Improvements in the Manufacture and Production of Sulphoacids of a Red Basic Naphthalene Colouring Matter.
Year: 1890

page_text: Date of Application, 3rd May, 1893
Complete Specification Left, 3rd Mar., 1891-Accepted, 4th Apr., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of Sulphoacids of
a Red Basic Naphthalene Colouring Matter.
1, 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 and Soda
Fabrik, of Ludwigshafen-on-the-Rhine, in the Empire of Germany,) to be as
follows:-
In the Specification of the Letters Patent No. 15259 of October 23rd 1888 granted
to me the preparation of three sulphoacids of a red basic naphthalene colouring
matter called rosinduline is described. The said sulphoacids are derived from
rosinduline itself and all the sulpho-groups are introduced by direct sulphonation
after the formation of the rosinduline molecule.
Now my foreign correspondents have found that if instead of the unsulphonated
materials which have heretofore been melted with aniline and hydrochloride of
aniline to produce unsulphonated rosinduline, suitable sulphonated materials be
used sulphonated derivatives of rosinduline result; and the sulphonated derivatives
or (in other words) sulphoncids of rosinduline produced in this way are new and
different in many respects from those obtained in accordance with the hereinbefore
mentioned previous invention of my foreign correspondents. By acting on these
new sulphoacids with sulphuric acid, fuming sulphuric acid or chlorhydrin sulphuric
acid other new sulphoacids can be obtained. All of these are either dyestuff's
themselves which dye animal fibre from the acid bath or else are useful as raw
material for the manufacture of dyestuffs.
As an instance of the production of new sulphoacids of rosinduline from sulpho-
nated materials, I give the following example to illustrate more fully the nature
of this invention; the parts being by weight.
Take about 50 parts of amidonaphtho-quinoneimide sulpho acid (biimidonapthol-
sulphoacid obtained in the well known way from dinitro-alpha-naphthol sulphoacid,
Berichte der deutschen Chemischen (iesellschaft 1881 p. 2030) and about 50 parts
of aniline hydrochloride and about 175 parts of aniline and mix them well in an
enamelled vessel heating for about three or four hours to about 150° Centigrade,
then raise the temperature slowly to about 160° C. and keep this mixture at this
temperature for about ten hours or until no increase of purity is noticeable in the
green colour of successive test portions dissolved in strong sulphuric acid. Pour
the melt while still warm (having a temperature of say about 60° C.) into about
200 parts of hydrochloric acid (containing about thirty per cent. of real acid HCI)
and then add about one thousand parts of water and boil the mixture. Add about
two thousand parts of water and when cold filter, wash with cold water and press.
To purify the crude sulpho acid of rosinduline thus obtained it is converted into its
difficultly soluble crystallizing sodium salt. For this purpose, the product of the
above operations is boiled in a mixture of 2000 parts of water and 110 parts of
soda lye containing about 32 per cent. NaOH. A partial solution is formed from
which on cooling the sodium salt separates still in an impure condition. Filter and
again boil the residue with about five parts of soda lye (containing about thirty
two per cent. of sodium hydrate) and about six thousand parts of water. A partial
solution is again formed and during cooling the sodium salt again separates out;
practically completely so. Filter when the temperature has fallen to about 45° C.
and then boil again with about two thousand parts of water, filter again at about
45° C. wash with warm water and press. To reconvert into the free sulphoacid stir

page_text: the press cakes with about 1000 parts of water and bring to the boil then saturate
with hydrochloric acid, collect the free acid on the filter wash press and dry. By
repeating the above operations several times still greater purity can be attained.
The sulphoneid thus obtained hereinafter called sulphoacid lis, (like its sodium
salt) practically insoluble in hot water but by treating it with strong or fuming
sulphuric acid or the like it can be converted into new soluble sulpho acids as
described below.
Example 2. Mix about ten parts of sulphoacid with about thinty parts of
funing sulphuric acid containing about twenty three per cent, of free anhydride
keeping the mixture cold, and stir well at a temperature of about 15 to 20ª Centi-
grade till a test portion poured on to about three times the quantity of ice gives
a precipitate which is completely soluble in hot water. Pour the melt when cold
onto one hundred and fifty parts of ice and collect the new sulpho acid on a filter
and press. To purify dissolve the product in one thousand parts of boiling water
and add caustic soda till the liquid is only faintly acid and then add enough
ammonia to make it distinctly alkaline and further one hundred parts of a
saturated solution of common salt and continue boiling till the smell of ammonia
is no longer perceptible. On cooling, the sodium salt of the sulphoneid therein-
after called sulphoneid II) separates out in the crystalline form. Filter press
and dry.
Sulpho acid dyes animal fibre from the acid bath a blueish-red colour.
A similar, or identical, acid results from the prolonged nction of ordinary
concentrate sulphuric acid on sulpho neid I at the temperature of the water-bath.
By further sulphonating sulpho acid 11 or by more energetically sulphonating
sulphu acid there is obtained a third sulphoacid sulphoneid "111) which is
readily soluble in cold water, is non-crystalline and yields non-crystalline salts nud
which dyes animal fibre a less blueish shade of red. On account of its non-
crystallizing properties this acid is difficult to purify and it is therefore advisable
to start from pure materials such as the purified sulphoneid 11.
Example 3. Take about ten parts of sulphoacid II and stir well with about
sixty parts of fuming sulphuric acid (containing about twenty-three per cent, of
free anhydride) and then heat on the water bath till a test portion after conversion
into sodium salt is not precipitated by common salt. This point being arrived at.
dilute the melt when cold with about seven hundred parts of water. neutralize with
milk-of-line, convert the lime salt of the sulphoneid into the sodium salt by
treatment with sola in the usual way and evaporate the solution of the sodium salt
to dryness.
Ahongh I have given detailed examples of the production of sulphonated
rosindaline from amidonaphthoquinoneimidesulpho neid and the production of dye-
stuffs therefrom, the invention is not confined to the use of the said amidonaphtho-
quinoneimide sulphoacid as other sulphonated materials such as for instance
naphthol yellow S, can in a similar manner be male to yield identical or analogous
sulphonated rosindulines which on further sulphonation give reddish coloring
matters.
Datod this 3rd day of May 1890.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture and Production of Sulphoacids of
a Red Basic Naphthalene Colouring Matter.
1, JAMES YATE Jouxsox, 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 and Soda Fabrik of
50

page_text: 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 the Letters Patent No. 15259 of October 23rd 1888
granted to me there is described the preparation of three sulpho acids of a
red basic naphthalene colouring matter then known as rosinduline, but which
has recently received the name of phenylrosinduline (sec Journal of the
Chemical Society Vol. 58, page 909 and Annalen der Chemic Vol. 256
page 235) The said sulpho-acids are derived from phenylrosinduline itself and
all the sulpho groups are introduced by direct sulphonation after the formation
of the phenylrosinduline molecule. Now my foreign correspondents have
found that if, instead of the unsulphonated materials which have heretofore been
melted with aniline and hydrochloride of aniline to produce unsulphonated phenyl-
rosinduline, suitable sulphonated materials be used; sulphonated derivatives of
phenyl-rosinduline are obtained directly from the melt: and the sulphonated
derivatives or (in other words) sulpho-acids of phenylrosinduline produced in
this way are isomeric with, and differ in some respects from those obtained in
accordance with the hereinbefore mentioned previous invention of my forsign
correspondents. By acting on these new sulpho-acids with sulphuric acid, fuming
sulphuric acid, or chlorhydrin sulphuric acid, other new sulpho-acids can be
obtained.
All the new sulpho-acids are either dyestuffs themselves which dye animal fibre
from the acid bath or else are useful as raw materials for the inanufacture of
dyestuffs.
The unsulphonated materials recommended for use in the manufacture of phenyl-
rosinduline in the Specification to the above named Letters Patent No. 15,259 of
1888 are derivatives of alpha- and beta-naphtho-qquinone, or nitroso- or azo-com-
pounds of the naphthalene group and the suitable sulphonated materials which can
be used in carrying out this present invention are sulpho-acids of these or analogous
compounds.
These suitable sulphonated materials belong to the following classes of
compounds.
(1) Sulphonated derivatives of alpha- and beta- naphtho-quinone.
(2) Nitro- naphthol- sulpho-derivatives.
(3) Nitroso- naphthol- sulpho-derivatives.
(4) Azo-compounds derived from aniline (or its homologues or analogues) and
naphthol or naphthylamine-sulpho-acids.
In all cases at least one sulpho-group in the compound used must be attached to
that half of the naphthalene nucleus to which the amido, nitro, nitroso, azo, or
hydroxy-groups are not attached.
Not all such compounds can be used but by the aid of the following test a
person skilled in the art can readily ascertain whether a body belonging to one of
the above classes and sulphonated in the manner described is suited for use for the
purposes of this invention.
Take say about one pound of the body and mix with it about twice the weight
of aniline hydrochloride and about three times the weight of aniline and raise the
temperature of the mixture first to or about one hundred and forty degrees
Centigrade and afterwards carefully and slowly during about from eight to ten
hours raise the heat to say one hundred and eighty degrees Centigrade, with-
drawing at short intervals during the whole time good sized test portions from the
melt. The test portions are treated as follows:-
Saturate with hydrochloric acid, boil with very dilute hydrochloric acid, filter
and repeat these operations until the excess of aniline is removed; then dissolve the
residue in concentrated sulphuric acid, the production of a green solution from
any of the test portions proves the suitability of the compound for use for the
purposes of this invention.
As an instance of the production of new sulpho-acids of phenylrosinduline from

page_text: sulphonated materials. I give the following examples to illustrate the mammer in
which this invention may be carried into practical effect (by parts are meant part-
by weight).
Example 1. Take about 50 parts of amido-naphtho-quinone-imide sulpho-acid
(biimidonaphthol-sulphoacid obtained in the well known way from dinitro-alpha-
naphthol-sulpho-acid-naphthol-yellow S--(Berichte der deutschen chemischen
Gesellschaft 1881, p. 2030) and about 50 parts of aniline hydrochloride and about
175 parts of aniline and mix them well in an enamelled vessel henting for about
three or four hours to about 150° Centigrade; then raise the temperature slowly
to about 160° Centigrade and keep the mixture at this temperature for about ten
hours or until no increase of purity is noticeable in the green colour of successive
test portions dissolved in strong sulphuric acid.
Pour the melt while still warm (having a temperature of say about 60" (.) into
alout 200 parts of hydrochloric acid (containing about thirty per cent, of real
acid HCl) and then add about one thousand parts of water af boil the mixture.
Add about two thousand parts of water and when cobl filter, wash with cold water.
and press. To purify the crude sulpho-neid of phenyl-ro-induline tlms obtained it
is converted into its difficultly soluble crystallizing sodium salt. For this purpose
the pret of the above operations is builed in a mixture of 2011 parts of water
and 110 parts of soda lye containing about 32 percent. Na011. A partial solution
is formed from which on cooling the sodium salt separates still in an impure condi
tion. Filter and again boil the residue with about five parts of sola lye tcontaining
about thirty two jer ut, of sodium hydrate) and about six thousand parts of
water. A partial solution is again formel and during cooling the sodium salt again
separates out practically completely. Filter when the temperature has fallen to
about 15 Centigrule and then boil again with about two thous and parts of water.
filter again at about 45° Centigrade, wah with warm water and press. To
reconvert into the free sulpho-neid stir the press-cakes with about 1000 parts of
water and bring to the boil then saturate with hydrochloric acid, collet the free
ail on the filter, wash, press and dry. By repeating the above operations several
times still greater purity can be attained. The sulpho-acid thus obtained is herein-
after callel sulpho-acid I and is (like its solium salt after separation from solution)
practically insolable in hot water and can therefore not be used for dyeing but by
treating it with strong or fuming sulphuric acid or the like it can be converted
into new soluble sulpho acids as hereinafter described.
Example 2. Mix about ten parts of saly hosteid. V with down thirty parts of
fuming lphuric acid containing about imenty three porn free anhydride
Keeping the mixture cold, al stir well at a tempercome of about 15 to 20
Centigrade till a test portion portred on to about three times the quantity of see
gives a precipitate which is completely soluble in hot water. Pour the melt when
cold on to one hundred and fifty parts of ice and collect the new sulpho acid on a
filter and press. To purify the product dissolve it in one thousand parts of boiling
water and add caustic soda till the liquid is only faintly acid and then add enough
ammonia to make it distinctly alkaline and further add one hundred parts of a
saturated solution of common salt and continue boiling till the smell of ammonia is
no longer perceptible. On cooling, the sodium salt of the sulpho-acid (hereinafter
called sulpho acid II) separates out in the crystalline form. Filter, press and dry.
Sulpho acid 11 dyes animal fibre, from the acid bath, a bluish-red colour.
A similar, or identical, acid results from the netion of about five times the weight
of ordinary concentrated sulphuric acid on sulpho-acid I at the temperature of the
water bath until the above described test is satisfied. This method is to be recom-
mended as the product can more easily be purified than can that olaained when
fuming sulphuric acid has been used,
By further sulphonating sulpho-acid II or by more energetically sulphonating
sulpho acid there is obtained a third sulpho arid or mixture of sulpho-acids
(sulpho acid (11) which is readily soluble in cold water, and which dyes animal

page_text: fibre a less bluish shade of red. This acid cannot be readily purified and it is
therefore advisable to start from pure materials such as the purified sulphoacid II.
Example 3. Take about ten parts of sulpho acid II and stir well with about
sixty parts of fuming sulphuric acid (containing about twenty three per cent. of
free anhydride) and then heat on the water bath till a test portion after conversion
into sodium salt is not precipitated by common salt. This point being arrived at
dilute the melt when cold with about seven hundred parts of water, neutralize
with milk of lime, convert the lime salt of the sulpho-acid into the sodium salt by
treatment with soda in the usual way and evaporate the solution of the sodium salt
to dryness.
The proportions of aniline and aniline hydrochloride recommended in Example 1
and the temperature of the melt can be varied within very wide limits. With
some bodies it is advisable to heat to a higher temperature but in all cases the
colour of the sulphuric acid solution of a test portion of the melt, preferably after
extraction with hydrochloric acid and water, affords a certain criterion of the
progress of the reaction.
The following are instances of bodies which can be substituted for the amido
naphtho- quinone- imide- sulpho-acid of the example.
Naphtholyellow S (di-nitro naphthol sulpho-acid).
Nitroso- beta-naphthol sulpho-acid (Schaeffer's acid) and the amido- naphtho-
quinone-imide sulpho acid, which can be obtained from Cleve's alpha-naphthol
sulpho-acid (14). To obtain this amido- naptho- quinone- imide- sulpho-acid the
Cleve's acid is treated with nitrous acid to yield a nitroso-compound and this is
converted, by nitric acid, into a dinitro- naphthol-sulpho-acid isomeric with uaphthol-
yellow S which like that body yields on reduction and subsequent oxidation an
amido- naphtho- quinone- imide-sulpho-acid.
Having now particularly described and ascertained the nature of this 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 a basic naphthalene colouring matter by
melting suitable sulphonated materials as herein before explained with aniline and
aniline hydrochloride.
(2.) The manufacture of sulpho-acids of a basic naphthalene colouring matter
by sulphonating the products of the manufacture claimed in the first claiming
clause by means of concentrated sulphuric acid, fuming sulphuric acid or chlorhydrin
sulphuric acid.
(3.) The manufacture of sulpho-acids of basic naphthalene colouring matters as
hereinbefore described under either of the Examples hereinbefore given.
(4.) The products obtained by the processes claimed under either of the pre-
ceding claiming clauses.
Dated this 3rd day of March 1891
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.