Improvements in or connected with the Manufacture of Azo Colouring Matters for Printing and Dyeing.
Year: 1889

page_text: Date of Application, 18th May, 1889
Complete Specification Left, 18th Mar., 1890-Accepted. 26th Apr., 1890
PROVISIONAL SPECIFICATION.
.
Improvements in or connected with the Manufacture of Azo
Colouring Matters for Printing and Dyeing.
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 The Farbenfabriken vormals Friedrich
Bayer & Co., of Elberfeld, in the Empire of Germany,) to be as follows
According to this invention fast azo colouring matters suitable for printing and
dyeing are obtained by the employment of certain acids such as amido benzoic acid,.
amido oxy benzoic acid, amido para oxy benzoic acid, amido salicylic acid and the
homologues thereof, amido oxy toluylic acid, amido phthalic acid, amido sulpho
benzoic acid, amido sulpho benzoic carbon. acid, amido sulpho oxy benzoic acid, amido
sulpho salicylic acid, 'amido sulpho oxy toluylic acid, amido sulpho cresol carbon
acid, amido naphthaline, carbon acid, amido naphthol carbon acid, amido naphthol
sulpho, carbon acid, and amido naphthaline sulpho. carbon acid, as herein after
described. To obtain useful products these acids are coupled with one molecule of
alpha naphthylamine the amido azo colouring matter obtained is further diazotised
and the diazo compound thereof is caused to act upon any amides phenols or the
sulpho and carbon acids or the sulpho carbon acid thereof.
The colouring matter, hereinbefore, referred to obtained from the aforesaid acids is
or maybe further diazotised being in combination with two molecules of alpha
naphthylamine and caused to act upon an, amide, a phenol or the sulpho and carbon
acids or the sulpho carbon acid thereof in order to obtain colouring matter according
to this invention as hereinafter described.
The colouring matters obtained according to this invention present the peculiarity
of being capable of forming with chromium a fast permanent lake or lac which enables
them to be employed with advantage for printing as well as for dyeing.
The products which directly result from the action of the diazo compounds of any
of the above mentioned acids upon a dyestuff component are of less consequence but
are capable of being employed with advantage for certain purposes.
The great value of the acids hereinbefore referred to becomes apparent when after
the acids have been coupled with the one molecule of alpha naphthylamine the
amido azo compound formed is further diazotised and then caused to act upon a
dyestuff component. The molecule of alpha naphthylamine inserted imparts to the
colouring matter a slight amount of solubility and a greater colouring power. The
shades are influenced in the same way being darker and from bright yellow brown
to the deepest blue black for example are obtained.
Notwithstanding the insertion of one molecule of alpha naphthylamine in the
dyestuff molecule the products derived from the dicarbon acids, the sulpho acids,
benzene and naphthalene phenol and naphthol are too readily soluble and on this
account cannot be made sufficiently fast on the fibre.
These colouring matters can be employed for the direct dyeing of wool in an acid
bath but are not suitable for printing. This disadvantage may be removed by the
introduction into the colouring matter of an additional molecule of alpha naphthyla-
mine that is to say by diminishing the solubility.
The amido salicylic acid, amido oxy toluylic acid and the amido benzoic acid for
example can be coupled with two molecules of the alpha naphthylamine. The peculiar
properties of these colouring matters is apparently connected with the presence of a
carboxyl group
and with the fact of the hydroxyl group being in the ortho position
to the carboxyl group.
The colouring matter or dyestuffs directly derived from the acids hereinbefore
specified are obtained in the usual manner by causing their diazo compounds to act,

page_text: upon dyestuff components the amines being thereby coupled in an acetic bath and the
phenols in an alkaline solution. On the other hand the process of manufacturing those
dyestuffs which contain alpha naphthylamine is somewhat more elaborate. In this
case the diazo compound of the above mentioned'acids is caused to flow into a bydro-
chloric acid solution of the calculated quantity of alpha naphthylamine.
On the addition of solid acetate of soda the new amido azo compound separates
without filtration, is then mixed with the theoretical quantity of a nitrite solution and
acidulated with hydrochloric acid; to complete the diazotising the materials are
allowed to stand for from about 12 to 24 hours and then the insoluble diazo compounds
separated by filtration are added or placed in the alkaline or acetic solution of the
component employed being alkaline with the employment of phenols and acetic when
amines are employed. The first are immediately formed but the second require
more time and at the end must be heated to boiling and made alkaline with
soda lye.
In employing the sulpho carbon acids of phenols and naphthols and the like the
coupling of the second molecule of alpha naphthylamine is proceeded with in such a
manner that the separated diazo compounds of the amido naphthaline azo compounds
are carried into the calculated quantity of the hydrochloric acid solution of alpha
naphthylamine and are treated with acetic acid. After standing for a short time the
materials are heated to about eighty degrees Contigrade, acidulated with hydrochloric
acid, filtered to separate any alpha naphthylamine that may have failed to enter in
reaction and the colouring matter obtained is then dissolved in an alkali. A nitrite
solution being then mixed with the alkaline solution the liquid is cooled and
acidulated.
The diazotising proceeds very rapidly and is completed when the insoluble diazo
compound settles at the bottom, being then separated by filtration the diazo com-
pounds are coupled in the usual manner with dyestuff components (amines in acetic,
phenols in alkaline solution).
Those fast colouring matters obtained substantially as herein before described can
evidently also be obtained by proceeding in the opposite way that is to say by
employing the acids hereinbefore specified as the component instead of employing
them at the outset as in the preceding example of the manufacture of the azo
colouring matter.
In this case it is evident that only those acids can be employed which in addition
to the carboxyl group contain a hydroxyl group and these are not employed as
amido acids but as phenol carbon acids or sulpho carbon acids such as salicylic
acid, oxytoluylic acid naphthol carbon acid, and naphthol sulpho carbon acid for
example.
In the production of this group of colouring matters a suitable amido azo compound
is diazotised and the diazo combination is caused to act upon an alkaline solution of
the above mentioned acid.
The production of antido sulpho salicylic acid and amido sulpho cresol carbon acid
employed for the purposes of this invention is performed as follows.
The amido sulpho salicylic acids are usually obtained by sulphurising amido sali-
cylic acid or nitro salicylic acid and reducing the resulting nitro sulpho salicylic
acid.
The acids thus obtained readily separate from or part with the carboxyl group in
the form of carbonic acid as in the case of ortho nitro salicylic acid for example and
on this account this process is not satisfactory in practice.
My foreign correspondents have now discovered a process which, (in opposition to
the usual method, in which sulpho salicylic acid must not react with nitric acid) is
based on the nitration of sulpho salicylic acid at a higher temperature. The sulpho
salicylic acid obtained by the introduction of one part of salicylic acid into three parts of
acid of 66 per cent. strength at a temperature of from about 90 to 100 degrees Centi-
grade, is mixed, without insulating or separation, with the calculated quantity of
nitric acid at a temperature of from about 52 to 70 degrees Centigrade. The melt
which was previously thick is thereby dissolved into a clear liquid of a deep yellow

page_text: colour. It is allowed to stand for about 24 hours at atmospheric temperature, poured
out upon ice and zine dust is added to the yellow nitro compound to effect the
reduction equivalent to 14 parts of the salicylic acid employed. The reduction
proceeds slowly at 80 degrees Centigrade, a clear solution results and on cooling the
amido sulpho salicylic acid separates in fine white needles. This product is readily
soluble in hot water sparingly soluble in cold and thus can be purified by dissolving it.
It forms a soluble diazo compound of a yellowish colour.
When, in place of the salicylic acid the m or p oxytoluylic acid is employed we
obtain by operating under the same conditions the heretofore unknown amido sulpho
acids the m and p oxytoluylic carbon acids. The free acils crystallise in fine needles
and produce soluble diazo compounds.
The following examples are given to explain the production of the new fast
azo colouring matters for printing and dyeing as manufactured according to this
invention.
Colouring matter with one molecule of alpha naphthylamine.
The production of the first intermediate product from the following acids namely
amido benzoic acid amido oxy benzoic acid, amido salicylic acid, amido para oxy
benzoic acid, amido oxy toluylic acid amido phthalic acid, amido sulpho benzoic
carbon acid, amido sulpho oxy benzoic acid amido sulpho salicylic acid, amido sulphó
cresol carbon acid and amido naphthol carbon acid, with one molecule of alpha
naphthylamine and the conversion of the diazo compotind thus obtained may be illus-
trated by the following example.
Process with p amido salicylic acid + alpha naphthylamine.
About eleven and a half parts by weight (115 kilos) of pamido salicylic acid are
dissolved in water cooled and a solution of about five parts by weight of nitrite is
added thereto. On the addition of hydrochloric acid the diazo compound separates in
crystals. After a few minutes the diazotising is complete and the diazo compound
thus obtained is caused to flow into a hydrochloric acid solution of about ten parts bý
weight (10 kilos) of alpha naphthylamine.
On the addition of acetic soda the formation of the intermediate product proceeds
and the originally then liquid thickens till it becomes a paste.
Without filtering or
heating this intermediate product after standing for about 2 or 3 hours can be further
treated for its conversion into its diazo compound. A solution of about five parts
(5 kilos) of nitrite is caused to flow into the acetic paste and it is acidulated with
hydrochloric acid with continual stirring.
a
The deposit or precipitate which was previously thick and black becomes gradually
thinner and assumes a clearer colour and after about 2 or 3 hours presents a golden
brown the formation of the diazo compound being completed.
The diazo compounds thus obtained from the acids hereinbefore specified arc
separated by filtration and caused to act upon amides and phenols, the sulpho and
carbon acids or the sulpho carbon acids thereof the coupling of the amide taking place
in an acetic solution and that of the phenol in an alkaline solution. To complete the
reaction the former are heated to about 80 degrees Centigrade and made alkaline with
soda lye.
Process with o amido salicylic acid + alpha naphthylamine + alpha naphthylamine
mono sulpho acid.
A quantity of filtered off diazo compound of o amido salicylic acid + alpha naph-
thylamine corresponding to about five parts by weight (5 kilos) of nitrite is
introduced into an acetic acid solution of about thirty parts by weight (30 kilos) of
alpha naphthylamine mono sulpho acid.
The action or the formation of the colouring matter proceeds slowly and the
materials must be allowed to stand for about 2 or 3 days at about 30 degrees, the
temperature is then slowly raised to 80 degrees and the materials neutralised with
soda lye. The colouring matter is separated in the usual way by salting out, it dyes
and prints a dark brown colour.
Process with amido meta oxytoluylic acid + alpha naphthylamine + alpha naphthol
mono sulpho acid.
:

page_text: A quantity of the diazo compound of amido meta oxy toluylic acid alpha naph-
thylamine corresponding to about five parts by weight (5 kilos) of nitrite is introduced
into a solution, maintained alkaline with soda, of about twenty five parts (25 kilos)
of alpha naphthol mono sulpho acid. The formation of the dyestuff proceeds
immediately.
As the diazo compound employed is insoluble it is preferred to heat the materials
to about 80 degrees Centigrade. The colouring matter formed is separated by
salting out in the usual way it prints a blue black and dyes wool the same shade.
Process with p amido phthalic acid + alpha naphthylamine + beta naphthol
The filtered off diazo compound of p amido naphthalic acid + alpha naphthylamine
containing about five parts by weight (5 kilos) of nitrite is introduced into an
alkaline solution of about twelve and a half (125 kilos) parts by weight of beta
naphthol. It is then heated to about 80 degrees and the colouring matter formed is
separated by filtration. It prints a brown colour.
1
Process with amido sulpho salicylic acid + alpha naphthylamine + alpha napthol
disulpho acid.
The filtered off diazo compound of amido sulpho salicylic acid + alpha naphthyl-
amine containing about five parts by weight (5 kilos) of nitrite is introduced into a
solution, maintained alkaline with soda, of about thirty five parts by weight (35 kilos)
of alpha naphthol disulpho acid. A deep blue colour results, the materials are
heated to about 80 degrees and the colouring matter formed is salted out. This
product dyes wool a deep blue black in an acid bath and prints blue.
Process with amido alpha naphthol carbon acid + alpha naphthylamine + alpha
naphthol sulpho acid.
The diazo compound of amido alpha naphthol carbon acid + alpha naphthylamine
containing about five parts by weight (5 kilos) of nitrite is introduced into an
alkaline solution of about twenty five parts (25 kilos) of alpha naphthol mono sulpho
acid, the temperature is raised to about S0 degrees and the materials are filtered.
This colouring matter is sparingly soluble and prints a blue black.
Obtaining colouring matter with two molecules of alpha naphthylamine.
As hereinbefore explained an additional molecule of alpha naphthylamine can be
introduced in the colouring matter obtained with the employment of the acids herein-
before specified. The colouring matters thus obtained differ very essentially from
those obtained as herein before described. They are less soluble especially in the case
of the products derived from the amido benzoic acids and the amido salicyclic acids
or amido cresol carbon acids, and possess a darker shade throughout. They
also for the most part fail to possess the property of dyeing wool but are beiter
suited for printing purposes than are the corresponding products obtained with only
one molecule of alpha naphthylamine.
The coupling of a second molecule of alpha naphthylamine with the diazo com-
pounds obtained according to the process hereinbefore described proceeds very
smoothly in an acetic solution.
The production of the diazo compounds employed in this process from the following
acids namely amido benzoic acids, amido oxy benzoic acids, amido para oxy benzoic
acid and amido salicylic acid, amido oxy toluylic acid, amido phthalic acid, amido
sulpho benzoic carbon acid, amido sulpho oxy benzoic acid, amido sulpho salicylic
acid, amido sulpho cresol carbon acid and amido naphthol carbon acid with two
molécules of alpha naphthylamine may be illustrated by the following example
namely:
About thirty eight parts by weight (38 kilos) of the colouring matter (amido
sulpho salicylic acid + alpha naphthylamine + alpha naphthylamine) are dissolved in
alkali and being coupled are mixed with a solution of about five parts (5 kilos) of
nitrite. The product is acidulated with hydrochloric acid stirred in and then left to
stand for about 2 or 3 hours. The thick black precipitate formed on the addition of
the acid gradually becomes thin and of a clearer colour. The diazo compounds
produced in like manner from the above mentioned acids are separated by filtration
and caused to act upon dyestuff components.
1.

page_text: The best results are obtained with this process by using the naphthol sulpho acids
as these give pure blacks, the amides being brown black etc.
Process with o amido salicylic acid + alpha naphthylamine + alpha naphthyl-
amine alpha naphthol mono sulpho acid.
The diazo compound separated by filtration of o amido salicylic acid + alpha naph-
thylamine alpha naphthylamine containing about five parts by weight (5 kilos) of
nitrite are introduced into a solution, maintained alkaline by soda, of alpha naphthol
mono sulpho acid. The mixture is heated to about 80 degrees Centigrade and the
separating colouring matter is filtered off. This product is sparingly soluble and
prints black.
Process with amido sulpho salicylic acid + alpha naphthylamine + alpha naphthyl-
amine alpha naphthionic acid.
The diazo compound separated by filtration of amido sulpho salicylic acid + alpha
naphthylamine + alpha naphthylamine containing about five parts by weight (5 kilos)
of nitrite is introduced into an acetic acid solution of about thirty parts by weight
(30 kilos) of alpha naphthylamine mono sulpho acid.
The action proceeding very
slowly the mixture is heated to about 30 degrees and allowed to stand at this tem-
perature for about two or three days, the temperature is then raised to 80 degrees
and the solution made alkaline with soda lye. The dyestuff thus obtained prints a
brown black.
Process with amido sulpho meta oxy toluylic acid + alpha naphthylamine + alpha
naphthylamine + beta naphthol disulpho acid.
By causing the diazo compound of amido sulpho meta oxy toluylic acid alpla
naphthylamine + alpha naphthylamine containing about five parts by weight (5 kilos)
of nitrite to act upon about thirty five parts by weight (35 kilos) of beta naphthol
disulpho acid in an alkaline solution a beautiful blue black colouring matter is obtained
which prints a fast blue black.
Process with amido sulpho benzoic acid + alpha naphthylamine + alpha naphthyl-
amine alpha naphthol mono sulpho acid.
In this process the diazo compound of amido sulpho benzoic acid + alpha naph-
thylamine + alpha naphthylamine being caused to act upon alpha naphthol mono
sulpho acid a splendid black printing colour is obtained.
Process with amido alpha naphthol carbon acid + alpha naphthylamine + alpha
naphthylamine + alpha naphthol disulpho acid.
The diazo compound of amido naphthol carbon acid + alpha naphthylamine con-
taining about five parts by weight (5 kilos) of nitrite being caused to act upon about
thirty five parts (35 kilos) of alpha naphthol disulpho acid in an alkaline solution
leads to a very insoluble grey black colouring matter printing a black.
Daied this 18th day of May 1880
;
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
Improvements in or connected with the Manufacture of Azo
Colouring Matters for Printing and Dyeing.
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
vorm. Friedr.
to me from abroad by The Farbenfabriken
communicated
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 :-
:
According to this Invention fast azo colouring matters suitable for printing and
dyeing are obtained by the employment of certain acids namely amido-benzoic acids
amido hydroxy-benzoic acids such as amido para-hydroxy-benzoic acid, amido-
salicylic-acid and amido bydroxy toluic acids; amido phthalic acids; amido-sulpho

page_text: .
:
benzoic acids amido sulpho salicylic acids ; amido sulpho-cresol carboxy acids and the
amido methoxy-benzoic acids as hereinafter described.
To obtain useful products these acids are coupled with any azo dyestuff component
or first with alphanaphthylamine, then re-diazotized and combined with amines or
phenols, their sulpho or carboxy acids.
.
The colouring matters obtained according to this Invention present the peculiarity
of forming with chromium or iron salts fast permanent lakes which enables them to be
employed for dyeing and printing purposes.
By the combination of the diazo compounds of the above named amido carboxy
acids with amines phenols, their sulpho or carboxy acids, azo-dyestuffs result, some
only of which are new and valuable. They are derived especially from dioxynaph-
thalenes and carboxy acids iz. 1, 8 and 1, 2 dioxynaphthalenes naphtholcarboxy acids,
salicylic acid and cresol carboxy acids. The dioxynaphthalenes afford violet blue to
blue black dyestuffs according to the nature of the dioxynaphthalenes and the amido
carboxy acids employed. Salicylic acid, the cresol carboxy acids, the amido benzoic
acids, the amidophthalic acids and the amidoanisic acids give fine yellow to yellowish
red dyestuffs, but the other amido carboxy acids cannot be employed with good
results. The naphtholcarboxy acids yield catechu brown to red brown dyestuffs. All
these dyestuffs possess the property of being adapted for printing purposes if they be
printed with any chromium salt. They owe this property to the carboxylic group
which they all contain and which enables them to form fast chromium lakes which are
suited for printing purposes. They can also be employed for dyeing purposes either for
dyeing wool in a weak acid bath or with oxalic acid and sulphate of iron, or for dyeing
wool which has been mordanted with chromium salts.
Another new series of dyestuffs is derived from these amido carboxy acids if they
be first combined with alpha naphthylamine and the resulting amido naphthalene
azo-dyestuffs be diazotised again and then combined in the well known manner with
any amine phenol or a sulpho or carboxy acid thereof. By this increase of the
dyestuff molecule by the addition of one molecule of alpha naphthylamine a great
technical effect is obtained. The dyestuffs which are formed by the combination of
the diazo compounds of the above named amido carboxy acids with amines, their
sulpho acids and the sulpho acids of phenols are too soluble and therefore worthless,
but by the present process for the manufacture of dyestuffs they are rendered of
great technical value. They are more difficultly soluble in water and are now suitable
for a technical employment.
Further the shades of the dyestuffs are much influenced by the employment of
the new process and from bright yellow or brown to the deepest blue black dyestuffs
are obtained.
The intensity of the new dyestuffs and their affinity to fibres are likewise advan-
tageously influence..
Those dyestuffs which are difficultly soluble are employed for dyeing wool,
mordanted with any chromium salt in a weak acetic acid bath, but those which are
easily soluble, dye wool directly with oxalic acid and sulphate of iron or alone
with sulphuric acid or with common salt. The colours thus obtained are absolutely
fast to soap, milling and sunlight.
For printing purposes they can not be employed so well as the first class of new
carboxy acid dyestuffs, herein before described, because by the increase of their
molecule by the addition of alpha naphthylamine they lose in a remarkable degree the
property of forming absolutely fast lakes with chromium salts. The colouring matters
derived from the acids herein before specified and the phenols are manufactured in the
usual manner by causing the diazo compounds of the amido carboxy acids to act
on an alkaline solution of the phenols and their carboxy acids. On the other hand
the process for the manufacture of dyestuffs which contain one molecule of alpha'
naphthylamine in their dyestuff molecule is somewhat more difficult. In this case
the diazo compounds of the above mentioned acids are added to a hydrochloric acid
solution of the calculated quantity of alphanaphthylamine.
":
13

page_text: brown crystals. After a few minutes the diazotising is complete and the diazo com-
pound thus obtained is caused to flow into a hydrochloric acid solution of about ten
parts by weight of alpha naphthylamine. On the addition of sodium acetate the
formation of the intermediate product proceeds and the originally thin liquid thickens.
till it becomes a paste. After standing for some hours it is heated, to 50 degrees
Centigrade and filtered off. To convert it into its diazo compound it is dissolved in
alkali, and to this solution is added a solution of about five parts by weight of sodium
nitrite and the mixture is acidulated with hydrochloric acid.
. The precipitate which was previously thick and black becomes gradually thinner
and assumes a clearer colour and after about 2 or 3 hours presents a golden brown
colour the formation of the diazo compound being completed. The diazo compounds
thus obtained from the acids herein before specified are separated by filtration and if.
soluble in water, are salted out and caused to act upon amides and phenols, the sulpho
and carboxy acids or the sulpho carboxy acids thereof, the coupling of the amido com-
pound taking place in an acetic acid solution and that of the phenol in an alkaline
solution. To complete the reaction the former are heated to about 80 degrees
Centigrade and made alkaline with soda lye.
EXAMPLE IV. BROWN DYESTUFF FROM ORTHO-AMIDO-SALICYLIC ACID + ALPHA-
NAPHTHYLAMINE + SALICYLIC ACID.
A quantity of the separated diazo compound of amido salicylic acid alpha
naphthylamine corresponding to about five parts by weights of sodium nitrite is
introduced into an acetic acid solution of about 12 parts by weight of salicylic acid.
The mixture is cooled by ice and slowly neutralized with diluted soda lye. After
standing for 12 hours a fine brown dyestuff results which dyes chromium mordanted
wool yellow brown.
EXAMPLE V. VIOLET DYESTUFF FROM AMIDO-SALICYLIC AOID + ALPHA
NAPHTHYLAMINE + ALPHA-NAPHTHYLAMINE-MONOSULPHO ACID.
The diazo compound of the dyestuff of amido-salicylic acid + alpha naphthylamine
corresponding to 5 kilos of sodium nitrite is introduced into an acetic acid solution of
about 20 kilos of alpha naphthylamine monosulpho acid. After standing for some
hours.it is heated to about 70 degrees Centigrade made alkaline with soda lye and the
resulting dyestuff is salted out. It dyes violet.
EXAMPLE VI. BLUE BLACK DYESTUFF FROM AMIDO
META-HYDROXYTOLUIC
ACID ALPHA NAPHTHYLAMINE + ALPHA-NAPHTHOL MONO SULPHO ACID.
A quantity of the diazo compound of amido meta hydroxy-toluic acid + alpha
naphthylamine corresponding to about five parts by weight of sodium nitrite is
introduced into a solution of about twenty five parts by weight of alpha naphthol
mono sulpho acid, maintained alkaline with soda. The formation of the dyestuff
proceeds immediately. As the diazo compound employed is insoluble, it is preferable
to heat the materials to about 80 degrees Centigrade. The colouring matter thus
formed is separated by common salt. It dyes mordanted wool blue black, wool direct
violet black.
EXAMPLE VII. BLUE BLACK DYESTUFF FROM AMIDO SULPHO SALICYLIC
ACID NAPHTHYLAMINE + BETA NAPHTHOL.

page_text: 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 :-
I. The process for the manufacture of azo colouring matters for dyeing and
printing:
(a). By combining the diazo compounds of the amido carboxylic acids viz.-
Amido benzoic acids,
Amido hydroxy benzoic acids,
Amido-cresol carboxy acids,
Amido phthalic acids,
Amido sulpho benzoic acids,
Amido sulpho salicylic acids,
Amido sulpho-cresol carbo acids,
Amido anisic acids,
with 1, 8 and 1, 2 dioxynaphthalenes, alpha and beta naphtholcarboxy acids.
(b). By combining the diazo compounds of the amido carboxy acids of
Amido benzoic acids,
Amido phthalic acids,
Amido anisic acids with salicylic acids and cresol-carboxy acids.
(c). By combining the amido carboxy acids mentioned in claim I with one
molecule of a naphthylamine, again diazotising the resulting amido azo com-
pounds and combining the new diazo compounds with amines, phenols, their
sulpho and carboxy acids.
II. As new articles of manufacture products such as are produced according to the
foregoing claiming clause.
Dated this 18th day of March 1890.