The Manufacture or Production of Colouring-matters and New Materials therefor.
Year: 1893

page_text: Date of Application, 18th Oct., 1893
Complete Specification Left, 18th July, 1894-Accepted, 18th Aug., 1894
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Colouring-matters and New
Materials therefor.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have described in the Application for Letters Patent
No. 8898, dated 3rd May 1893, that dialkylnaphthylene diamines, or sulpho acids
thereof, are obtained by heating naphthylamine sulpho acids (especially those which
contain one sulpho group in meta position to the amido group) with a primary
aromatic amine, in or without the presence of a salt of the amine employed, at
elevated temperatures, or by heating alkylnaphthylamine sulpho acids (containing
aromatic alkyl groups) with a primary aromatic amine, in or without the presence
of a salt of the amine employed at elevated temperatures. It is also stated in the
said Specification, that dialkylnaphthylene diamines, or dialkylnaphthlene diamine
sulpho acids, in which two different alkyl groups are substituted for two hydrogen
atoms in both amido groups, can be produced either by heating naphthylamine
sulpho acids with two different aromatic primary amines, in or without the presence
of salts of the respective amines, or by heating aromatic alkylnaphthylamine sulpho
acids with a primary aromatic amine, in or without the presence of a salt of the
respective amine, which differs from the amine employed for producing the said
alkylnaphthylamine sulpho acid.
Such alkylated amido naphthalene compounds also result according to
the Specification of my Application for Letters Patent No. 16780, dated
6th September 1893, if naphthol sulpho acids, amido naphthol sulpho acids, or
dihydroxynaphthalene sulpho acids, which contain at least one sulpho group in
meta position to an amido or hydroxylic group, are treated at elevated temperatures
with primary aromatic amines, in or without the presence of salts thereof.
The above processes can also be carried out, when naphthylene diamine sulpho
acids, especially those which contain one sulpho group in meta position to the
amido group, are employed. Naphthylene diamine sulpho acids, when treated with
primary aromatic amines, in or without the presence of salts thereof, yield trialkyl-
triamido naphthalene, tetra alkyltetraamido naphthalene, or the like or sulpho
derivatives of such or similar polyalkylpolyamido naphthalenes.
My foreign correspondents have now found, that in the processes above referred
to, in place of phenylnaphthylamine sulpho acids, tolylnaphthylamine sulpho acids,
or the like, alkylated naphthylamine sulpho acids, amido naphtholsulpho acids, or
naphthylene diamine sulpho acids, containing fatty radicles, or alkyl group, in the
amido group, can be used. The latter alkyl naphthylamine sulpho acids can be
produced, for instance, by heating naphthylamine sulpho acids, amido naphthol
sulpho acids, or naphthylene diamine sulpho acids, with alkylsulphuric salts,
alkylhaloids, or other alkylating agents, according to the process described in the
Specification of the German Patent No. 41506.
One method of producing the last named alkylnaphthylamine sulpho acids is
illustrated by the following example, the parts being by weight.

page_text: MANUFACTURE OF ETHYLPHENYL-a₁ ẞ, NAPHTHYLENE DIAMINE a SULPHO
ACID.
30 parts of the above-mentioned ethyl-a, naphthylamine-, a-disulpho acid are
mixed with 90 parts of aniline and 30 parts of aniline hydrochloride. The resulting
mixture is heated during from 5 to 6 hours, at from 160 to 170 degrees centigrade.
Sulphur dioxide is disengaged during this operation. The mass, when cool, is
poured into 90 parts of dilute muriatic acid, and the precipitated ethylphenyl-
a, B, naphthylene diamine-a-sulpho acid is filtered off. The latter can be purified
by boiling with alcohol. It forms a yellow powder. The sodium salt of the
ethylphenyl-a, ẞ, naphthylene diamine-a, sulpho acid easily dissolves in hot water,
and can be salted out, with readiness, by means of common salt.
The other alkylnaphthlamine sulpho acids (such as methyl-, ethyl-, amyl, benzyl
naphthylamine sulpho acids) can be converted into the corresponding dialkylated
products, in a manner analogous to that illustrated by the above Second Example.
The process also proceeds in a similar manner, if alkyl amido naphthol sulpho
acids, alkylnaphthylene diamine sulpho acids, or the like alkylated acids containing
alkyl groups of the fatty series (such as methyl, ethyl, amyl, including benzyl or
the like), are employed in the above Second Example, in place of ethyl-a, naphthyl-
amine ẞ2 a disulpho acid.
In order to produce these "mixed alkylated products," my foreign correspondents
do not limit themselves to the directions here given, as these can be varied. For
instance, the quantity of the amine, and of the salt thereof, and the temperature,
can vary within certain limits. The reaction can also be facilitated, in some cases,
by an addition of benzoic acid, or other agents facilitating the said process. If
alkylnaphthylamine monosulpho acids, alkyl amido naphthol monosulpho acids,
alkyl naphthylene diamine monosulpho acids (containing the sulpho group in meta
position to an amido group or hydroxylic group) be used in the process, as
illustrated by this Second Example," "mixed alkylated products" result, which are
destitute of sulpho groups and can, by a subsequent treatment with sulphonating
agents, be converted into sulpho derivatives soluble with greater readiness.
My foreign correspondents have found that the "mixed alkylated products"
above referred to, are capable of being employed for the production of dye stuffs.

page_text: The method of producing colouring matters derived from the said "mixed
alkylated products," in general, consists either in condensing the said "mixed
alkylated products" with nitroso compounds, or substances acting in a similar
manner (such as chlorimides, or the azo dye stuffs obtainable from diazo compounds,
and primary, secondary, or tertiary amines of the benzene or naphthalene series),
or in using, in place of the chlorimides or nitroso derivatives, the reduction
products thereof (such as para phenylene diamine toluylene diamine, paramido
dialkylaniline, or analogous diamines, or sulpho derivatives thereof, and in oxidizing
the latter reduction products, together with the above "mixed alkylated products,'
in the known manner. If, in these processes, products result, which are insoluble,
or dissolve with difficulty, these products are rendered more easily soluble by a
subsequent treatment with sulphonating agents.
The production of colouring matters derived from the above "mixed alkylated
products" is illustrated by the following two examples. The parts are by weight.
COLOURING MATTER FROM NITROSOETHYLBENZYLANILINE SULPHO ACID AND
ETHYLPHENYL-a1 B₂ NAPHTHYLENE DIAMINE а SULPHO ACID.
6-8 parts of ethylphenyl a ẞ, naphthylene diamine a sulpho acid are mixed
with 9-6 parts of nitrosoethylbenzylaniline sulpho acid and 2.7 parts of sodium
acetaté, and 20 parts of alcohol. The resulting mixture is heated, until the
nitroso compound no longer is distinguishable. The mass, when cool, is poured
into water. The liquid is then heated to boiling point, and the dye-stuff is
salted out.
DYE STUFF FROM PHENYL-AZO-PHENYL at NAPHTHYLAMINE a SULPHO ACID
AND ETHYLPHENYL a₁ ẞ₂ NAPHTHYLENE DIAMINE SULPHO ACID.
a
The
A mixture containing 6-8 parts of ethylphenyl-a, ẞ, naphthylene diamine a
sulpho acid, 12 parts of phenyl-azo-phenyl a naphthylamine a, sulpho acid, and
2.7 parts of sodium acetate, is dissolved in 40 parts of glacial acetic acid.
resulting solution is heated during 4 hours in a water bath. The mass is then
poured into hot water, and the colouring matter, which is slightly soluble, is
It is purified by redissolving in hot water with the addition of sodium
salted out.
carbonate.
It produces shades which are somewhat redder than those produced by the
analogous colouring matters from diphenyl naphthylene diamine sulpho acid
(α, ß, a₁).
The analogous colouring matters derived from the other "mixed alkylated.
products and nitroso compounds of secondary or tertiary aromatic amines, or
sulpho acids thereof, or substances acting in a similar manner (such as chlorimides
or azo dye stuffs), are produced in a manner analogous to that described in these
Third and Fourth Examples.
If the products thus obtained are only slightly soluble in water, they are
profitably treated with sulphonating agents (such as fuming sulphuric acid), in
order to convert them into dye-stuffs more easily soluble.
As above mentioned, in place of nitroso derivatives, such substances as act in a
similar manner, for instance, chlorimides, or amido azo dye stuffs of the benzene or
naphthalene series, can be employed for producing colouring matters from the
above "mixed alkylated products.
The researches of my foreign correspondents have also shown that the said basic
"amido azo dye-stuff's" can be replaced by azo products destitute of basic groups.

page_text: (such as amido- or alkylamido groups); for instance, by azobenzene, azoxybenzene,
hydrazobenzene, azonaphthalene, the homologues or analogues thereof.
It is noticeable, that the last defined azo products can be condensed not only
with the above "mixed alkylated products," but also with those polyalkyl
polyamido naphthalenes, and polyalkyl polyamido naphthalene sulpho acids, which
contain two or more equal alkyl groups.
The
If alkylated meta naphthalene diamines be employed, basic dye-stuffs result
which can, by sulphonation be converted into dye stuff sulpho acids.
colouring matters resulting from the alkylated naphthylene diamine sulpho acids
by heating them with the above azo products destitute of basic groups, are
likewise profitably converted into polysulpho acids by a subsequent treatment with
fuming sulphuric acid, or other reagents producing the same effect. The thus
formed dye-stuff sulpho acids produce on wool, in acid baths, shades ranging from
red to reddish-blue. The latter shades are different from those obtained by means
of the dye stuffs from amido azo compounds, as they come nearer to the red parts
of the spectrum.
The production of dye stuffs from azo products destitute of basic groups, is
illustrated by the following two examples :-
COLOURING MATTER FROM AZO BENZENE AND ETHYL PHENYL a₁ ẞ, NAPHTHY-
LENE DIAMINE-a SULPHO ACID.
6.8 parts of ethylphenyl a₁ 3, naphthylene diamines a sulpho acid, together with
5.46 parts of azo benzene and 1-36 parts of sodium acetate, are dissolved or
suspended in about 30 parts of glacial acetic acid. The mass is then heated at
from about 80 to 120 degrees centigrade, until the formation of the dye-stuff is
complete.
The colouring matter, isolated in the usual manner, can be used for dyeing,
after being previously treated with sulphonating agents.
DYE STUFF FROM DITOLYL-a₁ ẞ, NAPHTHYLENE DIAMINE a SULPHO ACID
AND AZO BENZENE.
A mixture containing 8.36 parts of ditolyl-a₁ ẞ, naphthylene diamine a sulpho
acid, 5-46 parts of azobenzene, 1.36 parts of sodium acetate, and 30 parts of glacial
acetic acid, is heated at from 80 to 100 degrees centigrade, until the liquid assumes
a red colour, and the latter no longer increases.
The monosulpho acid is obtained by pouring into water. It can be crystallised
from alcohol.
In order to convert this dye-stuff monosulpho acid into a soluble product, 1 part
thereof, and from 3 to 5 parts of fuming sulphuric acid (containing 25 per cent. of
anhydride), are heated at from 60 to 100 degrees centigrade, until a sample taken
out is soluble in hot water.
When this stage is arrived at, the mass is poured out ice water, the dye-stuff
polysulpho acid (soluble with difficulty) is filtered off, and, for the purpose of
purification, transformed into the ammonium salt.
The dye-stuff thus obtained produces on wool clear bluish-red shades, which are
superior to those produced by similar colouring matters, as they are extremely even,
and are more able to withstand the action of light.
Other dye-stuffs result in a manner analogous to that illustrated by the above
Fifth aud Sixth Examples, if, in place of azobenzene, other azo products destitute of
basic groups (such as amido or alkylamido groups) are used, or if the ethyl

page_text: phenyl a naphthylene diamine-a sulpho acid, or ditolyl-a-ß, naphthylene
diamine-a, sulpho acid, are replaced by analogous polyalkyl polyamido naphthalenes,
or sulpho derivatives thereof.
My foreign correspondents have described in the above examples three, four, five,
and six, some distinct methods of producing some dye-stuffs of the above defined
series. Naturally, they do not limit themselves to the directions given, as these
can be modified, without the nature of the present invention being altered by such
variations or modifications.
Dated this 18th day of October 1893.
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Colouring-matters and New
Materials therefor.
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:―
33
My foreign correspondents have described in the Specification of Letters Patent
No. 8898, dated 3rd May 1893, the manner in which dialkyl alpha, beta, naphthy-
lenediamines, or dialkylalpha, beta, naphthylenediamine sulphonic acids, are obtained
from alphanaphthylaminesulphonic acids, or alkaline salts of alphanaphthylamine
sulphonic acids containing a sulphonic group in the "meta" position relatively to
the amido group, by heating them with primary aromatic amines and a salt of the
amine used, at elevated temperatures, or from monoalkylalphanaphthylamine
sulphonic acids, or alkaline salts of monoalkylalphanaphthylamine sulphonic acids
containing a sulphonic group in the "meta position relatively to the alkylamido
group, by heating them with primary aromatic amines and a salt of the amine used,
at elevated temperatures, in either case adding benzoic acid, or other agents capable
of facilitating the action, if desirable. It is also stated in the said Specification,
that so-called mixed dialkylalpha, beta, naphthylenediamines, or dialkylalpha, beta,
naphthylenediamine sulphonic acids, containing two different aromatic alkyl groups,
one in each of the amido groups, can be produced from monoalkylnaphthylamine-
sulphonic acids, or alkaline salts of monoalkylnaphthylamine sulphonic acids con-
taining a sulphonic group in the "meta" position relatively to the amido group,
into which an aromatic a kyl group has been introduced, by heating them, at
elevated temperatures, with a primary aromatic amine, and a salt of the amine used,
the said amine being one which contains an aromatic radicle other than that con-
tained in the alkylamido group of the alkylnaphthylamine sulphonic acids used
initially, adding benzoic acid or other agents capable of facilitating the action, if
desirable.
Dialkyl alpha, beta, naphthylene diamines, and dialkyl alpha, beta, naphthylene-
diaminesulphonic acids, are also obtained, as desired, in the Specification of my
Application for Letters Patent No. 16,780, dated 6 September 1893 from naphthol-
sulphonic acids, or alkaline salts of naphtholsulphonic acids containing a sulphonic
group in the "meta" position relatively to the bydroxylic group, by heating them
at elevated temperatures with primary aromatic amines and a salt of the amine used,
adding benzoic acid or other agents capable of facilitating the action, if desirable.
My foreign correspondents have now found that in the processes described in the
Specification of the said Letters Patent No. 8898 of 1893, monoalkylnaphthylamine
sulphonic acids containing a fatty alkyl group in the amido group, and containing a

page_text: sulphonic group in the " meta "position relatively to the alkyl amido group, can be
used in place of phenylnaphthylamine sulphonic acids, tolylnaphthylaminesulphonic
acids, or the like aromatic alkylnaphthylaminesulphonic acids used in the last
named process. These alkylnaphthylaminesulphonic acids containing fatty alkyl
groups in the amido groups, cau be produced by heating naphthylamine sulphonic
acids in the presence of alkalies with alkylsulphuric salts, alkylhaloids, or the like
alkylating agents, for instance, by means of the process described in the Specifica-
tion of the German Patent No. 41,506.
One method of producing the said monoalkylnaphthylaminesulphonic acids
containing alkyl groups of the fatty series in the amido groups, and a sulphonic
group in the "meta" position relatively to the alkyl amido group, is illustrated by
the following example, the parts being by weight.
4
PRODUCTION OF ALPHA1 ETHYLNAPHTHYLAMINE BETA, ALPHA DISULPHONIC
ACID.
A mixture of 32 parts of alpha, naphthylamine beta, alpha, disulphonic acid,
25 parts of sodium ethylsulphate, 4-5 parts of soda, and 100 parts of water,
heated during from 6 to 8 hours at from 150 to 170 degrees centigrade in a closed
vessel capable of withstanding pressure. When cool, the mass is dissolved in hot
water, and the solution having been neutralised with sodium carbonate, is filtered,
and mixed with muriatic acid and a small quantity of common salt, which causes
the precipitation of the acid sodium salt of alpha, ethyl naphthylamine beta, alpha,
disulphonic acid. This acid sodium salt readily dissolves in hot water, separating
in colorless needles from concentrated solutions, as they cool.
The other alkylated naphthylamine sulphonic acids (such as methylnaphthyl
amine sulphonic acids, or ethylnaphthylamine sulphonic acids, or the like, or,
benzylnaphthylamine sulphonic acids, or the like) can be produced in a manner
similar to that illustrated by this Example A, if either in place of alpha, naphthyl-
amine beta, alpha, disulphonic acid, other naphthylaminesulphonic acids containing
a sulphonic group in the "meta
position relatively to the amido group are used,
or if other alkylsulphuric salts or alkylhaloids, such as methylsulphuric salts,
methylhaloids, ethylhaloids, or the like, benzylhaloids, or the like, are used in place
of the ethylsulphuric salt used in the foregoing Example A.
""
In the following Example B, my foreign correspondents describe a method of
converting the said alkylnaphthylamine sulphonic acids into alpha, beta2 dialkyl-
naphthylenediamines, or alpha, beta, dialkylnaphthylenediaminesulphonic acids;
the parts are by weight.
MANUFACTURE OF ALPHA1 BETA, ETHYLPHENYLNAPHTHYLENEDIAMINE
ALPHA SULPHONIC ACID.
30 parts of the above mentioned alpha, ethylnaphthylamine beta, alpha, disul-
phonic acid, are mixed with 90 parts of aniline and 30 parts of aniline hydrochloride,
and the mixture is heated during from 5 to 6 hours at from 160 to 170 degrees
centigrade. Sulphur dioxide is disengaged during this operation. When cool, the
mass is poured into 90 parts of dilute muriatic acid, and the precipitated alpha,
beta-ethylphenylnaphthylenediamine alpha sulphonic acid is filtered off. It can
be purified by boiling with alcohol.
The other above-defined alkylnaphthylamine sulphonic acids (such as methyl-,
ethyl-, benzyl-naphthylamine sulphonic acids, or the like) can be converted into the
corresponding alpha, beta, dialkylnaphthylene diamines, or alpha, beta, dialkyl-
naphthylenediaminesulphonic acids, in a manner analogous to that illustrated by

page_text: the above Example B. If, for instance, the corresponding quantities of ortho-
toluidine and orthotoluidine hydrochloride are used in place of the aniline and
aniline hydrochloride used in the foregoing Example B, alpha, beta, ethyl-ortho-
tolyl-naphthylenediamine alpha, mono sulphonic acid is obtained.
The alpha, beta, dialkyl naphthylene diamines, and alpha, beta, dialkyl naphthy-
lenediamine sulphonic acids thus produced, contain a fatty alkyl-group in the one,
and an aromatic alkyl group in the other amido group, and they are hereinafter
termed "mixed alpha beta, dialkyl naphthylenediamines and sulphonic acids
thereof."
In order to produce these "mixed alpha₁ beta, dialkylnaphthylenediamines
and sulphonic acids thereof," my foreign correspondents do not limit themselves to
the directions here given, as these can be varied. For instance, the quantity of
the amine and of the salt of the amine used, and the temperature, can vary within
certain limits. The action can also be facilitated, in some cases, by an addition of
benzoic acid or other agents facilitating the said alkylating action.
"
If alkylnaphthylamine mono-sulphonic acids (containing a sulphonic group in
the "meta
position relatively to the alkylamido group) be used in the process, as
illustrated by this Example B, mixed alpha, beta, dialkyl naphthylene diamines are
formed which do not contain sulphonic groups. According to the researches of my
foreign correspondents, these mixed alpha, beta, dialkylnaphthylene diamines can
be converted by subsequent treatment with sulphonating agents, into sulphonic
derivatives, that is to say, into the corresponding "mixed alpha, beta, dialkyl
naphthylene diamine sulphonic acids."
My foreign correspondents have found that the "mixed alpha, beta, dialkyl
naphthalene diamines and sulphonic acids thereof" above referred to, may be used
for the production of dye-stuffs.
The method of producing these dye-stuffs, in general, consists either in condensing
the said "mixed alpha, "beta, dialkyl alpha, beta, naphthylene diamines, or
sulphonic acids thereof," with nitroso compounds of secondary or tertiary aromatic
amines, or with substances acting in a similar manner (such as quinone dichlorimide,
or azo compounds such as are obtainable by coupling diazo derivatives with primary,
secondary, or tertiary amines, or substituted amines), particularly sulphonic acids
thereof, amidophenols, or amidophenolethers, or in using, in place of the nitroso
derivatives above referred to, the corresponding amido compounds containing the
amido group in place of the nitroso group (such as paramidomonalkylaniline,
paramido dialkylaniline, or analogous diamines or sulphonic derivatives thereof,
containing either one or two radicles in one of the amido groups), and in oxidising
the last defined amido compounds, together with the "mixed alpha, beta, dialkyl-
naphthylene diamines, or sulphonic acids thereof," above referred to, in a suitable
manner. If the products of these processes are insoluble, or dissolve with difficulty,
such are profitably rendered more soluble by a subsequent treatment with
sulphonating agents.
This production of coloring matters from the "mixed alpha, beta, dialkyl-
naphthylenediamines, or sulphonic acids thereof," is illustrated by the following
two examples. The parts are by weight.
COLORING MATTER FROM
AND ALPHA1 BETA2
SULPHONIC ACID.
SULPHONIC ACID
NITROSOETHYLBENZYLANILINE
ETHYLPHENYLNAPHTHYLENE DIAMINE ALPHA
A mixture containing 6-8 parts of alpha, beta, ethylphenylnaphthylene diamine
alpha sulphonic acid, 9-6 parts of nitrosoethylbenzylanilinesulphonic acid, 2.7
parts of sodium acetate, and 20 parts of alcohol, is heated until the nitroso

page_text: compound is no longer to be distinguished. When cool, the mass is poured into
water. The liquid is then heated to the boiling point, and the dye stuff is
salted out.
DYE
STUFF FROM PHENYLAZOPHENYLALPHA₁ NAPHTHYLAMINE ALPHA
SULPHONIC ACID AND ALPHA1 BETA, ETHYLPHENYL NAPHTHYLENE-
DIAMINE ALPHA SULPHONIC ACID.
A mixture of 6.8 parts of alpha, beta, ethylphenylnaphthylene diamine alpha.
sulphonic acid, 12 parts of phenylazo phenylalpha, naphthylamine alpha, sulphonic
acid, and 2-7 parts of sodium acetate, is dissolved in 40 parts of glacial acetic acid.
The solution is heated during 4 hours on a water bath. The mass is then poured
into hot water, and the coloring matter, which is slightly soluble, is salted out.
It is purified by redissolving it in hot water, adding sodium carbonate.
The two coloring matters obtainable as described in the foregoing Examples C
and D, produce shades which are somewhat redder than those produced by the
analogous coloring matters from alpha, beta, diphenylnaphthylenediaminealpha
sulphonic acid.
The analogous coloring matters derived from the other "mixed alpha, beta,
dialkylnaphthylenediamines, or sulphonic acids thereof," and nitroso compounds of
secondary or tertiary aromatic amines, or amidosulphonic acids, or substances
acting in a similar manner (such as quinone chlorimide or azo compounds),
are produced in a manner analogous to that described in these Examples C and D.
If the products thus obtained are only slightly soluble in water, they are
profitably treated with sulphonating agents (such as fuming sulphuric acid), in
order to convert them into more soluble dye-stuffs.
As above mentioned, in place of nitroso derivatives, substances which act in a
similar manner, for instance, quinone chlorimide, or amido azo compounds of the
benzene or naphthalene series, obtained from diazo-products, and primary secondary
or tertiary amines, or substituted amines, can be used in producing coloring matters,
from the "mixed alpha, beta, dialkyl naphthylene diamines, or sulphonic acids
thereof."
The researches of my foreign correspondents have also shown, that instead of
the last named basic "amido azo compounds," azo products destitute of basic
groups (such as amido or alkylamido groups) can be used, for instance, azobenzene,
bydrazobenzene, azonaphthalene, the homologues or analogues thereof.
It is noticeable that the last mentioned azo products without basic groups, can
be condensed not only with the "mixed alpha, beta, dialkylnaphthylenediamines,
or sulphonic acids thereof," hereinbefore referred to, but also with the symmetrical
and mixed alpha, beta, dialkylnaphthylenediamines, or sulphonic acids thereof,
obtainable as described in the Specification of Letters Patent No. 8898, dated
3rd May 1893, and in the Specification of Application for Letters Patent No. 16780,
dated 6th September 1893.
If alpha beta, dialkylnaphthylene diamines be employed, basic dye-stuffs are
formed which can be converted by sulphonation into dye-stuff sulphonic acids.
The coloring matters which are obtained from alpha, beta, dialkylnaphthylene
diamine sulphonic acids, by heating them with the above mentioned azo products
without basic groups, are also profitably converted into polysulphonic acids by a
subsequent treatment with fuming sulphuric acid, or other agents producing the
same effect. The dye-stuff sulphonic acids thus formed, produce shades ranging
from red to reddish-blue on wool in acid baths. The latter shades differ from
those obtained by means of the dye-stuffs from amido azo compounds, as they come
nearer to the red part of the spectrum.
The production of dye-stuffs from azo products without basic groups, is
illustrated by the following two examples.

page_text: COLOURING-MATTER FROM AZOBENZENE AND ALPHA BETA, ETHYLPHENYL
NAPHTHYLENE DIAMINE ALPHA MONOSULPHONIC ACID.
A mixture containing 6.8 parts of alpha beta, ethyl phenyl-naphthylene-
diamine-alpha, monosulphonic acid, 5.46 parts of azobenzene, and 1.36 parts of
sodium acetate, dissolved or suspended in about 30 parts of glacial acetic acid, is
heated at from about 80 to 120 degrees centigrade, until the formation of the dye-
stuff is completed.
The colouring-matter separates, on cooling. It is profitably sulphonated, in
order to render it more fit for dyeing purposes.
DYE-STUFF PRODUCED FROM ALPHA₁ BETA2 DIPARATOLYL NAPHTHYLENE-
DIAMINE-ALPHA-SULPHONIC ACID AND AZOBENZENE.
A mixture containing 8.36 parts of alpha, beta, diparatolyl naphthylene
diamine-alpha4-monosulphonic acid, 5.46 parts of azobenzene, 1-36 parts of sodium
acetate, and 30 parts of glacial acetic acid, is heated at from 80 to 110 degrees
centigrade, until the liquid assumes a red colour, and the colour no longer increases
in intensity.
The product, which is a monosulphonic acid, is separated by pouring into water.
It can be crystallised from alcohol.
In order to convert this monosulphonic acid into a soluble dye-stuff, 1 part
thereof, and from 3 to 5 parts of fuming sulphuric acid (containing 25 per cent. of
anhydride), are heated at from 60 to 100 degrees centigrade, until a sample is
found to be soluble in hot water. When this stage is arrived at, the mass is
poured into ice water.; the product thus obtained, which is a difficultly soluble
polysulphonic acid, is filtered off, and, for the purpose of purification, is converted
into the ammonium salt, which is the finished colouring-matter.
This dye-stuff produces, on wool, clear bluish-red shades which are superior to
those produced by similar colouring-matters, as they produce shades which are
more even, and withstand in a higher degree the action of light.
Other dye-stuffs are formed in a manner analogous to that illustrated by the
foregoing Examples E and F, if, in place of azobenzene, equivalent quantities of
other azo products without basic groups (such as amido- or alkylamido groups) are
used, or if, instead of alpha, beta, ethylphenyl naphthylene diamine-alpha- mono-
sulphonic acid, or alpha, beta, ditolyl naphthylene diamine alpha-monosulphonic
acid, the corresponding quantities of other mixed or symmetrical alpha, beta,
dialkyl naphthylene diamines, or sulphonic acids thereof, are used.
My foreign correspondents have described in the preceding Examples C, D, E,
and F, several distinct methods of producing dye-stuffs of the above-defined series.
Naturally, they do not limit themselves to the directions given, as these can be
modified, and all the methods can be used which are known or in use for analogous
purposes, the nature of the present invention being unaltered by such variations or
modifications. For instance, other solvents or diluents can be used, and the
processes can be carried out at higher temperatures. According to the researches
of my foreign correspondents, a difference caused by the use of certain solvents or
diluents, only becomes apparent when condensing the above-defined azo products
with the alpha, beta, dialkyl naphthylene diamines, or alpha, beta, dialkyl
naphthylene diamine sulphonic acids, which can be used in the processes herein-
before referred to. On using neutral or basic solvents or diluents, or also on
B

page_text: effecting the change at temperatures above 100 degrees centigrade, dye-stuffs are
formed differing from those obtained, as the case may be, either by means of acid
solvents or diluents, or at less elevated temperatures. The difference thus
•
produced is similar to that which my foreign correspondents have fully described
in the Specification of Application for Letters Patent No. 11892, dated 6th June
1893.
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 what I claim is :--
1. The process for producing "mixed alpha, beta, dialkyl-naphthylene diamines, or
sulphonic acids thereof," in which a fatty alkyl group is substituted for a hydrogen
atom of the one amido group, and an aromatic alkyl group is substituted for a
hydrogen atom of the other amido group, which process consists in heating alkyl
naphthylamine monosulphonic acids or alkylnaphthylamine polysulphonic acids
containing a fatty alkyl group in the alkylamido group, and a sulphonic group in
the "meta "
position relatively to this alkylamido group, with primary aromatic
amines and a salt of the amine used, at elevated temperatures, adding benzoic acid
er other agents capable of facilitating the action, if desirable.
2. The production of "mixed alpha, beta, dialkyl-naphthylene diamine sulphonic
acids," by sulphonating the "mixed alpha, beta, dialkyl-naphthylene diamines,"
obtainable, by the process claimed in the foregoing claim, from alkylnaphthyl-
amine monosulphonic acids containing a fatty alkyl group in the amido group,
and the sulphonic group in the "meta" position relatively to the alkylamido
group.
3. The process for producing basic azine dye-stuffs, or sulphonic acids thereof,
which are more or less difficultly soluble, by the action of nitroso derivatives of
secondary or tertiary aromatic amines, or amidosulphonic acids, on the "mixed
alpha, beta, dialkyl-naphthylene-diamines, or sulphonic acids thereof," obtainable
by means of the processes claimed in the foregoing Claims one and two.
1
4. The production of basic azine dye-stuffs, or sulphonic acids thereof, which
are more or less difficultly soluble, by allowing the "mixed alpha, beta, dialkyl-
naphthylene-diamines, or sulphonic acids thereof," obtainable by means of the
processes claimed in the foregoing Claims one and two, to act in the presence of
acid, neutral, or basic solvents, at more or less elevated temperatures, on quinone
dichlorimide, or on amidoazo- or alkylamidoazo compounds produced by the
combination of diazo compounds with primary, secondary, or tertiary amines of the
benzene or naphthalene series, or amidophenols or amidophenolethers.
5. The process for producing basic azine dye-stuffs, or sulphonic acids thereof,
which are more or less difficultly soluble, which process consists in subjecting the
"mixed alpha, beta, dialkylnaphthylenediamines, or sulphonic acids thereof,"
obtainable as described in the foregoing Claims one and two, together with
alkylated paradiamines, or paradiamine sulphonic acids, containing, in one of their
amido groups, either one or two alkyl groups, to oxidation, conjointly in the
presence of suitable solvents or diluents.
6. The production of basic azine dye-stuffs, or sulphonic acids thereof, which are
more or less difficultly soluble, from the "mixed alpha, beta, dialkyl-naphthylene
diamines, or sulphonic acids thereof," obtainable as described in the foregoing Claims
one and two, or from the symmetrical and mixed alpha, beta, dialkyl-naphthylene
diamines, or sulphonic acids thereof, obtainable as described in the Specification of
Letters Patent No. 8898, dated 3rd May 1893, and in the Specification of
Application for Letters Patent No. 16780, dated 6th September 1893, which
process consists in condensing these alpha, beta, dialkyl-naphthylene-diamines, or
alpha, beta, dialkyl-naphthylene diamine sulphonic acids, in the presence of acid;
neutral or basic solvents or diluents, with azobenzene, hydrazobenzene, azo
naphthalene, or homologous or analogous azo products, without basic groups (such
as amido groups or alkylamido groups).

page_text: 17. The conversion of the difficultly soluble basic azine dye-stuffs, or sulphonic
acids thereof, obtainable as claimed in the foregoing Claims three, four, five,
and six, into more readily soluble acid dye-stuffs, by a treatment with sulphonating
agents.
8. As new products of manufacture:―
a.) The new mixed alpha, beta, dialkyl naph-
thylene diamines and alpha, beta, dialkyl-
naphthylene diamine-sulphonic acids; and
b.) The new colouring-matters
produced by the processes
herein before defined, or by
any other means affording
the same result.
Dated this 17th day of July 1894.
NEWTON & SON,
Agents for the Applicant.
NEWTON & SON,
Agents for the Applicant.