The Manufacture of New Colouring Matters.
Year: 1892

page_text: Date of Application, 16th Apr., 1892
Complete Specification Left, 16th Jan., 1893-Accepted, 25th Feb., 1893
PROVISIONAL SPECIFICATION.
The Manufacture of New Colouring Matters.
I, BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of London
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by the Farbenfabriken vormals Friedrich Bayer
& Co. of Elberfeld in the Empire of Germany) to be as follows:—
My foreign correspondents have found that the substituted naphthylamine sulpho
acids or alkylnaphylamine sulpho acids, are of high technical value as they can
be employed for the production of new colouring-matters suitable for dyeing wool.
These new dye-stuffs are in general obtained by combining the alkyl-naphthyl-
amine-sulpho acids with the diazo derivatives of those amido-azo compounds which
are obtained by coupling the diazo compounds of amines, substituted amines,
amido-phenols, amido-phenol-ethers, amido-sulpho-acids or substited amido-sulpho
acids of the benzene and naphthalene series amido-azo-benzene, its homologues or
sulpho acids thereof with alpha naphthylamine, Clève's alpha naphthylamine mono-
sulpho acids By and 8, alphanaphthylamine-ortho monosulpho acid described in
the German Patent No. 56563, amidonaphtholsulpho acids, amidonapholether
sulpho acids, or amido naphtoxy acetic sulpho acids.
The following is given as an example for the production of these new dye-stuffs
the parts being by weight.
Dye-stuff obtained by combining diazotised alphanaphthylamine with Clève's
alphanaphthylamine monosulpho acid ẞ and coupling the diazo product of the
resulting amido azo compound with the phenyl alpha naphthylamine monosulpho
acid (NHCH, SO,H=1:8).
:
14-3 parts of alphanaphthylamine are diazotised in the well known manner by
means of 7 parts of sodium nitrite and the diazo solution thus obtained is added to
a cooled solution in water of 24.3 parts of the sodium salt of Clève's alpha-naphthyl-
amine mono-sulpho acid ẞ and about 48 parts of sodium acetate. After some days
the liquid is heated for a short time at from about 60 to 73 degrees centigrade in
order to complete the formation of the amido-azo compound which corresponds
with the following formula :
SO,H
After rendering alkaline and adding common salt the amido azo product is
filtered off, mixed with a watery solution of 7 parts of sodium nitrite and
diazotised by gradually acidulating with muriatic acid. When the diazotising is
finished the mixture is introduced into a solution in water of 32-1 parts of the
sodium salt of phenylalphanaphthylamine monosulpho acid (1-8) and about 64 parts
of sodium acetate. After some hours the whole mass is heated for a short time at
about 70 degrees centigrade and after rendering alkaline, the dye-stuff is isolated
in the known manner by salting out filtering off pressing and drying. It possesses
the following composition :—
SO,Na
SO,Na
It produces on wool a beautiful deep black. In an analogous manner similar
dyestuffs are obtained on employing instead of the phenyl-alpha-naphthylamine
mono sulpho acid (1-8) other substituted naphthylamine sulpho acids or alkyl-
nanhthylamine sulpho acids.

page_text: When Clève's alpha-naphthylamine mono-sulpho acid ẞ of the preceding example
is replaced by the isomeric acids, viz. Clève's alpha-naphthylamine mono sulpho
acid y or or alpha-naphthylamine-ortho-mono-sulpho acid described in the German
Patent No. 56563 the process can be carried out in the same manner, whilst in
employing amido-naphthol-sulpho acid, amido-naphthol-ether sulpho acid or amido-
naphthoxy-acetic sulpho acid instead of Clève's alpha-naphthylamine mono sulpho
acid of the preceding example the production of the intermediate amido-azo
products can be carried out most practically in moderately alkaline solution.
The shades produced by these dye-stuffs are in general form blue or bluish-black
to pure black.
Similar colouring-matters result when instead of alphanaphthylamine of the
foregoing example beta-naphthylamine, amido-naphthol, amido-naphthol-ether,
naphthylamine sulpho acids, aniline, toluidine, xylidine cumidine, amido-phenol,
amido-cresol, amido-phenolether, nitro-aniline, nitro-toluidine, nitro-xylidine, amido-
azo-benzene, homologues thereof or sulpho acids of either of these compounds are
employed.
My foreign correspondents have also found that valuable dye-stuffs are obtained
when the phenyl-naphthylamine sulpho acid of the preceding example is replaced
by naphthylamine or substituted naphthylamines such as phenylnaphthylamine,
tolylnaphthylamine, dinaphthylamine, or analogous or homologous-compounds, or
by alkylated aniline, toluidine, xylidine or analogous, or homologous compounds,
such as diphenylamine phenyltolylamine, ditolylamine or the like.
In order to illustrate the process of producing these colouring-matters the
following example is given the parts being by weight.
Dye-stuff obtained by combining diazotised betanaphthionic acid with Clève's
alphanaphthylamine-monosulpho acid ẞ and coupling the diazo derivative of the
amido-azo product thus formed with phenyl-alphanaphthylamine.
24.5 parts of the sodium salt of beta-naphthionic acid are diazotised in the known
manner by means of 7 parts of sodium nitrite and the resulting diazo solution is
added whilst stirring to a cooled solution in water of 24.5 parts of the sodium salt
of Clève's alpha-naphthylamine-mono-sulpho acid 6 and about 15 parts of sodium
acetate. After about 24 hours the formation of the amido azo product is com-
pleted. It possesses the following composition.

page_text: The process is also to be carried out in the same manner when Clève's alpha-
naphthylamine monosulpho acid ẞ is replaced by Clève's alpha-naphthylamine
monosulpho acid y or 8, or by the isomeric alpha-naphthylamine-ortho-mono-sulpho
acid described in the German Letters Patent No. 56563. In employing instead of
the said naphthylamine-sulpho acids amido-naphthol-sulpho acid, amido-naphthol-
ether-sulpho acid or amido-naphthoxy-acetic sulpho acid the production of the
intermediate amido azo compounds is effected most practically in alkaline solution.
The shades produced by these new dye-stuffs are in general from bluish-black or
greenish-black to pure black.
If the beta-naphthionic acid of the last preceding example be replaced by the
isomeric naphthylamine sulpho acids or naphthylamine di or tri sulpho acids,
amido-naphthol-sulpho acids, amido-naphthol ether sulpho acids, sulpho acids of
aniline, toluidine, xylidine or analogous compounds, dye-stuffs result which produce,
on wool, violet-black shades whilst in the employment of amines, or substitution
products thereof, instead of the beta-naphthionic acid of the last preceding example
colouring matters are obtained which produce on wool, shades which are of a more
violet colour.
All the dye-stuffs resulting by the employment of alkyl-naphthylamine-sulpho
acids or alkyl-naphthylamines are similar to those which are described in the
Specification of Letters Patent No. 14442 granted to me and dated 8th October
1888.
1000
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture of New Colouring Matters.
I, BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld in the Empire of Germany) and in what manner the
same is to be performed to be particularly described and ascertained in and by the
following statement :-
My foreign correspondents have found that the substituted naphthylamine sulpho
acids (so called alkylnaphthylamine sulpho acids) can be employed for the produc-
tion of new colouring-matters suitable for dyeing wool.
These new dye-stuffs are in general produced by combining the said alkylnaph-
thylamine sulpho acids with the diazo derivatives of the amido-azo compounds
which are obtained by coupling the diazo compounds of amines, substituted
amines, amido-phenols, amido-phenol ethers, amido sulpho acids, or substituted
amido sulpho acids of the benzenc, and naphthalene, series, or amido-azo benzenc,
its analogues, or homologues, or sulpho acids thereof with alphanaphthylamine,
Cleve's alphanaphthylamine-monosulpho acids (beta, or delta,) alphanaphthyl-
amine-ortho-monosulpho acid (described in the German Patent No. 56563) or
such amidonaphtholsulpho acids, amidonaphtholether sulpho acids, or amidouaph-
toxy acetic sulpho acids, the amido group of which, in the resulting amido
azo products, can be further diazotised.
By alkylnaphthylamine sulpho acids my foreign correspondents understand
particularly phenyl or tolyl naphthylamine sulpho acids.
The following is given as an example of the method of producing these new
dye stuffs the parts being by weight.
Dye-stuff obtained by combining diazotised alpha-naphthylamine with Cleve's
alphanaphthylamine-monosulpho-acid (beta) and coupling the diazo product of
the resulting amidoazo compound with phenylalphanaphthylamine-mono-sulpho
acid (1:8).

page_text: 14-3 parts of alphanaphthylamine are diazotised, in the well known manner,
by means of 7 parts of sodium nitrite, and the diazo-solution thus obtained is
added to a cooled solution in water of 24-5 parts of the sodium salt of Cleve's
alphanaphthylamine-monosulpho acid (beta) and about 48 parts of sodium acetate.
After several days the liquid is heated for a short time at from about 60 to 70 5
degrees centigrade in order to complete the formation of the amido-azo compound
represented by the following formula :—
Sun
The mixture is then rendered alkaline and common salt is added and the
amido azo product is filtered off mixed with a solution in water of 7 parts of
sodium nitrite and diazotised by gradually acidulating with muriatic acid. When
the diazotising process is complete the mixture is introduced into a solution in
water of 32-1 parts of the sodium salt of phenylalphanaphthylamine-monosulpho
acid (18) and about 64 parts of sodium acetate. After some hours the whole
mass is heated for a short time at about 70 degrees centigrade. It is then rendered
alkaline and the dye stuff is isolated in the usual manner by salting out, filtering
off, pressing and drying. It possesses the following composition :-
It produces on wool a beautiful deep bluish-black colour. Similar dye stuffs are
obtained in an anologous manner by employing instead of phenylalphanaphthylamine-
monosulpho acid (1: 8) other phenylnaphthylamine sulpho acids, or tolylnaphthyl-
amine-sulpho acids.
When Cleve's alphanaphthylamine mono-sulpho acid beta, of the preceeding
example, is replaced by the isomeric acids vizt. Cleve's alphanaphthylamine mono-
sulpho acid (delta) or the alpha naphthylamine-ortho-monosulpho acid described
in the German Patent No. 56563 the process can be carried out in the manner
as above described whilst if amidonaphtholsulpho acid, amidonaphtholethersulpho
acid, or amidonaphthoxyaceticsulpho acid, be used instead of Cleve's alphanaph-
thylamine-monosulpho acid as described in the preceding example the production
of the intermediate amidoazo products is most practically effected in a moderately
alkaline solution.
The shades produced by these dye-stuffs are in general from blue, or bluish-
black to pure black.
Similar colouring matters result on employing instead of the alphanaphthylamine
of the foregoing example beta naphthylamine, amidonaphthol, amidonaphtholether,
naphthylamine-sulpho acids, aniline, toluidine, xylidine, cumidine, amido-phenol,
amido-cresol, amido-phenol-ether, amido-cresol-ether, nitroaniline, nitrotoluidine,
nitroxylidine or amido-azobenzene, or analogues, or homologues thereof, or sulpho
acids of these compounds.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
:-
First. The production of colouring matters by combining the diazo-derivatives
of amines, amido-phenols, amido-phenol-ethers, of the benzene, or naphthalene,
series, the sulpho-carboxylic- or sulpho-carboxylic derivatives thereof, amidoazo-
benzene, its analogues, or homologues, or sulpho derivatives thereof; with
alphanaphthylamine, Clève's alpha-naphthylamine-beta-mono-sulpho acid (beta, or
delta,) alphanaphthylamine-ortho-mono-sulpho acid, or such amidonaphtholsulpho
acids, amidonaphtholether sulpho acids, or amidonaphthoxyacetic sulpho acids,

page_text: Date of Application, 16th Apr., 1892
Complete Specification Left, 16th Jan., 1893-Accepted, 25th Feb., 1893
SO₂H
\SO,H
After cooling the mass is treated with diluted hydrochloric acid and the phenyl-
naphthylamine sulpho acid which separates is filtered off and redissolved in a
solution of sodium carbonate and the resulting alkaline solution is boiled until the
odour of aniline has totally ceased. After filtering the phenyl-alpha-naphthylamine-
monosulpho acid (1-8) of the foregoing formula is precipitated by adding muriatic
acid to the resulting solution. In order to purify the acid thus obtained it be
converted into its lime salt and after crystallizing the latter the new acid is obtained
in a perfectly pure state, by decomposing the lime salt with any acid. The phenyl-
naphthylamine-sulpho acid so formed crystallizes in colourless needles which
dissolve in water with difficulty but which dissolve readily in watery solutions of
sodium acetate.
may
Of course, the new acid can be separated out of the mixture obtained according
to the foregoing process by adding diluted soda-lye, distilling off the aniline by
means of steam and decomposing the alkaline solution with acids. The new acid
The
thus separated may further be purified in the herein before described manner.
acid may also be isolated in other ways and the process of separation is not restricted
to the methods hereinbefore described.
In an analogous manner the other substituted naphthylamine sulpho acids can be
produced, either by employing instead of the alphanaphthylamine alpha-monosulpho
acid (1-8) of the foregoing example other alpha naphthylamine mono sulpho acids,
di- or trisulpho acids of alpha- and beta-naphthylamine or amido-naphthol-sulpho
acids, or by replacing the aniline employed in the foregoing example by toluidine,

page_text: xylidine, cumidine, or analogous primary aromatic amines, or derivatives thereof
substituted in the benzene nucleus.
Dated this 20th dox of June 1800
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Alkylated Naphthylamine
Sulpho Acids.
I, BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of
Middlesex Patent Agent do hereby declare the nature of this invention (which
has been communicated to me from abroad by Farbenfabriken vormals
Friedrich Bayer & Co. of Elberfeld in the Empire of Germany) and in what
manner the same is to be performed to be particularly described and ascertained in
and by the following statement:-
This invention relates to the manufacture of naphthylamine sulpho acids alkylised
in the amido group.
My foreign correspondents have found that substituted naphthylamine sulpho
acids (so called alkylnaphthylamine sulpho acids) can be obtained by heating
certain alpha- or beta-naphthylamine sulpho acids with primary aromatic amines
preferably in most cases together with a salt of the amine such as the hydrochloride
or benzoate or in some cases a mixture of two such salts.
The following example is given in order to illustrate the method, the parts being
by weight.
SO,H
\SO₂H
The cooled mass having been treated with diluted hydrochloric acid the
phenylnaphthylamine sulpho acid which separates is filtered off and redissolved in a
solution of sodium carbonate, and the resulting alkaline solution is boiled until the
odour of aniline is no longer perceptible. The liquid is then filtered and the
phenylalphanaphthylaminemonosulpho acid (18) represented by the foregoing
formula is precipitated by adding muriatic acid. In order to purify it the lime
salt of the acid thus obtained may be prepared and purified and the new acid be
obtained from it in a pure state by treating it with any suitable acid. The phenyl-
naphthylamine sulpho acid so formed crystallizes in colourless scales. It dissolves
in water with difficulty, but readily dissolves in aqueous solutions of sodium acetate
forming a sodium salt which crystallizes in hydrated needles melting in the
water of crystallisation at a slightly elevated temperature.
Obviously the new acid can be separated from the mixture obtained in the fore-
going process by adding diluted soda-lye, distilling off the aniline by means of
steam and decomposing the alkaline solution with acids. The product thus
separated may be further purified in the hereinbefore described manner. The acid
may also be isolated in other ways, as the process of separation is not restricted to
the methods hereinbefore described.
In an analogous manner my foreign correspondents have prepared other phenyl-
naphthylamine sulpho acids by heating from 2 to 4 parts, by weight, of aniline, and

page_text: I part, by weight, of aniline hydrochloride with 1 part, by weight, of either of the
following naphthylamine sulpho acids viz. :-alphanaphthylamine alphamonosulpho
acid (15), Clève's alphanaphthylamine-beta-monosulpho acid (1.3), Clève's alpha-
naphthylamine-beta-monosulpho acid (1-6). Clève's alphanaphthylamine-beta-mono-
sulpho acid (1-7), beta-naphthylamine-gamma-mono-sulpho acid (25), beta-
naphthylamine-beta-monosulpho acid (2.6), beta-naphthylamine-delta-mono-sulpho
acid (2-7), betanaphthylamine-alpha-monosulpho acid (2-8), beta-naphthylamine
disulpho acid G and beta-naphthylamine-disulpho acid R.
The researches of my foreign correspondents show that the process takes place
in an analogous manner, if aniline and aniline hydrochloride are replaced by the
corresponding quantities of para-toluidine and paratoluidine-hydrochloride. My
foreign correspondents have produced, in this way, the paratolyl derivatives of the
following naphthylamine sulpho acids viz.-alpha-naphthylamine-alpha-inonosulpho
acid (14), alpha-naphthylamine-alpha-mono-sulpho acid (1-5), alpha-naphthyl-
amine-alpha-monosulpho acid (1.8), Clère's alpha-naphthylamine-beta-monosulpho
acid (1-3), Clève's alpha-naphthylamine-beta-monosulpho acid (1-6), Clève's alpha-
naphthylamine-beta-monosulpho acid (1-7), beta-naphthylamine-gamina-monosulpho
acid (2.5), beta-naphthylamine-beta-monosulpho acid (2-6), beta-naphthylamine-
delta-monosulpho acid (2-7), beta-naphthylamine-alpha-monosulpho acid (2-8), beta-
naphthylaminedisulpho acid G and beta-naphthylamine disulpho acid R.
My foreign correspondents have further prepared the orthotolyl derivative of
alpha-naphthylamine-alpha-monosulpho acid (1-8) by heating this latter acid with
orthotoluidine and a salt of this base, employing in general the quantities herein-
before defined of these substances.
Of the acids mentioned the alkylnaphthylamine sulpho acids which are derived
from alphanaphthylamine-alpha-monosulpho acid (1.8) possess the greatest value
according to the researches of my foreign correspondents.
The temperatures at which the aforesaid reactions are preferably effected differ
for the different products. A temperature of from 100 to 180 degrees is sufficient
in most cases. For instance, in transforming alphanaphthylamine-monosulpho
acids (13 or 1-5) into the corresponding phenyl or tolyl derivatives a tempera-
ture not rising above 140 degrees centigrade is preferably employed, whilst the
other alpha-naphthylamine sulpho acids and the beta-naphthylamine sulpho acids
enumerated are converted into their phenyl- or tolyl-derivatives at somewhat
higher temperatures.
The proportions of aniline and toluidine and the hydrochlorides thereof can be
varied within certain limits. In place of the hydrochlorides the corresponding
quantities of the sulphates can also be employed.
The researches of my foreign correspondents show also that it is not absolutely
necessary to add a salt of the base to the mixture of naphthylamine sulpho acid
and base, but such an addition advances the reaction in most cases.
My foreign correspondents have also found that an addition of benzoic acid to
the mixture before heating is sometimes productive of better results, that is to say
that it is sometimes better to use a mixture of salts such as a benzoate and hydro-
chloride instead of a simple salt.
A good result is obtained, if, for example, 1 part, by weight, of alpha-naphthyl-
amine-alpha-monosulpho acid (1-8) is heated with from 2 to 4 parts, by weight, of
aniline with the addition of about 0·1 of a part, by weight, of benzoic acid.
By means of this new method my foreign correspondents have converted beta-
naphthylamine-alpha-monosulpho acid (2-8) into phenyl-beta-naphthylamine-alpha-
monosulpho acid by heating it with aniline and aniline hydrochloride and in the
same manner have prepared from beta-naphthylamine-gamma-mono-sulpho acid (2-5)
the corresponding phenyl-beta-naphthylamine-gamma-monosulpho acid and they
have found that the former of these acids is identical with the phenylnaph-
hylamine supho acid B described in the Specification of Letters Patent No. 10934
lated 6th July 1889, whilst the latter is identical with the phenylnaphthylamine
ulpho acid A described in the Specification of the same Letters Patent.

page_text: My foreign correspondents have ascertained that the phenyl- or tolyl-naphthyl-
amine-sulpho acids obtained by this new process from naphthylamine-sulpho acids
are identical with those alkylnaphthylamine sulpho acids formed from the corre-
sponding naphtholsulpho acids by means of aniline, orthotoluidine, and the hydro-
chlorides thereof as described in the Specification of the German Patent No. 38424
dated 31st March 1886.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The process for producing the above named phenylnaphthylamine sulpho
acids derived from alphanaphthylamine-alpha-mono-sulpho acid (1.5 or 1.8), Clève's
alphanaphthylamine-beta-monosulpho acids (beta, gamma, or delta), beta-naph-
thylamine-gamma-monosulpho acid (2-5), hetanaphthylamine-beta-monosulpho
acid (2-6), betanaphthylamine-delta-monosulpho acid (2-7), betanaphthylamine-
alpha-monosulpho acid (28), beta-naphthylamine-disulpho acid (G or R) by heating
the last named alpha- or beta-naphthylamine sulpho acids either with aniline alone,
or with aniline and a salt thereof, with, or without, adding benzoic acid in either
case.
2. The process for producing paratolyl-naphthylamine-sulpho acids derived from
alphanaphthylamine-alpha-monosulpho acid, (14, 1-5, or 1-8), Clève's alpha-naph-
thylamine-beta-monosulpho acid, (beta, gamma, or delta, beta-naphthylamine-
gamma-monosulpho acid (2.5), beta-naphthylamine-beta-monosulpho acid (2-6),
beta-naphthylamine-delta-monosulpho acid, (2.7), beta-naphthylamine-alpha-mono-
sulpho acid (2.8), beta-naphthylamine disulpho acid (G or R), by heating the last
named alpha- or beta-naphthylamine sulpho acids either with paratoluidine alone,
or with para-toluidine and a salt thereof, with, or without, adding benzoic acid in
either case.
3. The process for producing orthotolyl-alphanaphthylamine-alpha-monosulpho
acid (18) by heating alphanaphthylamine-alpha-monosulpho acid (1-8) either with
orthotoluidine alone, or with orthotoluidine and a salt thereof, with, or without,
adding benzoic acid in either case.
Dated this 14th day of January 1893.

page_text: the amido group of which can be further diazotised when these acids have been
coupled with diazo compounds, and subsequently coupling the diazo derivatives of
the amido azo-compounds so formed with phenyl- or tolyl-naphthylamine-sulpho
acids.
Second. As new articles of manufacture the new colouring matters hereinbefore
defined.