Year: 1885

page_text: I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of said Invention which has been
communicated to me from abroad by Farbenfabriken vorm Friedrich Bayer
and Company of Elberfeld in the Empire of Germany to be as follows:-
This Invention relates to a process for the production of yellow red and blue
azo dyes by the action of the tetrazo compounds of the methyl, ethyl, amyl and
benzyl ethers of the diamidodiphenols or of the diamidodi kresols upon phenol,
resorcin, phenol carbo acids and resorcyl acids, alpha and beta naphthols and their
mono and disulpho acids dioxynaphthalines alpha and beta naphthylamines and
their mono and disulpho acids, alpha and beta oxynaphthoic acids and the substi-
tution products of these substances.
By the conversion of "dianisidines" which term is hereinafter employed to
designate the ethers of diamidodiphenols (which are most advantageously obtained
by alkaline reduction of nitrophenol or nitrokresol-ethers and transposition
(umlagerung) of the hydrazo compounds formed) into their tetrazo compounds and
causing this product to act upon phenols, naphthols amides and their sulpho-acids,
carbo-acids and substitution products there is obtained a large number of new
yellow, red and blue azo dyes of a blue or green tinge or shade which will dye.
unmordanted cotton in an alkaline bath in the same way as benzidine and tolidine
dyes-Diamedodiphenetol diazotised by known means furnishes a tetrazo compound
or tetrazodiphenetol which is readily soluble in water which produces dyes of
various shades, from yellowish to blueish red and sensitive to the action of light;
by acting upon phenols and dioxyphenols; or yellow not affected by light; by
acting on phenol carbo acids; or from greenish blue to violet; by acting on alpha
and beta naphthol sulpho acids; or red; by acting on naphthol carbo acids or from
very fine yellowish red to deep blueish red by acting on alpha and beta naphthyl-
amine sulpho acids.
In the place of the diamidodiphenetol or the ethyl ether of the diamido diphenols,
the methyl, ethyl amyl or benzyl ethers of diamido diphenol or diamidodikresol
may be employed with the same effect,

page_text: These new dyes are most advantageously obtained by mixing the products
employed in effecting the combination of the tetrazo compounds of the dianisidines
with phenols naphthols and the sulpho and carbo acids thereof in an alkaline
solution; or in an organic acid solution in effecting the combination of the same
with alpha and beta naphthylamines and the sulpho acids thereof-The formation
of a dye may however be accomplished by reversing this method.
The following may be given as examples of the formation of a dye according to
this Invention :-
I. A practically useful acid proof blue dye much greener than the corresponding
tolidine product known in commerce as azo blue is obtained by causing tetrazo-
dianisol or tetrazodiphenetol to act upon alpha naphthol alpha mono sulpho acid-
An aqueous solution containing a diamidodiphenetol salt whose strength has been
ascertained by titration with sodium nitrite is diazotised at a low temperature
with the employment of muriatic acid in excess and the calculated quantity of
sodium nitrite The tetrazo compound thus formed and which is readily soluble
in water is then allowed to run slowly into a solution (maintained alkaline to the
end by means of soda) of soda salt of alpha naphthol, mono sulpho acid which is
thoroughly stirred at the same time and is obtained by combining sulphuric acid
and alpha naphthol or by boiling alpha diazo naphthaline mono-sulpho acid with sul-
phuric acid About thirty six parts by weight of the alpha naphthol, alpha mono
sulpho acid soda are employed to ten parts by weight of the sodium nitrite for
example After standing for several hours the dye separates in the form of a
reddish blue precipitate the precipitation of which may be completed by means of
salt The deposit is then collected by filtering and dried.
By this process a dark blue powder presenting a slight bronze lustre is obtained
which may be dissolved with a red colour in soda lye or with an intense blue in
concentrated sulphuric acid and will dye unmordanted cotton a greenish blue in an
alkaline bath preferably prepared with potash.
.
II. In order to produce a red dye with a blueish tinge the tetrazo compound
obtained as aforesaid of the diamido dianisol or of the diamido diphenetol is mixed
with water containing an excess of fine beta naphthylamine beta mono sulpho acid
(formed by combining beta naphthylamine with fuming sulphuric acid or sulphu-
rising the same by the Neville-Winter process) in suspension-In this case about ten
parts by weight of sodium nitrite are employed to from say about thirty seven to
forty parts by weight of beta naphthionic acid-An organic acid salt preferable
acetate of soda is then to be added until all the muriatic acid is combined and the
solution acquires a strong smell of acetic acid.
The materials are then allowed to stand about 24 hours until the brown deposit
originally formed has become red and after neutralising with alkali the deposit is
separated by filtering and dried with care-A red powder is thus obtained which
is very readily dissolved in water, is unchanged by alkalies, is turned blue by
concentrated acid and will dye raw cotton a splendid blueish red in the same way
as saffranine in an alkaline bath preferably prepared with potash.
The dyes obtained by the action of tetrazodiphenol or tetrazodik resol ethers with
alpha and beta naphthol alpha and beta naphthylamine are insoluble in water but
may be sulphurised by treatment with fuming sulphuric acid at a low temperature
and are thereby rendered soluble in water.

page_text: I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been
communicated to me from abroad by Farbenfabriken vorm Friedrich Bayer &
Compy 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:-
By the conversion of "dianisidines" which term is hereinafter employed to
designate the ethers of diamido diphenols (which are most advantageously obtained
by alkaline reduction of nitrophenol or nitrokresol ethers and transposition
(umlagerung) of the hydrazo compounds formed into their tetrazo compounds and.
causing this product to act upon phenols napthols amides and their sulpho-acids
carbo acids and substitution products there is obtained a large number of new
yellow red & blue azo dyes of a blue or green tinge or shade which will dye
unmordanted cotton in an alkaline bath in the same way as benzidine and tolidine
dyes. Diamedo diphenetol diazotised by known means furnishes in the same way
a described by Möhlan in the Journal für Proktische Chemie (2) 13,383, and
by Bellstein. the Handbuch der organishen Chemie (1883) 1354 a tetraazo
compound or tetrazo diphenetol which is readily soluble in water which produces
dyes of various shades from yellowish to blueish-red and sensitive to the action of
light by acting upon phenols and dioxyphenols, or yellow not affected by light, by
acting on phenol carbo acids, or from greenish blue to violet by acting on alpha
and beta naphthol sulpho acids, or red by acting on naphthol carbo acids, or very
fine yellowish red to deep blueish red by acting on alpha and beta naphthylamine
sulpho acids.
In the place of the diamido diphenetol or the ethyl ether of the diamido
diphenols, the methyl ethyl amyl or benzyl ethers of diamido diphenol or diamido
dikresol may be employed with the same effect.
These new dyes are most advantageously obtained by mixing the products
employed in effecting the combination of the tetrazo compounds of the dianisidines
with. phenols, naphthols and the sulpho and carbo acids thereof in an alkaline
solution, or. in an organic acid solution in effecting the combination of the same
with. amides alpha and beta naphthylamines and the sulpho acids. thereof The
formation of a dye may however be accomplished by reversing this method.
The following may be given as examples of the formation of a dye according to
this invention.
a) A practically useful acid proof blue dye much greener than the corresponding
tolidine product known in commerce as azo blue is obtained by causing tetrazo
dianisol or tetrazo diphenetol to act upon alpha uaphthol, alpha mono sulpho acid.
An: aqueous solution containing a diamido diphenetol salt, who strength has been
ascertained by titration with sodium nitrite is diazotised at a low temperature
with the employment of muriatic acid in excess and the calculated quantity of
sodium nitrite. The tetrazo compound thus formed and which is readily soluble
in water is then allowed to run slowly into a solution (maintained alkaline to the
end by means of soda) of soda salt of alpha naphthol mono sulpho acid which is

page_text: thoroughly stirred at the same time and is obtained by combining sulphuric acid
and alpha naphthol or by boiling adpha diazo naphthaline mono sulpho acid with
sulphuric acid. About thirty six parts by weight of the alpha naphthol alpha mono
sulpho acid soda are employed to ten parts by weight of the sodium nitrite for
example After standing for several hours the dye separates in the form of a reddish
blue precipitate the precipitation of which may be completed by means of salt.
The deposit is then collected by filtering and dried.
By this process a dark blue powder presenting a slight bronze lustre is obtained
which may be dissolved with a red colour in soda lye or with an intense blue in
concentrated sulphuric acid and will dye unmordanted cotton a greenish blue in an
alkaline bath preferably prepared with potasb.
(b) In order to produce a red dye with a blueish tinge the tetrazo compound
obtained as aforesaid of the diamido dianisol or of the diamido diphenetol is mixed
with water containing in suspension an excess of fine beta naphthylamine beta
mono sulpho acid (formed by combining beta naphthylamine with fuming sulphuric
acid or sulphurising the same by the Neville-Winter process) in suspension. In
this case about 10 parts by weight say 10 kilos of sodium nitrite are employed to
from about thirty seven to forty parts by weight or from 37 to 40 kilos of beta
naphthionic acid. An organic acid salt preferably acetate of soda is then to be
added until all the muriatic acid is combined and the solution acquires a strong
smell of acetic acid. The materials are then allowed to stand about 24 hours until
the brown deposit originally formed has become red and after neutralizing with
alkali the deposit is separated by filtering and dried with care, otherwise it is liable
to melt in the drying. A red powder is thus obtained which is very readily
dissolved in water, is unchanged by alkalies, is turned blue by concentrated acid,
and will dye raw cotton a splendid blueish red in the same way as saffranine, in an
alkaline bath preferably prepared with potash.
The dyes obtained by the action of tetrazo diphenol, or tetrazo dikresol ethers
with alpha and beta naphthol alpha and beta naphthylamine, are insoluble in
water, but may be sulphurised by treatment with fuming sulphuric acid, at a low
temperature and are thereby rendered soluble in water.
In carrying out the process in the manner herein before described one molecule
of the tetrazo compound is always employed to act upon two molecules of phenol
etcetera, or phenol etcetera in excess. By the action of one molecule of the tetrazo
diphenol ether upon one molecule of a phenol or a phenol sulpho acid, an amide
or an amido sulpho acid, substances are produced possessing no colouring properties
in themselves but are capable of forming dyes by subsequent action upon phenols
amides and the sulpho and carbo acids thereof. When in two successive operations
the same phenol or phenol sulpho acid, amide or amido sulpho acid is caused to act
upon the diazotised dianisidine the dyes herein before described are obtained, but if
in the second operation another or different phenol' amide etcetera be employed
dyes can also be produced which in the same way as the dye described in the first
instance, possess the property of dyeing unmordanted wool in an alkaline bath.
The combinations thus rendered possible are very numerous.
The processes
next hereinafter described serve as examples of the production of dyes by means
of this reaction.
(a) Dyes obtained from dianisidine, alpha naphthylamine sulpho acid and alpha
naphthylamine.
The diamido diphenol ether is transposed or converted as described into its
tetrazo compounds and then allowed to run slowly into a solution of acetate of
soda containing the exact quantity of alpha, naphthylamine sulpho acid requisite
for one molecule. For example if say 10 kilos of nitrite of soda have been used
for diazotising the dianisidine solution, about 16 kilos of naphthionic acid and
about 32 kilos of acetate of soda will be required. After standing for a short time
a brown deposit is formed which forms the intermediate product hereinbefore
referred to. Now if to this first combination an aqueous solution of acetate of
alpha naphthylamine be added and the mixture allowed to stand with frequent

page_text: stirring for about twenty four hours and neutralised with an alkali a dye is obtained
which is insoluble in cold water, being soluble with difficulty in hot water, and
which dyes cotton a deep blueish red.
Similar results may be obtained by employing beta naphthylamine or beta
naphthylamine sulpho acids in place of the alpha naphthylamine.
(b) Dyes obtained from dianisidine, beta naphthylamine sulpho acid and alpho
naphthol sulpho acid. By substituting for the alpha naphthylamine sulpho acid,
beta naphthylamine employed under the same conditions as described in the
preceding example and allowing the intermediate product so obtained to act upon
a solution of alpha naphthol sulpho acid maintained alkaline to the end with soda
a new reddish blue dye is produced.
The shade of the dye may be changed or modified by substituting alpha or
beta naphthol or one of the known beta naphthol sulpho acids for the alpha
naphthol sulpho acid.
(c) Dyes obtained from dianisidine alpha naphthol and alpha naphthol sulpho
acids.
A good strong dye of greenish blue colour is obtained by allowing the inter-
mediate product obtained by the combination of a tetrazo diphenol ether.solution
with the quantity of alpha naphthol calculated for one molecule in an acetic acid
solution to act upon naphthol sulpho acid. To 10 kilos for example of nitrite of
sodium about 10 kilos of alpha naphthol about 20 kilos of acetate of soda and about
18 kilos of alpha naphthol mono sulpho acid soda are required.
(d) Dyes obtained from dianisidine sulphanilic acid (sulphanilsaure) and
salicylic acid.
Reddish yellow dyes whose properties resemble those of the dyes obtained by
the action of one molecule of dianisidine upon two molecules of salicylic acid are
obtained by the successive action of sulphanilic acid and salicylic acid upon tetrazo
diphenol ether the sulphanilic acid being employed in an organic acid bath, such
as a solution of acetic acid, and the salicylic acid being employed in an alkaline
solution.
Assuming that 10 kilos for example of nitrite of sodium have been employed for
the diazotising about 12.4 kilos of sulphanilic acid and about 10 kilos of salicylic
acid will be required.
The process may be modified by allowing the salicylic acid to act in the first
instance and the sulphanilic acid in the second instance.
The foregoing examples suffice to shew that the reactions herein before described
may be variously combined and applied. In carrying out the same any of the
materials hereinafter enumerated may be employed with good practical results.
1. Phenols. Phenol, cresol, resorcin alpha and beta naphthol and the ethers of
these compounds.
2. Phenol sulpho acids.-Phenol and cresol sulpho acid resorcyl acid alpha and,
beta naphthol mono and di-sulpho acids.
3. Phenol carbo acids.-Oxybenzoic acids (salicylic acid) and alpha and beta
oxynaphthoic acid.
4. Amides. Aniline, toluidine, xylidine, cumidine alpha and beta naphthylamine
and the mono and di-alkyl derivatives of these substances.
5. Amido sulpho acids.-Mono and di-sulpho acids of aniline toluidine, xylidine,
cumidine, alpha and beta naphthylamine.
6. Amido carbo acids.-Amido benzoic acids.
Having now particularly described and ascertained the nature of the said
Invention and the manner in which the same is to be performed I declare that
what I claim is :-
First. A process for the production of yellow red and blue azo dyes which will
dye unmordanted cotton in an alkaline bath the said process consisting in causing
tetrazo compounds of the methyl, ethyl, amyl and benzyl ethers of the diamido
diphenols or of the diamido dikresols to act upon phenol, resorcin, phenol carbo

page_text: acids and resorcyl acids, alpha and beta naphthols and their mono and disulpho
acids dioxynaphthalines alpha and beta naphthylamines and their mono and
disulpho acids, alpha and beta oxynaphthoic acids and the substitution products of
these substances substantially as herein before described.
Second. Treating the dyes obtained by the action of the dianisidines enumerated
in claim 1 upon alpba and beta naphthol or alpha and beta naphthylamine with
fuming súlpburic acid at a low temperature in order to render them soluble in
water substantially as herein before described.
Third. The process for obtaining azo dyes which will dye unmordanted cotton
in an alkaline bath the said process consisting in causing one molecule of the
intermediate product formed by the action of one molecule of a tetrazo diphenol
ether (such as methyl, ethy!, propyl, butyl and amyl ether) on one molecule of a
phenol, amide or the sulpho or carbo acids thereof to act upon one molecule of the
same or of another phenol, amide or their mono and disulpho acids or carbo acids
substantially as hereinbefore described.
Fourth. As a new product of manufacture the dye obtained by the process
referred to in the first claiming clause.
Fifth. As a new product of manufacture the dye obtained by the combination
of processes referred to in the second claiming clause.
Sixth. As a new product of manufacture the dye obtained by the modified
process referred to in the third claiming clause.
Dated this Lot day of Anil 1996