The Manufacture and Production of New Sulpho-acids and of New Colouring Matters therefrom.
Year: 1891

page_text: Date of Application, 24th Aug., 1891
Complete Specification Left, 9th May, 1892-Accepted, 18th June, 1892
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Sulpho-acids and of New
Colouring Matters therefrom.
I 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 communicated to me from abroad by The Badische Anilin & Soda Fabrik
of Ludwigshafen on Rhine in the Empire of Germany, to be as follows:-
In the Specification of Letters Patent No. 6874 of 1890 the manufacture of
substantive dyestuffs from 11' dihydroxynaphthalene is described and the superiority
of the dyes obtained from this 1.11 dihydroxynaphthalene over those obtained from
isomeric bodies and due to the relative position of the hydroxy groups is
commented on.
Now the present invention is based on the discovery that the said 1·1' dihydroxy-
naphthalene can by appropriate treatment be made to yield new sulpho-acids, of
which some combine with diazo-compounds to give dyestuffs which are also
characterized by very valuable properties.
The new sulpho-acids are obtained by the direct sulphonation of 1.1' dihydroxy-
naphthalene by means of sulphuric acid. In this way a mixture of acids is obtained
and means have to be adopted for isolating the useful acids in a condition suitable
for use in the manufacture of dyes.
To obtain the dyestuffs the isolated acids are combined with diazo compounds in
alkaline or acetic acid solution; a large variety of diazo-compounds can be used,
and the colour of the dyestuffs obtained varies with each sulpho-acid and according
to the diazo compounds employed.
To further illustrate the nature of the invention the following examples are given
which describe one method of carrying this invention into effect, but they are merely
to be regarded as typical, and as the invention is not restricted thereto. The parts
are by weight.
EXAMPLE 1. PRODUCTION OF NEW SULPHO-ACIDS OF 1·11 DIHYDROXY-
NAPHTHALENE.
Dissolve about ten parts of 1.1' dihydroxynaphthalene in about 40 parts of
concentrated sulphuric acid (containing about ninety five per cent. of real sulphuric
acid) at a temperature of about ten to fifteen degrees centigrade when the dihydroxy-
naphthalene has all been added, heat the mixture to about 50 degrees centigrade,
and maintain this temperature for say about forty-five to fifty minutes, or until a
test portion dissolves clearly or practically clearly in water. Then allow the
mixture to cool, and pour it into about two hundred parts of ice water, and neutralize
with saturated barium-hydrate solution. Boil and filter, and wash the barium
sulphate well with boiling water. The combined filtrates, which should only be
slightly alkaline, are boiled down until only about two hundred and sixty parts of
solution remain. Allow the solution to cool and then the barium salt of a sulpho-
acid crystallizes out which may be called barium salt I. When the crystallization
is complete, filter and wash the crystals with a little cold water, and boil down the
filtrate together with the wash-water until only about fifty parts of solution remain.
Allow the solution to cool again, when a second barium salt crystallizes out (this
may be called barium salt II). This salt differs from barium salt I in being readily
soluble in hot water, whereas barium salt I is only slightly soluble in both cold and
hot water.
A third salt which may be called barium salt III, is still present in the mother

page_text: liquor of barium salt II. This can be obtained by further evaporation, it is readily
soluble in both cold and hot water.
The barium salts can be converted into the sodium salts, by dissolving in boiling
water and adding the requisite quantity of sodium-carbonate or sodium-sulphate
solution.
The sulpho-acids in the barium salts II and III are of the greatest value in the
manufacture of azo-dyes, and I call the sulpho acid in barium salt II 1·1' dihydroxy-
naphthalene disulpho acid Y, and the sulpho acid in barium salt III, 1.1' dihydroxy-
naphthalene disulpho acid R.
EXAMPLE 2. PREPARATION OF AN AZO DYE FROM 11 DIHYDROXY-
NAPHTHALENE DISULPHO ACID
AND DIAZOBENZENE.
Take a solution of the sodium salt of this disulpho acid Y, prepared by the
treatment of the barium salt II with sodium sulphate, and titrate a portion of the
solution, with diazobenzene in the presence of acetic acid. Then dilute or
concentrate the solution by evaporation, till it contains about 20 per cent. of the
free dihydroxynaphthalene-di-sulpho-acid Y. Take one hundred and sixty parts
of this solution (corresponding to thirty-two parts of the free sulpho-acid Y.) and
add about thirty five parts of crystallized acetate of soda and run the requisite
diazobenzene chloride into this solution at a temperature of about ten degrees
centigrade, and stir well. The diazo-benzene-chloride required is obtained, by
treatment of nine and three tenth parts of aniline dissolved in about twenty parts of
water and about forty parts of hydrochloric acid (containing about thirty per cent.
real hydrochloric acid HCl), in the presence of about fifty parts of ice, with a
solution of seven parts of sodium nitrite. As a rule the whole of the solution of
diazobenzene chloride may be mixed with the 1.11 dihydroxynaphthalene-disulpho-
acid Y; but in any case it is possible to ascertain whether a sufficient quantity has
been added, by taking test-portions, precipitating the dyestuff formed with common
salt, and trying, by mixing with diazo-benzene solution on filter paper, whether a
further addition still causes more dyestuff to form. As soon as only a slight
formation of dyestuff can be observed sufficient diazo-compound has been added.
The deep-red solution soon begins to deposit crystals. When the crystallization
is complete, filter, press and dry. If the dyestuff be prepared in a too dilute
solution, this crystallization will not take place or will take place only incompletely
and in that case, the solution should be boiled and common salt solution added,
until practically all the dyestuff crystallizes out from a test portion on cooling, then
the whole is allowed to cool and the crystalline precipitate is worked up as
described.
The production of the dyestuff may be effected in an alkaline solution; for this
purpose, fourteen parts of calcined soda are used instead of the sodium acetate
described in the foregoing example. An excess of diazo-compound in this case is
to be most carefully avoided, as otherwise impure dyes are obtained. The dyestuff
is precipitated from the alkaline solution by means of common salt and is worked
up in the usual way.
This dyestuff is a brownish-red powder which dyes wool a blueish-red colour from
the acid bath.
In a similar manner a dyestuff can be obtained from the 1'1' dihydroxy-naphtha-
lene-di-sulpho-acid R, which dyes wool in the same way but gives a more blueish
shade of red.
Instead of diazo-benzene, other diazo-compounds can as aforesaid be used, as will
be readily understood by chemists.
Dated this 24th day of August 1891.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.

page_text: COMPLETE SPECIFICATION.
The Manufacture and Production of New Sulpho-acids and of New
Colouring Matters therefrom.
I 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 communicated to me from abroad by. The Badische Anilin & Soda Fabrik,
of Ludwigshafen on Rhine, 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 :-
In the Specification of Letters Patent No. 6874 of 1890 the manufacture of
substantive dyestuffs from 1.11 dihydroxynaphthalene is described and the
superiority of the dyes obtained from this 11' dihydroxynaphthalene over those
obtained from isomeric bodies and due to the relative position of the hydroxy
groups is commented on.
Now the present invention is based on the discovery that the said 1·1' dihydroxy-
naphthalene can by appropriate treatment be made to yield new sulphoacids,
of which some combine with diazocompounds to give dyestuffs which are also
characterized by very valuable properties.
The new sulpho-acids are obtained by the direct sulphonation of 1.1' dihydroxy-
naphthalene by means of sulphuric acid. In this way a mixture of acids is obtained,
and means have to be adopted for isolating the useful acids in a condition suitable
for use in the manufacture of dyes.
To obtain the dyestuffs the isolated acids are combined with diazo-compounds in
alkaline or acetic acid solution. A large variety of diazo-compounds can be used,
the colour of the dyestuffs obtained varying with each sulpho-acid and according
to the diazo-compound employed.
To further illustrate the nature of the invention and the manner in which it can
be carried into practical effect the following examples are given, but they are merely
to be regarded as typical, as the invention is not restricted thereto. The parts are
by weight.
EXAMPLE 1. PRODUCTION of
NEW SULPHO-ACIDS OF 1·11 DIHYDROXY-
NAPHTHALENE.
Add in small quantities at a time about ten parts of 1·1' dihydroxynaphthalene
to about forty parts of concentrated sulphuric acid (containing about ninety
five per cent. of real sulphuric acid) at a temperature of about ten to fifteen
degrees centigrade. When the dihydroxynaphthalene has all been added, heat
the mixture to about fifty degrees centigrade, and maintain this temperature for
say about forty five to fifty minutes, or until a test portion dissolves clearly or
practically clearly in water. Then allow the mixture to cool and pour it into
about two hundred parts of ice water and neutralize with saturated barium hydrate
solution. Boil and filter, and well wash the barium sulphate with boiling water.
The combined filtrates (which should only be slightly alkaline) are boiled down
until only about two hundred and sixty parts of solution remain. Allow the
solution to cool, and then the barium salt of a sulpho acid crystallizes out
which may be called barium salt I. When the crystallization is complete, filter
and wash the crystals with a little cold water. Boil down the filtrate together
with the wash-water until only about fifty parts of solution remain. Allow
the solution to cool again, when a second barium salt crystallizes out (this may
be called barium salt II). This salt differs from barium salt I in being readily
soluble in hot water, whereas barium salt I is only slightly soluble in both cold
and hot water,

page_text: A third salt which may be called barium salt III is still present in the mother
liquor of barium salt II. This can be obtained by further evaporation, it is readily
soluble in both cold and hot water.
The barium salts can be converted into the sodium salts, by dissolving in boiling
water and adding the requisite quantity of sodium carbonate or sodium sulphate
solution.
The sulpho-acids in the barium salts II and III are of very great value in the
manufacture of azo-dyes and I call the sulpho-acid in barium salt 11-" 1·1' di-
hydroxynaphthalene disulpho acid Y" and the sulpho-acid in barium salt III-
"1.1 dihydroxynaphthalene disulpho-acid R."
EXAMPLE 2. PREPARATION OF AN AZO-DYE FROM 11 DIHYDROXY-
NAPHTHALENE DISULPHO ACID Y AND DIAZOBENZENE.
Take a solution of the sodium salt of this disulpho-acid Y, prepared by the
treatment of the barium salt II with sodium sulphate, and titrate a portion of
the solution in the well known way, with diazo-benzene in the presence of acetic
acid. Then according to the ascertained strength of the solution either dilute it
or if too weak concentrate it by evaporation, so as to obtain a solution containing
about twenty per cent. of the dihydroxynaphthalene disulpho-acid Y regarded as
free acid. Take one hundred and sixty parts of this solution (corresponding to
thirty two parts of the free sulpho-acid Y) and add about thirty five parts of
crystallized acetate of soda and run the requisite diazobenzene chloride into this
solution at a temperature of about ten degrees centigrade and stir well. The
diazo-benzene-chloride required is obtained, in the well known way, by treatment
of nine and three tenths parts of aniline dissolved in about twenty parts of water
and about forty parts of hydrochloric acid (containing about thirty per cent. real
hydrochloric acid HCl) in the presence of about fifty parts of ice with a solution
of seven parts of sodium nitrite. As a rule the whole of the solution of diazo-
benzene chloride may be mixed with the 11 dihydroxynaphthalene-disulpho-
acid Y but in any case it is possible to ascertain whether a sufficient quantity has
been added by taking test portions, precipitating the dyestuff formed with common
salt, and trying (by mixing with diazobenzene solution on filter paper) whether a
further addition still causes more dyestuff to form; as soon as only a slight
formation of dyestuff can be observed, sufficient diazo-compound has been
added.
The deep red solution soon begins to deposit crystals. When the crystallization
is complete, filter, press and dry. If the dyestuff be prepared in a solution which
is too dilute this crystallization will not take place or will take place only
incompletely and in that case the solution should be boiled and common salt
solution added until practically all the dyestuff crystallises out from a test portion
on cooling, then the whole is allowed to cool and the crystalline precipitate is
worked up as described.
The production of the dyestuff may be effected in an alkaline solution. For
this purpose fourteen parts of calcined soda are used instead of the sodium acetate
described in the foregoing example. An excess of diazo-compound in this case is
to be most carefully avoided as such excess will result in the obtainment of impure
dyes. The dyestuff is precipitated from the alkaline solution by means of common
salt and is worked up in the usual way.
This dyestuff is a brownish red powder which dyes wool a blueish-red colour
from the acid bath.
In a similar manner a dyestuff can be obtained from the 1'1'dihydroxy-naphthalene-
di-sulpho-acid R, which dyes wool in the same way but gives a more blueish shade
of red.
Instead of diazo-benzene any other diazo compounds used in the manufacture of
azo-dyes can be employed as will be readily understood by chemists,

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 :-
1. The manufacture of 1.1 dihydroxy-naphthalene-sulpho acids, by sulphonat-
ing 11 dihydroxy-naphthalene and separating the sulpho-acids in the mixed
product so obtained by fractional crystallization all substantially as hereinbefore
described.
2. The manufacture of 1-11 dihydroxy-naphthalene sulpho-acids in the form
of barium salts by treating 11' dihydroxy-naphthalene-sulpho-acid with con-
centrated sulphuric acid, converting the sulpho-acids formed into barium salts and
separating these by fractional recrystallization, all substantially as described under
Example 1.
3. As new articles of manufacture the 11' dihydroxy-naphthalene-disulpho-
acids Y and R such as can be obtained substantially as hereinbefore described.
4. The manufacture of azo dyes by the combination of the 1'1' dihydroxy-naphtha-
lene disulpho acid Y or R herein described with diazo compounds substantially as
herein explained.
5. The manufacture of azo dyes by the combination of diazo-benzene with the
new 11 dihydroxy-naphthalene-disulpho acid Y or R substantially as herein
described in Example 2.
6. As new articles of manufacture the new azo-dyes such as can be obtained
substantially as hereinbefore described.
ol
Ma 1802
J. H. JOHNSON & CO.,
Agents.