The Manufacture of Azo Dyes and of Materials therefor.
Year: 1889

page_text: Date of Application, 9th May, 1889
Complete Specification Left, 10th Mar., 1890-Accepted. 12th Apr. 1890
PROVISIONAL SPECIFICATION.
The Manufacture of Azo Dyes and of Materials therefor.
I, BENJAMIN WILLCOX, of 47 Lincolns 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 the Farbenfabriken vormals Friedrich Bayer & Co
of Elberfeld, in the Empire of Germany,) to be as follows:-
This Invention relates to the manufacture of direct acting azo dyes and to the
preparation of materials employed in the manufacture of these dyes as hereinafter
described. The employment of the ortho benzidine sulpho acid which is known to be
obtained by the reduction of meta nitro benzene sulpho acid in an alkaline solution
and transposing the hydrazo benzene sulpho acid resulting therefrom in the first place
produces. tetrazo dyestuffs which do not dye unmordanted cotton in an alkaline bath.
My foreign correspondents have now discovered that this acid can be readily converted
into a new ortho derivative of benzidine which in opposition to the ortho benzidine
disulpho acid yields direct dyeing dyestuffs.
When for example the ortho benzidine disulpho acid is treated with caustic
alkalies preferably in a closed vessel-under a pressure of from about 30 to 40
atmospheres and at a temperature of from say about 150 to 300 degrees Centigrade
it is converted into diamido diphenylene oxide. At the same time there is obtained
along with this substance, especially when operating with a low pressure or in an
open vessel, an intermediate product which is soluble in a soda (protoxide of sodium)
Iye insoluble in carbonate of sodium lye and when heated is converted with separation
of water into the diamido diphenylene oxide.
In like manner to the orthobenzidine disulpho acid the next higher homologue
thereof the ortho tolidine disulpho acid (obtained by alkaline reduction of ortho nitro
toluol meta sulpho acid and conversion of the resulting hydrazo sulpho acid) can be
melted with caustic alkalies and in this case we obtain a diamnido ditoluylene oxide.
Here also an intermediate product is formed which is converted by itself by heating
into the diamido ditoluylene oxide with separation of water.
In order to obtain the diamido diphenylene oxide about 5 parts by weight of the
soda salt of ortho benzidine disulpho acid are introduced into about 46 parts by
weight of soda lye of 40 per cent. strength and heated for from about 6 to 8 hours in a
closed vessel under a pressure of about 36 atmospheres. The diamido diphenylene
oxide formed being for the most part separated in the form of a crystalline crust on
the surface of the melt when cooled can be removed mechanically. The remaining
melt is dissolved in water, and mixed with hydrochloric acid until a slight alkaline
reaction takes place and the diamido diphenylene oxide therchy further obtained
is isolated by filtration.
For further purification the diamido diphenylene oxide thus obtained is dissolved in
dilute hydrochloric acid and the hydrochlorate is precipitated from the filtrate with
salt. The base itself is obtained from its hydrochlorate by neutralising with caustic
alkali. It crystallizes out of hot water in white needles whose melting point is from
about 150 to 152 degrees Centigrade is readily soluble in ethereal solvents, and forms
with hydrochloric acid a readily soluble salt but with sulphuric acid a salt that is
soluble with difficulty.
Treated with nitrous acid it yelds a readily soluble yellow tetrazo compound which
being combined with dyestuff components produces valuable direct acting colouring
matter. With beta naphthionic acid there is obtained a readily soluble red dyestuff of the
same shade as delta purpurine 5 B. In this process very little of the above mentioned
intermediate product is obtained but it is obtained in greater quantities when the.
above mentioned proportions of materials are allowed to react on one another for,

page_text: only about 2 or 3 hours under a pressure of about 20 atmospheres or in an open
vessel at higher temperature for a correspondingly longer period. An incomplete
melt is thus obtained in which the intermediate product is found on dissolving it in
water and acting on the soda lye with hydrochloric acid in the filtrate of the filtered
and separated diamido' diphenylene oxide together with unchanged ortho benzidine
disulpho acid.
When the filtrate is acidulated and neutralised with soda (sodium carbonate) the
ortho benzidine disulpho acid goes into solution again but the intermediate product
remains undissolved. This product forms with acids readily soluble salts; is soluble
in soda lye (protoxide of sodium) insoluble in carbonate of sodium and forms-a-soluble
yellowish brown tetrazo compound which in the combination with amides and phenols
leads to direct dyeing dyestuffs.
When heated alone or with the aid of dehydrating agents it is converted into diamido
diphenyleneoxide with separation of water.
Diamido toluylene oxide can be obtained by proceeding as hereinbefore described
with reference to diamido diphenylene oxide, the next higher homologue of the ortho
benzidine disulpho acid namely the ortho tolidine disulpho acid being substituted for
the said benzidine sulpho acid.
This product namely the dianiido ditoluylene oxide possesses properties closely
resenibling those of the diamido diphenylene oxide; it produces a soluble tetrazo
compound crystallises out of hot water in white needles is readily soluble in ethereal
solvents and with sulphuric acid forms a sparingly soluble salt.
In its production an intermediate product is formed which when heated' is converted
into the dianiido ditoluylene oxide with separation of water. This intermediate
product is soluble in protoxide of sodium lye but insoluble in the carbonate. It
produces' a soluble tetrazo compound.
All the compounds the diamido diphenylene oxide, the diamido ditoluylene oxide
and their intermediate products yield soluble tetrazo compounds and are employed in
the production of direct acting dyestuffs as hereinafter described.
With this object the tetrazo compound of the diamido diphenylene oxide and
diamido ditoluylene oxide is caused to act upon two molecules of an amide, a phenol
or the sulpho or carbon' acid or sulpho carbon avid thereof and on the dyestuffs
known in the trade as chrysoidines and bismark browns or the said compound is
united with one molecule of an amide or a plienol or the sulpho or carbon acid or
sulpho carbon acid thereof and with the aforesaid chrysoidines and bismark browns
so as to forin'an interinediate product which is combined with a molecule of any other
amide or phenol or the sulpho or carbon acids or the sulpho or carbon acids thereof and
any other chrysoidines' and bismark browns.
The process for the production of this new series of direct dyeing colouring
matter consists in converting the diamido diphenylene oxide and diamido ditoluylene
oxide in a hydrochloric acid solution into their tetražo compounds by the addition
of the theoretical quantity of nitrite solution and causing the solutions of the product
to flow into two molecules of an amide, a plienol or the sulpho or carbon acid thereof
the amide being coupled in an acetic acid solution and the phenol in an alkaline
solution: The product of the coupling with 'aides is allowed to stand for a longer
time and the reaction is finally completed by heating to about 80 degrees Centigrade
and the product is neutralised with soda lye. The naphthol dyestuffs on the other
hand are formed direct and can be separated by salting out.
For obtaining mixed dyestuffs the dianido diphenylene oxide and diamido
ditoluylene oxide are likewise suitable in the same way as benzidine and tolidine for
example. The process for the production of this kind of dyestuff is as follows, One
molecule of the tetrazo compounds of diamido diphenylene oxide and diamido
ditoluylene oxide are caused to act upon one molecule of an ainido or phenol or the
sulpho or carbon acid thereof in an acetic acid solution and the intermediate product
formed is combined with one molecule of any other amile; plienol or the sulpho or
carbon acid thereof whereby in the same way as herein before described for two
molecules the amide is coupled in acetic acid solution and the phenol in an alkaliné

page_text: solution and further treated as before.
The dyestuffs thus obtained yield the greatest
variety of colours from yellow, red to voilet.
The following are given as examples of the process as actually performed for the
production of the new direct dying dyestuffs according to this invention.
I. A. Obtaining spirit soluble dyestuffs from one molecule of the tetrazo compounds
of diamido diphenylene oxide diamido ditoluylene oxide and two molecules of a
component not containing any sulpho group.
These dyestuffs are obtained as hereinbefore stated when the tetrazo compounds of
diamido diphenylene oxide and diamido ditoluylene oxide are caused to act upon
amides and phenols or dyestuffs such as aniline, toluidine, xylidine, dimethyl aniline,
diphenylamine, m phenylene diamine, in toluylene diamine, alpha naphthylamine, beta
naphthylamine, phenyl naphthylamine, toly! naphthylamine, dinaphthylamine, phenol.
resorcin, orcin, alpha naphthol, beta naphthol, dioxynaphthaline, chrysoidine and
bismark brown also the homologues and isomers thereof.
1. Obtaining dyestuffs from diamido, diphenylene oxide and alpha naphthylamine.
A solution of tetrazo diphenylene oxide containing 1 kilos of nitrite (being
readily obtained by causing the calculated quantity of a solution of nitrite to flow into
the hydrochloric acid solution of the diamido diphenylene oxide) is added to a
hydrochloric acid solution of 25 kilos of alpha naphthylamine. On the addition of
acetate of soda the formation of the dyestuff proceeds, the materials are allowed to
stand for a time, the temperature is raised to about 80 degrees Centigrade and the
materials are treated with hydrochloric acid and filtered. The dyestuff thus, obtained
dissolves in alcohol with a red colour.
2. Obtaining a dyestuff from diamido diphenylene oxide and 2 molecules of alpha
naphthol.
A solution of the tetrazo combination of diamido diphenylene oxide corresponding
to 10 kilos of nitrite is introduced into an alkaline solution of 25 kilos of alpha
naphthol. The dyestuff which separates immediately is heated filtered and dried.
These dyestuffs obtained by means of the aforesaid amides, phenols, chrysoidines
and bismark browns or the isomers and homolognes thereof are insoluble in water
but can be rendered soluble in water by a sulphurising process.
1. Dyestuff from diamido diphenylene oxide + 2 molecules alpha naphthylamine
(sulphurising process).
10 parts by weight of the spirit soluble dyestuff obtained according to example 1
are introduced into 30 parts by weight of fuming sulphuric acid containing 20 per cent.
of anhydride at from about 15 to 30 degrees Centigrade and the sulphurising
mixture is allowed to stand until a sample dissolves readily in alkaline water. The
mel is poured out on ice, the separating dyestuff acid is filtered and converted into
the dyestuff by dissolving in alkali.
B. Obtaining souble dyestuffs from one molecule of the tetrazo compounds of
diamido diphenylene oxide, diamido ditoluylene oxide and 2 molecules of any com-
ponent containing a sulpho or carboxyl group.
These dyestuffs are formed by the action of the tetrazo compounds of diamido
diphenylene oxide and diamido ditoluylene oxide upon two molecules of the sulpho or
carlo acids of amides or phenols and dyestuffs such as aniline sulpho acid, toluidine
sulpho acid, xylidine sulpho acid, diphenylamine sulpho acid, dimethyl aniline sulpho
acid, m-phenylene diamine sulpho acid, -toluylene diamine sulpho acid, alpha and
beta naphthylamine sulpho acid, alpha and beta alkyl naphthylamine sulpho acid,
alpha and beta naphthol sulpho acid, salicylic acid oxytoluylic acid, resorcylic acid,
alpha and beta oxynaphthoic acid, alpha and beta sulpho naphthol carbon acid, dioxy
naphthaline sulpho acid, chrysoidine and bismark brown or the homologues and
isomers thereof.
1, Obtaining dyestuffs from diamido diphenylene oxide and 2 molecules of alpha
naphthylamine mono sulpho acid.
A solution of the tetrazo compound of diamido diphenylene oxide corresponding to
10 kilos of nitrite is introduced into an acetic acid solution of 45 kilos of alpha
naphthylamine mono sulpho acid. After standing for 24 hours the mixture which

page_text: acquires the consistency of a thick paste is rendered alkaline with soda lye and the
separating dyestuff is removed by filtration. The readily soluble product thus
obtained is of a beautiful fiery blue red colour.
2. Obtaining dyestuffs from diamido diphenylene oxide + 2 molecules of alpha
naphthol sulpho acid.
By causing the tetrazo compound containing 10 kilos of nitrite to be poured into
a solution of 45 kilos of alpha naphthol mono sulpho acid maintained alkaline to the
end by means of soda the prepared dyestuff immediately separates, it dyes with a
bordeaux like colour.
3. Obtaining dyestuffs from one molecule of diamido diphenylene oxide and
2 molecules of chrysoidine (sulphanilic acid + m-phenylene-diamine).
A solution (corresponding to 10 kilos of nitrite) of tetrazo diphenylene oxide is
caused to flow into an alkaline solution of 40 kilos of chrysoidine paste of 50
per cent.
strength the mixture is boiled and the dyestuff is precipitated from the filtrate by the
addition of salt. This dye dyes cotton a vivid yellow brown.
11. The diamido diphenylene oxide, and diamido ditoluylene oxide are suitable for
the production of what are termed mixed dyestuffs and thus lead to a series of new
direct acting azo dyestuffs of great commercial value.
The process for the production of this class of colouring matters closely follows the
well known process employed for the para diamines such for example as benzidine
and tolidine and consists in causing one molecule of the tetrazo compounds of diamido
diphenylene oxide and diamido ditoluylene oxide, to combine in the first place with
one molecule of any amide, phenol or their sulpho and carbon acids and then causing
this intermediate product to act upon any other amide, phenol or the sulpho or carbon
acid thereof. The second coupling takes place according to the nature of the com-
ponents in either an alkaline or an acetic solution.
A. Obtaining spirit soluble dyestuffs from one molecule of the tetrazo compounds
of diamido diphenylene oxide and diamido ditoluylene oxide and two different
molecules of an amide, a phenol, a chrysoidine or a bismark brown which does not
contain any sulpho or carboxyl group.
Example. Obtaining dyestuffs from diamido diphenylene oxide and one molecule of
alpha naphthylamine and one molecule of m-phenylene diamine.
(a.) To a solution of the tetrazo compound of diamido diphenylene oxide contain-
ing parts by weight of nitrite, an hydrochloric acid solution of 10 parts by weight
of alpha naphthylamine is added and the mixture is acidulated by the addition of
acetate of soda. The intermediate product which is formed in a short time is intro-
duced into an acetic acid solution of 15 parts by weight of m-phenylene diamine.
After standing for 24 hours it is heated to 80 degrees until the reaction is completed,
it is then acidulated with hydrochloric acid and the spirit soluble dyestuff is separated
by filtration.
(b.) A similar spirit soluble dyestuff is obtained when the intermediate product
described in the preceding example obtained from the tetrazo compound of the
diamido diphenylene oxide and alpha naphthylamine is introduced into an alkaline
solution of 25 kilos of alpha naphthol. The dyestuff which is immediately formed
dissolves with violet colour in alcohol.
(c.) Bismark brown when substituted for the alpha naphthol in the preceding
example yields, coupled in an acetic acid solution a dyestuff which dissolves in alcohol
with a brown colour. All the dyestuffs obtained by this process are insoluble in
water but can be rendered water soluble by a sulphurising process.
10 parts by weight of the spirit soluble dyestuff described in example 1ª are intro-
duced into 30 parts of fuming (sulphuric) acid containing 20 per cent. of anhydride
and the melt is allowed to stand until a sample dissolves in alkali with a violet colour.
It is then poured out upon ice and the separated dyestuff acid after filtration is
converted by solution into the dyestuff which can then be separated by salting out.
II. B. Obtaining soluble dyestuffs from one molecule of the tetrazo compounds of
diamido diphenylene oxide and diamido ditoluylene oxide and two different inolecules
of any component one at least of which must contain a sulpho or carboxyl group.

page_text: These dyestuffs are obtained by causing one molecule of the tetrazo compounds of
diamido diphenylene oxide and diamido ditoluylene oxide to act in the first place upon
one molecule of an amide and phenol or chrysoidine and bismark brown containing a
sulpho or carboxyl group in an acetic solution being a process analogous to that
described in section II (A.) and then combining the same with any other component,
the amide being coupled in an acetic solution and the phenol in an alkaline solution.
Example. Dyestuff obtained from diamido diphenylene oxide and one molecule of
alpha naphthylamine sulpho acid (one molecule of alpha naphthol mono sulpho acid).
The tetrazo compound of the diamido diphenylene oxide containing 10 parts by
weight of nitrite is caused to flow into an acetic solution of 16 parts by weight of
alpha napthionic acid and the intermediate product forme is introduced into an
alkaline solution of 25 parts by weight of alpha naphthol mono sulpho acid. The
dyestuff being immediately formed is separated by filtration and dried.
בד
11
1
1000
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
The Manufacture of Azo Dyes and of Materials therefor.
I BENJAMIN WILLCOX of 47 Lincolns 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 the 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 direct dyeing colouring matters and
to the preparation of materials employed in the manufacture of these dyes as herein-
after described.
By the employment of the ortho benzidine di-sulpho acid which is known to be
obtained by the reduction of meta nitro-benzene sulpho acid in an alkaline solution
and transforming the resulting hydrazo-benzene disulpho acid into the diamido
compound by treating with hydrochloric acid tetrazo dyestuffs are produced which
do not dye unmordanted cotton in an alkaline bath.
My foreign correspondents have now discovered that this acid can be readily con-
verted into a new ortho derivative of bezidine, which in opposition to the ortho
benzidine disulpho acid yields direct dyeing dyestuffs..
When for example the ortho benzidine disulpho acid is treated with caustic alkalies,
preferably in a closed vessel under a pressure of from about 30 to 40 atmospheres and
at a temperature of from say about 150 to 300 degrees Centigrade it is converted into
diamido diphenylene-oxide. At, the same time there is obtained along with this
substance, especially when operating at a low pressure or in an open vessel, an inter-
mediate product which is soluble in a caustic soda lye, but insoluble in carbonate of
soda, and when this is heated it is converted into the diamido diphenylene oxide,
water becoming separated.
Like the ortho benzidine disulpho acid the next higher homologue thereof the ortho
tolidine disulpho acid (obtained by alkaline reduction of ortho-nitro-toluene meta
sulpho acid and conversion of the resulting hydrazo sulpho acid into the diamido
compound) can be fused with caustic alkalies and in this case diamnido ditoluylene
oxide is formed.
In order to obtain diamido diphenylene oxide about 5 parts by weight of the sodium
salt of ortho-benzidine disulpho acid are introduced into about 46 parts by weight of
soda lye of 40 per cent. strength and heated for from about 6 to 8 hours in a closed
vessel under a pressure of about 36 atmospheres. The diamido-diphenylene oxide
thus formed for the most part separates in the form of a noncrystalline crust on the
surface of the cooled melt and can be removed mechanically. The remaining melt is
dissolved in water and mixed with hydrochloric acid until the reaction is slightly

page_text: alkaline and the further quantity of diamido-diphenylene oxide thus obtained is
separated by filtration. To further purify the diamido-diphenylene oxide thus obtained
it is dissolved in dilute hydrochloric acid and the sulphate is precipitated from the
filtrate with sulphate of soda. The base itself is obtained from its hydrochloride by
neutralising with caustic alkali.
It is readily soluble in ether and alcohol and forms with hydrochloric acid a readily
soluble salt, but with sulphuric acid a salt that is soluble with difficulty.
When treated with nitrous acid it yields a readily soluble yellow tetrazo compound
which when combined with dyestuff components, produces valuable direct dyeing
colouring matters. With beta naphthionic acid it affords a readily soluble red dye-
stuff of the same shade as deltapurpurine 5 B.
In this process very little of the above mentioned intermediate product is obtained,
but it is obtained in greater quantities when the above mentioned proportions of
materials are allowed to read on one another for only about 2 or 3 hours under a
pressure of about 20 atmospheres or in an open vessel at a higher temperature for a
correspondingly longer period. An incomplete melt is thus obtained from which the
intermediate product is obtained by dissolving the same in water, neutralising with
hydrochloric acid and acidulating the filtrate. It is separated and the intermediate
product together with unchanged ortho-henzidine disulpho acid is now neutralised
with sodium carbonate. The ortho-benzidine-disulpho-acid then redissolves but the
intermediate product remains undissolved. This product forms with acids readily
soluble salts and it is soluble in caustic soda lye but insoluble in carbonate of sodium
and forms a soluble yellowish brown tetrazo compound, which on combination with
amides and phenols yields direct dyeing coloring matters.
When heated alone or with the aid of dehydrating agents it is converted into
diamido diphenylene-oxide water being separated.
Diamidoditoluylene-oxide can be obtained by proceeding as hereinbefore described
with reference to diamido-diphenylene-oxide, if the next higher homologue of the
ortho-benzidine disulpho acid, namely the ortho-tolidine-disulpho acid be substituted
for the said benzidine disulpho acid.
This product, namely the diamido ditoluylene oxide possesses properties closely
resembling those of the diamido diphenylene oxide; it affords a soluble tetrazo
compound. It does not crystallise but forms an oil readily soluble in ethereal solvents
and affording with sulphuric acid a sparingly soluble salt.
In its production an intermediate product is formed which when heated is converted
into the diamido ditoluylene oxide, water being separated. This intermediate product
is soluble in caustic soda lye but insoluble in the carbonate. It affords a soluble
tetrazo compound.
All these compounds diamido-diphenylene-oxide, diamido-ditoluylene oxide and their
intermediate products yield soluble tetrazo compounds and are employed in the pro-
duction of direct dyeing coloring matters.
The process for the production of these new dyestuffs consists in converting the
diamido diphenylene-oxide and diamido-ditoluylene-oxide in a hydrochloric acid
solution into their tetrazo compounds by adding the theoretical quantity of a solution
of sodium nitrite and allowing the solutions of the resulting tetrazo compounds to
flow into a solution of 2 molecular proportions of an amide, a phenol or the sulpho
or carbo acid thereof, the amides being coupled in an acetic acid solution and the
phenols in an alkaline solution.
The products of the coupling with the amides are allowed to stand say for about
twelve hours and the reaction is finally completed by heating to about 80 degrees
Centigrade and neutralising with soda lye. The naphthol dyestuffs on the other hand
are rapidly formed and can be separated by salting out.
Diamido diphenylene oxide and diamido ditoluylene oxide are likewise suitable for
the manufacture of so called mixed dyestuffs in the same way as are benzidine and
tolidine for example.
The process for the production of this kind of dyestuff is as follows. One molecular
proportion of the tetrazo compound of either diamido diphenylene oxide or diamido

page_text: ditoluylene oxide is caused to act upon one molecular proportion of an amide, a phenol,
or the sulpho or carbo acid thereof in an acetic acid solution and the intermediate
product thus formed is combined with one molecular proportion of any other amide,
phenol or the sulpho or carbo acid thereof whereby in the same way as hereinbefore
described in the case of two molecular proportions the amide is coupled in an acetic
acid solution and the phenol in an alkaline solution and further treated as before.
The dyestuffs thus obtained yield the greatest variety of shades from yellow red to
violet and blue.
I now proceed to give some examples of the manner in which the new coloring
matters may be manufactured according to this invention.
I. A. Dyestuffs soluble in spirit from one molecular proportion of the tetrazo com-
pounds of diamido diphenylene oxide, diamido ditoluylene oxide and two molecular
proportions of any dyestuff component not containing a sulpho or carboxylic
group.
These dyestuffs are obtained as herein before stated when the tetrazo compounds of
diamido diphenylene oxide and diamido ditoluylene oxide are caused to act upon
amines and phenols, such as aniline, toluidine, xyli line, dimethyl-aniline, diphenylamine,
meta phenylene diamine, meta toluylene diamine, alphanaphthylamine, beta naphthy-
lamine, phenyl-naphthylamine, tolyl-naphthylamine, dinaphthylamine, phenol resorcin,
orcin, alpha-naphthol," heta-naphthol, dioxy-naphthaline also the homologues and
isomers thereof.
I. Dyestuffs from diamido diphenylene oxide and 2 molecular proportions of alpha
naphthylamine.
A solution of tetrazo diphenylene-oxide equivalent to 10 kilos of sodium nitrite
(readily obtained by causing the calculated quantity of a solution of nitrite to flow
into the hydrochloric acid solution of the diamido-diphenylene oxide) is added to a
hydrochloric acid solution of 25 kilos of alpha naphthylamine. On the addition of
sodium acetate, the formation of the dyestuff proceeds and after standing for some
hours it is completed by heating at about 80 degrees Centigrade. The mixture is
acidulated with hydrochloric acid in order to remove any alpha naphthylamine which
may not have taken part in the reaction and the product is then filtered off and dried.
The dyestuff thus obtained dissolves in alcohol with a red colour.
2. A dyestuff from diamido diphenylene oxide and 2 molecular proportions of alpha
naphthol.
A solution of the tetrazo compound of diamido diphenylene-oxide equivalent to
10 kilos of sodium nitrite is poured into an alkaline solution of 25 kilos of alpha-
naphthol. The dyestuff which separates immediately is filtered off and dried.
The dyestuffs obtained by means of the aforesaid amides and phenols or their
isomers and homologues are mostly insoluble in water. They can be rendered soluble
in water by a sulphurizing process.
1. Dyestuff from diamido diphenylene oxide + 2 molecular proportions alpha-
naphthylamine (sulphurizing process).
10 parts by weight of the dyestuff soluble in spirit obtained according to
example I are introduced into 30 parts by weight of fuming sulphuric acid, con-
taining 20 per cent. of anhydride at from about 15 to 30 degrees Centigrade. The
sulphurizing mixture is allowed to stand until a sample dissolves readily in alkaline
water. The melt is poured onto ice, the dyestuff acid which separates is filtered off
and converted into the dyestuff by dissolving in alkali.
B. Soluble dyestuffs from one molecular proportion of the tetrazo compounds of
diamido-diphenylene-oxide, diamido-ditoluylene-oxide and two molecular proportions
of any component containing a sulpho or carboxylic group.
These dyestuffs are formed by the action of the tetrazo compounds of diamido-
diphenylene oxide and diamido ditoluylene-oxide on two molecular proportions of the
sulpho or carbo acids of amides or phenols, such as aniline sulpho acid, toluidine-
sulpho-acid, xylidine-sulpho acid, diphenylamine-sulpho acid, dimethylaniline sulpho
acid, meta-phenylene-diamine-sulpho acid. meta-toluylene-diamine sulpho acid alpha
and beta naphthylamine sulpho-acid, alpha and beta alkyl-naphthylamine sulpho acid,

page_text: alpha and beta naphthol sulpho acid, salicylic acid, oxytoluylic acid, resorcylic acid,
alpha and beta oxy-naphthoic acid, dioxynaphthaline sulpho acid or the homologues
and isomers thereof.
I. Dyestuff; from diamido diphenylene oxide and two molecular proportions of
alpha naphthylamine-mono-sulpho acid.
A solution of the tetrazo compound of diamido-diphenylene-oxide equivalent to
10 kilos of sodium nitrite is introduced into an acetic acid solution of 45 kilos of
alpha-naphthylamine-mono-sulpho acid. After standing for 24 hours, the mixture,
which acquires the consistency of a thick paste is heated at about 80 degrees Centigrade
and then rendered alkaline with soda lye. The resulting dyestuff is salted and filtered
off and dried. It is readily soluble dyestuff of a beautiful fiery blue red shade.
2. Dyestuff from diamido-diphenylene-oxide + 2 molecular proportions of alpha
naphthol-sulpho acid.
If the tetrazo compound of diamido-diphenylene-oxide equivalent to 10 kilos
of sodium nitrite be poured into an alkaline solution of 45 kilos of alpha naphthol
mono-sulpho acid maintained alkaline with sodium carbonate a dyestuff is immediately
formed which dyes cotton in an alkaline bath with a bordeaux like colour.
II. So called mixed dyestuffs.
A. Dyestuff's soluble in spirit; from one molecular proportion of the tetrazo com-
pounds of diamido-diphenylene-oxide and diamido-ditoluylene-oxide and two molecular
proportions of different amides or phenols which do not contain any sulpho or
carboxylic group.
Example: Dyestuffs from diamide diphenylene oxide and one molecular proportion
of alpha-naphthylamine and one molecular proportion of metaphenylene diamine.
a) To a solution of the tetrazo compound of diamido diphenylene oxide equivalent
to 10 kilos by weight of sodium nitrite, a hydrochloric acid solution of 10 kilos by
weight of alpha naphthylamine is added and the mixture made acid by the addition of
sodium acetate. The intermediate product which is soon formed is introduced into an
acetic acid solution of 15 parts by weight of meta-phenylene-diamine. After standing
for 24 hours, the mixture is heated to 80 degrees Centigrade until the reaction is
completed; it is then acidulated with hydrochloric acid and the dyestuff soluble in
spirit is separated by filtration.
b) A similar dyestuff soluble in spirit is obtained when the intermediate product
described in the preceding example obtained from the tetrazo compound of the diamido
diphenylene oxide and alpha naphthylamine is introduced into an alkaline solution
of 12.5 kilos by weight of alpha naphthol. The dyestuff which is immediately formed
dissolves with violet colour in alcohol.
c) All the dyestuffs which can be obtained by this process are for the most part
insoluble in water; they can be rendered soluble in water by a sulphurizing process.
10 parts by weight of the dyestuff soluble in spirit described in example 1 are
introduced into 30 parts of fuming sulphuric acid containing 20 per cent. of anhydride
and the melt is allowed to stand until a sample dissolves in alkali with a brown colour.
It is poured onto ice and the separated dyestuff acid after filtration converted into the
dyestuff by dissolving in alkalies which can be separated by salting out. It dyes
brown.
B. Soluble dyestuffs from one molecular proportion of the tetrazo compounds of
diamido-diphenylene oxide and diamido ditoluylene oxide and two molecular proportions
of different components.
These dyestuffs are obtained by causing one molecular proportion of the tetrazo
compounds of diamido-diphenylene oxide and diamido ditoluylene oxide to act in the
first place upon one molecular proportion of an amide or phenol containing a sulpho
or carboxylic group in an acetic solution, being a process analogous to that described
in section II. A. and then combining the product with any other component, the
amides being coupled in an acetic solution and the phenols in an alkaline solution.
Example. Dyestuffs obtained from diamido-diphenylene-oxide and one molecular
proportion of alpha naphthylamine-sulpho acid, and one molecular proportion of alpha
naphthol-mono-sulpho-acid.

page_text: The tetrazo compound of the diamido-diphenylene oxide equivalent to 10 kilos by
weight of sodium nitrite is caused to flow into an acetic solution of 16 parts by weight
of alpha-naphthionic acid. The intermediate product then formed is introduced into
an alkaline solution of 25 parts by weight of alpha-naphthol-mono-sulpho acid.
The dyestuff being immediately formed is separated by filtration and dried. It dyes
a claret colour.
Having now particularly described and ascertained the nature of the said Inven-
tion and in what manner the same is to be performed, I declare that what I
claim is.
First. The process for the manufacture of diamido-diphenylene-oxide or diamido
ditoluylene oxide by melting ortho benzidine disulpho acid or ortho tolidine disulpho
acid with soda lye in either closed or open vessels (with or without the employment of
pressure) at elevated temperatures as herein before referred to.
Second. The process for the manufacture of direct dyeing-colouring matters from
diamido-diphenylene-oxide and diamido ditoluylene oxide by combining the tetrazo
compounds of diamido diphenylene oxide and diamido ditoluylene oxide:
(a.) With two molecular proportions of any amide, phenol, their sulpho or carbo
or sulpho carbo acids.
(b.) With one molecular proportion of any amide, phenol, their sulpho or carbo
or sulpho carbo acids for the manufacture of the so-called intermediate
products and then with a molecular proportion of any other amide, phenol,
their sulpho, carbo, or sulpho carbo acids.
Third. The process for rendering soluble the dyestuffs claimed in the above second
claiming clause which are only soluble in alcohol, by treating the samo with
sulphurizing agents; such as sulphuric acid or monochlorhydrine.
Fourth. As new articles of manufacture dyestuffs such as those which are produced
according to the foregoing claims II and III.
Dated this 10th day of March 1890
J. H. JOHNSON & Co.,
Agents.