Year: 1886

page_text: Date of Application, 30th Dec.. 1886
Complete Left, 29th Sept., 1887
Complete Accepted, 1st Nov., 1887
JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been communi-
cated to me from abroad by Farbenfabriken vormals Friedrich Bayer and Company
of Elberfeld in the Empire of Germany to be as follows:-
This Invention relates to the production of dyes soluble in spirit or in water by the
action of the tetrazo compounds of benzidine, tolidine, diamido di xylyl diamido di
phenol ether, diamido stilbene, diamido fluorene, diamido azo benzol and their homo-
fogues or their mono or di sulpho acids upon the mono or di methylised, ethylised,
propylised, butylised, amylised, or benzylised alpha or beta maphthylamine or the
mono or di sulpho acids thereof as hereinafter described.
Dyes which are essentially bluer and possess the same properties as those obtained
by the action of tetrazo compounds of the di para diamines of the di phenyl series
upon naphthylamines and their sulpho acids, can be formed by substituting in place
of the latter the mono or di alkylised derivatives thereof. These dyes are obtained
according to this invention by causing an aqueous solution of the tetrazo salt to flow
into a similar solution of the salt of the mono or di sulpho acid of the alkylised alpha
or beta naphthylamine and saturating or neutralising any mineral acid that may be
present by means of salts of organic acids such for example as acetate of soda. In
place of the aforesaid solutions with water alcoholic solutions may be employed and
the free acids may be substituted for the sulpho acid salts herein before referred to.
The dyes (soluble in spirit) obtained by the action of the tetrazo compounds upon the
alkylised naphthylamines proferably in alcoholic solution are rendered soluble in water
by a sulphating process such as treatment with sulphuric acid or other sulphating
agent.
The di para diamines of the diphenyl series herein before referred to include
benzidine, tolidine, diamido di xylyl, diamido di phenol ether, diamido stilbene,
diamido fluorene, diamido azo benzol or their homologues, diamido azo xylol and
dianido azo toluol or the sulphones or the mono or di sulpho acids of these
substances.

page_text: The alkylised naphthylamines herein before referred to include mono or di methylised,
ethylised, propylised, butylised, amylised, or benzylised alpha or beta naphthylamines
or the mono or di sulpho acids thereof whether obtained by sulphating the corre-
sponding alkylised maphthylamine or by correspondingly alkylising the naphthylamine
sulpho acid.
The processes next hereinafter described serve to show how the dyes may be
manufactured in practice according to this Invention.
1. In order to produce a beautiful blue red dye of a saffranine shade for example
tetrazo ditolyl salts are caused to act upon dimethyl beta naphthylamine beta sulpho
acids. About fifty parts by weight of tolidine sulphate finely suspended in water are
mixed with about fifty parts by weight of hydrochloric acid at 21 degrees Beaumé
and about 22-2 parts by weight of sodium nitrite dissolved in about 100 parts by
weight of water are caused to run slowly into the aforesaid solution which is cooled
by means of ice. Tetrazo di tolyl chloride is then formed.
This solution is then added to a watery solution of about ninety parts by weight of
dimethyl beta naphthylamine beta mono sulphate of soda, about one hundred and fifty
parts by weight of acetate of soda are added thereto and the mixture is slowly heated.
The dye acid of the newly formed dye then appears in the form of a black deposit
soluble with difficulty in water, melting when heated and dissolving with a beautiful
blue red colour by the addition of alkalies and capable of being isolated or separated
in the form of a blackish brown powder by salting out pressing and drying.
This product dyes cotton a splendid blueish red like saffranine in an alkaline bath
and differs essentially from the corresponding dye known in commerce as benzo
purpurine 1B which is obtained by the action of tetrazo ditolyl upon beta naphthyl-
amine beta mono sulpho acid.
II. (a) About fifty parts by weight of hydrochlorite of diamido stilbene are
dissolved in water and mixed with an equal quantity of hydrochloric acid of a density
of about 21 degrees Beaumé and converted by pouring in a watery solution of
about twenty five parts by weight of sodium nitrite into the tetrazo compounds. The
latter is then caused to flow with stirring into an alcoholic solution of about eighty
four parts by weight of benzyl alpha naphthylamine. A brown insoluble deposit is
then formed representing the resulting dye soluble in spirit. This is filtered and
dried.
(b) About fifty parts by weight of the carefully dried dye soluble in spirit are
introduced slowly and with stirring into three times the quantity of fuming sulphuric
acid containing about twenty per cent of anhydride at a temperature of about fifteen
degrees centigrade. The molten or fluid mass of a deep blue colour thus obtained is
allowed to stand at ordinary temperature until the action of the sulphuric acid
(sulphating) is complete, the materials are then run off on to ice, the separated sulpho
acid is filtered off and converted into its alkali salt by treatment with alkalies.
2011
1000
J. HENRY JOHNSON,
47, Lincoln's Inn Fields, London, W.C.,
Agent.

page_text: CHO
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 commu-
nicated to me from abroad by "The Farbenfabriken vormals Friedrich Bayer and
Company 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 production of dyes soluble in spirit or in water by the
action of the Tetra-compounds of benzidine tolidine diamido-dixylyl, diamido-di-
phenol-ether, diamido-stilbene, diamido-fluorene, diamido-azo-benzol and their homo-
logues or their mono- or di-sulpho-acids upon the methylised ethylised, propylised,
butylised, amylised, or benzylised, alpba- or beta-napthylamine or the mono- or di-
sulpho-acids thereof as hereinafter described.
Dyes which are essentially bluer and possess the same properties as those obtained
by the action of tetrazo compounds of the di-para-diamines of the diphenyl series upon
naphthylamines and their sulpho-acids can be formed by substituting in place of the
latter the alkylised derivatives thereof. These dyes are obtained according to this
Invention by causing an aqueous solution of the tetrazo-salt to flow into a similar solu-
tion of the salt of the mono- or di-sulpho-acid of the alkylized alpha- or beta-naphthyl-
anine and saturating or neutralizing any mineral acid that may be present by means
of salts of organic acids such for example as acetate of soda. In place of the aforesaid
solutions with water, alcoholic solutions may be employed and the free acids may be
substituted for the sulpho-acid salts herein before referred to. The dyes (soluble in
spirit) obtained by the action of the tetrazo-compounds upon the alkylised naphthyl-
amines preferably in alcoholic solution are rendered soluble in water by a sulphonating
process such as treatment with sulphuric acid or other sulphonating agents.
The di-para-diamines hereinbefore referred to include benzidine, tolidine, diamido-
di-xylyl, diamido-di-phenol-ether diamido-stilbene, diamido-fluorenc, diamido-azo-
benzol, diamido-azo-xylol and diamido-azo-toluol or the sulphones or the mono- or di-
sulpho-acids of these substances.
The alkylised naphthylamines hereinbefore referred to include mono- or di-methyl-
ised ethylised, propylised, butylised, amylised, or benzylised, alpha- or beta-naphthyl-
amines or the mono- or di-sulpho-acids thereof whether obtained by sulphonating the
corresponding alkylised naphthylamine or by correspondingly alkylising the naphthyl-
amine sulpho-acids.
I will now proceed to give examples of processes by which the dyes may
factured in practice according to this Invention.
be manu-
Example 1-In order to produce a beautiful blue-red dye of a saffranine shade for
example tetrazo-ditolyl salts are caused to act upon methyl-beta-naphthylamine-beta-
sulpho-acid. About fifty parts by weight of tolidine sulphate finely suspended in water are
mixed with about fifty parts by weight of hydrochloric acid at 21 degrees Beaumé
and about 22.2 parts by weight of Sodium Nitrite dissolved in about 100 parts by
weight of water are caused to run slowly into the aforesaid solution which is cooled
by means of ice. Tetrazo-di-tolyl chloride is then formed.
This solution is then added to a watery solution of about ninety parts by weight of
the soda salt of methyl-beta-naphthylamine-beta mono-sulpho acid; about one hundred

page_text: and fifty parts by weight of acetate of soda are added thereto and the mixture is
slowly heated. The dyc acid of the newly formed dye then appears in the form of a
black deposit soluble with difficulty in water melting when heated and dissolving
with a beautiful blue red color by the addition of alkalies and capable of being
isolated or separated in the form of a blackish-brown powder by salting out pressing
and drying.
This product dyes cotton a splendid bluish-red like saffranine in an alkaline bath
and differs essentially from the corresponding dye known in commerce as Benzo-
purpurine 1 B" which is obtained by the action of tetrazo-ditolyl upon beta-naphthyl-
amine-beta-mono-sulpho-acid.
Example II (a). About fifty parts by weight of hydrochlorate of diamido stilbene
are dissolved in water and mixed with an equal quantity of hydrochloric acid of a
density of about 21° Beaumé and converted, by pouring in a watery solution of about
25 parts by weight of sodium nitrite, into the tetrazo compounds. The latter is then
caused to flow, with stirring, into an alcoholic solution of about 84 parts by weight of
benzyl-alpha-naphthylamine. A brown insoluble deposit is then formed representing
the resulting dye soluble in spirit. This is filtered and dried.
(b) About fifty parts by weight of the carefully dried dye soluble in spirit are
introduced slowly and with stirring into three times the quantity of fuming sulphuric
acid containing about twenty per cent. of anhydride at a temperature of about fifteen
degrees Centigrade. The molten or fluid mass of a deep blue colour thus obtained is
allowed to stand at ordinary temperature until the action of the sulphuric acid
(sulphonating) is complete the materials are then run off onto ice the separated
sulpho-acid is filtered off and converted into its alkali salt by treatment with
alkalies.
Example III. Another method of manufacturing new blue-red azo-colours consists
in combining first one molecule of the tetrazo-compound with one molecule of the
alkalised amines or their mono- or di-sulpho-acids. The product so obtained, still
contains one free diazo-group and is capable of being combined again with another
alkylised amine or the mono- or di-sulphonic acid thereof, or with amines, phenols, or
their sulpho- or carbo-acid. Or the product obtained by combining one molecule of
the tetrazo-compounds hereinbefore referred to with one molecule of a phenol, or
amine, or sulpho- or carbo-acid may be mixed with an alkylised amine or sulpho-acid.
Having now particularly described and ascertained the nature of the said Invention
and in what manner the same is to be performed 1 declare that what I claim is :-
First. The process for producing azo-dyes or colours by combining the tetrazo-
compounds of benzidine, tolidine, diamido-di-phenol-ethers, diamido-stilbene, diamido-
fluorene, diamidoazobenzol, diamidoazotoluol, and diamidoazoxylol, or their sulpho-
or carbo-acids with the alkylised naphthylamines or sulpho-acids substantially as
herein before described.
Second. The rendering of the insoluble colours obtained as aforesaid soluble in
water by a sulphonating process substantially as herein before described.
Third. The preparation substantially as described of the mixed azo-dye stuffs herein
described by the reaction of the tetrazo compounds named in the foregoing first
claiming clause with alkylised amines or sulpho-acids and another amine, phenol, or
sulpho-acid or alkylised derivatives thereof.
Fourth. As new manufacture or products the novel azo-dye stuffs hereinbefore
described.