Improvements in the Manufacture of Sulpho-acids of a Red Basic Naphthalene Dyestuff.
Year: 1890

page_text: Date of Application, 25th Nov., 1890
Complete Specification Left, 17th June, 1891-Accepted, 18th July, 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Sulpho-acids of a Red Basic
Naphthalene Dyestuff.
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 him from abroad by Badische Anilin and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany to be as follows :—
In the Specification to Letters Patent No. 15259 of 1888 granted to me I have
described three sulpho-acids of a red basic naphthalene colouring matter then
known as rosinduline but which has since received the name of phenylrosinduline
(see Journal of the Chemical Society Vol. 58 page 909, Annalen der Chemie
vol. 256, page 235). These sulpho acids are distinguished from one another by
their relative solubility in water and by their crystallizing power the monosulpho
acid is crystalline and practically insoluble in water the disulpho-acid is slightly
soluble in cold water readily soluble in hot water and possesses a most decided
crystallizing power, the third sulpho acid is readily soluble in cold water and does
not crystallize.
Now my foreign correspondents have discovered that it is possible to obtain a
trisulpho-acid of phenyl-rosinduline which may be regarded as an intermediate
compound between the aforesaid readily crystallizing disulpho-acid and the
Like the
aforesaid non-crystalline sulpho-acid readily soluble in cold water.
former the trisulpho-acid can readily be obtained in the crystalline form and like
the latter it is readily soluble in cold water.
This trisulpho acid is frequently present in the said product readily soluble in
cold water prepared according to the process claimed in the third claim of the
Specification of the aforesaid Letters Patent No. 15259 of 1888 and can be
separated therefrom by means of the process hereinafter described. By this
process not only is the trisulpho-acid isolated but the sulpho-acid readily soluble
This invention
in cold water is obtained free from crystallizable substance.
includes the production of the sulpho-acid readily soluble in cold water free from
crystallizable product by the direct sulphonation of phenyl rosinduline or its lower
sulpho-acids to the requisite extent.
If, in the sulphonation of phenyl-rosinduline, the process be carried beyond the
formation of the aforesaid readily crystallizable disulpho-acid slightly soluble in
cold water the trisulpho acid begins to form and as its quantity increases that of
the disulpho acid diminishes until the latter wholly disappears. Similarly by
carrying the sulphonation still further the quantity of uncrystallizable product
readily soluble in cold water gradually increases and the quantity of crystallizable
trisulpho-acid diminishes. In the following examples to illustrate the nature
of the invention I give, (without necessarily limiting myself to the precise
details)
(1) Directions for the sulphonation of phenyl-rosinduline so as to obtain a
mixture rich in the crystallizable tri-sulpho-acid.
(2) Directions for the isolation of the crystallizable tri-sulpho-acid from a
mixture with the uncrystallizable product readily soluble in cold water.
(3) Directions for sulphonating so as to obtain directly the uncrystallizable
product readily soluble in cold water free from crystallizable trisulpho acid.
In these examples the parts are by weight.

page_text: EXAMPLE 1.—THE PRODUCTION OF A MIXTURE RICH IN THE CRYSTALLIZABLE
TRISULPHO-ACID.
Mix well about ten parts of phenyl-rosinduline (or a similar quantity of its mono
or disulpho acid) with about 40 parts of fuming sulphuric acid containing about
21 per cent. of free anhydride (SO3) cool well while mixing and subsequently heat
the mixture on the water bath until a sample completely dissolves in about 40 times
its volume of water. This usually requires the application of heat for from 6 to
8 hours. Next mix the entire product with about 40 times its weight of water
neutralize with milk of lime and work up the solution of the lime salts into neutral
sodium salts in the usual way by treating with soda and evaporating the filtered
solution to dryness.
EXAMPLE 2.-SEPARATION OF THE CRYSTALLIZABLE TRISULPHO-ACID FROM
THE UNCRYSTALLIZABLE PRODUCT READILY SOLUBLE IN COLD WATER.
(A). Dissolve about ten parts of the mixed sodium salts obtained for instance as
above described in about 100 parts of water and add about 30 parts of dilute
sulphuric acid containing about ten per cent. of real sulphuric acid (H₂SO₁). Allow
the mixture to stand for about 12 hours that the separation of precipitate may be
as complete as possible, filter, press, and recrystallize from about ten times the
quantity of hot water adding a little common salt solution. The mother liquor
from the first precipitate contains the sulpho acid readily soluble in cold water
practically free from crystallizable product. This can be obtained in the form of
sodium salt by neutralizing the sulphuric acid with milk of lime and evaporating
the filtered solution to dryness.
I give the above separating process A first because it is more perfect than that
which I give under B and is applicable not only to mixtures rich in crystallizable
sulpho acid but also to poorer mixtures such for instance as result from the process
claimed in the third claim of the Specification of the aforesaid Letters Patent
No. 15259 of 1888.
In the case of rich mixtures the following process may be used.
B. Pour the crude product of the sulphonation when cold onto about 5 times the
quantity of ice and allow the mixture to stand, when the crystallizable trisulpho-
acid separates out and the more soluble acid remains in solution filter and press.
The acid so obtained can be used directly for dyeing or be worked up in the usual
way by treatment with lime and soda. The mother liquor can also be worked up
by treatment with milk of lime and subsequently with soda to obtain the sodium
salt of the uncrystallizable product readily soluble in water. By this process of
separation it is not so easy as it is with Example A. to obtain either the
crystallizable trisulpho acid or the more soluble product pure and isolated from one
another.
EXAMPLE 3.-PRODUCTION OF THE UNCRYSTALLIZABLE PRODUCT READILY
SOLUBLE IN COLD WATER DIRECTLY BY SULPHONATION AND
FROM CRYSTALLIZABLE TRI-SULPHO-ACID.
FREE
Mix about ten parts of the mono-sulpho acid of phenylrosinduline with about
60 nants

page_text: The trisulpho acid of phenylrosinduline now first isolated is in the form of free
acid readily soluble in cold water and in hot alcohol, but is almost insoluble in
concentrated hydrochloric acid. The acid sodium salt obtained by the process
described under A of Example 2 is readily soluble in hot water and but very
slightly soluble in hot alcohol.
Dated this 25th day of November 1890.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents..
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Sulpho-acids of a Red Basic
Naphthalene Dyestuff.
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 The Badische Anilin and 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. 15259 of 1888 granted to me I have
described three sulpho acids of a red basic naphthalene colouring matter then
known as rosinduline but which has since received the name of phenylrosinduline.
(See Journal of the Chemical Society, Volume 58, p. 909, Annalen der Chemie
Vol. 256, p. 235.) These sulpho acids are distinguished from one another by their
relative solubility in water and by their crystallizing power, the monosulpho-acid is
crystalline and practically insoluble in water, the disulpho-acid is slightly soluble
in cold water, readily soluble in hot water and possesses a most decided
crystallizing power, the third sulpho-acid is readily soluble in cold water and does
not crystallize.
My foreign correspondents have discovered that it is possible to obtain a tri-
sulpho-acid of phenylrosinduline, which may be regarded as an intermediate com-
pound between the aforesaid readily crystallizing disulpho-acid and the aforesaid
non-crystalline sulpho-acid readily soluble in cold water. Like the former the tri-
sulpho-acid can readily be obtained in the crystalline form and like the latter it in
readily soluble in cold water.
This trisulpho-acid is frequently present in the said product (readily soluble in
cold water) prepared according to the process claimed in the third claim of the
Specification of the aforesaid Letters Patent No. 15259 of 1888 and can be
separated therefrom by means of the process hereinafter described. By this process,
not only
the trisulpho-acid isolated but the sulpho acid readily soluble in cold
water is obtained practically free from crystallizable substance. This invention
includes the production of the sulpho-acid readily soluble in cold water free from
crystallizable product by the direct sulphonation of phenylrosinduline or its lower
sulpho acids to the requisite extent.
If, in the sulphonation of phenylrosinduline, the process be carried beyond the
formation of the aforesaid readily crystallizable disulpho acid slightly soluble in
cold water, the trisulpho acid begins to form, and as its quantity increases that of
the disulpho-acid diminishes, until the latter wholly disappears. By carrying the
sulphonation still further, the quantity of uncrystallizable product readily soluble
in cold water gradually increases and the quantity of crystallizable trisulpho-acid
diminishes. In the following examples to illustrate the nature of the invention and
the manner in which it can be carried into practical effect, I give,
(1) Directions for the sulphonation of phenylrosinduline so as to obtain a mixture
rich in the crystallizable trisulpho-acid.
(2) Directions for the isolation of the crystallizable trisulpho-acid from a mixture
thereof with the uncrystallizable product readily soluble in cold water.

page_text: (3) Directions for sulphonating, so as to obtain directly the uncrystallizable
product readily soluble in cold water free from crystallizable trisulpho-acid.
In these examples the parts are by weight.
EXAMPLE 1.-THE PRODUCTION OF A MIXTURE RICH IN THE CRYSTALLIZABLE
TRISULPHO-ACID.
Mix well about ten parts of phenylrosinduline (or a similar quantity of its mono-
or di-sulpho acid) with about forty parts of fuming sulphuric acid, containing about
twenty one per cent. of free anhydride (SO3). Cool well while mixing, and sub-
sequently heat the mixture on the water bath until a sample completely dissolves in
about forty times its volume of water. This usually requires the application of
heat for from six to eight hours. Next mix the entire product with about forty
times its weight of water, neutralize with milk of lime, and work up the solution of
the lime salt into neutral sodium salt in the usual way by treating with soda and
evaporating the filtered solution to dryness.
EXAMPLE 2.-SEPARATION OF THE CRYSTALLIZABLE TRISULPHIO ACID FROM
THE UNCRYSTALLIZABLE PRODUCT READILY SOLUBLE IN COLD WATER.
(A). Dissolve about ten parts of the mixed sodium salts obtained for instance as
herein before described in about one hundred parts of water and add about thirty
parts of dilute sulphuric acid containing about ten per cent. of real sulphuric
acid (H₂SO). Allow the mixture to stand for about twelve hours that the
separation of precipitate may be as complete as possible, filter press and recrystallize
from about ten times the quantity of hot water adding a little common salt solution.
The mother liquor from the first precipitate contains the sulpho-acid readily soluble
in cold water practically free from crystallizable product. This can be obtained in
the form of sodium salt by neutralizing the sulphuric acid with milk of lime and
evaporating the filtered solution to dryness.
give the aforesaid separating process (A) first, because it is more perfect than
that which I hereinafter give under B, and is applicable not only to mixtures rich
in crystallizable sulpho-acid but also to poorer mixtures, such for instance as result
from the process claimed in the third claim of the Specification of the aforesaid
Letters Patent No. 15,259 of 1888. In the case of rich mixtures the following
process may be used.
(B). Pour the crude product of the sulphonation, when cold, onto about five times
the quantity of ice and allow the mixture to stand when the crystallizable trisulpho-
acid separates out and the more soluble acid remains in solution, filter and press.
The acid so obtained can be used directly for dyeing or be worked up in the usual
way by treatment with lime and soda. The mother liquor can also be worked up
by treatment with milk of lime and subsequently with soda to obtain the sodium
salt of the uncrystallizable product readily soluble in water. By this process of
separation it is not so easy as it is with the process described under A of this example
to obtain either the crystallizable trisulpho-acid or the more soluble product pure
and isolated from one another.
MXAMPLE 3.-1'RODUCTION OF THE UNCRYSTALLIZABLE PRODUCT READILY
SOLUBLE IN COLD WATER AND FREE FROM CRYSTALLIZABLE TRISULPHO-
ACID DIRECTLY BY SULPHONATION.
Mix about ten parts of phenylrosinduline (or a similar quantity of mono-, di-, or
tri-sulpho-acid) with about sixty parts of funing sulphuric acid containing about
twenty three per cent. of free anhydride (SO2) taking all the usual precautions,
and then heat the mixture on the boiling water-bath until a test portion, treated
with milk of lime and soda, yields only sodium salt completely soluble in cold
hydrochloric acid containing about 95
:1 ,is
TI
MXAMPLE 3.-I'RODUCTION OF THE UNCRYSTALLIZABLE PRODUCT READILY
SOLUBLE IN COLD WATER AND FREE FROM CRYSTALLIZABLE TRISULPHO-
ACID DIRECTLY BY SULPHONATION.
Mix about ten parts of phenylrosinduline (or a similar quantity of mono-, di-, or
tri-sulpho-acid) with about sixty parts of funing sulphuric acid containing about
twenty three per cent. of free anhydride (SO2) taking all the usual precautions,
and then heat the mixture on the boiling water-bath until a test portion, treated
with milk of lime and soda, yields only sodium salt completely soluble in cold
hydrochloric acid containing about 25 per ant of real acid (HCl). The common

page_text: salt formed by the treatment of the sodium salt with the hydrochloric acid may
remain undissolved. This point being reached the whole product is diluted with
water, treated with milk of lime and soda in the well known way, and the solution
of sodium salt is evaporated to dryness.
The trisulpho acid of phenylrosinduline now first isolated is, in the form of free
acid, readily soluble in cold water and in hot alcohol but is almost insoluble in
concentrated hydrochloric acid.
The acid sodium salt obtained by the process described under A of Example 2
is readily soluble in hot water and but very slightly soluble in hot alcohol.
Both the crystallizable trisulpho acid and the uncrystallizable product dye animal
fibre from the acid bath giving beautiful red shades.
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 The manufacture of a mixture of sulpho acids of phenylrosinduline rich
in the crystallizable trisulphoacid by sulphonating phenylrosinduline or the mono-,
or di-, sulpho acid thereof substantially as hereinbefore described.
Second The manufacture of the crystallizable trisulphoacid of phenylrosinduline
and of the uncrystallizable product readily soluble in cold water and free from
crystallizable sulpho acid by separating mixtures of these products substantially as
hereinbefore described.
Third The manufacture of a sulpho acid of phenylrosinduline readily soluble in
cold water and free from crystallizable trisulphoacid by direct sulphonation of
phenylrosinduline or its mono-, di-, or tri-sulpho acid substantially as hereinbefore
described.
Dated the 17th day of June 1901
J. H. JOHNSON & Co.,
Agents.