The Manufacture of Sulpho-acids of a Red Basic Naphthalene Colouring Matter.
Year: 1890

page_text: Date of Application, 27th Oct., 1890
Complete Specification Left, 15th July, 1891-Accepted, 15th Aug.,
1891
PROVISIONAL SPECIFICATION.
The Manufacture of Sulpho-acids of a Red Basic Naphthalene
Colouring Matter.
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) to be as follows:-
In the Provisional Specification of my application for Letters Patent No. 14,836
of 1890 I have described the production of a new sulpho-acid constituting a yellowish-
red dyestuff.
The present invention is based upon the discovery that this yellowish-red dyestuff
can, by melting with aniline and aniline hydrochlorate, be converted into a new
sulpho-acid (hereinafter called sulpho-acid A) of the red basic naphthalene colouring
matter now known as phenyl-rosinduline, though formerly called rosinduline (see
Journal of the Chemical Society Vol. 58, page 909. Annalen der Chemie Vol. 256,
page 235). This new sulpho-acid A can by the action of sulphuric acid (containing
about 95 per cent. H, SO, at the temperature of about 100 degrees Centigrade be
converted into a second new sulpho-acid (hereinafter termed sulpho-acid B) and
finally by more energetically sulphonating either sulpho-acid A or sulpho-acid B
by means of fuming sulphuric acid or its equivalent a third sulpho-acid (sulpho-
acid C) can be obtained.
Sulpho acid A is so slightly soluble in both hot and cold water that it cannot be
used for dy cing from the acid bath; sulpho-acid B is but slightly soluble in cold
but readily soluble in hot water and is a valuable dyestuff dyeing wool from the
acid bath most evenly, and giving a shade of red slightly bluer than that obtained
with the disulpho-acid of phenyl-rosinduline the subject of Letters Patent
No. 15,259 of 1888 known in commerce as azocarmine: sulpho-acid C is readily
soluble in cold and hot water, and resembles sulpho-acid. B in its dyeing properties,
but giving a slightly yellow shade.
This sulpho acid C appears to be identical with the sulpho acid readily soluble in
cold water of the said Letters Patent 15259 of 1888 and all these sulpho acids
resemble those of the said Letters Patent in yielding bright green solutions when
dissolved in sulphuric acid.
For the sake of convenience I describe a way in which the sulpho-acid, described
in the said Provisional Specification of the Application No. 14836 of the year 1890
can be obtained, to be used in carrying out this invention. About ten parts (by
weight) of the sodium salt of the higher sulpho-acid of phenyl-rosinduline readily
soluble in cold water described in the Specification of the Letters Patent
No. 15259 of 1888 are mixed with about one hundred and fifty parts of diluted
sulphuric acid (containing about seventy-five per cent. H, SO,) and the mixture is
boiled until a sample withdrawn and diluted with about ten times the quantity of
water gives a copious precipitate and the mother liquor has a yellowish red colour.
The entire product when cold is poured into one hundred and fifty parts of ice,
filtered and pressed. The crude acid thus obtained can be purified by converting it
into its sodium salt, dissolving this in water, filtering the solution and finally repre-
cipitating the free acid by means of dilute sulphuric acid. It is then collected,
pressed and dried.
In order to more fully illustrate the nature of the present invention I give the
following examples without binding myself to details. The parts are by weight:

page_text: J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.
COMPLETE SPECIFICATION.
The Manufacture of Sulpho Acids of a Red Basic Naphthalene
Colouring Matter.
1 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 com-
municated 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

page_text: 15 to be performed to be particularly described and ascertamed in and by the
following statement :-
In the Specification of Letters Patent No. 15259 of 1888 granted to me there
are described three sulpho acids of a red basic naphthalene. colouring matter then
known as rosinduline but which has since received the name of phenyl-rosinduline
(see Journal of the Chemical Society Vol. 58 page 909; Annalen der Chemie
Vol. 256 page 235).
Of these sulpho-acids the crystallizable disulpho-acid there described is widely.
applied in the dyeing industry under the name of "azocarmine" and was the first
red dye stuff known belonging to the induline series and containing a naphthalene
nucleus in its molecule.
In the Specification accompanying my Application for Letters Patent No. 14836
of 1890 the production of a sulpho-acid which constitutes a yellow red dyestuff is
described. This yellow-red dyestuff results from the action of dilute sulphuric acid
on the higher sulpho-acid" of phenylrosinduline which is described and claimed
in the Specification of the aforesaid Letters Patent No. 15259 of 1888 and which
is characterized by its ready solubility in cold water.
38
In the prosecution of their researches on this group of dyestuffs, my foreign
correspondents have discovered that it is possible to convert the aforesaid yellow-
red dyestuff into sulpho-acids of phenyl-rosinduline (including analogues thereof)
by treating the said dyestuff with aniline and aniline salt (or analogues thereof).
The sulpho acids of phenyl rosinduline (including its analogues) thus obtained can
be further sulphonated by the action of ordinary or fuming sulphuric acid so as to
yield higher sulpho acids of phenylrosinduline (including its analogues). Thus if
the sulpho acid or yellow red dyestuff described in the Specification of the appli-.
cation for Letters Patent No. 14836 of 1890 be melted with aniline and aniline.
hydrochlorate a new mono-sulpho-acid of phenyl-rosinduline is obtained which my.
foreign correspondents call "sulpho acid A." If this sulpho-acid A. be treated with
ordinary concentrated sulphuric acid at the temperature of the boiling water-bath
until a test portion yields a clear solution in ten times the quantity of boiling water,
a new disulpho-acid of phenylrosinduline is obtained which may betermed sulpho
acid B." If this sulpho acid B be further sulphonated or if sulpho acid A be more
energetically sulphonated with fuming sulphuric acid a third sulpho acid or mixture
of sulpho-acids is obtained apparently identical with the higher sulpho acid of
phenyl-rosinduline readily soluble in cold water, described in the aforesaid Specifi-
cation of Letters Patent No. 15259 of 1888. To this sulpho acid so obtained the
name sulpho acid C may be given.
55
Now if instead of melting the yellow-red dyestuff with aniline, a homologue
thereof be taken such as ortho-toluidine or meta-xvlidine a corresponding
homologous-sulpho-acid A can be obtained which can in the same way be converted
into sulpho acids B and C. Thus the sulpho-acid resulting from melting together
the yellow-red dyestuff with ortho-toluidine is a mono-sulpho acid of ortho-tolyl-
rosinduline which may be distinguished as sulpho-acid Ao-t: On sulphonating
this with ordinary and with fuming sulphuric acid sulpho-acids are obtained corre-
sponding to the B and C acids from the product of the aniline melt and they may.
be termed sulpho acid B o-t" and "sulpho acid Co-t respectively. In the same.
way three acids can be obtained by the use of meta-xylidine, and these are called.
respectively sulpho-acid A. m-a "sulpho-acid B m-a" and "sulpho acid C m-a."
By using para-toluidine, the sulpho-acids corresponding to the acids A and B can
be obtained but the C acid cannot readily be prepared. These two. acids are.
termed respectively "sulpho acid A p-t" and "sulpho acid B p-t." The mono-
sulpho-acids or sulpho acids A. are too insoluble in water to be used as dyestuffs;
the disulpho-acids or sulpho-acids B are isomeric or homologous with azo carmine
and have similar valuable properties; they dye slightly different shades of red; the
sulpho-acids Bo-t and Bmx giving slightly yellower shades of red while the
others give bluer shades. The sulpho-acids C give in cach case slightly yellower.
shades than the corresponding.sulpho acids B.
23

page_text: The following examples illustrate the nature of the invention and the manner in
which it can be carried into practical effect. The parts are by weight.
EXAMPLE 1. THE PRODUCTION OF. THE NEW SULPHO-ACID A.*
Melt together about ten parts of the yellow red sulpho-acid (obtained as herein-
before described or in any other way) with about thirty parts of aniline and ten
parts of aniline hydrochlorate, at a temperature of about from one hundred and
fifty to one hundred and ninety degrees Centigrade stirring continuously. The
end of the reaction can be determined by the following test. Stir a test portion of
the melt with dilute hydrochloric acid and then make slightly alkaline with dilute
caustic soda, boil and filter, and allow a few drops of the filtrate to run out on filter
paper. At the margin of the stain add a drop of hydrochloric acid (containing
about 25 per cent. H CI). If a change of colour to yellow take place, unchanged
yellow-red dyestuff is still present in the melt. Continue melting until no diminution
of this quantity can be noticed. Allow the melt to cool and then pour it into
sufficient dilute hydrochloric acid to saturate all the aniline, filter and wash with
water till practically free from aniline or aniline salt. Mix the residue (which
consists of crude sulpho acid A) with about three hundred parts of water and boil.
To the mixture add sufficient caustic soda-solution to make it slightly alkaline,
when the sodium salt of the new sulpho-acid is obtained and separates out, especially
on cooling. Collect and separate from the mother liquor, crush and then boil im
about three hundred parts of water and precipitate again with caustic soda. This
purification with caustic soda should be repeated until no more yellow-red dyestuff
can be discovered in the mother liquor, by means of hydrochloric acid which causes
a change of colour to yellow, as long as this body is present. Collect the sodium
salt again, boil with water and precipitate the free sulpho-acid by adding a sufficient
quantity of a mineral acid, wash, press and dry.
If in this example, instead of the aniline and aniline hydrochlorate, equivalent
quantities of the immediate analogues of aniline, ortho and para-toluidine and their
hydrochlorates, or meta-xylidine and its hydrochlorate, be taken, the analogous
sulpho-acids result, namely from the ortho-toluidine melt, the sulpho-acid A. o-t is
obtained, and from the para-toluidine melt the acid A. p-t, and from the meta-xylidine
melt the acid A m-a. In working up the para-toluidine melt, it is advisable to
purify with the aid of ammonia, instead of caustic soda. The mixture of crude
sulpho-acid and water is made strongly alkaline with ammonia and filtered hot.
The residue is boiled with water and a mineral acid, filtered, washed, pressed and
dried. The sulpho-acids A are too insoluble in water to be used as dyestuffs, but
they are useful as material for the manufacture of soluble-dyes; by sulphonation, as
herein before described.
EXAMPLE 2. THE PRODUCTION OF THE NEW SULPHO ACID B.
Stir about ten parts of the sulpho-acid A, obtained as above described (or-in any
other way) into about fifty parts of sulphuric acid (containing about 95 per
cent. H S.O) and heat the mixture for about five hours on the water bath or until
a test portion yields a clear solution on mixing with ten times the quantity of
boiling water.
Cool and then pour the mixture into about three hundred parts of
ice water; and filter off the new sulpho-acid B, which is nearly insoluble in the acid
mother liquor, press, dissolve in hot water, and neutralise the boiling solution with
milk of lime, filter and to the filtered 'solution add soda, to convert the calcium salt
into sodium salt. Filter from the precipitated calcium carbonate and evaporate the
solution to dryness. In this way the sulpho-acid B is obtained in its commercial
form of sodium salt.
If instead of the sulpho acid A, taken in the above example there be taken
equivalent quantities of the other sulpho-acids-A'such as are obtainable by the use

page_text: explained then the analogous B acid .will be produced in each case, and, can be
worked up and brought into the commercial form of sodium salt exactly as described
in the example 2. In the case of paratoluidine the sulphonation is continued until
a sample of the melt precipitated with ice water is completely soluble in hot dilute
ammonia. The melt is then poured into a dilute solution of common salt, filtered
and pressed, and the press-cake dissolved in water containing an excess of ammonia,
from which the ammonium salt is precipitated by means of common salt.
Boil
again with saturated salt solution, filter, press and dry.
The sulpho-acids B o-t, B p-t and B3 m-x, thus obtained are closely analogous to
the sulpho-acid B from the product of the aniline melt, and dye animal fibre from
the acid bath in a similar way, giving slightly different shades of red.
EXAMPLE 3. A PROCESS FOR THE PREPARATION OF SULPHO-ACID C.
Take about ten parts of sulpho-acid A, or of sulpho acid B (both obtained either
as hereinbefore described or in any other way) and add them gradually to about
fifty parts of fuming sulphuric acid (containing about twenty three per cent. of free
anhydride SO). Keep the sulphuric acid cold during the addition and stir well.
Subsequently, heat the mixture in the boiling water bath, for about four hours, or
until a test portion dissolves clearly in about fifteen parts of cold water. Dilute the
whole product with cold water neutralize with milk of lime and work up in the well
known way to obtain the sodium salt.
If instead of the sulpho-acid A or B, taken in this example there be taken
equivalent quantities of the sulpho acids A or B such as are obtainable by the use
of ortho-toluidine or meta-xylidine, in the melt instead of aniline, as hereinbefore
explained, then the analogous C-acids will be produced, and can be worked up
exactly as described in example 3. The sulpho-acids C, C o-t, and C m- thus
obtained, are all readily soluble in cold water, and dye animal fibre from the
acid bath slightly yellower shades of red, than the corresponding sulpho-acids B.
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 sulpho-acids of phenyl-rosinduline, or of an analogous
basic naphthalene colouring matter, hereinbefore included under sulpho-acids A, by
melting the yellow red dyestuff described in the Specification No. 14836 of 1890
with a mixture of aniline and its hydrochlorate, or with a homologue of aniline
herein before mentioned, in mixture with its hydrochlorate all substantially as
hereinbefore described.
2. The manufacture of the sulpho-acids hereinbefore included under sulpho-
acids B-by sulphonating the sulpho-acids A with ordinary concentrated sulphuric
acid, all substantially as hereinbefore described.
3. The manufacture of the sulpho-acids hereinbefore included under sulpho-
acids C-by sulphonating certain of the acids A or B hereinbefore mentioned with
fuming sulphuric acid, all substantially as herein before described.
4. The manufacture of sulpho-acids of a red basic naphthalene dyestuff substan-
tially as hereinbefore described respectively in the examples 1. 2 and 3.
5. As new products, the sulpho-acids such as can be obtained as herein before
described and termed sulpho acid A.; sulpho-acid A o-t; sulpho-acid A p-t; sulpho-
acid A m-x; sulpho-acid B; sulpho-acid Bo-t sulpho acid B p-t; sulpho-
acid B m-x; sulpho acid C o-t; and sulpho-acid C m-a.
Toted this 15th dex of T.... 1901
J. H. JOHNSON & Co.,
Agents.