
the tetrazo compounds may be combined first with one molecular proportion of one
of these two a₁ a amidonaphtholmonosulpho acids, and then with one molecular
proportion of an amine or substituted amine," and the compounds thus produced
(after diazotising) can be combined with two molecular proportions of known
dye-stuff components (including the above two new a₁ a amidonaphthol mono-
sulpho acids).
66
The last named trisazo dye-stuffs can be produced in a manner similar to that
described in the foregoing eighth example.
"
In order to produce so called tetrakisazo dye-stuff's by means of the above
two ai as.
amidonaphtholmonosulpho acids, my foreign correspondents commence
with the intermediate products resulting from the combination of one molecular
proportion of the tetrazo derivatives of diamines, or substituted diamines, with
two molecular proportions of the above named "amines or substituted amines
(including the above two as a amidonaphtholmonosulpho acids); the resulting
intermediate products can be again diazotised, and then combined with two
molecular proportions, of either of the above two a₁ α amidonaphtholmonosulpho
acids, or with one molecular proportion of the one, and one molecular proportion
of the other of these two a₁ a amidonaphtholmonosulpho acids, (in any order)
with one molecular proportion of one of these a₁ a amidonaphtholmonosulpho acids
and one molecular proportion of another dye-stuff component. If the said two
a₁ a, amidonaphthol acids are employed as middle components, other dye stuff
components can be used as last components.

page_text: The coloring matters which result from the last named process will be termed
"tetrakis azo dye-stuffs," as they contain four times the azo group (-N-N-).
The process for producing them is illustrated by the following example. The
parts are by weight.
COLOURING-MATTER
FROM ONE MOLECULAR PROPORTION OF TETRAZO
DIPHENYLCHLORIDE, TWO MOLECULAR PROPORTIONS OF ALPHA AMIDO
BETA NAPHTHOLETHER DELTA MONOSULPHO ACID, AND TWO MOLECULAR
PROPORTIONS OF a₁ a₁ AMIDONAPHTHOL ẞ: MONO SULPHO ACID.
18.4 parts of benzidine, in hydrochloric solution, are converted in the known
manner, by means of 14 parts of sodium nitrite, into the tetrazo chloride, and the
resulting solution of tetrazo diphenylchloride is allowed to flow into a weak acetic
acid or alkaline solution of 53-4 parts of alpha amido betanaphtholether delta
mono sulpho acid. The liquid mixture is heated at 50 degrees centigrade during
several days, and finally at 90 degrees centigrade for a short time. When the
combination is effected in acid solution, the mixture is rendered alkaline, and the
intermediate product is isolated by salting out, filtering off, pressing, and drying.
It is then mixed with a concentrated watery solution of 14 parts of sodium nitrite,
and is diazotised by slowly adding muriatic acid; the thus formed complete
tetrazo chloride is filtered off after about 24 hours, and introduced into a solution
in water of 48 parts of a, a, amido naphthol ẞ, mono sulpho acid, and 25 parts of
sodium carbonate. In order to complete the reaction, the mixture is finally heated
(at 90 degrees centigrade) for a short time, and the dye-stuff is isolated by
salting out, filtering off, pressing, and drying. It possesses the following
formula:
\OC,H
It yields bluish-black shades on unmordanted cotton.
SO,Na
The other tetrakisazo dye-stuffs result in a manner analogous to that described
in the last example, if, on the one hand, the a, a, amido naphthol ẞ, monosulpho
acid is replaced by the isomeric a₁ a, amido naphthol a, mono sulpho acid, or if (in
any order) one molecular proportion of the one and one molecular proportion of
the other of the said two a₁ a amidonaphthol monosulpho acids are used, or if
equal molecular proportions of one of these a₁ a amido naphthol mono sulpho
acids and another dye stuff component are employed, or if, on the other hand, in
place of the amidonaphtholether sulpho acids used as middle components, two
inolecular proportions of an amine or substituted amine (including the above
a a amido naphthol mono sulpho acids) are used (employing the same or two different
oues), or if the benzidine is replaced by other diamines or substituted diamines.
If the said two a₁ a amidonaphthol monosulpho acids are employed as middle
components, other dye-stuff components can be used as last components. B

page_text: On coupling the amido naphthol sulpho acids in alkaline solution, dye-stuffs
result which generally yield from bluish-black, greenish-black, to pure black
shades, whilst the analogous products obtained by coupling the amido naphthol
sulpho acids in acid solution, in general yield redder shades.
"
According to the further researches of my foreign correspondents, valuable
direct dyeing dye-stuffs are obtained by combining with the above named
a a amidonaphtholsulpho acids, the diazo products of those amido azo compounds
which result on combining the diazotised thio condensation products from para
toluidine, metaxylidine, pseudo cumidine, or the diazo compounds of the sulpho
acids of these thio bases with the above named "amines or substituted amines
(including the above a, a, amidonaphthol mono sulpho acids). My foreign corre-
spondents also obtain valuable products by combining the diazo derivatives of
the said thio products with the above a₁ a amido naphthol mono sulpho acid,
rediazotising the so-formed amido azo products, and coupling the diazo compounds
thus obtained with known dye-stuff components.
By "thio condensation products or thio amido con pounds," my foreign corre-
spondents mean, for instance, the following substances, viz., Dehydrothio para
toluidine (melting at 191 degrees centigrade, and obtainable by heating para
toluidine with sulphur), dehydro thio metaxylidine, and dehydro thio pseudo
cumidine (obtainable in an analogous manner from meta xylidine and pseudo
cumidine, and the so-called primuline base, which is formed together with dehydro
thio para toluidine, on heating para toluidine with sulphur, and which can be
employed either in raw or in purified form. Other thio amido products (such as
the technically known " chromine," "polychromine," thiochromogene," or the
like, can, however, also be used.
،،
These dye stuffs are formed by coupling the diazo compounds of the said
thio amides, or sulpho acids thereof, with the above named "amines or substituted
amines" (including the above two a, a, amido naphthol sulpho acids), diazotising
the resulting amido azo products, and combining the thus formed diazo derivatives
either with the new a₁ a amido naphthol sulpho acids or other dye stuff
components.
The process for producing these dye-stuffs is analogous to that which my
foreign correspondents have described for the production of analogous colouring
matters derived from thio condensation products, or sulpho acids thereof, in the
Specification of Letters Patent No. 11533 of 1892.
My foreign correspondents have also found that the above mentioned a₁ a amido
naphthol sulpho acids can be employed advantageously for the production of new
disazo colouring matters suitable dyeing wool black in acid baths. These disazo
dye-stuffs result by combining the diazo derivatives of amines, amidophenols,
amidophenol ethers, amido azo products of the benzene or naphthalene series, or
substitution products thereof (especially sulpho or carboxylic acids, including the
above two a₁ a, amidonaphthol mono sulpho acids) with "amines or substituted
amines," or the said two a₁ a amido naphthol mono sulpho acids, by further
diazotising the resulting amido azo products, and coupling the thus obtained
diazo compounds either with the said a₁ a, amido naphthol mono sulpho acids, or
other dye-stuff components.
These disazo dye-stuffs are obtained in the usual manner, viz., by diazotising
aniline, toluidine, or the like (including the above two a₁ a amidonaphthol mono
sulpho acids), combining these diazo derivatives with "amines or substituted
amines," or the said a₁ a amido naphthol mono sulpho acids, rediazotising the
so-formed amido azo products, and coupling the resulting diazo compounds either
with the said α₁ α amido naphthol mono sulpho acids, or with the known dye stuff
components.
Of course, amidomono alkylaniline, amido dialkylaniline, the mono acetyl
derivatives of para phenylene diamine or naphthalene diamine, or similar diamines,
or the sulpho derivatives of these products, can be employed as first components in
the production of the above disazo dye-stuffs adapted for dyeing wool in acid baths.

page_text: mono acetyl deriva
acetylated disazo dye-stuffs result, which will be treated in a suitable manner in
order to separate the acetyl group. On employing, as first components, mono
nitro amines (such as nitro aniline, nitro naphthylamine, or the like, or sulpho acids
of mono nitro amines), nitro disazo_colouring matters result which subsequently
are converted into the amido disazo dye stuffs by suitable treatment with reducing
agents.
My foreign correspondents have also found that the above two a₁ a amido
naphthol mono sulpho acids can be used for producing simple azo dye-stuffs capable
of dyeing wool in acid baths. These colouring matters result by combining the
diazo compounds of amines, amido phenols, amido phenolethers, amido azo products
of the benzene or naphthalene series, sulpho or carboxylic acids thereof (including
amido
the new a₁ a amido naphthol mono sulpho acids), with the above a, a
naphthol mono sulpho acids, or other dye stuff components.
In the production of such simple azo dye stuffs, amidomono alkylaniline, amido
dialkylaniline, or analogous amines or substitution derivatives thereof, can be
employed as first components. If the diazo compounds of mono acetylated
phenylene diamine, mono acetylated naphthylene diamine, or analogous mono-
acetylated diamines, or substitution products thereof (such as sulpho acids of mono
acetylated diamines), are coupled with the above named a, a, amido naphthol mono
sulpho acids, monoacetylated azo dye-stuffs result which can be converted into the
corresponding amido azo dye-stuffs by separating the acetyl group. On employing
the diazo derivatives of mono nitro amines, nitro azo colouring matters are obtained
which are transformed into the corresponding amido azo dye stuffs by treating with
reducing agents.
The production of these mono azo dye stuffs suitable for dyeing wool is effected
in the usual way. The shades produced by means of these dye-stuffs on wool in
acid baths, are in general from red, violet, to blue.
The following example will serve to illustrate the production of these mono azo
colouring matters. The parts are by weight.
TENTH EXAMPLE.
DYE-STUFF FROM DIAZO BENZENE CHLORIDE AND а₁ a AMIDO NAPHTHOL
B. MONO SULPHO ACID.
The solution of diazo benzene chloride obtained, in hydrochloric solution, from
9-3 parts of aniline by means of 7 parts of sodium nitrite, is allowed to flow into an
icy-cold solution of 24 parts of ai a4 amido naphthol ẞs monosulpho acid, rendered
alkaline by means of sodium carbonate. The formation of the dye-stuff, which
isolated
instantly begins, is finished after about 24 hours. The colouring matter
in the usual manner, viz., by salting out, filtering off, pressing, and drying. It
produces bluish-red shades on wool in an acid bath.
If the coupling be effected in moderately acidulated solution (for instance,
acidulated by means of acetic acid), a dye-stuff results which yields somewhat
yellower shades.
az az
amido
The other colouring matters result in an analogous manner, if, on the one hand,
diazobenzene is replaced by the diazo products of other amines or amidophenols,
amidophenolethers, amido azo compounds of the benzene or naphthalene series,
sulpho or carboxylic acids thereof (including the above a, a, amido naphthol mono
sulpho acids), and if these diazo products are combined with the said
naphtholmono sulpho acids (in an alkaline or acid solution), or if, on the other
hand, the latter acid is replaced by the isomeric a₁ a amido naphthol a, mono
sulpho acid, and is combined with the diazo compounds of amines, amido phenols,
amidophenolethers, amido azo compounds of the benzene or naphthalene series, or
sulpho or carboxylic acids thereof, effecting the combination either in an alkaline
or an acid solution.

page_text: Of course the diazo compounds derived from mono acetylated diamines (such as
mono acetylated phenylene diamine, mono acetylated naphthylene diamine, or the
like, or sulpho acids of mono acetylated diamines) from mono nitro amines (such as
nitro aniline, nitro naphthylamine), or from the analogues or homologues or
substitution products, can be used for the production of such simple azo dye-stuffs.
Diamines alkylated in the one amido group (such as mono alkylphenylene diamine,
dialkyl phenylene diamine) and the analogues, homologues, or substitution products
thereof, likewise can be used as first components.
The last named colouring matters are superior to those obtained from other
amido naphthol sulpho acids, by their capability of yielding even shades, and
withstanding the action of alkalies.
The researches of my foreign correspondents have also shown that valuable
colouring matters capable of dyeing unmordanted cotton, result on coupling the
diazo compounds of the aforesaid thio condensation products (such as dehydro thio
para toluidine, or the like) with the above a, a, amidonaphtholsulpho acids.
The combination of the latter two acids with the said diazo products can be
effected either in alkaline or in acid solution.
The process of producing these mono azo dye-stuffs, capable of dyeing
unmordanted cotton, is effected in the usual manner.
My foreign correspondents have further found, that the above a1 a
amido-
naphthol mono sulpho acids possess the capability of reacting with two molecular
proportions of diazo compounds (employing either the same or two different ones),
valuable dye-stuffs being thus formed which yield from blue to bluish-black shades.
The colouring matters obtainable in this manner particularly are distinguishable
by their dyeing power, by their capability of easily striking on the fibre, and
producing on the latter, shades which withstand the action of light.
The method of producing these new disazo colouring matters is analogous to that
described in the Specification of application of Letters Patent No. 9894 dated
17th May 1893, and consists either in allowing two molecular proportions of the
same diazo component to act on one molecular proportion of the above mentioned
a a amidonaphthol mono sulpho acids (preferably in alkaline solution), or in
combining one molecular proportion of the latter acids with one molecular
proportion of a diazo compound, and in subsequently reacting with one molecular
proportion of another diazo derivative on the so-formed intermediate product,
effecting in the latter case, the first coupling preferably in acid solution, whilst
the second combination is carried out profitably in alkaline solution.
In order to illustrate the method of producing these dye-stuffs, the following
examples are given, the parts being by weight.
a
AMIDO
DYE-STUFF FROM TWO MOLECULAR PROPORTIONS OF DIAZO NAPHTHALENE
CHLORIDE AND ONE MOLECULAR PROPORTION OF a1
NAPHTHOL a, MONO SULPHO ACID.
The solution of alpha diazo naphthalene chloride obtained in the usual manner
from 28-6 parts of alpha naphthylamine by means of 14 parts of sodium nitrite, is
allowed to flow (on carefully cooling) into a watery solution prepared by dissolving
24 parts of a₁ a amido naphthol a, mono sulpho acid, and about 120 parts of
anhydrous sodium carbonate. The mixture is cooled with ice, and repeatedly
stirred until the formation of the dye-stuff is complete. After, say, about 24 hours,
the mixture is slowly heated to boiling, and the dye-stuff, which is soluble with
difficulty, is filtered off after cooling.
It produces deep bluish-black shades on wool in acidulated baths.

page_text: COLOURING
MATTER FROM EQUI-MOLECULAR PROPORTIONS OF DIAZO-
BENZENE CHLORIDE, AND
ACID.
a a AMIDO NAPHTHOL ẞ MONO SULPHO
A solution of diazo benzene chloride, obtained in usual way from 9-3 parts of
aniline, by means of 7 parts of sodium nitrite (on cooling), is stirred into a
mixture containing 24 parts of a₁ a amido naphthol ẞ, mono sulpho acid, and a
small quantity of muriatic acid. As soon as the formation of the intermediate
product is complete, the mass is rendered alkaline by means of sodium carbonate,
and a solution of diazo benzene sulpho acid (corresponding to 7 parts of sodium
nitrite) is then added. The reaction mixture is cooled by ice, and the combination
is facilitated by stirring. The formation of the dye-stuff is complete after a very
short time, and the complete dye-stuff is then isolated in the manner described
in the last example. It produces bluish-black shades on wool in acid baths.
Analogous dye-stuffs result in a similar manner, if, in the preceding examples
eleven and twelve, the diazo compounds employed are replaced by the corresponding
quantities of other diazo products derived from amines of the benzene or
naphthalene series. In place of the diazo products derived from amido compounds
of the benzene or naphthalene series, those derived from substituted amines of
these two series likewise can be used, employing, for instance, the diazo derivatives
of amido phenols, amido phenolethers, amido carboxylic acids, amido sulpho acids,
or substitution products thereof.
The shades obtained by means of the last named disazo dye-stuffs in general
are distinguishable by their intensity and fastness against the action of light.
My foreign correspondents have described in the above examples, four, five,
six, seven, eight, nine, ten, eleven, and twelve, some distinct methods of practically
producing some of the dye-stuffs herein before defined. Of course, my foreign
correspondents do not limit themselves to the particulars or directions above given,
as the latter can be varied, and the production of the colouring matters herein-
before defined can be effected by means of all those methods which are known to
chemists, and in use for the production of analogous or similar dye stuffs.
Dated this 10th day of August 1893.
NEWTON & SON,
Agents for the Applicant.
5
COMPLETE SPECIFICATION.
The Manufacture or Production of Amidonaphtholsulpho Acids and
Colouring Matters therefrom.
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
particularly described and ascertained in and by the following statement :—
My foreign correspondents have found, that alpha, naphthylamine alpha, alpha.
disulphonic acid, and alpha, naphthylamine-beta, alpha, disulphonic acid, are
converted into amidonaphtholsulphonic acids when fused with alkalies, the sulphonic
group in the so-called peri position relatively to the amido group being displaced.
by the hydroxyl group, the acids thus formed being the alpha, amido-alpha

page_text: naphthol-alpha, monosulphonic acid, and alpha, amido-alpha, naphthol-beta, mono-
sulphonic acid, represented by the following formulæ respectively :-
The following example will serve to illustrate the production of the alpha,
amido-alpha, naphthol-alpha-monosulphonic acid. The parts mentioned are by
weight.
PRODUCTION OF ALPHA AMIDO ALPHA NAPHTHOL-ALPHA, MONOSULPHONIC
ACID.
100 parts of alpha, naphthylamine alpha, alpha disulphonate of sodium are
mixed with 250 parts of potash-lye (containing 75 per cent. of pure potassium
hydroxide), and heat is applied, care being taken that the temperature does not
rise above from 150 to 160 degrees centigrade; action then takes place, and it is
unnecessary to apply further heat. The fused mass is subsequently dissolved in
water, and the solution is neutralized by adding about 400 parts of muriatic acid
(at 20 degrees Baumé), whereupon the alpha, amido a naphthol-alpha, mono-
sulphonic acid separates as a heavy precipitate, which is filtered off and carefully
washed with cold water.
That the amidonaphtholsulphonic acid thus obtained possesses the aforesaid
composition, is proved by the fact that by heating it with dilute alkalies it is
converted into the alpha, alpha, dihydroxynaphthalene alpha, monosulphonic acid
of the formula :-
The researches of my foreign correspondents have shewn, that the aforesaid
alpha, amido a naphthol-alpha, monosulphonic acid, is identical with the 25
1.8.5 amido naphthol sulphonic acid claimed and described in the Specification of
Letters Patent No. 4613, dated 2nd March 1893, in which, moreover, the

page_text: production of certain dye-stuffs from the said alpha₁ amido naphthol alpha,
monosulphonic acid is also described. Naturally my foreign correspondents do not
claim the production of these dye-stuffs.
If, in the above example, the isomeric alpha, naphthylamine beta, alpha
disulphonic acid is used in place of alpha, naphthylamine alpha, alpha, disulphonic
acid, the process proceeds in an analogous manner, viz. the sulphonic group.
contained therein in the "peri" position relatively to the amido group, being
displaced by the hydroxyl group.
The last named new alpha, naphthylamine-beta, alpha disulphonic acid can be
obtained by sulphonating acetylated alpha, naphthylamine alpha, monosulphonic
acid, removing the acetyl group, and separating the alpha, naphthylamine beta,
alpha disulphonic acid from the isomeric alpha, naphthylamine alpha, alpha
disulphonic acid, which is produced in the same process. The latter separation
can be profitably effected by utilizing the difference in solubility in water of the
salts of these two acids.
The production of the said alpha, naphthylamine beta, alpha, disulphonic acid,.
is illustrated by the following example. The parts are by weight.
PRODUCTION OF ALPHA, NAPHTHYLAMINE BETA, ALPHA DISULPHONIC ACID..
10 parts of alpha, naphthylamine alpha, monosulphonic acid are mixed with
60 parts of glacial acetic acid, 12 parts of acetic anhydride, and 6 parts of sodium
acetate. The mixture is boiled during 8 hours. After cooling to about 40 degrees.
centigrade, 6.6 litres (in case the parts are kilos. by weight) of commercial
muriatic acid are added. The acetylated compound separates in white needles as
the liquid cools.
10 parts of the acetylated alpha, naphthylamine alpha, mono sulphonic acid are
introduced into 50 parts of fuming sulphuric acid (containing 25 per cent. of
anhydride), and the mixture is allowed to stand at ordinary temperature during
from one to two days. It is then poured onto ice, and the liquid thus obtained is
mixed with such a quantity of water that the whole volume is 300 litres (in case
the parts mentioned are kilos. by weight). This solution is boiled during from.
3 to 4 hours in order to effect the separation of the acetyl group. To remove the
sulphuric acid, milk of lime is then added, until the liquid is alkaline; the calcium
sulphate is filtered off, and the filtrate mixed with sodium carbonate. After
removing the precipitated calcium carbonate, the filtrate is evaporated, until a
skin forms on the surface of the hot liquid, which is then allowed to cool and stand
24 hours. The pure sodium salt of alpha, naphthylamine-alpha, alpha, disulphonic
acid S separates almost entirely, during this time, in the form of crusts. This is.
filtered off from the liquid and the filtrate is acidulated and allowed to stand
24 hours. A second salt then crystallises out in the form of white needles, which
aggregate in balls, the separation of which takes place slowly, but nearly
perfectly, as only a trace thereof can be salted out from the mother liquor. This
last mentioned salt, which is contained in the aforesaid filtrate, is the acid sodium
salt of the new alpha, naphthylamine beta, alpha, disulphonic acid.
My foreign correspondents have ascertained the composition of the latter acid
in the following manner :-
On displacing the amido group contained therein by hydrogen, by the hydrazine.
method, a naphthalene disulphonic acid is obtained, which my foreign correspondents
have converted by treatment with phosphorus pentachloride, into the corresponding
naphthalene disulphonic chloride. This latter melts at 138 degrees centigrade,.
and is found to be identical in its chemical properties with the naphthalene
disulphonic chloride first prepared by Armstrong & Wynne (see Abstracts of the

page_text: Alpha, naphthylamine-alpha, monosulphonic acid being used initially in preparing
the new naphthylamine disulphonic acid, the latter must therefore possess the 5
composition represented by the following formula :-
The process for converting this new alpha, naphthylamine beta, alpha disulphonic,
into the new beta sulphonic acid of alpha, amido-a, naphthol, is illustrated by the
following example, the parts being by weight.
PRODUCTION OF
ALPHA-AMIDO-ALPHA NAPHTHOL-BETA, MONOSULPHONIC
ACID.
10 parts of alpha, naphthylamine-beta, alpha, disulphonic acid (in the form of
acid sodium salt) are mixed with 20 parts of potash-lye (containing 50 per cent. of
potassium hydroxide), and the mixture is heated during 6 hours, at from 180 to
190 degrees centigrade in a closed vessel capable of withstanding pressure, and
provided with a stirring apparatus. The temperature is then raised to 200 degrees
centigrade, and kept thereat during 2 hours. When it is cool, 200 litres (in case
the parts are kilos. by weight) of commercial muriatic acid are added to the
product thus obtained. The new alpha, amido alpha, naphthol beta, monosulphonic
acid crystallises out from the acid liquid in minute white needles. It yields dye-
stuffs when combined with diazo compounds, and differs in its properties and actions
from all isomeric acids known up to the present time.
My foreign correspondents do not limit themselves to the directions above given
for the production of the two amidonaphtholsulphonic acids, as these can be varied.
For instance, instead of the naphthylamine sulphonic acids, the salts thereof can

page_text: be used, and instead of potash-lye, soda-lye, or mixtures of potash-lye and soda-
lye, can be used; moreover, the strength of the lye can be varied within certain
limits, and either a higher or lower degree of beat can be applied, in which case,
the time during which the reaction takes place is shortened or extended according
to circumstances. Such modifications do not alter the nature of this part of the
present invention.
is
The last named alpha, amido alpha, naphthol beta, monosulphonic acid, differs
from all the isomeric amido naphtholsulphonic acids, and the researches of my
foreign correspondents have shewn that the said acid also differs from the amido-
naphthol beta sulphonic acid described in the Specification of the Letters Patent
No. 6972, dated 22nd April 1891, though Friedländer (see Chemiker Zeitung of
the year 1893, page 1413) states that the amido naphtholsulphonic acid formed on
fusing the 1-8 naphthylene diamine-beta sulphonic acid with alkalies (which process
is also described in the Specification of the aforesaid Letters Patent No. 6972º¹)
1-amido-8-naphthol-6-sulphonic acid, or alpha, amido alpha, naphthol beta,
sulphonic acid. According to the researches of my foreign correspondents, the
said two acids, viz. :-alpha, amido alpha, naphthol beta, monosulphonic acid
(obtainable by means of the process illustrated in the above Example C), and
amido naphthol-beta-sulphonic acid described in the Specification of the above
named Letters Patent No. 6972", altho' in some respects alike, differ materially in
behaviour. Thus, alpha, amido alpha, naphthol-beta, sulphonic acid forms a
sodium salt which can be easily salted out in white needles by adding common salt
to its solution in water, whereas the sodium salt of the other amido naphthol-beta-
sulphonic acid cannot be salted out, or only with very great difficulty. On adding
ferric chloride to a solution in water of the said alpha, amido alpha, naphthol-beta,
monosulphonic acid, a green coloration at first appears, a dull coloured precipitate
being subsequently produced, whereas, when added to solutions of the other above
mentioned amidonaphthol-beta-sulphonic acid, ferric chloride produces a brown
colour, but no precipitate. Moreover, the disazo dye-stuffs formed by combining
the said alpha, amido alpha, naphthol beta, sulphonic acid with tetrazo derivatives
of para diamines, produce shades on unmordanted cotton which are much bluer
than those obtained with the aid of the analogous colouring matters derived from
the other amidonaphthol-beta-sulphonic acid.
My foreign correspondents have further found, that the said two amidonaphthol
mono-sulphonic acids can be profitably used in producing the dye-stuffs hereinafter
defined.
The researches of my foreign correspondents have shown, that new disazo
colouring matters can be obtained, if the aforesaid alpha amido alpha, naphthol-
beta, sulphonic acid is allowed to act on the tetrazo compounds of "benzidine, its
analogues or homologues." The dye-stuff's thus obtained are distinguished by the
beauty and intensity of the shades produced therewith.
By "benzidine, its analogues or homologues," the following substances, for
example, are ineant, viz., Benzidine, tolidine, diamido phenylotolyl, diamido diphenol-
ether, diamido alkyl-hydroxydiphenyl, diamidoalkylhydroxyphenyltolyl, diamido-
azobenzene, diamidoazotoluene, diamidoazoxylene, diamidoazoxybenzene, diamido
azoxytoluene, diamidostilbene, diamidofluorene, diamidonaphthalene, diamido-
carbazol, diamidodiphenylene oxide, diamidoditoluylene oxide, para-phenylene
diamine, paratoluylenediamine, benzidine sulphone, tolidine sulphone, diamido-
phenyltolylsulphone, diamidodiphenoxyacetic acid, diamidodiphenyleneketoxine,
diamidophenylbenzinidazols, amidobenzene azo-alpha naphthylamine, amidotoluene
azo alpha naphthylamine, amidoxylene azo alpha naphthylamine, amido benzene
(amidotoluene or amidoxylene) azo paraxylidine, amidobenzene (amidotoluene or
amidoxylene) azo meta (or azo ortho) amido paracresolether, amidobenzene (amido-
toluene or amidoxylene) azo beta alkyloxyalpha naphthylamine, the sulpho or
carboxylic acids thereof.
Similar diamines, or substitution derivatives thereof, which can be converted into
tetrazo salts, either directly, or by means of their monacetyl derivatives, can also
C

page_text: be used, and the corresponding mononitramines can be used. Instead of the
monacetylated diamines, in the latter case, the resulting nitrazo compounds must
be reduced, again diazotised, and combined with dyestuff components, while on
using monacetylated diamines, the monoacetylamidoazo derivatives which are
first formed, must be suitably treated, in order to separate the acetyl group, again
diazotised, and combined with the respective dyestuff components, or the above
named alpha, amido-alpha, naphthol beta, monsulphonic acid.
The combination of the tetrazo salts of the above named diamines with the said
alpha, amido alpha, naphthol beta, monosulphonic acid, can be effected in au
alkaline, or in a moderately acid solution.
In order to illustrate this process, the following example is given, the parts
being by weight :-
COLOURING MATTER FROM ONE MOLECULAR PROPORTION OF TOLIDINE AND
TWO MOLECULAR PROPORTIONS OF ALPHA AMIDO ALPHA NAPHTHOL
BETA MONOSULPHONIC ACID.
A solution of tetrazoditolyl prepared from 21-2 parts of tolidine, is allowed to
flow into a solution prepared by dissolving 50 parts of alpha, amido-alpha.
naphthol-beta,-monosulphonic acid, the latter solution being rendered alkaline by
means of sodium carbonate, and cooled by means of ice. The formation of the
dyestuff begins instantly, and is completed after about 24 hours. The colouring
matter is isolated in the usual manner, pressed, and dried. It yields blue shades
or unmordanted cotton, and is represented by the following formula :-
DYE STUFF
FROM BENZIDINE, ALPHA₁ NAPHTHOL ALPHA, MONOSULPHONIC
ACID, AND ALPHA AMIDO-ALPHA NAPHTHOL BETA, MONOSULPHONIC
ACID.
18.4 parts of benzidine are converted into the tetrazo compound in the usual
manner, and the tetrazo solution is allowed to flow into a solution prepared by
dissolving 24-6 parts of alpba, naphthol alpha,-monosulphonate of sodium, and
30 parts of sodium acetate, in water. When the formation of the intermediate 3
product is complete, a carefully cooled solution of 24 parts of alpha, amido-alpha

page_text: naphthol beta, monosulphonic acid is added. The production of the mixed dye-
stuff instantly begins, and is completed by heating. The colouring matter is
isolated in the usual manner, and pressed and dried. It produces violet shades on
unmordanted cotton.
Its composition is represented by the following formula:-
The production of the said mixed disazo dye-stuffs can, as a matter of course,
also be effected in the inverse order, viz. by combining the tetrazo compound first
with the said alpha, amido alpha naphthol beta, monosulphonic acid, and then
with another dye-stuff component.
Dye-stuffs analogous to those described in the foregoing Examples D and E, are
produced, if, instead of tolidine or benzidine respectively, the equivalent quantities
of other para diamines, or the like, are used, or if, in the Example E, instead of
alpha, naphthol-alpha,-monosulpho acid, another naphtholsulphonic acid, or,
generally, a phenol, an amine, diamine, amidophenol, amido phenolether of the
benzene or naphthalene series, or a sulphonic or carboxylic acid thereof, is used.
By means of the processes illustrated by the above Examples D and E, dye-stuffs
are formed which chiefly yield reddish brown, brown, violet, bluish-violet, blue or
greenish-blue shades, remarkable on account of the manner in which they withstand
the action of alkalies. The colouring matters can be rediazotised when fixed on
fibres, and then combined with phenols, amines, diamines, amidophenols, amido
phenolethers of the benzene or naphthalene series, or sulphonic or carboxylic
acids of these components, shades being thus produced which vary from brown
to grey and black, and withstand in a high degree the action of fulling.
My foreign correspondents have ascertained that the above two amido naphthol-
monosulphonic acids, viz.: alpha, amido alpha, naphthol alpha, sulphonic acid, and
alpha, amido alpha, naphthol beta, sulphonic acid, can also be profitably used in
producing valuable so-called tris- and tetra-kisazo dyestuffs, which are formed if
tetrazo derivatives of diamines are first combined, either with one or two molecular
proportions of "amidocompounds of the benzene or naphthalene series," and the
resulting intermediate products, after being rediazotised, are combined with two
molecular proportions of one of the above two amidonaphtholmonosulphonic acids,
or with one molecular proportion of one of these amidonaphtholsulphonic acids, and
one molecular proportion of another dye stuff component; or, inversely, first
with one molecular proportion of a dye-stuff component, and then with one
molecular proportion of one of the said amidonaphtholmonosulphonic acids.
My foreign correspondents inean by the expression "amidocompounds of the
benzene or naphthalene series," which can be used as middle components, all those
amido compounds which, when combined with diazo compounds, yield amidoazo
compounds which can be further diazotised, for instance, paraxylidine, ortho
amido para cresolether, metamido-para-cresolether, alphanaphthylamine, amido-
naphthols, amidonaphtholethers, alpha-naphthylamine beta inonosulphonic acids
Clève's beta and delta acid), the amidonaphtholsulphonic acids hitherto known

page_text: (including the two alpha, alpha, amidonaphthol monosulphonic acids herein before
described), amidonaphtholether sulphonic acids, amidonaphthoxy acetic acids,
amidonaphthoxy acetic sulphonic acids, or the like.
If the tetrazo salts of diamines are combined with one molecular proportion of
one of the said "amido compounds of the benzene or naphthalene series,"
intermediate products are formed containing a free diazo group, which, after being
again diazotised, can be combined with two molecular proportions of either of the
above two amidonaphtholmonosulphonic acids, or with one molecular proportion
of each of these two acids, or with one molecular proportion of one of
these two acids, and one molecular proportion of another dye-stuff component,
(viz., an amine, diamine, phenol, amidophenol, amidophenolether of the benzene
or naphthalene series, a sulphonic or carboxylic acid thereof), or, inversely,
first with one molecular proportion of such a dye stuff component, and then with
one molecular proportion of one of the above alpha, alpha, amidonaphtholsulphonic
acids. Colouring matters are formed in this manner which contain the azo
group (NN-) thrice, and are briefly termed "trisazo dye stuffs." If the
said two alpha, amido alpha, naphthol sulphonic acids are used as middle
components, other dye-stuff components can be used as last components.
The following example will serve to illustrate the production of these "trisazo
dye-stuffs," the parts being by weight.
COLOURING
MATTER FROM ONE MOLECULAR PROPORTION OF TETRAZO-
DITOLYLCHLORIDE, ONE MOLECULAR PROPORTION OF ALPHANAPHTHYL-
AMINE BETA MONOSULPHONIC ACID (CLEVE'S DELTA ACID), AND TWO
MOLECULAR PROPORTIONS OF ALPHA, AMIDO ALPHA NAPHTHOL ALPHA, 2
MONOSULPHONIC ACID.
The tetrazo solution prepared from 21.2 parts of tolidine (or the corresponding
quantity of a tolidine salt) is allowed to flow slowly into a cold solution of
24.5 parts of the sodium salt of Clève's alpha naphthylamine betamonosulphonic
acid (delta) and 50 parts of sodium acetate. In this manner, a so called a
intermediate product is formed, which is represented by one or other of the
following formulæ.

page_text: Its composition is represented by the following formula :--
A colouring matter analogous to that described in the preceding Example F, is
obtained, if, in place of alpha, amido alpha, naphthol alpha, monosulphonic acid,
the isomeric alpha, amido alpha, naphthol beta, monosulphonic acid is used.
Instead of the alphanaphthylamine beta monosulphonic acid (Clève's delta acid),
the isomeric beta acid can be used; or the equivalent quantities of alpha-naphthyl-
amine, amidonaphthols, amidonaphtholether, amidonaphtholsulphonic acid, including
the above two alpha, amido a-naphtholmonosulphonic acids, amidonaphtholether-
sulphonic acid, amidonaphthoxyacetic acid, amidonaphthoxyacetic sulphonic acid,
paraxylidine, ortho-amido-para-cresolether, meta amido para cresolether, or, in
general, such amido compounds, as, when combined with diazo derivatives, yield
amidoazo compounds which are further diazotisable, and which are briefly termed
hereinbefore amido compounds of the benzene or naphthalene series." The
ainidonaphtholsulphonic acids used as middle components can be coupled either in
an alkaline or acid solution. Of course, when further diazctised, the intermediate
products can be coupled with one molecular proportion of each of the two amido-
naphtholmonosulphonic acids (in any order), or with one molecular proportion of
either of these two amidonaphtholmonosulphonic acids, and one molecular proportion
of another dyestuff component; or, inversely, first with one molecular proportion
of such a dyestuff component, and then with one molecular proportion of one of
the said two amidonaphtholmonosulphonic acids. The process can also be carried
out in an analogous manner, if, in place of tolidine, other diamines, or substituted
diamines, are used. If the aforesaid two alpha, amido-a, naphtholsulphonic acids
are used as middle components, other dye-stuff components can also be used as last
components.
The colouring matters thus obtained chiefly yield from bluish-black to pure black
shades on unmordanted cotton, when the amidonaphtholsulphonic acids are coupled
in alkaline solution, whereas the products formed in acid solutions generally yield
violet shades.
Analogous dye-stuffs (also trisazo dye-stuffs) are formed, if one molecular
proportion of a tetrazo compound is first combined with one molecular proportion
of a phenol, naphthol, dihydroxynaphthalene, a sulphonic or carboxylic acid
thereof, and the resulting intermediate products are then combined with one
molecular proportion of the "amido compounds of the benzene or naphthalene
series" above defined (including the above two alpha, amido alpha, naphthol
monosulphonic acids), and if the products thus formed (after being further
diazotised) are coupled with one molecular proportion of one of the above alpha
amido alpha, naphtholmonosulphonic acids, or, in case the latter acids be used as
middle components, also with one molecular proportion of another dye-stuff
component.
The last-named trisazo dyestuffs can be produced in a manner similar to that
described in the foregoing Example F.

page_text: "
"
In order to produce so-called "tetrakisazo dyestuffs" by means of the above
two alpha, amido alpha, naphtholmonosulphonic acids, my foreign correspondents
commence with the intermediate products obtained by combining one molecular
proportion of the tetrazo derivatives of "benzidine, its analogues or homologues
with two molecular proportions of the above named "amido compounds of
the benzene or naphthalene series (using either the same or two different
compounds, including the above two alpha, amido alpha, naphtholmonosulphonic
acids); the resulting intermediate products can be again diazotised, and then
combined with two molecular proportions of either of the above two alpha, alpha,
amidonaphtholmonosulphonic acids, or with a molecular proportion of each of the
two alpha, alpha, amidonaphthol monosulphonic acids, or (in any order) with one
molecular proportion of one of these alpha, amido a naphtholmonosulphonic acids,
and one molecular proportion of another dyestuff component. If the said two
alpha, alpha, amido naphthol sulphonic acids are used as middle components, other
dyestuff components can also be used as last components.
The colouring matters which are formed by the last named process, will be
termed "tetrakisazo dyestuffs," as they contain the azo group (- N = N-) four
times. The process for producing them is illustrated by the following example.
"The narts are by weight.
EXAMPLE G.
.
COLOURING MATTER FROM ONE MOLECULAR PROPORTION OF TETRAZO-
DIPHENYLCHLORIDE, TWO MOLECULAR PROPORTIONS OF ALPHAAMIDO-
BETANAPHTHOLETHER DELTAMONOSULPHONIC ACID, AND TWO MOLECULAR
PROPORTIONS OF ALPHA₁ AMIDO ALPHA, NAPHTHOLBETA: MONOSULPHONIC
ACID.
18.4 parts of benzidine, dissolved in muriatic acid, are converted in the known
manner, by means of 14 parts of sodium nitrite, into the tetrazo chloride, and the
solution of tetrazodiphenylchloride is allowed to flow either into a solution made
moderately acid with acetic acid, or into an alkaline solution of 53.4 parts of
alphaamidobetanaphtholetherdeltamonosulphonic acid. The liquid mixture is
heated at 50 degrees centigrade during several days, and finally during a short
time at 90 degrees centigrade. When the combination is effected in acid solution,
the mixture is rendered alkaline, and the intermediate product is isolated by salting
out, filtering off, pressing, and drying. It is then mixed with a concentrated
solution of 14 parts of sodium nitrite, and diazotised by slowly adding a slight
excess of muriatic acid. The tetrazo chloride thus formed is filtered off after about
.24 hours, and introduced into a solution in water of 48 parts of alpha, amido alpha
naphthol beta, monosulphonic acid and 25 parts of sodium carbonate. In order to
complete the action, the mixture is finally heated (at 90 degrees centigrade) a
short time, and the dye-stuff is isolated by salting out, filtering off, pressing, and
drying.
It is represented by the following formula :—

page_text: It yields bluish-black shades on unmordanted cotton.
The other "tetrakisazo dye-stuffs are formed in a manner analogous to that.
described in the last example, if, on the one hand, instead of alpha, amido alpha,
naphtholbetas monosulphonic acid, the isomeric alpha, amido alpha, naphthol alpha,
monosulphonic acid be used, or if (in any order) a molecular proportion of each of
the said two alpha, amido alpha, naphtholmonosulphonic acids be used, or if
molecular proportions of either of these alpha, amido alpha, naphtholmonosulphonic
acids and another dye-stuff component (in any order), are used; or if, on the other
hand, in place of the amidonaphtholethersulphonic acid used as middle component,.
two molecular proportions of another of the "amido compounds of the benzene or
naphthalene series herein before defined (using either one or two different com-
pounds, and including the above alpha, amido alpha, naphthol monosulphonic acids).
are used; or if, instead of benzidine, other diamines or substituted diamines are
used. If the said two alpha, alpha, amidonaphtholsulphonic acids are used as.
middle components, other dyestuff components can also be used as last components.
On coupling the amidonaphthol sulphonic acids in an alkaline solution, dye-stuffs.
are formed which generally yield from bluish-black, greenish-black, to pure black
shades, whilst the analogous products obtained by coupling the amidonaphthol--
sulphonic acids in acid solution, in general yield redder shades.
"
According to the further researches of my foreign correspondents, valuable direct.
dyeing dye stuffs are obtained by combining with the above named alpha, amido.
alpha, naphtholsulphonic acids, the diazo derivatives of those amidoazo compounds.
which are formed on combining the diazotised "thio condensation products" from
paratoluidine, metaxylidine, pseudocumidine, or the diazo compounds of the sulphonic
acids of these thio bases, with the above defined "amido compounds of the benzene
or naphthalene series" (including the above alpha, amido alpha, naphtholmono-
sulphonic acids). My foreign correspondents have also obtained valuable products.
by combining the diazo derivatives of the said thio products with the above
alpha, amido alpha, naphtholmonosulphonic acids, rediazotising the amidoazo
compounds so formed, and coupling the diazo compounds thus obtained with known.
dye-stuff components.
By "thio condensation products" my foreign correspondents mean, for instance, the
following substances, viz. Dehydrothio paratoluidine (melting at 191 degrees centigrade,
and obtainable by heating paratoluidinė with sulphur), dehydrothiometaxylidine,
and dehydrothiopseudo cumidine (obtainable in an analogous manner from meta-
xylidine and pseudo cumidine), and the so-called primuline base, which is formed.
together with dehydrothioparatoluidine on heating paratoluidine with sulphur, and
which can be used in either a crude or purified form. Other thio amido products.
(such as those known technically as "chromine," "polychromine," "thiochromo-
gene," or the like) can, however, also be used.
These dye-stuff's are formed by coupling the diazo derivatives of the said thio
products, or sulphonic acids thereof, with the above defined "amido compounds of
the benzene or naphthalene series" (including the above two alpha, amido alpha
naphtholsulphonic acids), diazotising the amido azo compounds, and combining the
diazo derivatives thus formed with the said alpha, amido alpha, naphthol mono-
sulphonic acids. If the latter acids are used as middle components, dye stuff
components other than these two amido naphtholsulphonic acids can also be used as
last components.
My foreign correspondents have also found that the above mentioned alpha
amido alpha naphthol beta, sulphonic acid can be advantageously used in pro-
ducing new diazo coloring matters suitable for dye wool black in acid baths..
These disazo dye-stuffs are formed by combining the diazo derivatives of amines,
amidophenols, amido phenolethers, amido azo derivatives of the benzene or
naphthalene series, or substitution products thereof (especially sulphonic or
carboxylic acids, including the last named alpha, amido alpha, naphthol betaa
monosulphonic acid) with "amido compounds of the benzene or naphthalene series,'
including the aforesaid alpha, amido alpha, naphthol beta, monosulphonic acid, by
"

page_text: further diazotising the amido azo compounds, and coupling the diazo compounds
thus obtained with the said alpha, amido alpha, naphtholbeta, monosulphonic acid.
If this latter acid be used as first or middle component, other dye stuff components
can also be used as last components.
These disazo dye-stuffs are obtained in the usual manner, viz., by diazotising
aniline, toluidine, or the like (including the said alpha, amido alpha, naphthol-beta,
monosulphonic acid), combining these diazo derivatives with the "amido-compounds
of the benzene or naphthalene series" herein before defined (including the said
alpha, amido alpha, naphthol-beta, monosulphonic acid), rediazotising the amido
azó compounds so formed, and coupling the diazo compounds thus obtained, either
with the said alpha, amido alpha, naphtholmonosulphonic acid, or with the known
dye-stuff components.
Amidomonoalkylaniline, amidodialkylaniline, the monacetyl derivatives of para-
phenylene diamine or naphthalene diamine, or similar diamines, or the sulphonic
derivatives of these products, can also, as a matter of course, be used as first
components in the production of the above, disazo dye-stuffs adapted for dyeing
wool in acid baths. If monoacetyl derivatives of diamines or substituted diamines
are used, monacetylated disazo dye-stuffs are formed, which can be suitably treated
in order to separate the acetyl group. On using mononitramines (such as nitro-
aniline, nitronaphthylamine, or the like, or sulphonic acids of mononitroamines as
first components, nitro disazo coloring matters are formed, which require to be
subsequently converted into the amido-disazo dye-stuffs by suitable treatment with
reducing agents.
My foreign correspondents have also found that the above alpha, amido alpha
naphthol beta, mono sulphonic acid can be used for producing simple azo dye stuff's
capable of dyeing wool in acid baths. These coloring matters are formed by
combining the diazo compounds of amines, amidophenols, amidophenolethers,
amidoazo compounds of the benzene or naphthalene series, sulphonic or carboxylic
acids thereof (including the said alpha, alpha, amidonaphthol monosulphonic acids)
with the above named alpha, amido alpha, naphthol-beta, monosulphonic acid. If
alpha, amido alpha, naphthol beta, mono sulphonic acid be used as first component,
dye-stuff components other than this amidonaphtholsulphonic acid can also be used
as last components.
In the production of such simple azo dye-stuffs, amidomonoalkylaniline, amido-
dialkylaniline, or analogous amines or substitution derivatives thereof, can be used
as first components. If the diazo compounds of monacetylated phenylene diamine,
monacetylated naphthylene diamine, or analogous mouacetylated diamines, or
substitution products thereof (such as sulphonic acids of monoacetylated diamines),
are coupled with the above-named alpha, amido alpha, naphthol beta, mono-
sulphonic acid, monacetylated azo dye-stuffs are formed which can be converted
into the corresponding amidoazo dye-stuffs by separating the acetyl group. On
using the diazo derivatives of mononitramines, nitroazo coloring matters are
obtained which are transformed into the corresponding amidoazo dye-stuffs by
means of reducing agents.
3
The production of these monazo dye-stuffs suitable for dyeing wool is effected in
the usual way. The shades produced by means of these dye-stuffs on wool in acid
baths, are chiefly from red to violet and blue.
The following example will serve to illustrate the production of these mono-azɔ
coloring matters. The parts are by weight.
DYE STUFF FROM DIAZOBENZENE CHLORIDE AND ALPHA ALPHA AMIDO-
NAPHTHOL BETA, MONOSULPHONIC ACID.
The solution of diazo benzene chloride obtained from 9.3 parts of aniline by

page_text: means of 7 parts of sodium nitrite, is allowed to flow into an ice-cold solution of
24 parts of alpha, amidoalpha, naphtholbeta, monosulphonic acid, rendered alkaline
by means of sodium carbonate. The formation of the dye-stuff, which instantly
begins, is finished after about 24 hours. The coloring matter is isolated in the
usual manner, viz., by salting out, filtering off, pressing, and drying. It produces
bluish red shades on wool in an acid bath.
If the coupling be effected in moderately acidulated solution (for instance, one
acidulated by means of acetic acid), a dye-stuff is formed which yields somewhat
yellower shades.
The other coloring matters are formed in an analogous manner, if, on the one
hand, instead of diazobenzene, the diazo derivatives of other amines, or amido-
phenols, amidophenolethers, amidoazo compounds of the benzene or naphthalene
series, sulphonic or carboxylic acids thereof (including the above alpha₁ amido
alpha, naphthol beta, monosulphonic acid) are used, and if these diazo derivatives
are combined with the said alpha, amido alpha, naphthol-beta monosulphonic acid
(in an alkaline or acid solution). If the said alpha, amido alpha naphthol betas
monosulphonic acid be used as first component, other dye-stuff components can also
be used as last components.
Of course, the diazo compounds derived from monacetylated diamines, (such as
monacetylated phenylenediamine, monacetylated naphthylene diamine, or the
like, or sulphonic acids of monacetylated diamines), from mononitrames (such
as nitraniline, nitronaphthylamine), or from the analogues or homologues or
substitution products, can be used for the production of such simple azo dye-stuffs.
Diamines alkylated in the one amido group (such as monalkylphenylene diamine,
dialkylphenylene diamine), and the analogues, homologues, or substitution products
thereof, can also be used as first components.
The last named coloring matters are in part superior to those obtained from
other amidonaphtholsulphonic acids, owing to their being capable of yielding even
shades withstanding the action of alkalies.
The researches of my foreign correspondents have also shown that valuable
coloring matters capable of dyeing unmordanted cotton are formed on coupling the
diazo derivatives of the aforesaid thio condensation products (such as dehydrothio-
paratoluidine or the like) with the above-named alpha, alpha, amidonaphthol-
sulphonic acids.
The combination of the latter two acids with the said diazo derivatives can be
effected either in alkaline or in acid solution.
The process for producing these monazo dye-stuffs, capable of dyeing unmordanted
cotton, is carried out in the usual manner.
My foreign correspondents have further found that the above alpha, amido
alpha, naphthol beta, monosulphonic acid is capable of interacting with two
molecular proportions of diazo compounds (using either one or two different
compounds), valuable dye-stuffs being thus formed which yield chiefly from blue to
bluish-black shades. The coloring matters obtainable in this manner are particularly
distinguished by their dyeing power, by their capability of easily striking on the
fibre, producing shades which withstand in a high degree the action of light.
The method of producing these new disazo coloring matters consists either in
allowing two molecular proportions of the same diazo compound to act on one
molecular proportion of the above mentioned alpha, amido alpha, naphtholbeta
monosulphonic acid (preferably in alkaline solution), or in combining one molecular
proportion of the latter acid with one molecular proportion of a diazo compound,
and in subsequently acting with one molecular proportion of another diazo
derivative on the intermediate product so formed, the first coupling being effected,
in the latter case, preferably in an acid solution, whilst the second combination is
advantageously carried out in alkaline solution.
In order to illustrate the method of producing these dye-stuffs, the following
examples are given, the parts being by weight.
D

page_text: DYE STUFF
FROM TWO MOLECULAR PROPORTIONS OF DIAZONAPHTHALENE
CHLORIDE AND ONE MOLECULAR PROPORTION OF ALPHA₁-AMIDO-ALPHA
NAPHTHOL BETA, MONOSULPHONIC ACID.
The carefully cooled solution of alpha diazo naphthalene chloride obtained, in
the usual manner, from 28.6 parts of alpha naphthylamine, by means of 14 parts of
sodium nitrite, is allowed to flow into a solution prepared by dissolving 24 parts
of alpha, amido-alpha, naphthol-beta, monosulphonic acid, and about 120 parts
of anhydrous sodium carbonate, in water.
The mixture is kept cool with ice, and repeatedly stirred, until the formation of
the dye-stuff is complete. After, say, about 24 hours the mixture is slowly heated
to the boiling point, and the dye-stuff, which dissolves with difficulty, is afterwards
filtered off from the cold solution.
It produces deep bluish-black shades on wool in acidulated baths.
COLOURING MATTER FROM MOLECULAR PROPORTIONS OF DIAZOBENZENE
CHLORIDE, DIAZO-BENZENE SULPHONIC ACID, AND ALPHA, AMIDO-ALPHA
NAPHTHOL-BETA, MONOSULPHONIC ACID.
A cooled solution of diazo benzene chloride obtained, in the usual way, from
9.3 parts of aniline by means of 7 parts of sodium nitrite, is stirred into a mixture
containing 24 parts of alpha, amido-alpha-naphthol-betas-monosulphonic acid, and
a small quantity of muriatic acid.
As soon as the formation of the intermediate product is at an end, the mass is
rendered alkaline by means of sodium carbonate, and a solution of diazobenzene
sulphonic acid (corresponding to 7 parts of sodium nitrite) is then added. The
mixture is cooled by ice, and the combination is facilitated by stirring. The
formation of the dye-stuff is complete within a very short time.
The dye-stuff is then isolated in the manner described in the last example.
It produces bluish-black shades on wool in acid baths.
Analogous dye-stuffs are formed in a similar manner, if, instead of the diazo.
compounds used in the preceding Examples I and K, the corresponding quantities
of other diazo compounds derived from amines of the benzene or naphthalene
series, are used.
In place of the diazo compounds derived from amido compounds of the benzene
or naphthalene series, those derived from substituted amines of these two series
can also be used, for instance, the diazo derivatives of amidophenols, amido-
phenolethers, amidocarboxylic acids, amidosulphonic acids, or substitution products
thereof.
The shades obtained by means of the last-named diazo dye-stuffs in general are
distinguished by their intensity and fastness on exposure to light.
My foreign correspondents have described in the above Examples D, E, F, G,
H, I, and K, several distinct methods of practically producing some of the
dye-stuffs hereinbefore defined.
But, as a matter of course, my foreign correspondents do not limit themselves to
the particulars or directions above given, as the latter can be varied, and the
production of the colouring-matters hereinbefore defined can be effected by means
of all those methods which are known to chemists & in use for the production of
analogous or similar dye-stuffs.

page_text: 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, I declare that what I claim is :-
1. The production of alpha-amido-alpha, naphthol-alpha, monosulphonic acid, or
salts thereof by fusing disulphonic acid, or salts thereof, with alkalies, alpha,
naphthylamine-alpha, alpha, and isolating the alpha, amido alpha-naphthol-alpha-
sulphonic acid so formed, either as such, or in the form of its salts.
2. The process for producing alpha-amido-alpha-naphthol-beta-monosulphonic
acid, or salts thereof, from alpha-naphthylamine-beta-alpha-disulphonic acid
(obtainable by sulphonating acetylated alpha,-naphthylamine-alpha-monosulphonic
acid, and subsequently splitting off the acetyl group), which process consists in
fusing the said alpha-naphthylamine-beta-alpha-disulphonic acid, or salts thereof,
with alkalies, and isolating the alpha-amido-alpha-naphthol-beta,-sulphonic acid
so formed, either as such, or in the form of its salts.
3. The production of disazo dye-stuffs by combining one molecular proportion of
the tetrazo derivatives of "benzidine, its analogues or homologues," either with two
molecular proportions of alpha-amido-alpha-naphthol-beta-monosulphonic acid,
or salts thereof, or (in any order) with one molecular proportion of the alpha-
amido-alpha-naphthol-betas-monosulphonic acid, or salts thereof, and with one
molecular proportion of an amine, a diamine, a phenol, amidophenol, amido-
phenolether of the benzene or naphthalene series, a sulphonic or carboxylic acid.
thereof.
4. The process for producing trisazo dye-stuffs from alpha,-amido-alpha-
naphthol-alphas-monosulphonic acid, alpha-amido-alpha-naphthol-betas-mono-
sulphonic acid, or salts thereof, which process consists in combining one molecular
proportion of the tetrazo derivatives of "benzidine, its analogues or homologues,"
with one molecular proportion of an "amido compound of the benzene or
naphthalene series," which, when combined with diazo or tetrazo derivatives, yields
a true amido azo compound, which can be diazotised, rediazotising the intermediate
products so formed, and coupling the resulting tetrazo-compounds, either with two
molecular proportions of one of the said two amidonaphtholmonosulphonic acids, or
with a molecular proportion of each of these two acids, or (in any order) with one
molecular proportion of either of these amidonaphtholsulphonic acids, and with one
molecular proportion of another dye-stuff component.
5. The production of trisazo dye-stuffs from alpha-amido-alpha-naphthol-alpha3-
monosulphonic acid, alpha-amido-alpha-naphthol-beta,-monosulphonic acid, or
salts thereof, by combining one molecular proportion of the tetrazo derivatives of
"benzidine, its analogues or homologues," with one molecular proportion of either
of the said amidonaphtholmonosulphonic acids, rediazotising the intermediate
products so formed and coupling the resulting tetrazo compounds, either with two
molecular proportions of one of the said two amidonaphtholmonosulphonic acids, or
with a molecular proportion of the one, and a molecular proportion of the other of
these two acids, or (in any order) with one molecular proportion of either of these
acids, and with one molecular proportion of another dye-stuff component, or with
two molecular proportions of dye-stuff components (using either one or two different
components).
6. The process for producing trisazo dye-stuffs from alpha-amido-alpha-
naphthol-alpha,-monosulphonic acid, alpha-amido-alpha-naphthol-beta-mono-
sulphonic acid, or salts thereof, which process consists in combining one molecular
proportion of the tetrazo derivatives of "benzidine, its analogues or homologues,"
with a molecular proportion of a phenol, naphthol, dihydroxy-naphthalene, a
sulphonic or carboxylic acid thereof, and also with a molecular proportion of an
"amido compound of the benzene or naphthalene series," which, when combined.
with diazo or tetrazo derivatives, yields true amido azo compounds capable of being
further diazotised (including the two said amidonaphtholmonosulphonic acids),,
rediazotising the mixed products so formed, and coupling the resulting diazo,
'

page_text: compounds, either with one molecular proportion of one of the said amidonaphthol-
monosulphonic acids, or (in case one of these amidonaphtholmonosulphonic acids be
used as middle component) with one molecular proportion of another dye-stuff
component.
7. The manufacture of tetrakisazo dye-stuffs from alpha-amido-alpha-naphthol-
alphas-monosulphonic acid, alpha,-amido-alpha,-naphthol-beta, monosulphonic acid,
or salts thereof, by combining one molecular proportion of the tetrazo derivatives
of "benzidine, its analogues or homologues," with two molecular proportions of
"amido compounds of the benzene or naphthalene series " (using either one or two
different amido compounds), which, when combined, yield true amidoazo
compounds that can be further diazotised, rediazotising the products so formed,
and coupling the resulting tetrazo compounds either with two molecular proportions
of one of the said two amidonaphthol monosulphonic acids or with one molecular
proportion of each of these two amidonaphtholmonosulphonic acids, or (in any
order) with one molecular proportion of either of these amidonaphtholmonosulphonic
acids and with one molecular proportion of another dye-stuff component.
8. The production of tetrakisazo dye-stuffs from alpha,-amido-alpha-naphthol-
alpha,-monosulphonic acid, alpha,-amido-alpha,-naphthol-beta,-monosulphonic acid,
or salts thereof, by combining one molecular proportion of the tetrazo derivatives
of "benzidine, its analogues or hemologues," either with two molecular proportions
of the said amidonaphthol monosulphonic acids (using either one or both of these
acids), or (in any order) with one molecular proportion of either of these amido-
naphtholmonosulphonic acids and one molecular proportion of an "amido compound
of the benzene or naphthalene series" (which, when combined, yields true
amidoazo compounds that can be further diazotised), rediazotising the products so
formed, and coupling the resulting tetrazo compounds, either with two molecular
proportions of either of the said amidonaphtholmonosulphonic acids, or with one
molecular proportion of each of the two amidonaphtholmonosulphonic acids, or (in
any order) with one molecular proportion of either of these amidonaphtholmono-
sulphonic acids, and with one molecular proportion of another dye-stuff component,
or with two molecular proportions of dye-stuff components (using either one or two
different components).
9. The process for producing disazo dye-stuffs from alpha-amido-alpha-
naphthol-alpha,-monosulphonic acid, alpha-amido-alpha-naphthol-beta,-mono-
sulphonic acid, or salts thereof, which process consists in coupling one molecular
proportion of the diazo derivatives of dehydrotbio-para-toluidine, dehydrothio-
meta-xylidine, dehydro-pseudo-cumidine, primuline base, or the like, or sulphonic
acids thereof, with one molecular proportion of an "amido compound of the benzene
or naphthalene series" (which, when combined, yield true amidoazo compounds
that can be further diazotised), or with one molecular proportion of the said
amidonaphtholmonosulphonic acids, rediazotising the products so formed, and
coupling the resulting diazo derivatives with one molecular proportion of one of the
said amidonaphthol monosulphonic acids, or (in case the said amidonaphtholmono-
sulphonic acids are used as middle components) with one molecular proportion of
another dye-stuff component.
10. The manufacture of disazo colouring-matters from alpha,-amido-alpha-
naphthol-beta,-monosulphonic acid, or salts thereof, by coupling one molecular
proportion of the diazo derivatives of amines, amidophenols, amidophenolethers of
the benzene or naphthalene series, sulphonic or carboxylic acids thereof (including
the said amidonaphtholmoposulphonic acid), with one molecular proportion of an
"amido compound of the benzene or naphthalene series" (which, when combined,
yields true amidoazo compounds that can be further diazotised), or with one
molecular proportion of the said amidonaphtholmonosulphonic acid, rediazotising
the amidoazo compounds so formed, and coupling the resulting diazo derivatives
with one molecular proportion of the said amidonaphtholmonosulphonic acid, or (in
case the said amidonaphtholsulphonic acid is used as first or second component)
alan with one molecular proportion of the usual dye-stuff.components.

page_text: 11. The production of azo dye-stuffs from alpha,-amido-alpha-naphthol-beta.--
monosulphonic acid, or salts thereof, by coupling one molecular proportion of the
diazo derivatives of amines, amidophenols, amidophenolethers, amidoazo compounds
of the benzene or naphthalene series, sulphonic or carboxylic or other derivatives.
thereof (including the said amidonaphthol monosulphonic acid), with one molecular
proportion of the said amidonaphtholmonosulphonic acid, or also with one
molecular proportion of any other dye-stuff component (in case the said amide-.
naphtholsulphonic acid is used as first component).
12. The process for producing azo colouring-matters from alpha,-amido-alpha-
naphthol-alpha,-inonosulphonic acid, alpha-amido-alpha-naphthol-beta,-mono-
sulphonic acid, or salts thereof, which process consists in combining one molecular
proportion of the diazo derivatives of dehydrothio-para-toluidine, dehydrothio-
meta-xylidine, dehydrothio-pseudo-cumidine, primuline base, or the like, or
sulphonic acids thereof, with one molecular proportion of the said amidonaphthol-
sulphonic acid.
13. The production of disazo dye-stuffs by means of alpha,-amido-alpha-
naphthol-betas-sulphonic acid, or salts thereof, which process consists in combining
one molecular proportion of the said amidonaphtholsulphonic acid, with two
molecular proportions of diazo compounds derived from amines, amidophenols,.
amidophenolethers, amidosulphonic or amidocarboxylic acids of the benzene or
naphthalene series (using either one or two different diazo compounds).
14. As new products of manufacture,
(a) The new alpha₁ amido-alpha
naphthol beta; monosulphonic
acid, and
-
(b) The new colouring-matters
produced by the processes herein before-
defined, or by any other process.
affording the same result.
ليمو