Improvements in the Manufacture of Basic Naphthalene Colouring Matters and of Sulpho Aoids thereof.
Year: 1891

page_text: Date of Application, 8th July, 1891
Complete Specification Left, 30th Mar., 1892-Accepted, 30th Apr., 1892
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Basic Naphthalene Colouring
Matters and of Sulpho Aoids thereof.
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 Rhine in the Empire of Germany, to be as follows:-
In the Annalen der Chemie vol. 256 pages 242 and 243, Fischer and Hepp
describe the production of normal- and iso-para-tolyl-rosinduline. The salts of
their normal product obtained by melting rosindone with para-toluidine and its
hydrochlorate they describe as yielding colours scarcely distinguishable from those
obtained with the salts of phenyl-rosinduline (formerly known as rosinduline).
According to this statement the substitution of a para-tolyl residue for a phenyl-
residue in the rosinduline molecule in the normal series has no effect on the colour
of the bodies so obtained.
Now my foreign correspondents have discovered that by suitably melting rosin-
done with ortho- and para-toluidine and with meta-xylidine and their hydrochlorates
in each case, products are obtained which are substitution compounds in the
normal series and all of them when properly purified give shades of red different
from phenyl-rosinduline. Thus the para-tolyl-rosinduline prepared and purified as
hereinafter explained gives a bluer shade and the ortho-tolyl- and meta-xylyl-
rosindulines yellower shades of red.
My foreign correspondents have further discovered, that all these red basic
naphthalene colouring matters can be sulphonated in a manner similar to that
described in the Specification of Letters Patent No. 15259 of 1888 and viold
analogous sulpho-acida. The differences in the shades of colour obtainable with the
dyestuff sulpho-acids is at least as great as with the bases from which they are
produced.
All three homologues of phenyl-rosinduline mentioned yield monosulpho-acids on
treatment with ordinary sulphuric acid at the temperature of the water bath.
These are in their properties analogous to the mono-sulpho-acid of phenylrosindu̟line
described in the Specification of Lotters Patent No. 15259 of 1888, and cannot be
further sulphonated with ordinary sulphuric acid.
To prepare the disulpho-acids, it is necessary to use fuming sulphuric acid. By
sulphonating the monosulpho-acids or the free bases with fuming sulphuric acid
and carefully regulating or moderating the reaction to the requisite extent, the
disulpho-acids are obtained. These are homologues of azocarmine and constitute
yellow-red to bluish-red dyestuffs of most excellent dyeing properties; they are
readily soluble in hot water, not very soluble in cold water, particularly in the
presence of mineral acids.
On more energetically sulphonating the bases ortho-tolyl-rosinduline and meta-
xylyl-rosinduline or the mono- or disulpho-acids derived therefrom a third sulpho
acid or mixture of sulpho-acids is obtained in each case which is readily soluble in
cold water. Para-tolyl-rosinduline appears to give no useful higher sulpho-aciu
analogous to the last named.
The following examples will serve to illustrate the nature of the invention but
they are merely to be regarded as typical and their details can be varied in many
respects. The parts are by weight.

page_text: EXAMPLE 1. PREPARATION OF ORTHO-TOLYL-ROSINDULINE.
Heat together about ten parts of rosindone ten parts of hydrochlorate of ortho-
toluidine and thirty parts of ortho-toluidine to a temperature of about one hundred
and fifty to one hundred and seventy degrees centigrade. Take test samples from
time to time and heat them with dilute hydrochloric acid; the ortho-tolyl-rosin-
duline formned dissolves and the operation of melting is continued until no increase
can be noticed in the quantity soluble in this way. This point being reached, pour
the mixture into about sixty parts of hydrochloric acid (containing about 25 per cent.
HCl) and about sixty parts of ice, and wash the precipitate formed with cold
water to get rid of the toluidine salt. The residue consists of the crude base in
the form of hydrochlorate, and if it be desired to prepare the sulpho acids and not
the pure base no further purification is necessary, for it is in that case preferable
to purify the monosulpho acid on account of the marked crystallizing power of its
sodium salt. If however the puro base is to be prepared, heat the crude hydro-
chlorate to boiling repeatedly with very dilute hydrochloric acid and precipitate
the dissolved salt from the solutions obtained, by means of common salt. Dissolve
the purified hydrochlorate thus obtained in alcohol and precipitate the free base
with ammonia. Recrystallize from.benzene.
Para-tolyl and meta-xylyl-rosinduline can be obtained in a similar way.
EXAMPLE 2. PREPARATION OF THE MONO-SULPHO ACID OF ORTHO-TOLYL-
ROSINDULINE.
Mix about ten parts of ortho-tolyl-rosinduline with about sixty parts of
concentrated sulphuric acid (containing about ninety five per cent. of real sulphuric
acid H₂SO) and heat the mixture on the water bath, take tests from time to time
and continue heating until the product after precipitation with water is completely
soluble in a hot diluted solution of caustic soda. Then pour the whole mixture
when cold into about ten times the quantity of water collect on the filter and press.
To further purify dissolve the press cakes in about twenty times the quantity of
boiling water adding sufficient caustic soda to make a neutral solution. On cooling
the sodium salt separates out in the form of crystals possessing a golden sheen or
lustre. Filter and press, and if it be desired to obtain the free sulpho-acid,
redissolve in boiling water and acidulate the solution with dilute sulphuric acid,
allow the solution to cool, filter, press and dry. The free mono-sulpho-acid so
obtained is but slightly soluble even in hot water, and is useful as a material which
can readily be obtained in the pure state, and is therefore well suited for the
preparation of the higher sulpho acids which are more soluble in water.
In a similar way the mono-sulpho acids of para-tolyl- aud meta-xylyl-rosinduline
can be obtained. The properties of these sulpho acids vary in a characteristic
mauner.
If a small portion of each of the mono-sulpho acids be stirred well with about
twenty times the quantity of cold water, and then caustic soda be added to each
till they are all slightly alkaline the ortho-tolyl- and the meta-xylyl-rosinduline
mono-sulpho-acids, dissolve, but the para-tolyl-rosinduline-sulpho-acid remains
undissolved. If now all the liquids be heated gradually to boiling, the sulpho-acid
from paratoluidine dissolves and on cooling, separates out; the solution of the
metaxylidine compound remains unchanged, and on cooling does not separate out;
in the solution of a compound derived from ortho-toluidine, crystals form when
the solution attains the temperature of about forty to fifty degrees centigrade,
these dissolve again on boiling, and on cooling, the sodium salt separates out in
shining crystals as already described.
EXAMPLE 3.
Mix about tan
PREPARATION OF THE DISULPHO-ACID OF
ROSINDULINE.
...1..
1..1..
ORTHO-TOLYL-
1

page_text: sixty parts of fuming sulphuric acid (maintained at a low temperature and con-
taining about twenty-three per cent. of free sulphuric anhydride SO). Then
stir well, allowing the temperature to rise to about twenty degrees centigrade.
At this temperature it will take about twelve hours to attain the desired degree of
sulphonation. The operation may be regarded as finished when a test portion
dissolves completely in cold dilute ammonia. This point being attained pour the
mixture when cold, gradually, into about twenty times the quantity of ice water,
filter off the sulpho-acid which separates out and press. Dissolve the press-cakes
in water, adding ammonia, and precipitate the ammonium salt formed with common
Balt; filter press and dry.
In preparing the disulpho-acid of para-tolyl-rosinduline, it is advisable to heat
the mixture of mono-sulpho-acid with fuming sulphuric acid, to a temperature of
about fifty degrees centigrade, and to maintain this temperature, till the degree
of solubility above described as the test, is attained. The product can be worked
up in the same way as above described. The disulphio-acid of meta-xylyl-
rosinduline forms a more soluble calcium salt than the other disulpho acids;
advantage may be taken of this by working up with the aid of milk of line and
sodium carbonate in the well-known way.
EXAMPLE 4. PREPARATION OF THE SULPHO-ACID OF
ROSINDULINE READILY SOLUBLE IN COLD WATER.
ORTHO-TOLYL-
Mix about ten parts of ortho-tolyl-rosinduline mono-sulpho-acid with about sixty
parts of fuming sulphuric acid (containing about twenty-three per cent. of free
sulphuric anhydride SO,) keeping the mixture well cooled. After all the
monosulpho-acid is added, heat the mixture on a boiling water-bath until a sample
completely dissolves in about twenty times the quantity of cold water. Then
dilute the entire product with twenty times the weight of cold water, neutralize
with milk of lime filter, convert the calcium salt in the mother liquor into sodium
salt in the well known way, and evaporate to dryness.
The readily soluble sulpho-acid of meta-xylyl-rosinduline is obtained in the
same way; para-tolyl-rosinduline or its mono-sulpho-acid, treated in this way gives
no useful product, as decomposition takes place.
Dated this 8th day of July 1891.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Basic Naphthalene Colouring
Matters and of Sulpho-acids thereof.
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 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 Annalen der Chemie vol. 256 pages 242 and 243, Fischer & Hepp describe
the production of normal and iso-para-tolyl-rosinduline. The salts of their normal
product obtained by melting rosindone with para-toluidine and its hydrochlorate
they describe as yielding colours scarcely distinguishable from those obtained with
the salts of phenyl-rosinduline (formerly known as rosinduline). According to
this statement the substitution of a para-tolyl-residue for a phenyl-residue in the
rosinduline molecule in the normal series has no effect on the colour of the bodies
80 obtained.
Now my foreign correspondents have discovered that by suitably melting

page_text: EXAMPLE 2. PREPARATION OF THE MONO-SULPHO-ACID OF ORTHO-
TOLYL ROSINDULINE.
Mix about ten parts of ortho-tolyl-rosinduline with about sixty parts of concen-
trated sulphuric acid (containing about ninety-five per cent. of real sulphuric
acid H.SO), and heat the mixture on the water bath; take tests from time to
time and continue heating till the product, after precipitation with water, is com-
pletely soluble in a hot diluted solution of caustic soda. Then pour the whole
mixture, when cold, into about ten times the quantity of water, collect on the filter
and press. To further purify, dissolve the press-cakes in about twenty times the
quantity of boiling water adding sufficient caustic soda to make a neutral solution.
On cooling, the sodium salt separates out in the form of crystals having a golden
sheen. Filter and press, and, if it be desired to obtain the free sulpho-acid,
redissolve in boiling water and acidulate the solution with dilute sulphuric acid;
allow the solution to cool, then filter, press and dry. The free mono-sulpho-acid so
obtained is but slightly soluble even in hot water and is useful as a material which
can readily be obtained in the pure state, and is therefore well suited for the
preparation of the higher sulpho acids which are more soluble in water.
In a similar way the mono-sulpho-acids of para-tolyl- and meta-xylyl-rosinduline.
can be obtained. The properties of these sulpho-acids vary in a characteristic
manner.
If a small portion of each of the mono-sulpho-acids be stirred well with about
twenty times the quantity of cold water, and then caustic soda be added to each
till they are all slightly alkaline, the ortho-tolyl- and the meta-xylyl-rosinduline-
mono-sulpho-acids dissolve but the para-tolyl-rosinduline-sulpho acid remains
undissolved. If now all the liquids be heated gradually to boiling, the sulpho-acid
from the para-toluidine derivative dissolves and on cooling separates out; the
solution of the meta-xylidine compound remains unchanged and, on cooling, does
not separate out. In the solution of the compound derived from ortho-toluidine,
crystals form when the solution attains the temperature of about forty to fifty
degrees centigrade; these dissolve again on boiling, and on cooling, the sodium
salt separates out in shining crystals as already described.
EXAMPLE 3. PREPARATION OF THE DISULPHO-ACID OF ORTHO-TOLYL-
ROSINDULINE.
Mix about ten parts of ortho-tolyl-rosinduline-mono-sulpho acid with about
sixty parts of fuming sulphuric acid (containing about twenty-three per cent. of free
sulphuric anhydride SO₁). Keep the acid well cooled while mixing. Then stir
well, allowing the temperature to rise to about twenty degrees centigrade. At
this temperature it will take about twelve hours to attain the desired degree of
sulphonation. The operation may be regarded as finished when a test portion
dissolves completely in cold dilute ammonia. This point being attained, gradually
pour the mixture, when cold, into about twenty times the quantity of ice water, filter
off the sulpho acid which separates out and press. Dissolve the press-cakes in
water, adding ammonia, and precipitate witli common salt the ammonium salt
formed filter, press and dry.
In preparing the disulpho-acid of para-tolyl-rosinduline, it is advisable to heat
the mixture of mono-sulpho-acid with fuming sulphuric acid to a temperature of
about fifty degrees centigrade and to maintain this temperature, till the degree of
solubility above described as the test, is attained. The product can be worked up
in the way hereinbefore described. The disulpho acid of meta-xylyl-rosinduline
forms a more soluble calcium salt than do the other di-sulpho-acids and advantage
may be taken of this fact by working up with the aid of milk of lime and sodium
carbonate in the well known way.

page_text: EXAMPLE 4. PREPARATION OF THE SULPHIO-ACID OF ORTHO-TOLYL-
ROSINDULINE READILY SOLUBLE IN COLD WATER.
Mix about ten parts of ortho-tolyl-rosinduline-mono-sulpho-acid with about
sixty parts of fuming sulphuric acid (containing about twenty three per cent. of
free sulphuric anhydride 80) keeping the mixture woll cooled. After all the
mono-sulpho-acid is added, heat the mixture on the boiling water-bath, until a
sample completely dissolves in about twenty times the quantity of cold water.
Then dilute the entire product with twenty times the weight of cold water,
neutralize with milk of lime, filter, convert the calcium salt in the mother liquor
into sodium salt in the well known way, and evaporate to dryness.
The readily soluble sulpho-acid of meta-xylyl-rosinduline is obtained in the same
way; para-tolyl-rosinduline, or its mono-sulpho-acid, treated in this way, gives no
useful product, as decomposition takes place.
Having now particularly described and ascertained the nature of this inven
tion and in what manner the same is to be performed I declare that what 1
claim is:-
1. The manufacture of basic naphthalene colouring-matters by melting rosindone
with ortho-toluidine, or meta xylidine and the hydrochlorate of the base employed'
in each case, substantially as herein before described.
2. As new articles of manufacture the basic naphthalene colouring matters
hereinbefore described namely normal ortho-tolyl-rosinduline and normal meta-
xylyl-rosinduline all such as can be obtained substantially as hereinbefore
described.
3. The manufacture of new mono-sulpho-acids, insoluble or practically insoluble
in water, by treating the basic colouring-matters liereinbefore described (viz., normal
ortho-tolyl-, para-tolyl-, or meta-xylyl-rosinduline) with concentrated sulphuric
acid, substantially as hereinbefore described.
4. As new articles of manufacture the new mono-sulpho-acids of the basic
naphthalene colouring-matters herein before described, such as can be obtained
substantially as hereinbefore described.
5. The manufacture of the disulpho-acids of the basic naphthalene colouring-
matters hereinbefore mentioned by treating the mono-sulphio-acids or the basic
colouring-matters themselves with fuming sulphuric acid in the. regulated and
moderated manner substantially as hereinbefore described.
6. As new articles of manufacture the dyestuffs hereinbefore described being
the disulpho-acids of the basic naphthalene colouring-matters hereinbefore
mentioned:
7. The manufacture of the higher sulpho-acids of normal ortho-tolyl-rosinduline
and normal meta-xylyl-rosinduline by treating these bases or the mono- or the
di-sulpho-acids thereof energetically with fuming sulphuric acid substantially as
hereinbefore described.
8. As new articles of manufacture the hereinbefore described higher sulpho-acids
readily soluble in cold water such as can be obtained substantially as 'herein before
described.
Dated this 30th day of March 1892.
J. H. JOHNSON & Co.,
Agents.