Year: 1886

page_text: Date of Application, 29th Apr., 1886.
Complete Left, 27th Jan., 1887.
Complete Accepted, 1st Mar., 1887.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention to be as follows:-
This Invention relates to the production of a new chemical product or compound
hereinafter referred to as beta-naphthylamine delta mono Sulpho Acid and to the
treatment of this product or compound for the purpose of obtaining azo dyes there-
from. In carrying out this Invention a new beta naphthylamine mono sulpho Acid
is obtained by the action of Sulphuric Acid upon beta Naphthylamine at a temperature
of from about 170 to about 190 degrees Centigrade. This compound is used for producing
dyes by causing the diazo compounds of the said beta Naphthylamine delta mono
Sulpho Acid to act upon Phenol, resorein, alpha or beta naphthol, alpha or beta
Naphthylamine and the mono and di sulpho acids of these substances or by causing
the diazo or tetrazo compounds of aniline, toluidine, xylidine, cumidine, alpha or beta
naphthylamine, benzidine, tolidine, diamido diphenol ethers, diamido compounds to
act upon the heta naphthylamine delta mono sulpho acid.
By utilizing the action of a preferably large proportion of Sulphuric Acid upon
beta Naphthylamine at a high temperature a sulpho acid is obtained which is not
readily soluble in water and which according to analysis represents a mono Sulpho
Acid but differs essentially as regards its salts and dyes from the Sulpho Acids
heretofore known. In cold water this new Sulpho Acid is not readily soluble but in
hot water it dissolves readily and crystallizes out of the cooled solution in long delicate
needles. Its alkali salts are readily dissolved in heated spirit and differ essentially
from Alpha and gamma mono sulpho Acids.
With tetrazo diphenyl chloride a red dye is formed readily soluble in water but
with tetrazo ditolyl chloride a splendid red product is obtained which is considerably

page_text: bluer than the corresponding substance obtained from beta mono Sulpho Acid. For
example the aforesaid new Sulpho Acid may be produced and dyes obtained therefrom
by treating the materials as next hereinafter described.
About fifty parts by weight of beia Naphthylamine are introduced into about three
hundred parts by weight of Sulphuric Acid at about 66 degrees Beaune heated to
about one hundred and seventy degrees Centigrade and the temperature is then raised
and maintained at from about 180 to 190 degrees Centigrade until a sample treated
with Tetrazo ditolyl chloride yields a bluish red product. The temperature must be
so regulated as to avoid the generation of Sulphurous Acid. The heated solution is
poured over ice or cooled and the Sulpho Acid which now separates is allowed to stand
for a time it is then filtered and the residue boiled out with water. The greater part
of the new Sulpho Acid then goes into the solution whilst the beta mono sulpho
produced along with it being undissolved is left behind. The new Sulpho Acid which
my Foreign Correspondents designate as delta mono Sulpho Acid can then be purified
by producing the baryta or alkali (soda) salts which are insoluble in Cold water and
repeatedly crystallizing the same.
A series of new azo dyes can be obtained from this new sulpho acid either by the
action of its diazo compounds upon amides phenols or the Sulpho and Carbo Acids
thereof or by the action of the diazo or tetrazo compounds of the known amides and
amido Sulpho Acids on the same.
In order to obtain a bluish red dye for example about ten parts by weight of the
new beta Naphthylamine delta mono Sulpho acid obtained as hereinbefore described
are suspended in about 200 parts by weight of water: About ten parts by weight of
Muriatic or hydrochloric Acid at about 21° Beaune are added and the mixture is
diazotized by mems of a solution of about 31 parts by weight of Sodium Nitrite.
A colourless solution of the diazo Napthaline delta mono Sulpho acid is thereby
obtained which by slowly adding about 12 parts by weight of a Soda Salt of Alpha
Naphthol Alpha mono Sulpho Acid in about 500 parts by weight of water and about
10 parts by weight of Soda produces a dye which dyes wool a very beautiful bluish red.
A very beautiful bluish red dye capable of dyeing vegetable fibres (cotton) in an
Alkaline bath without the aid of a mordant is obtained by causing tetrazo ditolyl
Chloride to act upon the new Sulpho Acid obtained as hereinbefore described. For
this purpose about 50 parts by weight of tolidine Sulphate in a fine state of division
aro placed in suspension with an equal quantity of hydrochloric Acid at about
21° Beaune and diazotised with an aqueous solution of about 22 parts by weight of
Sodium Nitrite. The tetrazo ditolyl chloride is formed and the solution is allowed to
run slowly into water holding about 73 parts by weight of the beta Naphthylamine
delta mono Sulpho Acid in a fine state of division in suspension, the free mineral acid
is saturated or neutralized by adding Acetate of Soda and after standing for a short
time a bluish red deposit or precipitate is obtained which by heating and neutralizing
with Soda lye or Soda is reduced to a Soda Salt. On cooling the dye separates
quantitatively in the form of a red powder.
"זברזולוז-
TATAK
JOHNSON,
47, Lincolns Inn Fields, London, W.C.

page_text: A Process for Producing a New Sulpho Acid and Obtaining
Azo Dyes therefrom.
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 communi-
cated to me from abroad by Farbenfabriken Vormals Friedrich Bayer & Co. of
Elberfeld in the Empire of Germany, and in what manner the same is to be performed,
to be particularly described and ascertained in and by the following statement:-
This Invention relates to the production of a new chemical product or compound
hereinafter referred to as beta napthyl amine delta mono sulpho acid and to the
treatment of this product or compound for the purpose of obtaining azo dyes there-
from. In carrying out this invention the new beta napthylamine mono sulpho acid is
obtained by the action of sulphuric acid upon beta napthylamine or its salts at a
temperature of from about 100 to about 200 degrees centigrade. This compound is
utilized for producing azo dyes by causing the diazo compounds of the beta napthyl-
amine delta-mono-sulp-acid to act upon phenol resorcin alpha or beta napthol alpha
or beta napthylamine and the mono and di-sulpho acids of these substances or by
causing the diazo or tetrazo compounds of aniline, toluidine xylidine cumidine, alpha,
or beta naphthylamine and diazo benzol amidoazobenzol amidoazotoluol or their nitro-
products such as especially para nitraniline, benzidine, tolidine, diamidodiphenol ethers,
diamido, stilbene diamidofluorine diamidotolan diamidoazobenzol, alphanaphthylendia-
mine or the sulpho or carbonic acids of these substances to act upon the said beta
naphthylamine delta-mono-sulpho acid.
By utilizing the action of a large proportion of sulphuric acid upon beta naphthyl-
amine or its salts at a high temperature of from about 100 to 200 degrees centigrade
a sulpho acid is obtained which is not easily soluble in water and which according to
analysis represents a mono-sulpho-acid but differs essentially as regards its salts and
dyes from the sulpho acids heretofore known and which are insoluble in water.
In cold water this new sulpho acid is not readily soluble but in hot water it dissolves
readily and crystallises out of the cooled solution in long delicate needles.
Its alkaline salts are readily dissolved in heated spirit at about 90° and differ
essentially from alpha beta and gamma mono-sulpho-acids.
With tetrazo diphenyl-chloride the new sulpho acid obtained as aforesaid formis a
red dye readily soluble in water but with tetrazo-ditolyl chloride a splendid red
product is obtained which is considerably bluer than the corresponding substance
obtained from beta-mono-sulpho-acid.
For example the aforesaid new sulpho-acid may be produced and dyes obtained
therefrom by treating the materials as next hereinafter described.
About 50 parts by weight (say 50 kilos) of the sulphate of beta naphthylamine are
introduced into about three hundred parts by weight (say 300 kilos) of sulphuric acid
at about 66 degrees Beaumé heated to say from about one hundred and sixty to
one hundred and seventy degrees centigrade and this temperature is maintained

page_text: until a sample treated with tetrazo-ditolyl-chloride yields a blueish red product.
The temperature must be so regulated as to avoid the generation of sulphurous acid.
The heated solution is cooled by pouring it on to ice and the sulpho acid which
now separates is allowed to stand for a time being afterwards filtered and the residue
boiled down with water. The greater part of the new sulpho acid then goes into the
solution whilst the beta-mono-sulpho-acid produced along with it, being undissolved,
is left behind. The new sulpho acid which my foreign Correspondents designate as
delta-mono-sulpho-acid can then be purified by producing the baryta or alkaline (soda)
salts which are insoluble in cold water and repeatedly crystallising the same.
In certain cases it is advantageous to use sulphuric acid of less strength than that
hereinbefore specified; for example, acid of about 65 Beaumé may be employed the
invention not being limited either to the precise quantity or to the precise strength of
acid or degree of temperature.
Instead of the beta naphthylamine or its salts, the beta naphthylamine alpha or
gamma-mono-sulpho-acid may be taken with the same result. When heated with
sulphuric acid up to temperatures above 100° C. both acids are transformed into
beta naphthylamine delta-mono-sulpho acid, furthermore it is also possible instead of
previously separating the two acids to employ the direct fusion (smelt) of the two
acids which are produced by treatment of beta naphthylamine with sulphuric acid at
low temperatures.
A series of new azo dyes can be obtained from this new sulpho acid either by the
action of its diazo compounds upon amides, phenols or the sulpho and carbonic
acids thereof or by the action of the diazo or tetrazo compounds of the known
amides and amido-sulpho or carbonic acids on the same as hereinafter explained.
I. About ten parts by weight (say 10 kilos) of the new beta naphthylamine delta-
mono-sulpho acid obtained as hereinbefore described are suspended in a fine state of
division in about two hundred parts by weight of water (say 200 litres). About 10
parts by weight (say 10 kilos) of muriatic or hydrochloric acid at about twenty one
degrees Beaumé are added and the mixture is diazotized by means of a solution of
about 31 parts by weight (3.1 kilos) of sodium nitrite. A colourless solution of the
diazo naphthalene-delta-mono-sulpho-acid is thereby obtained which by slowly adding
about twelve parts by weight (say 12 kilos) of a soda salt of alpha-naphthol-alpha-mono
sulpho-acid in about 500 parts by weight (say 500 litres) of water and about 10 parts
by weight (say 10 kilos) of soda, produces a dye which dyes wool a very beautiful
blueish red.
II. A very beautiful blueish red dye capable of dyeing cotton in an alkaline bath
without the aid of a mordant is obtained by causing tetrazo ditolyl chloride to act
upon the new sulpho acid obtained as hereinbefore described. For this purpose about
fifty parts by weight (say 50 kilos) of tolidine-sulphate in a fine state of division are
placed in suspension with about fifty parts by weight (say 50 kilos) of hydrochloric
acid at about 21 degrees Beaumé and diazotized with an aqueous solution of about
22-2 parts by weight (say 222 kilos) of sodium nitrite. The tetrazo ditolyl-chloride
is formed and the solution is allowed to run slowly into water, holding about 73 parts
by weight (say 73 kilos) of beta-naphthylamine-lelta-mono-sulpho-acid, in a fine state
of division, in suspension, the free mineral acid is saturated or neutralised by adding
acetate of soda and after standing for a short time a blueish red deposit or precipitate
is obtained which by heating and neutralising with soda Ive or soda will form a fine
soda salt. On cooling the dye separates quantitatively in the form of a red powder.
Having now particularly described and ascertained the nature of the said Invention
and in what manner the same is to be performed I declare that what I claim is :-
First: A process for producing a new beta naphthylamine-mono-sulpho-acid by
the action of a large proportion of sulphuric acid upon beta naphthylamine or its salts
or heta naphthylamine alpha mono sulpho acid, or beta naphthylamine gamma mono
sulpho acid at a temperature of from about one hundred to two hundred degrees
centigrade substantially as hereinbefore described.

page_text: Second: A process for obtaining azo dyes by the action of the diazo compound of
beta napthylamine delta mono-sulpho-acid obtained as hereinbefore set forth upon
phenol, resorcin alpha or beta naphthol, alpha or beta naphthylamine and the mono
and di sulpho or carbonic acids of these substances substantially as hereinbefore
described.
Third A process for obtaining azo dyes by the action of the diazo or tetrazo
compound of aniline, toluidine, xylidine, cumidine, alpha or beta naphthylamine,
amidoazobenzol, amidoazotoluol, amidoazoxylol, or the nitro products, benzidine
tolidine, diamidodixylol, diamido-diphenol-ethers, diamido stilbene, diamidofluorine,
diamidotolan diamidoazobenzol diamidoazotoluol naphthylendiamines or the sulpho or
carbonic acids of these substances upon the beta naphthylamine delta-mono-sulpho
acid produced as hereinbefore set forth all substantially as hereinbefore described.
Fourth The improved manufacturing process consisting essentially in producing
beta napihylamine delta mono sulpho acid and obtaining dyes therefrom substantially
as hereinbefore described.
J. HENRY JOHNSON,
Agent.