The Manufacture or Production of Colouring Matters and Materials therefor.
Year: 1893

page_text: Date of Application, 3rd May, 1893
Complete Specification Left, 5th Feb., 1894-Accepted, 10th Mar., 1894
TRUVIDIONAL DU MULTIQATION.
[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 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 Specification of Letters Patent
No. 7337A, dated 16th April 1892, that certain naphthylaminesulpho acids can, by
heating with aniline, paratoluidine, or orthotoluidine, in without the presence of a
salt of the respective amine, be converted into phenylnaphthylamine sulpho acids,
paratolylnaphthylamine sulpho acids, or orthotolylnaphthylamine sulpho acid, these
reactions being facilitated by an addition of benzoic acid.
My foreign correspondents have now found that in heating naphthylamine sulpho
acids (particularly such as contain an amido group and a sulpho group in meta
position,) with a primary amine, for instance, aniline, toluidine, xylidine, alpha-
naphthylamine, betanaphthylamine, or the like, in or without the presence of a salt
of the respective amine (with or without adding benzoic acid), not only an alkylation
of the amido groups, that is to say, the formation of phenylnaphthylamine sulpho
acid, tolylnaphthylamine sulpho acid, xylylnaphthylamine sulpho acid, and so on,
takes place, but that under certain conditions simultaneously a sulpho group,-in
particular that which is in meta position to the amido group, is eliminated, and
replaced by the alkylamido group ( NHR), dialkylnaphthylene diamines, or
dialkylnaphthylene diamine sulpho acids, being thus produced.
-
For instance, in employing alphanaphthylamine-epsilon-disulpho acid, the
conversion of this acid into diphenylnaphthylene diamine mono sulpho acid can be
illustrated by the following equation :
The transformation of naphthylamine sulpho acids (illustrated by the foregoing
equation) into dialkylnaphthylene diamines, or dialkylnaphthylene diaminesulpho
acids, proceeds with great facility when employing those naphthylamine sulpho
acids which contain a sulpho group in meta position to an amido group.
For instance, the a, naphthylamine-2-monosulpho acid (Clève's y-acid) belongs to
these acids, which contain an amido group in meta position to the sulpho group.
In heating the last named acid with para toluidine and para toluidine hydro.
chlorate at from 120 to 135 degrees centigrade, a tolylnaphthylamine sulpho acid
is first produced (as described in the aforesaid Letters Patent No. 7337A of 1892).
If the temperature be raised over 140 degrees centigrade during this operation,
sulphurous acid is disengaged, and ditolyl-a, ẞ, naphthylene diamine results.

page_text: CONVERSION OF α-NAPHTHYLAMINE-EPSILON-DISULPHO ACID INTO DIPHENYL-
NAPHTHYLENEDIAMINE SULPHO ACID.
A mixture containing 100 parts of a-naphthylamine-epsilon-disulpho acid,
300 parts of aniline, and 100 parts of aniline hydrochlorate, is heated at
temperatures from 150 to 170 degrees centigrade, say, for from about 8 to
10 hours, until the disengagement of sulphurous acid ceases. Alkali in excess is
then added to the resulting mixture, and after driving off the aniline by means of
steam, the alkaline solution is treated with a suitable acid.
The diphenylnaphthylene diamine sulpho acid separates in yellowish brown
flakes. It can be purified by converting into the lime salt, and decomposing the
latter by means of muriatic acid. The diphenyl a₁ ß, naphthylene diamine a mono
sulpho acid thus obtained, is soluble in water with difficulty.
α
If, in the preceding example, aniline and its hydrochlorate are replaced by the
corresponding quantities of ortho toluidine, paratoluidine, metaxylidine, alpha-
naphthylamine, or betanaphthylamine, or analogous amines of the benzene or
naphthalene series, and of the hydro chlorates of the respective amines, the corre-
sponding ditolyl-dixyl, dinaphthyl- naphthylene diamine sulpho acids, or analogues
thereof, result in a similar manner. The latter acids are in general similar to the
diphenyluaphthylene diamine sulpho acid obtainable as described in the above first
example.
Other dialkylnaphthylene diamine sulpho acids, or dialkylnaphthylene diamines,
result, if a-naphthylamine ß, ẞ, a-trisulpho acid, a-naphthylamine-ß-sulpho acid,
or other uaphthylamine sulpho acids, are heated with primary aromatic amines,
and the hydrochlorates thereof (with or without adding benzoic acid).
Of course, in place of the bydrochlorates of the amines, other salts thereof, for
instance, hydro bromic salts, sulphates, or the like, can be employed, without
materially altering the manner of working.
Naturally, dialkylnaphthylene diamines and dialkylnaphthylene-diamine sulpho
acids can also be produced from alkylnaphthylamine sulpho acids (obtainable as
described, for instance, in the aforesaid Letters Patent No. 7337 of 1892, or by
any other way), viz., by further heating them with an aromatic primary amine in
or without the presence of a salt thereof (with or without adding benzoic acid).
My foreign correspondents do not limit themselves, in the production of the above
defined dialkylnaphthylene diamines, or dialkylnaphthylene diamine sulpho acids,
to the particulars described in the foregoing example, as the latter can be varied.
For instance, the proportions employed of the different ingredients (in particular,
the amines & salts thereof) can vary within certain limits. The reaction can also
be effected without adding a salt of the amine employed. In an analogous manner
to that described in the aforesaid Letters Patent No. 7337A of 1892, the conversion
of the naphthylamine sulpho acids can be facilitated by adding benzoic acid to the
mixture before heating.
As, in the above process, monoalkylnaphthylamine sulpho acids are first
produced, and these products (in the further reaction) are converted into dialkyl-
naphthylene diamines or dialkylnaphthylene diamine sulpho acids (a sulpho group
being eliminated), my foreign correspondents also have succeeded in obtaining such
dialkylnaphthylene diamines or dialkylnaphthylene diamine sulpho acids as contain
two different alkyl radicles replacing an hydrogen atom of either of the two amido
groups.
For this purpose, the operation must be carried out in such a manner, that
(according to the process described in the aforesaid Letters Patent No. 7337A
of 1892) monoalkylnaphthylamine sulpho acids are first formed, which (either
after isolating or without isolating) are then converted into the correspond-

page_text: ing dialkyl naphthylene diamines, or dialkylnaphthylene diamine sulpho acids,
employing an amine other than that first used (with or without adding a salt
thereof). The a₁ naphthylamine-3,-monosulpho acid (Clève's gamma acid) can be
transformed into a₁-phenylnaphthylamine-3,-monosulpho acid, by means of aniline &
aniline salt (according to the process described in the aforesaid Letters Patent
No. 7337A of 1892), and the resulting product can, by further treatment with
paratoluidine and a salt thereof, he converted into a phenyl-3-paratolylnaph-
thylene diamine. Both processes can be combined, that is to say, the a-naphthyl-
amine-B-mono sulpho acid above referred to, can be converted directly into the
last nained phenyl para tolylnaphthylene diamine, by treating the former with
aniline & paratoluidine, with or without adding a salt of the two amines (in or
without the presence of benzoic acid or substances producing the same or similar
result).
My foreign correspondents have also found that the mono alkylnaphthylamine
sulpho acids (obtainable as described in the Specification of the said Letters
Patent No. 7337A of 1892, or by any other process) can be transformed into such
dialkylnaphthylene diamines, or dialkylnaphthylene diamine sulpho acids, as contain
two different alkyl radicles, replacing a hydrogen atom of either amido group,
ri, by treating the said alkylnaphthylamine sulpho acid with an amine and a salt
thereof other than those used for the production of the former.
In the Specifications of the British Letters Patents No. 14283 dated
5th November 1886, and No. 3098 dated 26th February 1890, basic dye stuffs
are described which are obtained from substituted naphthylene diamines and the
nitroso derivatives of secondary or tertiary aromatic amines. The substituted
naphthylene diamines employed in the last named two Patents contain both amido
groups as beta substituents of the naphthalene nucleus.
My foreign correspondents have now found that the above defined dialkyl-
naphthylene diamines and dialkylnaphthylene diamine sulpho acids (in particular,
those derived from a ẞ naphthylene diamines) can be easily condensed with the
nitroso derivatives of secondary or tertiary aromatic amines, to form blue coloring
matters which are superior in brightness and fastness to the dye stuffs described
in the last named two Letters Patent.
The condensation of the dialkylnaphthylene diamines with the nitroso deriva-
tives of secondary or tertiary aromatic amines, is best effected in the presence of
a suitable solvent or diluent, such as glacial acetic acid, alcohol, or the like, and
by applying heat.
The following example is given in order to illustrate the condensation of nitroso
derivatives with dialkylnaphthylene diamines, the parts being by weight :—
COLORING MATTER OBTAINED FROM NITROSO DIMETHYLANILINE
CHLORATE AND DITOLYLNAPHTHYLENE DIAMINE.
HYDRO-
6-7 parts of ditolyl naphthylene diamine (obtainable from a naphthylamine
3, mono sulpho acid, para toluidine, and para toluidine hydrochlorate) are dissolved
in 30 parts of alcohol. After adding 53 parts of nitroso dimethylaniline hydro-
chlorate, the mixture is heated by means of a water bath until the nitroso
compound is no longer distinguishable. The resulting mass is poured into water,
and the dye stuff is salted out. The latter can be purified by redissolving and
salting out again. It produces clear blue shades on cotton prepared with tannic
acid or the like.
Again, analogous dye stuffs result if, on the one hand, ditolylnaphthylene diamine
is replaced by homologous or analogous diamines, or if, on the other hand, the
nitroso dimethylaniline is replaced by other nitroso derivatives of secondary or
tertiary aromatic amines. The latter dye stuffs differ but a little from the product
obtained by the process described in the above second example.

page_text: These coloring matters produced by means of dialkyl naphthylene diamines can,
by a subsequent treatment with sulphonating agents (as my foreign correspondents
have found) be converted into valuable sulpho acids, which are in particular
adapted for dyeing wool in acid baths. The blue shades produced therewith
possess great power of resistance to the action of soaping or washing.
According to the researches of my foreign correspondents, sulpho acids of the
last named basic dye stuffs also can be obtained either by acting with nitroso com-
pounds of secondary or tertiary amines on sulpho acids of dialkyl naphthylene
diamines, or by allowing the nitroso derivatives of secondary or tertiary amido
sulpho acids to act on dialkylnaphthylene diamines, or dialkylnaphthylene diamine
sulpho acids.
a
These dialkylnaphthylene diamine sulpho acids can be obtained either by sul-
phonating dialkylnaphthylene diamines, or (according to the process hereinhefore
described) by heating naphthylamine sulpho acids (in particular, those which
contain a sulpho group in meta position to the amido group, for instance,
naphthylamine epsilon disulpho acid, a naphthylamine ß, ẞs a trisulpho acid)
with primary aromatic amines and salts thereof. In the latter reaction, not only
the hydrogen atom of the amido group contained in the naphthylamine sulpho
acid employed, is replaced by an alkyl radicle, but, whilst sulphur dioxide is
disengaged, a sulpho group (preferably that which is in meta position to the amido
group) is replaced by the group NHR, the other sulpho groups remaining
intact.
The process for producing these dye stuff sulpho acids, either by condensing
nitroso derivatives and alkylated naphthylene diamine sulpho acids, or by acting
with sulpho acids of nitroso compounds on alkylated naphthylene diamines, or
alkylated naphthylene diamine sulpho acids, is analogous to that described in the
above second example.
In order to illustrate this process, the following example is given, the parts being
DYE STUFF RESULTING FROM NITROSO DIETHYLANILINE HYDROCHLORATE AND
a1 B-DITOLYLNAPHTHYLENE DIAMINE-ẞ3 α-DISULPHO ACID.
6.3 parts of nitroso diethylaniline hydrochlorate are added to a solution prepared
by dissolving 10 parts of a B-ditolylnaphthylene diamine-ẞ, a-disulpho acid in
30 parts of alcohol containing 50 per cent. spirit. The resulting solution is boiled
until the nitroso compound is no longer distinguishable. The liquid is then cooled
by means of ice, and after neutralising with sodium carbonate, the formed dye stuff
is salted out. It forms needles with bronze-like lustre, which dissolve in hot water,
and produce on wool, shades fast against the action of alkalies.
If the nitroso diethylaniline is replaced by other nitroso compounds of secondary
or tertiary aromatic amines, or if, in place of a₁ ẞ, ditolyl naphthylene diamine
ẞ, a disulpho acid, analogues or homologues thereof are employed, the analogous
dye stuffs result in a similar manner. The coloring matters thus obtainable yield
blue shades on wool in acid baths.
COLORING MATTER FROM NITROSO ETHYLBENZYLANILINE SULPHO ACID AND
a 3-DITOLYLNAPHTHYLENE DIAMINE-a4 MONO SULPHO ACID.
8.4 parts of a ditolylnaphthylene diamine-a-mono sulpho acid, are mixed
with 30 parts of acetic acid (containing 50 per cent. of pure acetic acid). 9.8 parts
of nitroso ethylbenzylaniline sulpho acid are added. and the resulting mixture is
heated whilst raising the temperature to 100 degrees centigrade. As soon as the
yellow color of the nitroso compound is no longer distinguishable, sodium acetate
is added. The dye stuff then separates as a reddish brown powder. It is filtered

page_text: off and dried. It produces on wool, blue shades fast against the action of
fulling.
The nitrosoethylbenzylaniline sulpho acid employed in the above fourth example,
can be replaced by the corresponding quantity of nitrosomethylbenzylaniline sulpho
acid, nitrosomonobenzylaniline sulpho acid, nitrosodibenzylaniline disulpho acid,
nitrosodiphenylamine mono sulpho acid, or analogous nitroso sulpho acids. In
place of a Brditolylnaphthylene diamine-a-mono sulpho acid, the aforesaid
B-ditolylnaphthylene diamine-ẞ, a,-disulpho acid, or ditolylnaphthylene diamines,
or homologues or analogues of these components, can be used.
If coloring matters result which contain but one sulpho group, they can, by
treatment with sulphonating agents, be converted into polysulpho acids, which.
possess the advantage of being more readily soluble.
My foreign correspondents have described in the above Examples II., III.,
and IV., distinct methods for practically producing some of these new dye stuffs.
Naturally, they do not limit themselves to the particulars given in these examples,
for the methods of producing these coloring matters can be varied, and all those
ways can be employed which are in use for the manufacture of analogous or similar
dye stuffs.
Dad h
911 1002
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Colouring Matters and 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 :—
My foreign correspondents have set forth in the Specification of Letters Patent
No. 7337A, dated 16th April 1892, the manner in which, by heating certain
naphthylamine sulphonic acids with aniline, para toluidine, or orthotoluidine, in the
presence of a salt of the amine, or not, as may be desirable, such sulphonic acids
are converted into phenylnaphthylamine sulphonic acids, paratolylnaphthylamine
sulphonic acids, or orthotolylnaphthylamine sulphonic acid, as the case may be,
these interactions being facilitated by an addition of benzoic acid.
.
My foreign correspondents have now found that, on heating alphanaphthyl-
amine sulphonic acids containing the amido group and sulphonic group relatively
in the "meta" position, with a primary amine, for instance, aniline, paratoluidine,
orthotoluidine, or the like, either alone, or together with a salt of the amine used
(and adding benzoic acid, if desirable), not only is an alkylation of the amido
group effected, but that, under certain conditions, the sulphonic group in the meta
position relatively to the amido group, is simultaneously eliminated, and displaced
by the alkyl amido group (-NHR), dialkylmetanaphthylene diamines, or
dialkylmetanaphthylene diamine sulphonic acids, being thus produced.
Thus, for example, alphanaphthylamine-epsilon-disulphonic acid undergoes
conversion into diphenyl-naphthylenediaminemonosulphonic acid in the manner.
illustrated by the following equation:
OH NH,
8
·SO,H
+
(C HẠNH,
CH,NH,HCI
SO₂H NHCH,
(NH,HCI
+
SO₂
NHCH
H₂O.

page_text: The transformation of naphthylamine sulphonic acids (illustrated by the foregoing
equation) into symmetrically substituted dialkylnaphthylenediamines, or dialkyl-
naphthylenediamine sulphonic acids, proceeds with great facility, on using
naphthylamine sulphonic acids containing a sulphonic group in the "meta
position relatively to the amido group, whereas other naphthylamine sulphonic
acids which do not contain a sulphonic group and the amido group in the said
position, are not acted on by amines in the said manner.
For instance, alpha-naphthylamine-beta,-monosulphonic acid (Clève's y acid)
is one of the acids containing an amido group in the "meta" position relatively to
the sulphonic group, and on heating the said acid, for example, with paratoluidme
and paratoluidine hydrochloride, at from 120 to 135 degrees centigrade,
a paratolylnaphthylaminesulphonic acid is first produced, as described in the
Specification of the aforesaid Letters Patent No. 7337a of 1892. If, however,
the temperature be raised above 140 degrees centigrade during this operation, sulphur
dioxide is disengaged, diparatolyl-alpha, beta, naphthylenediamine being formed.
In order to illustrate this new process, the following example, is given in which
my foreign correspondents use, as initial material, the aforesaid alpha-naphthyl-
amine-epsilon-disulphonic acid containing a sulphonic group and the amido group
relatively in the "meta" position. The parts are by weight.
CONVERSION OF ALPHANAPHTHYLAMINE-EPSILON-DISULPHONIC ACID INTO
DIPHENYLNAPHTHYLENE-DIAMINE SULPHONIC ACID.
A mixture containing 100 parts of alphanaphthylamine-epsilon-disulphonic acid,
300 parts of aniline, and 100 parts of aniline hydrochloride, is heated at
temperatures from 150 to 170 degrees centigrade, during from about 3 to 6 hours,
until the disengagement of sulphur dioxide ceases. Alkali is then added in excess
to the resulting mixture, and, after drawing off the aniline by means of steam, the
alkaline solution is acidulated with muriatic acid. The diphenylnaphthylenediamine
sulphonic acid separates in yellowish-brown flakes. It can be purified by mixing
one part of the raw product with two parts of alcohol, and heating the mixture to
boiling. The diphenyl alpha, beta-naphthylenediamine alpha, sulphonic acid being
.almost insoluble in alcohol, remains in the alcoholic liquid as a yellow crystalline
powder. It is filtered off and washed with alcohol.
If, in the preceding example, instead of aniline and its hydrochloride,
corresponding quantities of paratoluidine and paratoluidine hydrochloride are
used, the corresponding diparatolyl-alpha, beta, naphthylenediamine alpha
monosulphonic acid is produced in an analogous manner. This acid is similar to
the diphenylnaphthylene diamine sulphonic acid obtainable as described in
the above first example. Diphenyl-alpha₁ beta-naphthylene-diamine alpha
monosulphonic acid and di-para-tolyl-alpha, beta-naphthylenediamine-alpha-
monosulphonic acid, are very difficultly soluble in hot water, and they are also
very difficultly soluble even in boiling alcohol, but are somewhat more soluble in
glacial acetic acid. They dissolve in alcohol and glacial acetic acid with com-
parative case, if sodium acetate is added.
The sodium salts of the last named two acids easily dissolve in hot water, but
are difficultly soluble in cold water, producing almost uncoloured solutions. The
addition of mineral acids to the hot solutions in water of the sodium salts of these
two acids, effects the precipitation of the acids in the form of a powder
exhibiting an intense yellow colour.
Other dialkylnaphthylenediaminesulphonic acids, or dialkylnaphthylenediamines,
are produced, if alpha, naphthylamine-beta, sulphonic acid, alpha, naphthylamine
beta, beta, disulphonic acid, alpha, naphthylamine beta, beta, disulpho acid,
alpha, naphthylamine beta, beta, alpha, trisulphonic acid, or other naph-
thylaminesulphonic acids containing a sulphonic group in the
" meta
"

page_text: position relatively to the amido group, are heated with primary aromatic amines, an
the hydrochlorides thereof (and, if desirable, adding benzoic acid or other agents.
capable of facilitating the action).
If
alpha-naphthylamine-beta-monosulphonic acid is heated with either aniline
or paratoluidine, and a salt of the amine used (adding benzoic acid, if desirable),
diphenylalpha, beta,-naphthylenediamine and dipara tolyl alpha, beta, naphthylene
diamine are formed, which are insoluble in water, but easily dissolve in alcohol.
On adding concentrated muriatic acid to the alcoholic solutions of these dialkyl-
meta-naphthylenediamines, viz., diphenyl alpha beta, naphthylenediamine and
di-para-tolyl-alpha beta,-naphthylene diamine, the hydro-chlorides of these
dialkylated dianines are separated in the form of needles or scales, exhibiting a
slight yellow colour, but these salts undergo decomposition into their components.
in the presence of water.
Alpha, naphthylamine-beta, beta,-disulphonic acid and alpha, naphthylamine
beta, beta, disulphonic acid, when heated with either aniline or paratoluidine, and a
salt of the amine (and benzoic acid, if desirable), in the above defined mauner, are
transformed into di-phenyl-alpha, beta-naphthylene diamine beta,-monosulphonic
acid, dipara-tolyl-alpha, beta,-naphthylene diamine-betas monosulphonic ncil,
diphenyl alpha beta-naphthylene diamine beta, monosulphonic acid, and
di-paratolyl-alpha, beta-naphthylene-diamine-beta, monosulphonic acid, respec-
tively. The last-named dialkylated naphthylene diamine sulphonic acids are
almost insoluble, even in hot water and alcohol. The sodium salts thereof easily
dissolve in water, but can be precipitated by adding common salt to the resulting
solutions. The sodium salts also dissolve with ease in alcohol, producing solutions
which shew au intense blue fluorescence. A characteristic difference between the
last named acids becomes apparent in the dyestuffs derived therefrom by the action
of nitroso compounds, inasmuch as the colouring matters obtainable from diphenyl
or di-para-tolyl-alpha, beta, naphthylene diamine-beta-monosulphonic acid,.
generally give shades more red in hue than those produced by the corresponding
dyestuffs obtained from diphenyl or di para tolyl-alpha, beta-naphthylene diamine-
beta-monosulphonic acid, and the shades produced by means of the dye-stuffs from
di-para-tolyl-alpha, beta-naphthylene diamine beta- or beta-sulphonic acid, are
somewhat greener than those produced by the corresponding dye-stuffs from.
diphenyl-alpha, beta-naphthylene diamine beta, sulphonic acid.
On heating alpha, naphthylamine beta, beta, alpha-trisulphonic acid with aniline
or para toluidine in the presence of a salt of the amine used (and benzoic acid, if
desirable), diphenyl-alpha, beta, naphthylene beta-alpha,-disulphonic acid, and
di-paratolyl alpha, beta, naphthylene diamine betas alpha disulphonic acid are
obtained, which dissolve in cold water with slight readiness, affording yellow
solutions, and which, speaking generally, possess the same properties as the afore-
said diphenyl- or dipara-tolyl alpha, beta, naphthylene diamine alpha, monosulphonic
acid, or diphenyl- or diparatolyl alpha, beta-naphthylene diamine beta, mono-
sulphonic acid.
In place of paratoluidine and para toluidine hydrochloride used as above.
mentioned, orthotoluidine and orthotoluidine hydrochloride can be used. Diortho-
tolyl-alpha, beta, naphthylenediamines and diorthotolyl alpha beta, naphthylene
diamine sulphonic acids are obtained in this manner, viz., on heating such alpha-
naphthylamine sulphonic acids as contain a sulphonic group in the "meta" position
relatively to the amido group, with orthotoluidine and orthotoluidine hydro-
chloride, at elevated temperatures (if desirable, adding benzoic acid or other
agents capable of facilitating the action). The resulting diorthotolyl alpha, beta
naphthylenediamines and diorthotolyl alpha beta, naphthylene diamine sulphonic
acids, in general are similar to the above defined diphenyl alpha beta, uaphthylene
diamine, diparatolyl alpha, beta, naphthylene diamine, and the corresponding
sulphonic acids derived therefrom.
The researches of my foreign correspondents have also shown, that dialkyl-
naphthylene diamines and dialkylnaphthylene diamine sulphonic acids, can be

page_text: "
produced from alkylnaphthylamine sulphonic acids (obtainable as described, for
instance, in the aforesaid Letters Patent No. 7337A of 1892, or by any other way),
which contain a sulphonic group in the "meta position relatively to the alkyl-
amido group, viz. by further heating them, either with an aromatic primary amine
alone, or together with a salt thereof (if desirable, adding benzoic acid or other
agents capable of facilitating the action).
:
My foreign correspondents do not limit themselves, in producing the above
defined dialkyl meta naphthylene diamines, or dialkyl meta naphthylene diamine
sulphonic acids, to the particulars described in the foregoing example, as the latter
can be varied. For instance, the proportions of the different ingredients (in
particular, the amines and salts thereof) can vary within certain limits. Instead of
the hydrochlorides of the primary aromatic amines, other salts of the said amines,
for instance, hydrobromides, sulphates, or the like, can be used without materially
altering the manner of working. The action can also, in some cases, be effected
without adding a salt of the amine used. The conversion of the naphthylamine
sulphonic acids can be facilitated by adding benzoic acid (or other agents capable
of facilitating the action) to the mixture before heating.
As above mentioned, monoalkyl naphthylamine sulphonic acids are first produced
in the process hereinbefore defined, and as the change proceeds, these products are
converted into the dialkyl alpha, beta, (or meta) naphthylene diamines or dialkyl
alpha, beta, (or meta) naphthylene diamine sulphonic acids, a sulphonic group
being eliminated. Owing to this fact, my foreign correspondents have also
succeeded in obtaining "mixed " dialkyl alpha, beta, (or meta) naphthylene diamines,
or dialkyl alpha beta, (or meta) naphthylene diamine sulphonic acids, in which two
different alkyl radicles are substituted for a hydrogen atom of each of the two
amido groups.
For this purpose, the operation must be carried out in such a manner, that (for
instance, according to the process described in the aforesaid Letters Patent
No. 7337A of 1892) monoalkylnaphthylamine sulphonic acids containing a sulphonic
group in the "meta" position relatively to the alkylamido group, are first formed,
which are either isolated or not, and are then converted into the corresponding
dialkyl alpha, beta, (or meta) naphthylene diamines, or dialkyl alpha, betas (or
meta) naphthylene diamine sulphonic acids, by using an amine other than that
first used, adding a salt thereof, if desirable. Alpha, naphthylamine beta, mono-
sulphonic acid, for instance, can be transformed into alpha, phenylnaphthylamine
beta, monosulphonic acid, by means of analine and an analine salt (according to
the process described in the aforesaid Letters Patent No. 7337A of 1892), and by
subsequently heating the product with para toluidine and a salt thereof, it can
be converted into alpha, plienyl beta, paratolyl naphthylene diamine.
My foreign correspondents have also found, that finished monoalkylnaphthyl-
amine sulphonic acids, containing a sulphonic group in the "meta" position relatively
to the alkyl amido group (obtainable as described in the Specification of the said
Letters Patent No. 7337A of 1892, or by any other process) can be at once trans-
formed into dialkylnaphthylene diamines, or dialkylnaphthylene diamine sulphonic
acids, in which two different alkyl radicles are substituted for a hydrogen atom of
each of the two amido groups, by heating the said alkylnaphthylamine sulphonic
acids with an amine and a salt thereof other than that used for the production of
the monoalkylic compound.
In the Specification of the British Patents No. 14283, dated 5th November
1886, and No. 3098 dated 26th February 1890, azine dye-stuffs are described which
are obtainable from certain substituted naphthylene diamines and nitroso derivatives
of secondary or tertiary aromatic amines. The substituted naphthylene diamines
used in the last named two Patents contain both amido groups as beta substituents
of the naphthalene "nucleus," and are so called "hetero nucleal" compounds. The
resulting coloring matters are termed "isorosindulines" by Fischer & Hepp.
My foreign correspondents have now found, that the above defined dialkylmeta-
naphthylene diamines and dialkyl metanaphthylene diamine sulphonic acids derived

page_text: from naphthylamine sulphonic acids containing a sulphonic group in the "meta"
position relatively to the amido group, and which, so far as the two alkylamido
groups are concerned, must be termed "homonucleal" compounds), can be easily
condensed with the nitroso derivatives of secondary or tertiary aromatic amines,
forming bluish violet coloring matters which are superior in brightness and fastness
to the dye-stuffs described in the Specifications of the last named two Letters
Patent. The dye-stuffs thus obtainable probably do not belong to the isorosin-
duline series, but are rosinduline coloring matters, as the researches of my foreign
correspondents have shown that the said dye-stuffs produced from them are not
salts of ammonium bases.
The condensation of the dialkylmetanaphthylene diamines with the nitroso
derivatives of secondary or tertiary aromatic amines, is best effected in the presence
of a suitable solvent or diluent, such as glacial acetic acid, alcohol, or the like, and
by applying heat.
The following example is given in order to illustrate the condensation of nitroso
derivatives with the above defined dialkyl meta naphthylene diamines, the parts
COLORING MATTER OBTAINED FROM NITROSO DIMETHYL ANILINE HYDRO-
CHLORIDE AND DI-PARA-TOLYL-ALPHA₁ BETA-NAPHTHYLENE DIAMINE.
6.7 parts of ditolyl naphthylene diamine (obtainable from alpha, naphthylamine
beta, monosulphonic acid, para toluidine, and para toluidine hydrochloride) are.
dissolved in 30 parts of alcohol. After adding 5.5 parts of nitrosodimethylaniline
hydrochloride, the mixture is heated by means of a water bath, until the nitroso
compound is no longer distinguishable. The resulting mass is poured into water,
and the dye-stuff is salted out. The latter can be purified by dissolving it and again
salting out. It produces clear bluish-violet shades on cotton prepared with tannic
acid or the like. Its composition is represented by the following formula :-
Again, analogous dye-stuffs are formed, if, on the one hand, instead of the ditolyl-
naphthylene diamine used in the above Example B, the corresponding quantities of
analogous dialkyl metanaphthylene diamines are taken, or if, on the other hand, the
nitrosodimethylaniline hydrochloride is replaced by the corresponding quantities of
the salts of other nitroso derivatives of secondary or tertiary aromatic amines. The
dye-stuffs thus obtainable differ but slightly, in their dyeing properties, from the
product prepared as described in the above Example B.
For instance, the coloring matters from diphenyl or di-para-tolyl alpha, beta,
naphthylene diamine and nitrosodimethyl aniline hydrochloride, or the dye-stuff*
prepared from di-para-tolyl alpha, beta, naphthylene diamine, and nitrosomono-
methylaniline hydrochloride, easily dissolve in hot water, particularly in the presence
of a small quantity of acetic acid. On adding ammonia or soda-lye to the solutions,
the bases are separated in the form of brown precipitates.
The researches of my foreign correspondents have shown that, by a subsequent
treatment with sulphonating agents, for instance, fuming sulphuric acid, the last-
named coloring matters, produced by means of dialkylnaphthylene-meta-diamines,
B

page_text: can be converted into valuable sulphonic acids, which are especially adapted for
dyeing ordinary wool in acid baths, and also for dyeing chromated wool. The
blue, or greenish-blue, shades produced therewith, powerfully resist soaping or
washing.
According to the further researches of my foreign correspondents, sulphonic acids
of the last named basic dye-stuffs containing the sulphonic groups in distinct
positions, can be obtained either by acting with nitroso compounds of secondary or
tertiary amines on the above sulphonic acids of dialkylnaphthylenemetadiamines, or
by allowing the nitroso derivatives of secondary or tertiary amido sulphonic acids
to act on dialkylnaphthylene meta-diamines, or dialkylnaphthylene metadiamine
sulphonic acids.
These dialkylnaphthylene diamine sulphonic acids can be obtained either by
sulphonating dialkylnaphthylene-meta-diamines, or (according to the process herein-
before described), for instance, by heating naphthylamine sulphuric acids containing
a sulphonic group in the meta position relatively to the amido group with primary
aromatic amines and salts thereof. In this latter action, as before mentioned, not
only is the hydrogen atom of the amido group contained in the naphthylamine
sulphonic acid displaced by an alkyl radicle, but sulphur dioxide is disengaged, and
a sulphonic group which is in the meta position, relatively to the amido group, is
also displaced by the group NHR, the other sulphonic groups remaining intact, as
'hereinbefore set forth.
The process for producing these dye-stuff sulphonic acids, either by condensing
nitroso derivatives and dialkyl meta naphthylene diamine sulphonic acids, or by
acting with sulphonic acids of nitroso compounds on dialkyl meta naphthylene
diamines or dialkyl meta naphthylene diamine sulphonic acids, is analogous to that
described in the above Example B.
In order to illustrate this process, the following example is given, the parts being
hy weight
DYE-STUFF
FORMED
FROM
AND DIPHENYL-ALPHA1
DISULPHONIC ACID.
NITROSO DIETHYL ANILINE HYDROCHLORIDE
BETA NAPHTHYLENE DIAMINE-BETAS ALPHA
10 parts of diphenyl alpha, beta, naphthylene (diamine-beta, alpha, disulphonic
acid, are dissolved in 30 parts of alcohol (containing 90 per cent. spirit). After
adding sodium acetate, 6-3 parts of nitroso-diethyl-aniline hydrochloride are
introduced into the liquid. The mixture so formed is then boiled until the nitroso
compound is no longer distinguishable. The liquid is then cooled by adding ice,
and is neutralized with sodium carbonate, and the dye-stuff is then salted out. It
forms needles exhibiting bronze-like lustre, which dissolve in hot water. On
ordinary wool, it produces violet-blue shades which withstand alkalies, whilst, when
dyed on wool mordanted with chromium salt, it yields blue shades. Its composition
is represented by the following formula :-
If, instead of nitroso diethylaniline other nitroso compounds of secondary
tertiary aromatic amines, or sulphonic acids thereof, are used, or if, in place of
diphenyl-alpha, beta, naphthylene diamine betas alpha, disulphonic acid, other

page_text: diphenyl alpha, beta naphthylene diamine sulphonic acids, or di-para-tolyl alpha1
beta, naphthylene diamine sulpbonic acid, or dí-ortho-tolyl-alpha beta, naphthylene
diamine sulphonic acids, are taken, analogous dye-stuffs are produced in a similar
manner. The colouring matters obtainable in this manner produce blue shades on
wool in acid baths.
The dye-stuffs from nitroso ethylbenzylaniline sulphonic acid and di-para-tolyl-
alpha, beta, naphthylenediamine beta, alpha, disulphonic acid, is distinguished by
being readily soluble. It yields shades manisfesting great stability on exposure to
light.
The colouring matter obtainable from nitroso ethylbenzyl aniline sulphonic acid,
and di-para-tolyl-alpha, beta, naphthylene diamine-beta, sulphonic acid, dyes wool
a violet-blue, the dye stuff prepared from nitroso ethyl benzyl aniline sulphonic
acid and diphenyl-alpha, beta, naphthylene diamine beta, sulphonic acid producing
violet shades on wool.
COLOURING MATTER FROM NITROSO ETHYL BENZYLANILINE SULPHONIC ACID
AND DI-PARA-TOLYL-ALPHA BETA, NAPHTHYLENE DIAMINE ALPHA
MONO SULPHONIC ACID.
8.4 parts of di-para-tolyl alpha beta, naphthylene diamine alpha, monosulphonic
acid, are mixed with 30 parts of alcohol (containing 90 per cent. of pure alcohol)
and 6 parts of sodium acetate. 9-8 parts of nitroso ethyl benzylaniline sulphonic
acid are added, and the resulting mixture is heated, the temperature being raised
to 100 degrees centigrade. As soon as the yellow colour of the nitroso compound
is no longer distinguishable, sodium carbonate is added, which causes the dye-stuff
to separate. It is filtered off and dried. It produces on wool blue shades which
withstand fulling and alkalies. Its composition is represented by the following
formula:
Instead of the nitrosoethylbenzylaniline sulphonic acid used in the above
Example D, the corresponding quantity of nitrosomethylbenzylaniline sulphonic
acid, nitroso monobenzylaniline sulphonic acid, nitroso dibenzylaniline disulphonic
acid, nitroso-diphenylaminemonosulphonic acid, or analogous nitroso sulphonic acids.
can be used. In place of di-para-tolyl-alpha, beta, naphthylene diamine alpha4
monosulphonic acid, the aforesaid di-para-tolyl-naphthylene alpha, beta, diamine-
beta, alpha, disulphonic acid, or di para tolyl alpha, beta, naphthylene diamine, or
the like, or di ortho tolyl alpha, beta, naphthylene diamine, diphenyl alpha, beta,
naphthylene diamine, or sulphonic acids thereof, can be used.
If colouring matters are formed containing but one sulphonic group, they can be
converted, by treatment with sulphonating agents, into poly sulphonic acids
possessing the advantage of being more readily soluble. This process of sulphona-
tion is illustrated by the following example. The parts are by weight :-

page_text: COLOURING
NITROSO DIMETHYLANILINE
MATTER OBTAINED BY SULPHONATING THE PRODUCT FROM
HYDROCHLORIDE AND DI PARA TOLYL
ALPHA BETA, NAPHTHYLENE DIAMINE-ALPHA MONO SULPHONIC ACID.
8 parts of the dye stuff obtainable from nitroso dimethylaniline hydrochloride
and di para tolyl alpha, beta, naphthylene diamine alpha monosulphonic acid, are
introduced into 40 parts of fuming sulphuric acid (containing 25 per cent. of
sulphuric anhydride), the temperature being kept at from 0 to 10 degrees centi-
grade. The mass is stirred at this temperature until the precipitate obtained, on
pouring a portion of the sulphonated mass into water, and subsequently filtering off,
easily dissolves in boiling water. At this stage, the whole sulphonated mass is
poured onto four times its weight of ice, and after boiling the acid liquid, the dye-
stuff sulphonic acid, which is almost insoluble in dilute acids, is filtered off. In
order to purify this dye stuff sulphonic acid, it is neutralized by means of soda lye,
or solution of sodium carbonate, or ammonia solution; the liquid is then heated to
boiling, and the dye-stuff is precipitated by salting out.
The above defined colouring matters, in case they are difficultly soluble in water,
or the basic dye-stuffs destitute of sulphonic groups, are sulphonated in a manner
analogous to that described in the foregoing Example E.
The salts of dye stuff sulphonic acids thus obtainable, for instance, from the
products obtained on condensing nitrosodimethyl aniline, nitrosodiethylaniline, or
nitrosodiphenylamine, with di para tolyl alpha, beta, naphthylene diamine alpha.
monosulphonic acid, are violet paste-like masses easily soluble in hot water,
difficultly soluble in cold water, and produce on ordinary wool, in acid baths, from
bluish to bluish violet shades, whilst the shades produced therewith on chromated
wool, are somewhat more greenish.
The sulphonation can also be effected by means of sulphuric chlorhydrin, or
concentrated sulphuric acid, in place of fuming sulphuric acid. If concentrated
sulphuric acid is used as sulphonating agent, a somewhat higher temperature is
requisite to complete the action.
My foreign correspondents have described in the above Examples B. C. D.
and E, distinct methods of practically producing some of the new dye-stuffs herein-
before defined. Naturally, they do not limit themselves to the particulars given in
these examples, as the methods of producing these colouring matters can be varied,
and all methods can be employed which are known and in use for the manufacture
of analogous or similar dye-stuffs.
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, 1 declare that what I claim is :-
groups,
"
1. The production of dialkyl alpha, beta, naphthylene diamines, on dialkyl
alpha, beta, naphthylene diamine sulphonic acids, in which an aromatic alkyl group
is substituted for a hydrogen atom of each of the two amido
consists either in heating alpha naphthylamine sulphonic acids, or alkaline salts of
which process
alpha naphthylamine sulphonic acids, containing a sulphonic group in the "meta
position relatively to the amido group, with primary aromatic amines, and a salt of
the amine used, at elevated temperatures, or in heating monoalkyl-alpha naphthyl-
amine sulphonic acids, or alkaline salts of such mono alkyl alpha naphthylamine
sulphonic acids containing a sulphonic group in the meta position relatively to the
alkyl amido group, 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.

page_text: 2. The process for producing "symmetrical" diphenyl-alpha, beta, naphthylene
diamine, di-para-tolyl-alpha, beta, naphthylenediamine, or di-ortho-tolyl-alpha,
beta, naphthylenediamine, which process consists in heating alpha, naphthylamine
beta, mono sulphonic acid, or alkaline salts thereof, with either aniline or para
toluidine, or ortho toluidine, and a salt of the amine used, at elevated temperatures,
together with benzoic acid, or other agents capable of facilitating the action, if
desirable.
3. The process for producing "symmetrical" diphenyl alpha, beta naphthylene
diamine alpha monosulphonic acid, diphenyl alpha betaz naphthylene diamine
betas monosulphonic acid, diphenyl alpha, beta, naphthylene diamine beta, mono-
sulphonic acid, or diphenyl alpha, beta: naphthalene diamine betaa alpha
disulphonic acid, by heating either alpha, naphthylamine betag alpha, disulphonic
acid, alpha, naphthylamine beta, beta, disulphonic acid, alpha, naphthylamine
beta, beta, disulphonic acid, or alpha, naphthylamine, beta, betas alpha4 tri-
sulphonic acid, or an alkaline salt thereof, with aniline, and a salt of analine, at an
elevated temperature, together with benzoic acid or other agents capable of
facilitating the reaction, if desirable.
4. The production of "symmetrical" di-para-tolyl alpha beta, naphthylene
diamine alpha monosulphonic acid, di para tolyl-alpha, beta, naphthylene diamine
betas monosulphonic acid, di-para-tolyl alpha beta2 naphthylene diamine beta
monosulphonic acid, or di-para-tolyl alpha beta, naphthylene diamine beta,
alpha, disulphonic acid, or the corresponding di-ortho-tolyl alpha beta, naphthylene
diamine sulphonic acids, which process consists in heating alpha, naphthylamine
beta, alpha, disulphonic acid, alpha, naphthylamine betas betas disulphonic acid,
alpha naphthylamine beta beta4 disulphonic acid, or alpha₁ naphthylamine
beta, betas alpha trisulphonic acid, or an alkaline salt thereof, with either para
toluidine, or ortho toluidine, and a salt of the toluidine used, at elevated
temperatures, together with benzoic acid or other agents capable of facilitating the
action, if desirable.
5. The process for producing "mixed" dialkyl alpha, beta, naphthylene
diamines, or dialkyl alpha beta, naphthylene diamine sulphonic acids, containing
two different aromatic alkyl groups, one in each of the amidolgroups, which process
consists in heating, at elevated temperatures, monoalkylalpha naphthylamine
sulphonic acids, or alkaline salts of monoalkyl alpha naphthylamine sulphonic
acids, containing a sulphonic group in the meta position relatively to
the alpha amido group, into which an aromatic alkyl group has been introduced,
with a primary aromatic amine and a salt of the amine used (containing an aromatic
radicle other than that contained in the alkyl amido group of the alkylnaphthyl-
amine sulphonic acids used initially), adding benzoic acid, if desirable.
k
"
6. The production of diphenyl alpha beta, naphthylene diamine sulphonic acids,
di-para-tolyl alpha beta naphthylenediamine sulphonic acids, di ortho tolyi
alpha beta naphthylene diamine sulphonic acids, or other dialkyl alpha betu
naphthylene diamine sulphonic acids, which process consists in sulphonating
diphenyl alpha, beta naphthylene diamine, dipara tolyl alpha, betas naphthylene
diamine, diortho-tolyl-alpha, beta, naphthylene diamine, or other dialkyl alpha,
beta, naphthylene diamines.
7. The process for producing basic azine dye-stuffs, or sulphonic acids thereof,
more or less difficultly soluble, by acting with nitroso derivatives of secondary or
tertiary aromatic amines, or amidosulphonic acids, on the "symmetrical
"mixed" dialkyl alpha, beta, naphthylene diamines or dialkyl alpha, beta,
naphthylene diamine sulphonic acids hereinbefore defined.
or
8. The conversion of the basic azine dye-stuffs, or difficultly soluble sulphonic
acids thereof, obtainable as described in the foregoing sixth claim, into more
readily soluble acid dye-stuffs, by a subsequent treatment with sulphonating
agents.
9. The production of dye-stuffs by condensing nitroso monomethylaniline,
nitroso dimethylaniline, nitrosodiethylaniline, nitrosodiphenylamine, nitrosoethyl

page_text: benzyl aniline sulphonic acid, or analogous nitroso derivatives, with "symmetrical "
diphenyl alpha beta, naphthylene diamine, di-para-tolyl alpha beta, naphthylene-
diamine, di ortho tolyl alpha, beta, naphthylenediamine, diphenyl alpha beta2
naphthylene diamine-alpha, monosulphonic acid, di-para-tolyl alpha, beta, naph-
thylene diamine, alpha, mono sulphonic acid, diorthotolyl alpha, beta, naphthylene
diamine alpha, monosulphonic acid, diphenyl-alpha, beta, naphthylenediamine
beta, mono sulphonic acid, diparatolyl alpha, betas naphthylene diamine beta, mono
sulphonic acid, diorthotolyl alpha, beta, naphthylene-diamine-beta; monosulphonic
acid, diphenyl alpha, beta, naphthylene diamine beta, mono sulphonic acid, dipara
tolyl alpha, beta, naphthylene diamine beta, monosulphonic acid, diortho tolyl
alpha, beta, naphthylene diamine beta, mono sulphonic acid, diphenyl alpha₁ beta,
naphthalene diamine betas alpha, disulphonic acid, dipara tolyl alpha beta,
naphthylene diamine beta, alpha disulphonic acid, or diortho tolyl alpha,
beta, naphthylene diamine beta, alpha, disulphonic acid, or the analogous "mixed
dialkyl alpha, beta, naphthylenediamines, or dialkyl alpha, beta, naphthylene
diamine sulphonic acids, or those dialkyl alpha, beta, naphthylene diamine sulphonic
acids obtainable as described in the foregoing sixth claiming clause, if desirable,
subsequently sulphonating the so-formed condensation products.
33
10. As new products of manufacture, the new dialkyl alpha, beta, naphthylene
diamines, dialkyl alpha, beta, naphthylene diamine sulphonic acids, and the new
coloring matters produced by the processes herein before defined, or by any other
means affording the same result.
Dated this 5th day of January 1894.
NEWTON & SON,
Agents for the Applicant.