The Manufacture and Production of Sulpho Acids of the Naphthalene Series, and of Colouring Matters Obtainable therefrom.
Year: 1893

page_text: Date of Application, 7th Mar., 1893
Complete Specification Left, 7th Jec. 1893-Accepted, 27th Jan., 1894
PROVISIONAL SPECIFICATION.
Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture and Production of Sulpho Acids of the Naphthalene
Series, and of Colouring Matters Obtainable 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:-
By the researches of Schultz, Erdmann, Bernthsen, Nietzki, &c., a new series of
naphthalene derivatives has been made known, viz., the so-called "sultones," which
represent intramolecular anhydrides of naphtholsulpho acids.
Of the corresponding intramolecular anhydrides derived from amidonaphthalene-
sulpho acids, only one such product has been produced hitherto (and that, by
means of a wearisome process) by Bernthsen (Berichte der Deutschen Chemischen
Gesellschaft, volume 23, page 3094), viz., by heating the coloring matter from
diazotised xylidine and epsilon naphtholsulphamidosulpho acid, with a diluted
watery solution of sodium carbonate, and subsequently reducing the new dye stuff
thus formed. The last-named author assumes that the resulting acid is an intra-
molecular anhydride of an ortho naphthylenediaminedisulpho acid, and possesses the
following composition :-
--
My foreign correspondents have now found a simple method of producing such
intra-molecular anhydrides from amidonaphthalene sulpho acids. These intra-
molecular anhydrides of amido naphthalene sulpho acids, are briefly termed by my
foreign correspondents "naphthsultamesulpho acids."
This new process consists in heating, with fuming sulphuric acid, such naphthyl-
amine sulpho acids as contain the amido group and one sulpho group in peri-position.
In this case, a formation of anhydride between the substituents in peri-position is
effected, and sometimes a sulpho-group also enters into the molecule at the same
time, the above defined "naphthsultame sulpho acids" being thus produced.
The following peri naphthylamine sulpho acids can be employed, viz.: ai-naphthyl-
amine-a4-monosulpho acid, and a, naphthylamine-a, a-disulpho-acid (both described
in the German Patent No. 40571), ai-naphthylamine-as a-disulpho acid, a, naphthyl-
amine Ba-disulpho acid (described in the German Patent No. 45776), and
a-naphthylamine-ß, B3 a-trisulpho acid.
The following example illustrates the method of converting peri-naphthylamine-
sulpho acids into the corresponding naphthsultamesulpho acids, the parts being by

page_text: PRODUCTION OF NAPHTHSULTAME DISULPHO ACID
AMINE-a, a DISULPHO ACID.
FROM a1
NAPHTHYL-
300 parts of the acid sodium salt of the a naphthylamine as a disulpho acid are
gradually stirred into 500 parts of fuming sulphuric acid (containing 40 per cent.
of anhydride). A solution results which, on heating, at from 80 to 90 degrees
centigrade, solidifies as a white mass. Heating is continued until a test portion
taken out (after adding water) no longer yields a diazo compound, and the former
no longer reacts with diazo benzene sulpho acid to form a dye stuff. As soon as
the reaction is complete, the mixture is introduced into ice water, and lime water is
then added until the reaction is alkaline. After filtering off the separated gypsum,
the resulting filtrate is evaporated.
In case the sodium salt shall be produced, the above solution of the calcium salt
is mixed with a solution of sodium carbonate, and after filtering, the filtrate
obtained is evaporated to dryness. On adding alcohol to the hot concentrated
solution of the sodium salt, the latter salt separates almost entirely, on cooling, in
the form of brilliant yellow leaves, which contain water of crystallisation, and can
be easily crystallised from diluted alcohol.
My foreign correspondents have found, by analytical research, that this sodium
salt (when dried at 160 degrees centigrade) contains 16.26, and 16-35 per cent. of
sodium, corresponding with the formula:
き
as the theoretical amount of sodium therein is 1601 per cent.
Hence it follows, that in producing the above anhydride (as described in the
foregoing first example), a sulpho group also has entered into the molecule.
The aforesaid sodium salt easily dissolves in water, but is almost insoluble in
absolute alcohol. Its watery solution possesses a yellow color, and a strong green
fluorescence, the beauty and intensity of which is similar to the fluorescence of
fluoresceine. The fluorescence can be seen clearly even in much diluted solutions.
This peculiarity is to be ascribed to the circumstance that the sodium is directly
bound to nitrogen, as the fluorescence and the yellow color of the watery solutions
of the said trisodium salt completely disappear on the addition of acid (say, acetic
acid). On mixing the resulting acid solution with common salt, the disodium salt
crystallises in pure white thin needles.
The naphthsultame sulphonate of sodium in an acid solution, does not absorb
nitrous acid, and yields no coloring matter in the presence of diazo compounds. It
is not altered either on boiling with alkali lye, or on heating with diluted acids.
The "sultame" group, therefore, is much more stable, and stronger, than is the
" sultone " group, as the derivatives of naphthsultone are converted into the corre-
sponding naphthol sulpho acids, in most cases, readily on continued boiling with
water, but more quickly on heating with alkalies.
If the naphthsultame sulpho acids, or salts thereof, are heated with slacked lime,
a sublimate of alpha naphthylamine is obtained.
The naphthsultame disulpho acid obtainable as described in the foregoing first
example, likewise results in treating the aforesaid a₁ naphthylamine-a, monosulpho
acid with fuming sulphuric acid. Analogous products are formed by treating

page_text: a naphthylamine-a, a disulpho acid, a naphthylamine ẞ, a disulpho acid, and
naphthylamine B, ß, a trisulpho acid.
ཝi
Of course, in place of fuming sulphuric acid, sulphuric acid monochlorhydrine,
or other reagents acting in the same or similar manner, can also be used with the
like result.
The naphthsultame sulpho acids contain a stable nucleus of 5 atoms, which is
formed by the separation of water from the peri-substituents of the peri-naphthyl-
amine sulpho acids.
My foreign correspondents have observed that sulphur and nitrogen contained in
the sultame group, are separated by melting with alkalies, and amido naphthol
sulpho acids result from this process, which may be termed peri-amidonaphthol-
sulpho acids, the sulpho residue (SO2) in the sultame group being removed.
The process for producing amidonaphtholsulpho acids from the above naphth-
sultamesulpho acid, is illustrated by the following example, the parts being by
weight:
CONVERSION OF THE NAPHTHSULTAME
DISULPHO ACID, OBTAINABLE AS
DESCRIBED IN THE FOREGOING FIRST EXAMPLE, INTO AMIDO NAPHTHOL
DISULPHO ACID.
1 part of the sodium salt of the naphthsultamedisulpho acid (obtained as
aforesaid) is heated with 2.5 parts of potash or soda, and 0.2 of a part of water
at 170 degrees centigrade. When a test portion taken out (after combining with
diazo compounds) does not show any increase of the dye stuff formed, the melting
mass, after cooling, is dissolved in water, and the resulting liquid is acidulated, for
instance, with hydrochloric acid. The new amidonaphtholdisulpho acid then
separates in the form of its sodium salt, which forms colorless needles grouped into
the shape of balls. It may be purified easily by crystallisation from water. It
materially differs by its chemical reactions from the isomeric acids.
The corresponding amidonaphtholsulpho acids are obtained in an analogous
manner from the other naphthsultame sulpho acids.
My foreign correspondents have further found, that the above defined amido
naphtholsulpho acids which result from the so-called naphthsultame sulpho acids,
and which they briefly term " peri-amidonaphtholsulpho acids," in contradistinction
to the amido naphthol sulpho acids hitherto in use, are adapted, in an eminent
degree, for the production of azo dye stuffs. My foreign correspondents therefore
propose to employ these acids for the said purposes.
If the diazo derivatives of "benzidine, its analogues and homologues," are
allowed to act on these amido naphthol sulpho acids, disazo coloring matters (con-
taining two proportions of the azo group N N ) result, which produce
beautiful and intense shades.
-
-
By "benzidine, its analogues and homologues," the following substances, for
example, are meant, viz., benzidine, tolidine, diamidophenyltolyl, diamido phenol
ether, diamido alkylhydroxydiphenyl, diamidoalkylhydroxyphenyl tolyl, diamido-
azo benzene, diamido azo toluene, diamidoazoxylene, diamidoazoxybenzene, di-
amidoazoxytoluene, diamido stilbene, diamido fluorene, diamido naphthalene, diamido
carbazol, diamido diphenylene oxide, diamido ditoluylene oxide, para phenylene
diamine, para toluylene diamine, benzidine sulphone, tolidine sulphone, diamido-
phenyltolylsulphone, diamido diphenoxyacetic acid, dianidodiphenylene ketoxime,
meta paradiamidophenyl-benzimidazol, amidobenzeneazoalpha naphthylamine,
amidotoluene azo alpha naphthylamine, amidoxylene azo alpha naphthylamine,
amido benzene- (amido toluene,- amido-xylene-) azoparaxylidine, amido benzene-
(amido toluene, amido xylene-) azo-meta- or azo-orthoamidoparacresolether,
amidobenzene- (amidotoluene-, amido-xylene)- azo-beta alkyloxy-alphanaphthyl-
amine, the sulpho or carboxylic acids thereof.
°

page_text: 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 monoacetylised diamines, the corresponding mono nitro
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 monoacetylised diamines, the first produced mono acetyl amido
azo 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 periamidonaphtholsulpho acids.
The combination of the tetrazo salts of the above diamines, with the said peri-
amido naphthol sulpho 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 amido naphthol sulpho 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 PROPORTION OF DIANISIDINE,
AND TWO MOLECULAR PROPORTIONS OF THE PERIAMIDO-NAPHTHOL-
DISULPHO ACID OF THE FOREGOING SECOND EXAMPLE.
34.2 parts of the sulphate of diamidodiphenoldimethylether, or the equivalent
quantity of another dianisidine salt, are suspended, in a state of minute sub-
division, in 500 parts of water, with the addition of 30 parts of muriatic acid
(20 degrees Baumé). While stirring, a solution of 13.8 parts of sodium nitrite in
150 parts of water, is added. The resulting solution of tetrazo diphenolether is
then allowed to flow into a solution rendered alkaline by sodium carbonate, and
containing 726 parts of the said periamidonaphtholdisulphonate of sodium.
The formation of the dye stuff, which begins immediately, is complete within a
short time. The coloring matter formed is salted out by means of common salt,
filtered off, pressed, and dried. It produces, on unmordanted cotton, blue shades
which are fast against the action of alkalies. It possesses the following
composition:—

page_text: If the combination of the tetrazo diphenolether with the amidonaphtholdisulpho
acid is effected in acid solution (for example, in a moderately weak acetic solution),
a dyestuff results which yields violet shades on unmordanted cotton.
In a manner similar to that described in the foregoing last example, the analogous
coloring matters can be produced, if the diamidodiphenolether employed in the said
example is replaced by the corresponding quantities of other diamidodiphenolethers
(such as ethyl- propyl- butyl- or amylether), or by the equivalent quantities of
another of the diamines above defined, or sulpho or carboxylic acids thereof, or if
the periamidonaphtholdisulpho acid is replaced by the corresponding quantities of
the other periamidonapholsulpho acids.
On coupling in alkaline solution, products result which in general yield blue
shades possessing great fastness against the action of alkalies, whilst on combining
the respective components in acid solution, dyestuffs are obtained which produce
shades generally from reddish violet to violet.
My foreign correspondents have further found, that in place of combining
two molecular proportions of the above periamido naphthol sulpho acids with
one molecular proportion of a tetrazo compound, the latter can be coupled with
one molecular proportion of a periamido naphthol sulpho acid, intermediate
products being thus formed which contain a diazo group, and therefore are capable
of reacting again with a second molecular proportion of a dye-stuff component, such
as phenols, amines, diamines, amidophenols amidophenolethers of the benzene or
naphthalene series, a sulpho or carboxylic acid thereof, including the said
periamidonaphtholsulpho acids.
The production of these intermediate products, and the conversion of the latter
into dye stuffs, consist essentially in combining one molecular proportion of a
tetrazo salt, either first with one molecular proportion of the said periamido naphthol
sulpho acids (in alkaline or acid solution), and then with one molecular proportion
of phenol, amine, and the like (including the periamidonaphtholsulpho acids and
other amidonaphtholsulpho acids), or, inversely, first with one molecular proportion
of a phenol, amine, and the like (including the periamido naphthol sulpho acids,
and other amido naphthol sulpho acids). Amines, in general, are coupled most
conveniently in acid solution, whilst phenols are combined in alkaline solution. In
order to illustrate the method of producing these mixed dyestuffs, the following
example is given. The parts are by weight.
DYE-STUFF FROM EQUAL MOLECULAR PROPORTIONS OF BENZIDINE, ALPHA-
NAPHTHOL-ALPHA-MONO SULPHO ACID (1:4), AND PERIAMIDO NAPHTHOL-
DISULPHO ACID DESCRIBED IN THE ABOVE SECOND EXAMPLE.
184 parts of benzidine are converted in the usual manner into tetrazodiphenyl
chloride. The resulting solution (about 700 litres, if the parts are kilos. by weight)
is allowed to flow into a solution prepared by dissolving 27 parts of the sodium
salt of alpha naphthol alpha mono sulpho acid (1:4), and 30 parts of sodium acetate,
in 500 parts of water. After a short time, the formation of the intermediate
product begins, and is complete in from 4 to 5 hours. It separates in voluminous
dark flakes, and 36-3 parts of the sodium salt of periamidonaphthol disulpho acid,
& 12 parts of calcinated sodium carbonate are then added. The production of the
dye stuff proceeds slowly, and is practically facilitated by heated. After about

page_text: 24 hours, the dye stuff is filtered off, pressed, and dried. It produces, on
unmordanted cotton, blue shades, and possesses the following composition
-
The products analogous to that described in the preceding example result, if, in
the last example, benzidine is replaced by the equivalent quantity of its analogues
or homologues, or if, in place of alpha-naphthol alphamonosulpho acid (1:4), the
corresponding quantity of another dye-stuff component is used (viz. phenol, amine,
diamine, amidophenol, amido phenolether of the benzene or naphthalene series,
a sulpho or carboxylic acid thereof, including periamido naphthol sulpho acids, and
other amido naphtholsulpho acids), or if the periamidonaphtholdisulpho acid
employed is replaced by another of the above mentioned periamido naphthol
sulpho acids.
The combination of the two components with the tetrazo compounds can be
effected in any order, and the peri amido naphthol sulpho acid also can be coupled
in a moderately acid solution.
According to the researches of my foreign correspondents, the above periamido-
naphthol sulpho acids can be employed for producing valuable trisazo and tetrakisazo
dye stuffs. These coloring-matters result by combining the tetrazo compounds of
diamines or substituted diamines first with one or two molecular proportions of an
"amine or substituted amine," diazotising again the intermediate products, and
coupling the so-formed products with two molecular proportions of one of the above
defined periamido naphthol sulpho acids, or (in any order) with one molecular
proportion of the one, and one molecular proportion of another of these periamido
naphthol sulpho acids, or with one molecular proportion of a periamidonaphthol
sulpho acid and one molecular proportion of another dye stuff component. My
foreign correspondents mean by the expression "amines or substituted amines
which can be employed as middle components, all those amido compounds which,
when combined with diazo products, yield amido azo derivatives, further diazo-
table, viz., aniline, toluidine, xylidine, cresidine, the analogues, homologues, or sub-
stitution products thereof, alphanaphthylamine, amido naphthols, amidonaphthol
ethers, alpha naphthylamine beta monosulpho acids (Cléves beta and delta acid),
the amidonaphthol sulpho acids hitherto known & in use, the above mentioned
periamido-naphtholsulpho acids, amidonaphtholether sulpho acids, amidonaphthoxy-
acetic acid, amidonaphthoxy acetic sulpho acid, and the like.
"
If the tetrazo derivatives of diamines are combined with one molecular propor-
tion of one of the said "amines or substituted amines," intermediate products result
which contain a free diazo group, and after diazotising again, can be combined with
two molecular proportions of the same periamido naphtholsulpho acid, or with one
molecular proportion of the one, and one molecular of another, periamido naphthol
sulpho acid, (or with one molecular proportion of a periamido naphthol sulpho

page_text: acid, and one molecular proportion of another dye stuff component (viz., amine,
phenol, amidophenol, amidophenol ether of the benzene or naphthalene series, a
sulpho or carbonic acid thereof), or, inversely, first with one molecular proportion
of a dye stuff component, and then with one molecular proportion of a periamido,
naphthol sulpho acid. Coloring matters result in this manner, which contain three
times the azo group
N = N,
and briefly are termed trisazo dyestuffs.
The manufacture of these trisazo coloring matters is illustrated by the following
example. The parts are by weight.
-
COLORING MATTER FROM ONE MOLECULAR PROPORTION OF TETRAZODITOLYL-
CHLORIDE, ONE MOLECULAR PROPORTION OF ALPHA NAPHTHYLAMINE
BETA MONO SULPHO ACID (DELTA), AND TWO MOLECULAR PROPORTIONS OF
THE PERI AMIDO NAPHTHOLDISULPHO ACID (OBTAINABLE AS DESCRIBED
IN THE ABOVE SECOND EXAMPLE).
The solution of tetrazoditolyl chloride obtained from 21-2 parts of tolidine, or the
equivalent quantity of a tolidine salt, is allowed to flow slowly into a cold solution
prepared by dissolving 24.5 parts of the sodium salt of Cléve's alpha naphthyl-
amine monosulpho acid delta, and 50 parts of sodium acetate.
In this manner, an
intermediate product results, which possesses the composition :
When the formation of this intermediate product is complete, the latter is diazo-
tised by means of 7 parts of sodium nitrite in hydrochloric solution, and the diazo-
tizing being finished, the reaction mixture is introduced into a solution in water of
72.6 parts of the sodium salt of the above periamidonaphtholdisulpho acid, and
25 parts of sodium carbonate.
The formation of the dyestuff is complete within a few hours. It possesses the

page_text: and is isolated in the usual manner by salting out, filtering off, pressing, and
drying. It produces on unmordanted cotton, in an alkaline soap bath, bluish black
shades.
The analogous products result, if, in the last example, the periamidonaphthol-
disulpho acid is replaced by the equivalent quantity of another periamidonaphthol-
sulpho acid, or if the alphanaphthylamine beta monosulpho acid (Cléve's delta acid)
is replaced by the corresponding quantity of the isomeric beta acid, or alpha-
naphthylamine, amidonaphthol, amidonaphtholether, amidonaphtholsulpho acid
(including the above mentioned periamido naphthol sulpho acids), amidonaphthol-
ether sulpho acid, amidonaphthoxyacetic acid, amidonaphthoxy acetic sulpho acid,
aniline, toluidine, xylidine, cresidine, viz., by the correspondent quantities of the
"amines or substituted amines "herein before defined.
The amido naphthol sulpho acids (including periamidonaphthol sulpho acids)
which may be employed as middle or last components, can be combined in alkaline
or moderately acid solution.
Of course, the diazotised intermediate products can be combined (in any order),
first with one molecular proportion of a periamidonaphtholsulpho acid, and then.
with one molecular proportion of another periamidonaphthol sulpho acid, or with
one molecular proportion of a periamidonaphthols sulpho acid and one molecular
proportion of another dye-stuff component.
The process can also be carried out in an analogous manner, if, in place of
tolidine, other diamines or substituted diamines are employed.
The coloring matters thus obtainable yield from bluish black to pure black
shades on unmordanted cotton, when the periamidonaphtholsulpho acids are coupled
in alkaline solution, whilst the products resulting in acid solution generally yield
violet shades.
Analogous products (likewise trisazo dyestuffs) result, if one molecular proportion
of a tetrazo compound is first combined with one molecular proportion of a phenol,
naphthol, dihydroxynaphthalene, a sulpho or carbonic acid thereof, if the resulting
intermediate products are then combined with one molecular proportion of an
"amine or substituted amine, including the above periamidonaphtholsulpho acids,
and if the products thus formed (after further diazotising) are coupled with one
molecular proportion of a peri amido naphthol sulpho acid (in alkaline or acid
solution). Inversely, the tetrazo compounds may be combined first with one mole-
cular proportion of a peri amido naphthol sulpho acid, and then with one molecular
proportion of an "amine or substituted amine," and the compounds thus produced,
after diazotising, can be combined with one molecular proportion of any known dye
stuff components (including the new peri amido naphthol sulpho acids).
The last named trisazo dye stuffs can be produced in a manner similar to that
described in the foregoing fifth example.
In order to produce so-called tetrakisazo colouring matters by means of the peri
amido naphthol sulpho acids, as above described, my foreign correspondents com-
inence with the intermediate products resulting from the combination of one mole-
cular proportion of the tetrazo derivatives of diamines, or substituted diamines, with
two molecular proportions of the above named "amines or substituted amines
(including peri amido naphthol sulpho acids); the resulting intermediate products
can be again diazotised, and then combined with two molecular proportions of peri
amido naphthol sulpho acids (employing the same, or two different ones), or, in any
order, with one molecular proportion of a peri amido naphthol sulpho acid, and one
molecular proportion of another dye stuff component.
-
The colouring matters which result from the last named process will be termed
"tetrakisazo 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
being by weight.

page_text: DYE STUFF FROM ONE MOLECULAR PROPORTION of TETRAZODIPHENYL
CHLORIDE, TWO MOLECULAR PROPORTIONS OF ALPHA
DELTA MONOSULPHO ACID, AND TWO
PROPORTIONS OF PERIMIDO NAPHTHOL DISULPHO ACID.
NAPHTHOLETHER
AMIDO-BETA-
MOLECULAR
18.4 parts of benzidine are converted in the known manner, by means of 14 parts
of sodium nitrite into the tetrazo chloride, and the resulting solution of tetrazo
diphenyl chloride is allowed to flow into a weak acetic acid or alkaline solution
of 53-4 parts of alpha amido beta naphthol ether delta mono sulpho acid.
The
liquid mixture is heated, at 50 degrees, for 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
hydrochloric acid. The thus formed complete tetrazo chloride is filtered off, after
about 24 hours, and introduced into a solution, in water, of 72.6 parts of the peri
amido naphthol-disulphonate of sodium, and about 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 composition, viz. :—
\OC₂H
It yields, on unmordanted cotton, bluish-black shades.
\So¸Na.
The other tetrakisazo dye stuff's result in a manner analogous to that described
in the last example, if, on the one hand, the amido naphthol disulpho acid
employed is replaced by the corresponding quantities of other periamido naphthol
sulpho acids, or if (in any order) one molecular proportion of the one, and one
molecular proportion of another, periamido-naphthol sulpho acid are used, or if
equal molecular proportions of a peri amidonaphthol sulpho acid and another dye
stuff component are employed, or it, on the other hand, in place of the amido-
naphthol ether sulpho acids used as middle components generally, two molecular
proportions of an amine or substituted amine," or a periamido naphthol sulpho
acid, are used (employing the same or two different ones), or if the benzidine is
replaced by other diamines or substituted diamines.
B

page_text: On coupling the peri-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 said peri amido
naphthol sulpho acids in acid solution, in general, produce redder shades.
According to the further researches of my foreign correspondents, direct-dyeing
valuable dye stuffs are obtained by combining with the above named peri-amido
naphthol sulpho acids, the diazo products of those amido azo compounds which
result on combining the diazotised thio condensation products from paratoluidine,
meta xylidine, pseudo cumidine, or the diazo compounds of the sulpho acids of
these thio bases with the above named "amines or substituted amines," including
periamido naphthol sulpho acids.
My foreign correspondents also obtain valuable products by combining the
diazo derivatives of the said thio products with peri amido naphthol sulpho acids,
diazotising again the so-formed amidoazo products, and coupling the diazo
compounds thus obtained with the known dye-stuff components.
By "thio condensation products, or thio amido compounds," my foreign
correspondents mean, for instance, the following substances, viz. :-Dehydro thio-
para-toluidine (melting at 191 degrees centigrade, and obtainable by heating para
toluidine with sulphur), dehydro thio-meta-xylidine, and dehydrothio pseudo cumidine
(obtainable in an analogous manner from meta xylidine and pseudo cumidine),
primuline base, which is formed together with dehydro-thio-para toluidine, on heating
para toluidine with sulphur, and can be employed either in raw or in isolated state.
However, other thio amido products (such as the technically known "chromine,"
"polychromine," "thio chromogene, or the like) also can 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 peri amido naphthol sulpho acids), diazotising the resulting
amido azo products, and combining the thus-formed diazo derivatives either with
peri 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 derivatives thereof, in the
Specification of application for Letters Patent No. 11533º.
My foreign correspondents have also found that the above mentioned peri-amido
naphthol sulpho acids can be employed advantageously for the production of new
disazo colouring matters, suitable for dyeing wool a black, in acid baths. These
disazo dye-stuffs result by combining the diazo derivatives of amines, amidophenols,
amido phenolethers, amido azo products of the benzene or naphthalene series, of
substitution products thereof (especially sulpho or carboxylic acids, including the
above periamidonaphtholsulpho acids, with "amines or substituted amines," or peri-
amido naphthol sulpho acids, by further diazotising the resulting amidoazo
products, and coupling the thus-obtained diazo compounds either with periamido
naphthol 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 peri amido naphthol sulpho acids), com-
bining these diazo derivatives with "amines or substituted amines or likewise peri
amido naphthol sulpho acids, rediazotising the so-formed amido azo products, and
coupling the resulting diazo compounds, either with peri amido sulpho acids or the
known dye-stuff components.
Of course, amido mono alkyl aniline, amido dialkyl aniline, the mono acetyl
derivatives of para phenylene diamine or naphthylene 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.
If mono acetyl derivatives of diamines or substituted diamines are used, mono
acetylised 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

page_text: mono nitro amines), nitro disazo colouring matters are formed which subsequently
are converted into the amido disazo dye stuffs by suitable treatment with reducing
agents.
My foreign correspondents have now found that the above named -periamido
naphthol 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 phenol ethers, amido azo products of the
benzene or naphthaline series, sulpho carboxylic acids thereof (including the new
periamido naphthol sulpho acids) with the said periamido naphthol sulpho acids or
other dye-stuff components.
In the production of such simple azo dye-stuffs, amido mono-alkylaniline, amido
dialkylaniline, or analogous amines or substituted amines, can be employed as first
components. If the diazo compounds of mono acetyl phenylene diamine, mono
acetyl naphthylene diamine, or analogous mono-acetyl diamines or substitution
products (for instance, sulpho acids of such nono acetyl diamines) are coupled with
the above named peri amido naphthol sulpho acids, mono acetylised azo products
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 or substituted 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 red, violet, to blue.
The process is illustrated by the following example. The parts are by weight.
COLOURING-MATTER FROM
DIAZO
BENZENE AND PERI AMIDO NAPHTHOL
DISULPHO ACID (OBTAINABLE. AS DESCRIBED IN THE FOREGOING SECOND
EXAMPLE).
The solution of diazo benzene chloride obtained in hydrochloric solution from
02 parts of aniline by means of 7 parts of sodium nitrite, is allowed to flow into an
icy-cuid solution of 36-3 parts of the peri amido naphthol disulphouate of sodium,
which is previously rendered alkaline by means of sodium carbonate. The
formation of the dye-stuff, which begins immediately, is complete in about
24 hours.
The dye-stuff is isolated in the usual manner by salting out, filtering off, pressing,
and dreing
It nossesses the formula
and produces on wool, in acid baths, bluish-red shades.
If the combination of diazo
benzene and the amido naphthol disulpho acid, is effected in moderately acid
solution (for instance, in a weak acetic solution), a dye-stuff results which yields
somewhat yellowish shades.
The other dye-stuffs result in an analogous manner, if, on the one hand, diazo
benzene is replaced by the diazo products of other amines, or amido phenols, amido
phenolethers, amido compounds of the benzene or naphthlene series, sulpho or
carboxylic acids thereof (including the new peri amido naphthol sulpho acids), and if

page_text: these diazo products are combined with the said periamido-naphthol disulpho acid
(in alkaline or acid solution), or if, on the other hand, the latter acid is replaced by
other of the above mentioned peri amido naphthol-sulpho acids or other suitable
dye-stuff components.
Of course, the diazo compounds derived from mono acetyl diamines (such as mono
acetyl phenylene diamine, mono-acetyl naphthylene diamine, and the like) from
mononitro amines (such as nitro aniline, nitro naphthylamine and the like), or from
the analogues and homologues and substitution products thereof (such as sulpho
acids), can be used for the production of such simple dye-stuffs. Diamines
alkylated in the one amido group (such as mono-alkyl phenylene diamine, dialkyl
phenylene diamine), and the analogues, homologues, or substitution products
thereof, likewise can be used as first components.
Valuable mono-azo dye-stuffs capable of dyeing unmordanted cotton have further
been prepared by my foreign correspondents, by combining the diazo products of
the above named thio condensation products, or sulpho derivatives thereof (such as
dehydro thio para toluidine, and the like), with the new peri amido naphthol sulpho
acids in alkaline or acid solution.
The process for producing these cotton dye-stuffs is effected in the well known
manner.
My foreign correspondents have described in the examples two to seven, some
distinct methods by means of which the respective dye-stuffs can be obtained, but
they do not limit themselves to the directions given in the said examples, as these
can be varied, and all those methods can be employed which are in use for the
production of analogous colouring-matters.
Dated this 7th day of March 1893.
NEWTON & SON,
Agents for the Applicants.
COMPLETE SPECIFICATION.
The Manufacture and Production of Sulpho Acids of the Naphthalene
Series, and of Colouring Matters Obtainable therefrom.
I, HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Brings,
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:-
The researches of Schultz, Erdmann, Bernthsen, Nietzki, etc., have made known
a new series of naphthalene derivatives, viz., the so-called "sultones," which are
inner anhydrides of naphthol-sulphonic acids.
Only one of the corresponding inner anhydrides derivable from the amido
naphthalene sulphonic acids has been hitherto produced. It was prepared by
Bernthsen (Berichte der Deutschen Chemischen Gesellschaft, volume 23, page 3094),
by a wearisome process, by heating the coloring matter from diazotised xylidine and
epsilon naphthol sulphamidosulphonic acid, with a dilute solution of sodium
carbonate, and subsequently reducing the dye-stuff thus formed. This author
assumes that the resulting acid is an inner anhydride of an ortho-naphthylene
diaminedisulphonic acid, possessing the following composition:

page_text: My foreign correspondents have discovered a simple method of producing such
inner anhydrides from amidonaphthalene sulphonic acids. They term these inner
anhydrides of amidonaphthalenesulphonic acids "naphthasultamesulphonic acids."
This new process consists in heating such naphthylamine sulpho acids as contain
the amido group and one sulphonic group relatively in peri position, with fuming
sulphuric acid. In some cases, a sulphonic group also enters the molecule at the
same time that "naphthasultame sulphonic acids" are thus produced.
The following perinaphthylamine sulphonic acids can be used, viz., alpha,
naphthylamine alpha, monosulphonic acid, and alpha, naphthylamine alpha, alpha,
disulphonic acid (both described in the German Patent No. 40571), alpha, naphthyl-
amine alpha, alpha, disulphonic acid, alpha, naphthylamine beta, alpha, disulphonic
acid (described in the German Patent No. 45776), and alpha, naphthylamine beta,
beta, alpha, trisulphonic acid.
The following example illustrates the method of converting peri naphthylamine
sulphonic acids into the corresponding naphthasultame sulphonic acids, the parts
PRODUCTION OF NAPHTHASULTAME DISULPHONIC ACID FROM ALPHA
NAPHTHYLAMINE ALPHA, ALPHA DISULPHONIC ACID.
300 parts of the acid sodium salt of alpha, naphthylamine alpha, alpha
disulphonic acid are gradually stirred into 600 parts of fuming sulphuric acid
(containing 40 per cent. of anhydride), and the solution is heated at from 80 to
90 degrees centigrade. After a time, it solidifies as a white mass. Heating is
continued until a test portion diluted with water fails to yield a diazo compound, or
to form a dye-stuff with diazo benzene sulphonic acid. As soon as the action is
complete, the mixture is introduced into ice water, and neutralised with lime. The
separated gypsum is filtered off, and the resulting filtrate evaporated.
In case it is desired to produce the sodium salt, the solution of the calcium salt
is mixed with a solution of sodium carbonate, and the filtrate from the calcium
carbonate is evaporated to dryness. On adding alcohol to the hot concentrated
solution of the sodium salt, this salt separates almost entirely, on cooling the liquid,
in the form of brilliant yellow plates containing water of crystallisation. It can be
easily recrystallised from diluted alcohol.
My foreign correspondents have found that, when dried at 160 degrees centi-
grade, this sodium salt has the composition corresponding with the formula :

page_text: The naphthasultame disulphonic acid (termed "alpha, alpha, naphthasultame
disulphonic acid S") obtainable as described in the foregoing first example, is also
formed from the aforesaid alpha, naphthylamine alpha, nonosulphonic acid, when
this is acted on with fuming sulphuric acid. Analogous products may be formed
from alpha, naphthylamine alpha, alpha, disulphonic acid, alpha, naphthylamine
beta, alpha, disulphonic acid, and alpha, naphthylamine beta, beta, alpha, trisul-
phonic acid in a similar manner by means of fuming sulphuric acid. Alpha
naphthylamine beta, beta, alpha, trisulphonic acid is converted into alpha, alpha
naphthasultame beta, beta, disulphonic acid,-whilst alpha, naphthylamine alpha,
alpha disulphonic acid, and alpha, naphthylamine beta, alpha, disulphonic acid
yield acids which my foreign correspondents term respectively alpha, alpha, naphtha-
sultame disulphonic acid D, and alpha, alpha, naphthasultame disulphonic acid E.
The salts of the said naphthasultame disulphonic acids are not acted on in
an acid solution by nitrous acid. Although the above mentioned alpha, alpha
naphthasultame disulphonic acid S does not yield a coloring matter when brought
into contact with diazo benzene sulphonic acid, the other naphthasultame disulphonic
acids above referred to combine in alkaline solution with diazo benzene sulphonic
acid, forming dye-stuffs.
The basic trisodium salts of these naphthasultame disulphonic acids are of a
yellow color, and readily dissolve in water, affording yellow solutions exhibiting a
green fluorescence. The alpha, alpha, naphthasultame disulphonic acid S is highly
fluorescent.
On adding muriatic acid to the concentrated solutions of these basic trisodium
salts in water, the disodium salts separate in the form of colorless needles, either at
once, or on adding common salt.
The naphthasultame sulphonic acids are distinguished by the manner in which
they withstand the action of alkalies. They are not altered on boiling them with
alkali-lye or caustic ammonia or diluted acids. The "saltame" nucleus, there-
fore, is more stable than the "sultone" nucleus, as the derivatives of naphthasultone
are, for the most part, converted into the corresponding naphthol sulphonic acids,
even by prolonged boiling with water, and at once on heating them with alkalies.
My foreign correspondents have described in the above first example a distinct
method of producing one of the so-called naphthasultame sulphonic acids, but they
do not limit themselves to the directions given, as these can be varied. For
instance, in place of the fuming sulphuric acid used in the above example, sulphuric
monochlorhydrine, or other agents acting in the same or a similar manner, can be
used with the like result.
The researches of my foreign correspondents have also shown, that when melted
with alkali, the above naphthasultame sulphonic acids, viz., the alpha, alpha
naphthasultame a B₁ disulphonic acid S, alpha, alpha, naphthasultame beta, beta,
disulphonic acid, and alpha, alpha, naphthasultame disulphonic acid D, are trans-
ormed into the corresponding amidonaphtholdisulphonic acids, viz., alpha, alpha,
amido naphthol a, ẞ, disulphonic acid S, alpha, alpha, amidonaphthol beta, beta,
disulphonic acid, and alpha, alpha, amidonaphthol disulphonic acid D.
The process for producing alpha, alpha, amidonaphthol disulphonic acid S
from the above naphtha sultame disulphonic acid S, is illustrated by the following
example, the parts being by weight.
'
CONVERSION OF THE ALPHA ALPHA NAPHTHASULTAME DISULPHONIC ACID S,
OBTAINABLE AS DESCRIBED IN THE FOREGOING FIRST EXAMPLE, INTO 5
ALPHA AMIDO ALPHA NAPHTHOL ALPHA, BETA, DISULPHONIC ACID.
1 part of the sodium salt of the alpha, alpha, naphthasultame disulphonic acid S
(obtainable as described in the above first example) is mixed with 2.5 parts of

page_text: potash or soda, and 0-2 of a part of water. The resulting mixture is heated in an
open vessel at 170 degrees centigrade, until, on testing a portion with a diazo
compound, no further increase in the amount of dye-stuff formed is observed. The
cooled melted mass is dissolved in water, and the solution is acidulated, for instance,
with muriatic acid. The new alpha, amido alpha, naphthol alpha, beta, disulphonic
acid then separates in the form of its sodium salt, which forms ball-like colorless
aggregates of needles. It may easily be purified be re-crystillisation from water,
and then forms fine needles.
It easily dissolves in water, and is converted by heating with dilute soda lye into
the alpha, alpha, dihydroxynaphthalene alpha, beta, disulphonate of sodium, which
has been obtained from alpha, naphthol alpha, alpha, disulphonic acid, by
sulphonating and subsequently fusing with alkalies, as described in the Specifi-
cation of the Letters Patent No. 3397, dated 4th March 1890. On adding ferric
chloride to the solution in water of the acid alpha, amido alpha, naphthol alpha,
beta, disulphonate of sodium, a beautiful dark green color is produced, whilst
chloride of lime produces a brownish-green color which becomes reddish brown and
clearer on the addition of an excess of chloride of lime.
If, instead of the alpha, alpha, naphthasultame disulphonic acid S used in the
above second example, alpha, alpha, naphthasultame beta, beta, disulphonic acid be
used, the known alpha, amido alpha, naphthol beta, beta, disulphonic acid is formed,
and, in like manner, the above mentioned alpha, alpha, naphthasultame disulphonic
acid D yields a new alpha, amido alpha, naphtholdisulphonic acid, which my foreign
correspondents term alpha, amido alpha, naphthol disulphonic acid D. The acid
sodium salt of this latter acid crystallizes in needles, and is less soluble in water
than the acid sodium salt of the above mentioned alpha, amido alpha, naphthol
alpha, beta, disulphonic acid. On adding ferric chloride to the solution in water of
the acid sodium salt of alpha, amido alpha, naphtholdisulphonic acid D, a green
colored liquid is obtained, which becomes dull after some time, whilst the watery
solution of the last named acid sodium salt assumes a reddish-brown color when
chloride of lime is added to it, an excess of chloride of lime rendering the liquid
almost colorless.
My foreign correspondents have further found that the said new amido naphthol-
sulphonic acids, viz. alpha, amido alpha, naphthol alpha, beta, disulphonic acid, and
alpha, amido alpha, naphthol disulphonic acid D, are eminently adapted for use in
producing azo dye-stuffs. My foreign correspondents, therefore, propose to employ
these two acids, which they briefly term "peri amido naphthol sulphonic acids,'
for the said purposes.
If the diazo derivatives of "benzidine, its analogues and homologues" are allowed
to act on these amidonaphthol sulphonic acids, valuable disazo coloring matters
are formed containing the azo group NN twice.
By "benzidine, its analogues and homologues," the following substances, for
example, are meant, viz. :-Benzidine, tolidine, diamidophenyltolyl, diamido-
diphenolether, diamidoalkylhydroxydiphenyl, diamidoalkylhydroxyphenyltolyl,
diamidoazobenzene, diamidoazotoluene, diamidoazoxylene, diamidoazoxybenzene,
diamidoazoxytoluene, diamidostilbene,diamidofluorene, diamidonaphthalene, diamido-
carbazole, diamidodiphenylene oxide, diamidoditoluylene oxide, para phenylene
diamine, paratoluylene diamine, benzidine sulphone, tolidine sulphone, diamido-
phenyltolyl sulphone, diamidodiphenoxy acetic acid, diamidodiphenylene ketoxine,
meta para diamidophenylbenzimidazole, amidobenzene azo alphanaphthylamine,
amidotoluene azo alpha naphthylamine, amidoxylene azo alpha naphthylamine,
amido benzene (amido toluene, amido-xylene) azo-para-xylidine, amido benzene
(amido toluene amido-xylene) azo meta or azo ortho amido para cresolether,
amidobenzene (amidotoluene amidoxylene-) azo-beta alkyloxyalpha naphthylamine,
the sulphonic or carboxylic acids thereof.
Similar diamines, or substitution derivatives thereof, which can be converted into
tetrazo salts, either directly, or by means of the monacetyl compounds, can also
be used. In place of the monacetylated diamines, the corresponding mononitramines

page_text: can be employed; in the latter case, the resulting nitrazo products must be reduced,
again diazotised, and combined with dye-stuff components, whilst on using mon-
acetylated diamines, the monacetyl amidoazo derivatives first produced must be
suitably treated, in order to separate the acetyl group, again diazotised, and
combined with the respective dye-stuff components, or the above named periamido
naphthol sulphonic acids.
The combination of the tetrazo salts of the above named diamines with the said
periamidonaphthol sulphonic acids, can be effected in an alkaline, or a moderately
acetic acid solution.
In order to illustrate this process, the following example is given, the parts being
COLORING MATTER FROM ONE MOLECULAR PROPORTION OF DIANISIDINE
AND TWO MOLECULAR PROPORTIONS OF ALPHA, AMIDO ALPHA NAPHTHOL
ALPHA BETA DISULPHONIC ACID, OBTAINABLE AS DESCRIBED
FOREGOING SECOND EXAMPLE.
IN
THE
34.2 parts of the sulphate of diamido diphenoldimethylether, or the equivalent
quantity of another dianisidine salt, are suspended in a state of minute subdivision
in 500 parts of water, mixed with 30 parts of muriatic acid (20 degrees Baumé),
and a solution of 13.8 parts of sodium nitrite in 150 parts of water, is stirred in.
The resulting solution of tetrazo diphenolether is allowed to flow into a solution
rendered alkaline by sodium carbonate, and containing 72-6 parts of the aforesaid
alpha, amido alpha, naphthol alpha, beta, disulphonate of sodium.
The formation of the dye stuff begins immediately, and is complete within a
short time. The coloring matter is salted out by means of common salt, filtered
off, pressed, and dried. On unmordanted cotton, it produces blue shades which
withstand alkalies. It possesses the following composition :-
--
Analogous colouring matters are produced in a manner similar to that described
in the foregoing last example, if, instead of the diamidodiphenolether used in the said 3
example, either the corresponding quantities of other diamidodiphenolethers, or the
equivalent quantity of another of the diamines above defined, or sulphonic or
carboxylic acids thereof, are used or if alpha, amido alpha, naphtholdisulphonic
acid D, is substituted for the alpha, amido alpha, naphthol alpha, beta, disulphonic
acid used in the same example.
Products are thus obtained which in general yieldj blue shades of great fastuess
in presence of alkalies.
3

page_text: My foreign correspondents have further found, that in place of combining two
molecular proportions of the above peri amidonaphtholsulphonic acids with one
molecular proportion of a tetrazo compound, the latter can be coupled with
one molecular proportion of a periamidonaphtholsulphonic acid, intermediate
products being thus formed which contain a diazo group, and which therefore are
capable of again interacting with a second molecular proportion of any dye stuff
component, such as a phenol, amine, diamine, amidophenol, amidophenolether of
the benzene or naphthalene series, a sulphonic or carboxylic acid thereof, including
the said two periamidonaphthol sulphonic acids.
The production of these intermediate compounds, and the conversion of the
latter into dye stuffs, consists essentially in combining one molecular proportion of
a tetrazo salt, either first with one inolecular proportion of either of the said two
periamido naphtholsulphonic acids (in alkaline or weak acetic acid solution), and
then with one molecular proportion of a phenol, an amine, and the like (including
the above two peri amidonaphthol sulphonic acids and other amidonaphthol-
sulphonic acids), or, inversely, first with one molecular proportion of a phenol, an
amine, and the like (including the periamidonaphtholsulphonic acids and other
amidonaphtholsulphonic acids), and then with one molecular proportion of the
above periamidonaphtholsulphonic acids (in alkaline or acid solution). Amines in
general are most conveniently coupled in acid solution, whilst phenols are combined
in alkaline solution. In order to illustrate the method of producing these mixed
dye stuffs, the following example is given. The parts are by weight.
ALPHA-
DYE-STUFF FROM EQUIMOLECULAR PROPORTIONS OF BENZIDINE,
NAPHTHOLALPHAMONOSULPHONIC ACID (14) AND ALPHA1 AMIDO
ALPHA NAPHTHOL ALPHA, BETA, DISULPHONIC ACID.
184 parts of benzidine are converted, in the usual manner, into tetrazodiphenyl
chloride. The resulting solution (about 700 litres, if the parts are kilos. by weight)
is allowed to flow into a solution prepared by dissolving 24-6 parts of the sodium
salt of alphanaphtholalphamonosulphonic acid (14), and 30 parts of sodium
acetate, in 500 parts of water. The formation of the intermediate product begins
after a short time and is complete at the end of from 1 to 5 hours. It separates in
voluminous dark flakes. 36.3 parts of the sodium salt of alpha, amido alpha
naphthol alpha, beta, disulphonic acid, and 12 parts of calcined sodium carbonate,
are then added. The production of the dye-stuff proceeds slowly, and is
advantageously facilitated by heating. After 24 hours, the dye stuff is filtered off,
pressed, and dried. It produces blue shades on unmordanted cotton. The
following formula represents its composition
:-
-W
CH. NN-CH..
\SO₂Na
NH,
CH, NN – CH
-
OH
ASO Na

page_text: :
the last example, instead of benzidine, the equivalent quantity of its analogues or
homologues be used, or if, in place of alpha naphthol alpha monosulphonic
acid (14), the corresponding quantity of another dye-stuff component be used
(viz. a phenol, amine, diamine, amidophenol, amidophenolether of the benzene or
naphthalene series, a sulphonic or carboxylic acid thereof, including the above two
periamidonaphthol sulphonic acids and other amidonaphthol sulphonic acids), or if
alpha, amido alpha, naphthol disulphonic acid D be used in place of alpha, amido
alpha, naphthol alpha, beta, disulphonic acid.
The combination of the two components with the tetrazo compounds can be
effected in any order, and the aforesaid two peri-amidonaphthol sulphonic acids can
also be coupled in a moderately acid solution.
According to the researches of my foreign correspondents, the aforesaid two
periamidonaphtholsulphonic acids, viz.-alpha, amido alpha, naphthol alpha, beta
disulphonic acid, and alpha, amidoalpha, naphtholdisulphonic acid D, can be used
for producing valuable trisazo and tetrakis azo dye-stuffs. These coloring matters
are formed on combining the tetrazo compounds of "benzidine, its analogues and
homologues," first with one or two molecular proportions of an amine or substituted
amine," again diazotising the intermediate products, and coupling the products so
formed with two molecular proportions of one of these periamidonaphtholsulphonic
acids, or in any order-with one molecular proportion of the one and then with
one molecular proportion of the other of these periamidonaphthol sulphonic acids,
or with one molecular proportion of a periamidonaphtholsulphonic acid and one
molecular proportion of another dye-stuff component. My foreign correspondents
mean by the expression "amines or substituted amines," which can be used as
middle components, all those amido compounds which, when combined with diazo
products, yield amido azo derivatives which can be further diazotised, for instance,
paraxylidine orthamidoparacresolether, metamidoparacresolether, the analogues,
homologues, or substitution products thereof, alphanaphthylamine, amidonaphthols,
amidonaphthol ethers, alphanaphthylaminebetamonosulphonic acids (Clève's beta
and delta acid), amidonaphtholsulphonic acids (including the above mentioned
periamidonaphtholsulphonic acids), amido naphthol ether sulphonic acids, amido-
naphthoxy-acetic acids, amidonaphthoxy acetic sulphonic acids, and the like.
If the tetrazo derivatives of diamines are combined with one molecular propor-
tion of one of the said "amines or substituted amines," intermediate products are
formed containing a free diazo group, and which can be again diazotised, and
combined with two molecular proportions of the periamidonaphtholsulphonic acid,
or with one molecular proportion of the one, and one molecular proportion of the
other periamidonaphtholsulphonic acid, or with one molecular proportion of peri-
amidonaphtholsulphonic acid, 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 a dye stuff component, and then with one
molecular proportion of periamido naphtholsulphonic acid. Coloring matters are
formed in this manner which contain the azo group N = N - thrice, briefly termed
"trisazo dye-stuffs."
"
The manufacture of these "trisazo coloring matters is illustrated by the
following example. The parts are by weight.
COLORING MATTER FROM ONE MOLECULAR PROPORTION OF TETRAZODI-
PHENYLCHLORIDE, ONE MOLECULAR PROPORTION OF ALPHA NAPHTHYL- 5
AMINE BETA MONO SULPHONIC ACID (DELTA), AND TWO MOLECULAR
PROPORTIONS OF ALPHA1 AMIDOALPHA NAPHTHOL ALPHA2 BETA
DISULPHONIC ACID (OBTAINABLE AS DESCRIBED IN THE ABOVE SECOND
EXAMPLE).
The solution of tetrazo diphenyl-chloride obtained from 184 parts of benzidine, 5

page_text: or the equivalent quantity of a benzidine salt, is allowed to flow slowly into a cold
solution prepared by dissolving 24.5 parts of the sodium salt of Clève's alpha-
naphthylaminebetamonosulphonic acid (delta), and 50 parts of sodium acetate.
The intermediate product thus formed is represented by either the formula :-
and is isolated in the usual manner by salting ont, filtering off, pressing, and
drying. It produces bluish-black shades on unmordanted cotton in an alkaline
soap bath.
Analogous products are produced by substituting, in the last example, either
for the alpha, amido alpha, naphthol alpha, beta, disulphonic acid, the equivalent
quantity of the alpha, amido alpha-naphthol-disulpho acid D, or by using,
instead of the alphanaphthylamine betamonosulphonic acid (Clève's delta acid),
the corresponding quantity either of the isomeric beta acid, or of alphanaphthyl-
amine, amidonaphthol, amidonaphthol ether, amidonaphthol, sulphonic acid
(including the above mentioned peri amido naphthol sulphonic acids), amido-
naphthol ether sulphonic acid, amidonaphthoxyacetic acid, amidonaphthoxy-
acetic sulphonic acid, paraxylidine, orthoamidoparacresolether, metamidopara-
cresolether, i.e., the corresponding quantities of the amines or substituted amines
hereinbefore defined.
"
The amidonaphthol sulphonic acids (including the aforesaid two periamido
naphtholsulphonic acids) which may be used as middle or last components, can be
combined in alkaline or weak acetic acid solution.
The diazotised intermediate products can naturally be combined (in any order),

page_text: first with. one molecular proportion of the one of the peri amidonaphtholsulphonic
acids, and then, with one molecular proportion of the other of the periamidonaphthol
sulphonic acids, or with one molecular proportion of either periamidonaphthol
sulphonic acid, and one molecular proportion of another dye-stuff component.
The process can also be carried out in an analogous manner, if, in place of the
benzidine used in the above example, other diamines or substituted diamines are
taken. If the two new periamido naphtholsulpho acids are used as middle
components, the resulting intermediate products can be again diazotised, and
combined with two molecular proportions either of one or of two of the known
dye-stuff components. New coloring matters are thus produced.
The "trisazo coloring matters "thus obtainable mostly yield shades on unmor-
danted cotton varying from bluish-black to pure black.
Analogous products (which are also trisazo dye stuffs) are formed, if one
molecular proportion of a tetrazo compound be first combined with one molecular
proportion of a phenol, naphthol, dehydroxynaphthalene, a sulphonic or carboxylic
acid thereof, and the resulting intermediate product be then combined with one
molecular proportion of an "amine or substituted amine," including the above two
periamidonaphtholsulphonic acids, the product thus formed (after further diazo-
tising) being coupled with, one molecular proportion of a periamidonaphtholsulphonic
acid (in alkaline or acetic acid solution), or also, in case of the use of the two
periamido naphtholsulphonic acids, as middle components, with any other dye-stuff
component. Inversely, the tetrazo compounds can be combined first with one
molecular proportion of a periamidonaphtholsulphonic acid, and then with one mole-
cular proportion of an "amine or substituted amine," and the compounds thus
produced can be diazotised, and combined with the known dye-stuff components
(including the new periamido naphtholsulphonic acids). In the latter case, so called
"tetrakis azo dye stuffs' are obtained.
"
In order to produce other so-called "tetrakis azo coloring matters" by means of
the new periamidonaphtholsulphonic acids, as above described, my foreign corre-
spondents commence with the intermediate products formed by the combination of
one molecular proportion of the tetrazo derivative of "benzidine, its analogues or
homologues," with two molecular proportions of the above named "amines or
substituted amines" (including the two new peri amidouaphtholsulphonic acids);
the resulting intermediate products can be again diazotised, and then combined with
two molecular proportions of the two new periamidonaphthol sulphonic acids (using
either one or both of these two acids), or, in any order, with one molecular
proportion of a periamido naphtholsulphonic acid, and one molecular proportion of
another dye-stuff component.
If the two new periamidonaphtholsulphonic acids are used as middle components,
the resulting intermediate products can be again diazotised, and combined with two
molecular proportions of the known dye-stuff components (employing either one or
two different substances), new coloring matters being likewise thus obtained.
The coloring matters which are formed by the last named process, are termed
"tetrakisazo dye stuffs," as they contain the azo group (- NN-) four times.
The process for producing them is illustrated by the following example, the parts
being by weight.

page_text: betanaphtholetherbetamonosulphonic acid. The liquid mixture is heated at.
50 degrees during several days, and finally at 90 degrees centigrade during a. short
time. When the combination is effected in an 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
tetrazo chloride is filtered off after about 24 hours, and introduced into. a solution in
water of 72.6 parts of the peri amido naphtholdisulphonate of sodium, and about
25 parts of sodium carbonate. In order to complete the action, the mixture is finally-
heated, at about 90 degrees centigrade, during a short time, and the dye stuff is then
isolated by salting out, filtering. off, pressing, and drying.
Its composition is represented by the following formula::-
\OC₂H₂
SO,Na.
It produces green shades on unmordanted cotton. The other "tetrakis azo dye
stuffs are produced in a manner analogous to that described in the last example,
by using, on the one hand, instead of alpha, amido alpha naphthol alpha, beta
disulphonic acid, the corresponding quantity of alpha, amido alpha, naphthol
disulphonic acid D, or if (in any order) a molecular proportion of each of these
peri amido naphtholsulphonic acids be used, or if a molecular proportion of either of
these peri amido naphtholsulphonic acids and of another dye stuff compound be
taken, or if, on the other hand, in place of the amidobetanaphtholetherbetasulphonic
acid used as middle component, generally two molecular proportions of an "amine
or substituted amine," or periamidonaphthol sulphonic acid, be used, using either
one or two different components, or if other diamines or substituted diamines be
used instead of benzidine.
If the two periamidonaphthol sulphonic acids are used as middle components, the
known dye-stuff components can be used as last components, new coloring matters
being likewise thus produced.
According to the further researches of my foreign correspondents, valuable
dye-stuffs, capable of dyeing directly, are obtained by combining with the above
named two periamidonaphtholsulphonic acids (viz., alpha, amido alpha, naphthol
alpha, beta, disulphonic acid, and alpha, amido alpha, naphtholdisulphonic acid D),
the diazo derivatives of those amido azo compounds which are formed on combining
the diazotised "thio condensation products, or thio amido compounds," obtainable
from para toluidine, metaxylidine, psendo cumidine, or the diazo compounds of the
sulphonic acids of these thio bases, with the before-named "amines or substituted
amines," including peri amido naphthol sulphonic acids. My foreign correspondents
have also obtained valuable dye-stuffs by combining the diazo derivatives of the
thio products with periamidonaphthol sulphonic acids, again diazotising the

page_text: resulting amidoazo products, and coupling the diazo compounds thus obtained with
the known dye-stuff components.
By "thio condensation products, or thio amido compounds," my foreign corre-
spondents mean, for instance, the following substances, viz.: dehydrothioparatoluidine
(melting at 191 degrees centigrade, and obtainable by heating paratoluidine with
sulphur), dehydrothio meta xylidine and dehydro thio pseudo cumidine (obtainable
in an analogous manner from metaxylidine and pseudo cumidine), primuline base,
which is formed together with dehydrothioparatoluidine on heating paratoluidine
But other
with sulphur, and can be used either in a raw or in an isolated state.
thio amido products (such as those known technically as "chromine," "poly-
chromine," "thiochromogene," or the like, can also be used.
These dye-stuffs are formed by coupling the diazo derivatives, of the said thio
amides, or sulphonic acids thereof, with one of the above named amines or
substituted amines (including the two new periamidonaphtholsulphonic acids),
rediazotising the resulting amido azo products, and combining the diazo derivatives
thus formed, either with one of the two new periamidonaphtholsulphonic acids, or
(in cases where these periamidonaphtholsulpho acids are used as middle components),
either with one of the said periamidonaphtholsulphonic acids, or with 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 similar coloring matters derived
from thio condensation products, or sulphonic derivatives thereof, in the Specification
of Letters Patent 11533º.
My foreign correspondents have also found, that the above mentioned two new
periamidonaphtholsulphonic acids can be advantageously used for the production of
new disazo coloring matters, which are mostly suitable for dyeing wool, a black in
acid baths. These disazo dye-stuffs are formed by combining one molecular pro-
portion of the diazo derivatives of amines, amido phenols, amidophenolethers, amido
azo products of the benzene or naphthalene series, of substitution products thereof
(especially sulphonic or carboxylic acids), including the above two new periamido
naphtholsulphonic acids) with one molecular proportion of an "amine or substituted
amine" (again including the above two new peri amido naphthol sulphonic acids),
by further diazotising the resulting amido azo products, and coupling the diazo
compounds thus obtained with one molecular proportion either of one of the above
two periamidonaphthol sulphonic acids, or of another dye-stuff component.
These disazo dye stuffs are obtained in the usual manner, viz., by diazotising one
molecular proportion of aniline, toluidine, or the like (including the two new
periamido naphthol sulphonic acids), combining these diazo derivatives with one
molecular proportion of "an amine or substituted amine," (including also the above
two new periamidonaphthol sulphonic acids), rędiazotising the amido azo products
so formed, and coupling the resulting diazo compounds, either with one mole-
cular proportion of either of the above periamido naphtholsulphonic acids, or with
a molecular proportion of another dye-stuff component in case the said periamido-
naphthol disulphonic acids are used as first or middle components.
Amidomonalkylanilines, amidodialkylaniline, the monacetyl derivatives of para-
phenylenediamine or naphthylene diamine or similar diamines, or the sulpho
derivatives of these products, can also be used as first components in producing the
last-named disazo dye stuffs adapted for dyeing wool in acid baths. If monacetyl
derivatives of diamines or substituted diamines are used, monacetylated disazo dye-
stuffs are formed, which require to be finally treated in a suitable manner in order
to separate the acetyl group. On using, as first components, mononitramines (such
as nitraniline, nitronaphthylamine, or the like, or sulphonic acids of mono-
nitramines), nitrodisazo coloring matters are formed which are subsequently
converted into the amidodisazo dye stuffs by a suitable treatment with reducing
agents.
My foreign correspondents have also found that the above named periamido-
naphthol sulphonic acids can be used for producing azo dye-stuffs capable of dyeing

page_text: wool in acid baths. These coloring matters are formed by combining the diazo
compounds of amines, amidophenols, amidophenolethers, amidoazo products of the
benzene or naphthalene series, sulphonic or carboxylic acids thereof (including the
new periamidonaphthol disulphonic acids) with the new periamido naphtholsulphonic
acids, or with any other dye-stuff component, in cases in which the new periamido-
naphtholdisulphonic acids are used as first components.
In producing these azo dye stuffs, amidomonalkylanilines, amidodialkylanilines,
or analogous amines or substitution derivatives thereof can be used as first
components. If the diazo compounds of monacetyl phenylenediamine, monacetyl-
naphthylene diamine, or analogous monacetyl diamines or substitution products
thereof (for instance, sulphonic acids of such monacetyl diamines), are coupled with
the above defined periamidonaphtholsulphonic acids, monacetylated azo products are
formed which can be converted into the corresponding amido azo dye stuff's by
separating the acetyl group. On using the diazo derivatives of mononitramines, or
substituted mononitramines of the benzene or naphthalene series, or sulphonic
acids thereof, nitrazo coloring matters are obtained which are converted into
the corresponding amidoazo dye stuffs by a subsequent treatment with reducing
agents.
The production of these azo dye stuffs, which are 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 process is illustrated by the following example. The parts are by weight.
COLORING MATTER FROM DIAZOBENZENE CHLORIDE AND ALPHA₁ AMIDO
ALPHA NAPHTHOL ALPHA, BETA, DISULPHONIC ACID.
The solution of diazo benzene chloride obtained from 9.3 parts of aniline, by
means of 7 parts of sodium nitrite, is allowed to flow into an ice-cold solution of
36.3 parts of alpha, amido alpha, naphthol alpha, beta, disulphonate of sodium,
previously rendered alkaline by means of sodium carbonate. The formation of
the dye-stuff begins immediately, and is complete in about 24 hours.
The dye stuff is isolated in the usual manner by salting out, filtering off, pressing,
and drying. It is represented by the formula
and produces bluish-red shades on wool in acid baths.
The other dye stuffs are formed in an analogous manner if, on the one hand, the
diazo products of other amines, or amido-phenols, amidophenolethers, amido azo
compounds of the benzene or naphthalene series, sulphonic or carboxylic acids
thereof, are used in place of diazo benzene, and if these diazo products are
combined with the said alpha, amido alpha, naphthol alpha, beta, disulphonic acid
(in alkaline or acetic acid solution), or if, on the other hand, alpha, amido alpha
naphtholdisulphonic acid D be used instead of the latter acid.
Similar dye-stuffs are formed if one molecular proportion of the diazo derivatives
of the new periamidonaphtholsulphonic acids be combined with one molecular
proportion of a dyestuff component.
The diazo compounds derived from monacetyl diamines (such as monacetyl
phenylene diamine, monacetylnaphthylene diamine, and the like) from mono-
nitramines (such as nitraniline, nitronaphthylamine, and the like), or from the

page_text: analogues and homologues and substitution products thereof (such as sulphonic
acids), can, as a matter of course be used in producing such azo dye stuffs.
Diamines in which only one amido group is alkylated (such as monalkylphenylene
diamine, dialkylphenylene diamine), and the analogues, homologues, or substitution
products thereof, can also be used as first components. In this case, the aforesaid
two periamidonaphthol sulphonic acids are used as last components.
Mono azo dye stuffs capable of dyeing unmordanted cotton, have further been
prepared by my foreign correspondents, by combining one molecular proportion of
the above named thio condensation products, or thio amido compounds, on sulphonic
acids thereof (such as dehydrothioparatoluidine or the like), with one molecular
proportion of alpha-amido-alpha-naphthol-alpha, beta-disulphonic acid, alpha₁
amido alpha-naphtholdisulphonic acid D, or salts thereof, in alkaline or
moderately acetic acid solution. The process for producing these cotton dye stuffs
is effected in the well-known manner.
My foreign correspondents have described in the above Examples 3, 4, 5, 6, and 7,
several distinct methods by means of which the respective dye-stuffs can be
obtained, but they do not limit themselves to the directions given in the said
examples, as these can be varied, and all the usual methods of producing analogous
coloring matters are available for the purpose.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me
'from abroad, I declare that I do not claim the process for producing a, a naphtha
sultame disulphonic acid S by treating a₁ naphthylamine a, a, disulphonic acid with
fuming sulphuric acid or the like and for producing amido a naphthol a₂ B₁
disulphonic acid therefrom, nor do I claim the products obtained thereby, but what
'I claim is :-
1. The production of naphthasultame sulphonic acids by treating such alpha-
naphthylamine sulphonic acids as contain the amido group and one sulphonic group
relatively in the so-called peri position (alpha, alpha), with fuming sulphuric acid,
or agents acting in a similar manner.
2. The process for producing alpha, alpha, naphthasultame disulphonic acid S,
by treating alpha, naphthylamine alpha, monosulphonic acid, or salts thereof, with
fuming sulphuric acid.
3. The process for producing alpha, alpha, naphthasultame beta, beta, disulphonic
acid, which process consists in treating alpha, naphthylamine beta, beta, alpha
trisulphonic acid, or salts thereof, with fuming sulphuric acid.
4. The process for producing alpha, alpha naphthasultame disulphonic acid D,
and alpha, alpha, naphthasultame disulphonic acid E, by treating respectively
alpha, naphthylamine alpha, alpha, disulphonic acid, and alpha, naphthylamine
beta, alpha, disulphonic acid, or salts thereof, with fuming sulphuric acid.
5. The conversion of alphar' alpha, naphthasultame sulphonic acids excepting
a a naphtha sultame disulphonic acid S, into alpha amido alpha, naphthol-
sulphonic acids, by heating the alpha, alpha, naphtha sultame sulphonic acids, or
salts thereof, with alkalies, at elevated temperatures.
6. The production of alpha, amido alpha naphthol beta, beta, disulphonic acid,
alpha, amido alpha, naphthol disulphonic acid D, or salts thereof, by heating
respectively alpha, alpha, naphthasultame beta, beta, disulphonic acid, alpha
alpha, naphthasultame disulphonic acid D, or salts thereof, with alkalies, at elevated
temperatures.
7. The production of disazo coloring matters from alpha, amido alpha, naphthol
alpha, beta, disulphonic acid, alpha, amido alpha, naphtboldisulphonic acid D,
or salts thereof, which process consists in combining one molecular proportion of
the tetrazo derivative of "benzidine, its analogues or homologues," either with two
molecular proportions of either of the said acids or salts thereof, or with one
molecular proportion of the one and one molecular proportion of the other acid
or salts thereof, or (in any order) with one molecular proportion of either of the

page_text: said acids or salts thereof, and one molecular proportion of an amine, a diamine, a
phenol, amidophenol, amidophenolether of the benzene or naphthalene series, a
sulphonic or carboxylic acid thereof.
8. The process for producing trisazo dye-stuffs by means of alpha₁ amido
alpha, naphthol alpha, beta, disulphonic acid, alpha, amido alpha naphthol
disulphonic acid D, or salts thereof, which process consists in combining one
molecular proportion of the tetrazo derivative of " benzidine, its analogues or
homologues," with one molecular proportion of an "amine or substituted amine,"
of the benzene or naphthalene series (which, when combined, forms a true amido
azo product which can be further diazotised), rediazotising the intermediate
products so formed, and coupling the resulting tetrazo compounds, either with
two molecular proportions of one of the said two periamidonaphtholdisulphonic
acids, or with one molecular proportion of each of these two periamidonaphthol
disulphonic acids, or (in any order) with one molecular proportion of either of
these periamidonaphthol disulphonic acids, and with one molecular proportion
of another dye-stuff component.
9. The production of trisazo coloring matters from alpha, amido alpha, naphthol
alpha, beta, disulphonic acid, alpha, amido alpha, naphthol disulphonic acid D,
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 these periamido naphthol disulphonic acids, rediazotising the intermediate
products so formed, and coupling the resulting tetrazo compounds either with
two molecular proportions of one of the said two periamidonaphtholdisulphonic
acids, or with one molecular proportion of the one and one molecular proportion
of the other of these two periamido naphthol disulphonic acids, or (in any order)
with one molecular proportion of one of these two periamido naphthol disulphonic
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).
"
10. The process for producing trisazo dye-stuffs from alpha, amido alpha,
naphthol alpha, beta, disulphonic acid, alpha, amido alpha, amido naphthol
disulphonic acid D, 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 a phenol, naphthol, dihydroxy-
naphthalene, a sulphonic or carboxylic acid thereof, and with one molecular
proportion of an "amine or substituted amine of the benzene or naphthalene
series (which, when combined, yields a true amido azo compound which can be
further diazotised), including the two peri amido naphtholdisulphonic acids,
rediazotising the mixed products so formed, and coupling the resulting diazo
compounds, either with one molecular proportion of one of the said periamido
naphtholdisulphonic acids, or (in case a periamido naphthol disulphonic acid
be used as middle component) with one molecular proportion of another dye-stuff
component.
11. The manufacture of tetrakis azo coloring matters from alpha, amido alpha
naphthol alpha, beta, disulphonic acid, alpha, amido alpha, naphtholdisulphonic
acid D, or salts thereof, by combining one molecular proportion of the tetrazo
derivatives of "benzidine, its analogues or homologues," with two molecular
proportions of an "amine or substituted amine" of the benzene or naphthalene
series (using either one or two different "amines or substituted amines, which,
when combined, vield true amido azo products 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 peri amido naphthol
disulphonic acids, or with one molecular proportion of each of these two peri
amido naphthol disulphonic acids, or (in any order) with one molecular proportion
of either of these periamido naphthol disulphonic acids, and with one molecular
proportion of another dye-stuff component.
12. The production of tetrakis azo dye stuffs from alpha, amido alphaд naphthol
D

page_text: alpha, beta, disulphonic acid, alpha, amido alpha, naphtholdisulphonic acid D, or
salts thereof, by combining one molecular proportion of the tetrazo derivatives of
benzidine, its analogues or homologues," either with two molecular proportions
of the said periamidonaphtholdisulphonic acids (using either one or both of these
acids), or (in any order) with one molecular proportion of either of these periamido-
naphtholdisulphonic acids, and one molecular proportion of an "amine or substituted
amine" of the benzene or naphthalene series (which, when combined, yield true
amidoazo products 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 periamidonaphthol disulphonic acids, or with one
molecular proportion of each of the two periamido naphtholdisulphonic acids, or
(in any order) with one molecular proportion of either of these periamidonaphthol-
disulphonic acids, and with one molecular proportion of another dye-stuff component,
or with two molecular proportions of other dye-stuff components (using either one
or two different components).
73
13. The process for producing disazo dye-stuffs from alpha, amido alpha, naphthol
alpha, beta, disulphonic acid, alpha, amido alpha, naphtholdisulphonic acid D, or
salts thereof, which process consists in coupling one molecular proportion of the
diazo derivatives of dehydro thio para toluidine, dehydro thio metaxylidine, dehydro-
thio pseudo cumidine, primuline base, or sulphonic acids of these or similar
thio amido compounds, with one molecular proportion of "amines or substituted
amines of the benzene or naphthalene series (which, when combined, yield true
amido azo compounds that can be further diazotised), or with one molecular
proportion of the said periamido naphthol disulphonic acids, rediazotising the
products so formed, and coupling the resulting diazo derivatives with one molecular
proportion of one of the said periamidonaphtholdisulphonic acids, or with one
molecular proportion of another dye-stuff component (in case the periamido-
naphtholdisulphonic acids are used as middle components).
14. The manufacture of disazo coloring matters from alpha, amido alpha
naphthol alpha, beta, disulphonic acid, alpha, amido alpha, naphtholdisulphonic
acid D, 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 periamido
naphtholdisulphonic acids), with one molecular proportion of "amines or substituted
amines of the benzene or naphthalene series (which, when combined, yield true
amidoazo products that can be further diazotised), or with one molecular proportion
of the said periamidonaphthol disulphonic acids, rediazotising the amido azo
products so formed, and coupling the resulting diazo derivatives with one molecular
proportion of the said peri amidonaphthol disulphonic acids, or with one molecular
proportion of the usual dye-stuff components (in case the periamidonaphthol-
disulphonic acids are used as first or second components).
15. The production of azo dye-stuffs 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 periamidonaphthol disulphonic acids), with
one molecular proportion of alpha, amido alpha-naphthol alpha, beta, disulphonic
acid, alpha, amido alpha, naphtholdisulphonic acid D, or salts thereof, or with one
molecular proportion of another dye-stuff component (in case the peri amido-
naphtholdisulphonic acids are used as first components).
16. The process for producing azo coloring matters, which process consists in
combining one molecular proportion of the diazo derivatives of dehydrothiopara
toluidine, dehydrothio meta xylidine, dehydro thio pseudo cumidine, primuline base,
the sulphonic acids of these or similar thio amido products, with one molecular
proportion of alpha, amido alpha, naphthol alpha, beta, disulphonic acid, alpha
amido alpha, naphtholdisulphonic acid D, or salts thereof.
17. As new products of manufacture, the new alpha, alpha, naphthasultame
disulphonic acids excepting a₁ a naphtha sultame disulphonic acid S, the new alpba,

page_text: amido alpha, naphtholdisulphonic acids, excepting a
amido a naphthol a, ẞ₁
disulphonic acid, and the new coloring matters produced by the processes herein-
before described, or by any other process affording the same result.
Dated this 6th day of December 1893.
NEWTON & SON,
Agents for the Applicant.