The Production or Manufacture of Derivatives of Betanaphtho- hydroquinone, or Betanaphthoquinone, and of Colouring Matters therefrom.
Year: 1893

page_text: Date of Application, 13th Jan., 1893
Complete Specification Left, 10th Oct., 1893-Accepted, 25th Nov., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Production or Manufacture of Derivatives of Betanaphtho-
hydroquinone, or Betanaphthoquinone, and of Colouring
Matters therefrom.
I, HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
:-
The present invention relates to the production of derivatives of betanaphtho-
hydroquinone or betanaphthoquinone.
My foreign correspondents have found that the effect of sulphurous acid, when
employed in the state of an acid salt, on betanaphthoquinone, totally different
from that which takes place when aqueous sulphurous acid is allowed to act on the
same substance. In the latter case, betanaphthohydroquinone results, as described
by Liebermann and Jacobson in the Liebig's Annalen, volume 211, page 58.
If, however, betanaphthoquinone is introduced into from two to three times its
weight of a concentrated cold solution of sodium bisulphite, the quinone is first
dissolved, producing a yellowish brown color. After a short time, the liquid-
solidifies into the form of a jelly of colorless crystals, these latter being probably an
addition-product of the quinone with sodium bisulphite. These crystals are very
unstable, for if the reaction mixture is allowed to stand, they are again dissolved,
and from the solution thus obtained, another product separates, after some time, in
fine needles of a rather yellowish color. The latter substance, unlike the former,
is very stable, and represents the sodium salt of betanaphthohydroquinone sulpho
acid, as my foreign correspondents have ascertained.
In employing greater quantities of quinone, and introducing the latter into the
solution of sodium bisulphite, heat is spontaneously evolved, and the separation of
the above intermediate product does not take place in this case, while the sodium
salt of the naphthohydroquinone sulpho acid is then directly separated.
It is most advantageous, according to the researches of my foreign correspondents,
to isolate the beta naphtholydroquinone sulpho acid in the state of its potassium salt,
as the latter is only slightly soluble in cold water. In order to obtain this potassium
salt, the reaction liquid is mixed with an excess of potassium chloride.
manner, the potassium salt separates in beautiful large crystals.
In this
The production of betanaphthohydroquinone sulphonate of potassium is described
the fallming aromala
PRODUCTION OF THE POTASSIUM SALT OF
SULPHO ACID.
BETANAPHTHOHYDROQUINONE
10 parts (the parts are by weight) of betanaphthoquinone (employing a paste
containing 30 per cent. of pure quinone) are gradually introduced during agitation
into 30 parts of sodium bisulphite solution (specific gravity 14). After the whole
quinone has dissolved, the mass is allowed to stand for some hours, and after
filtering off small quantities of insoluble flakes, the filtrate is mixed with a
concentrated watery solution of 7.5 parts of potassium chloride. The separation
of the potassium salt of the formed betanaphthohydroquinone sulpho acid, soon
begins, and is complete after some time.

page_text: The potassium salt obtained in this manner, and isolated by filtering off, is
sufficiently pure for most purposes. By re-crystallizing, however, from a sodium
bisulphite solution, it is obtained in a perfectly pure state.
The analogous sodium salt forms fine needles easily soluble even in cold water,
whilst the potassium salt is soluble with ease in hot water, but only slightly soluble
in cold water, and separates, on cooling, from the hot solutions in beautiful
prismatic crystals.
->
The betanaphthohydroquinone sulpho acid obtained in such or analogous way,
is easily transformed into the corresponding betanaphthoquinone sulpho acid by
means of suitable oxidising agents.
On adding soda-lye to the watery solution of this hydroquinone sulpho acid
or its salts, a brownish liquid results, and the latter assumes a red color, when it is
allowed to stand for some time in the air. If, in the latter case, concentrated
solutions are employed, deep red colored crystals are separated, which represent
the sodium salt of beta hydroxy alpha naphthoquinone (OH: OH: OH = 1:2:4),
melting at about 190 degrees centigrade.
Hence follows, that the above named betanaphthohydroquinone sulpho acid
corresponds to the formula:
This latter substance is already obtained in other ways by O. N. Witt and
H. Kaufmann, viz. from alphanaphtholmonosulpho acid (1-4), as briefly mentioned
in the Berichte der Deutschen Chemischen Gesellschaft, volume XXIV.,
page 3163.
The sodium bisulphite employed in the above first example, can also be replaced
by other soluble acid salts of sulphurous acid, and the mode of working described
in the said example can likewise be considerably varied.
My foreign correspondents have found that the above naphthohydroquinone
sulpho acid (12 dihydroxynaphthalene 4 mono sulpho acid) is capable of being
employed with advantage as a photographic developer. Even in the presence of
salts of carbonic acid, this developer acts very rapidly, almost instantaneously,
bringing out the finest details even in the shadowy parts of photographic figures.
The figures gradually assume intensity only by further developing, and therefore
the degree of development can be readily fixed according to requirements. This
new substance, then, offers this additional advantage over the other naphthalene
derivatives hitherto known & in use for photographic purposes (such as eikonogen
and the like). It unites the advantages of the latter with those of hydroquinone,
and it is particularly adapted for being employed as developer in instantaneous
photography.
My foreign correspondents have also found that the thiosulphuric acid and its
salts act on betanaphthoquinone in an analogous manner to the sulphurous acid,
when the latter is employed in the state of acid salts. A well-characterised
derivative of betanaphthohydroquinone containing sulphur, is obtained by allowing
moderately acidulated solutions of thiosulphuric salts to act on molecular quantities
of betanaplithoquinone.
In order to illustrate the process for producing this new derivative of beta-
naphthohydroquinone, the following example is given. The parts are by weight.
1

page_text: PRODUCTION OF BETANAPHTHOHYDROQUINONE THIOSULpho acid.
1-6 parts of betanaphthoquinone are thoroughly mixed with 10 parts of water,
and a solution of 2.5 parts of sodium thiosulphate in 10 parts of water, is added to
the above mixture. The resulting mixture is then mixed, on stirring, with 3 parts
of acetic acid (containing 20 per cent. of pure acid). The quantities employed of
the said ingredients correspond to molecular proportions. The betanaphthoquinone
is rapidly dissolved, & after filtering off a small quantity of insoluble products,
a clear, slightly-brownish liquid results, which contains the new naphthohydro-
quinone derivative.
If the above solution is saturated with common salt, the sodium salt of the new
product separates, after some time, in fine grayish needles.
According to the researches of my foreign correspondents, it is more advantageous
to precipitate the new compound in the form of its potassium salt, as the latter is
less readily soluble, viz., by adding potassium chloride (in place of common salt) to
the reaction liquid. The potassium salt then separates in beautiful crystals.
The sodium salt of the resulting new acid is readily soluble even in cold water,
whilst the potassium salt easily dissolves in hot water, but with difficulty in cold
water. The potassium salt separates out of the concentrated hot solutions, on
cooling, in beautiful long needles or prismatic crystals containing no water.
It may
easily be purified by crystalising out of water, which is advantageously mixed with
a small quantity of sulphurous acid.
My foreign correspondents have ascertained by analytical research, that the
last-named potassium salt contains 12.01 and 12.07 per cent. of potassium, whilst
the theoretical amount thereof is 12.58 per cent., in accordance with a formula
CHISOR AR
The latter formula represents the composition of the new compound, which is
the potassium salt of betanaphthohydroquinonethiosulpho acid, as follows from
the chemical properties of the said substance, and from the above analytical
research.
It is noticeable that its watery solutions assume an intense reddish-violet color
when they are mixed with alkalies. The new substance materially differs by this
special property from the other known derivatives of betanaphthohydroquinone, as
the solutions thereof in water most assume a yellow to brown color, when alkalies
are added thereto. If the new product is heated with diluted mineral acids,
sulphurous acid is separated, a new substance being precipitated in crystals. It is
reduced, when treated with zinc dust, in the presence of acids, sulphuretted
hydrogen being disengaged, and a mercaptane resulting, which possesses the
following formula :-

page_text: In place of thiosulphuric salts, solutions of sulphur in salts of sulphurous acid
likewise can be employed in the foregoing second example.
The analogy between the above two acids, viz., betanaphthohydroquinonesulpho
acid and betanaphthohydroquinonethiosulpho acid, finds further expression in their
behaviour in the presence of oxidising agents. Both acids are easily transformed
into the corresponding quinone sulpho acids, viz., betanaphthoquinone sulpho acid
and betanaphthoquinonethiosulpho acid, by means of suitable oxidising agents.
The conversion of betanaphthohydroquinone sulpho acid into betanaphthoquinone
sulpho acid, is described in the following third example. The parts are by weight.
OXIDATION OF
BETANAPHTHOHYDROQUINONE
SULPHO ACID INTO
BETANAPHTHOQUINONE SULPHO ACID.
1 part of the above naphthohydroquinone sulpho acid, is dissolved in about
20 parts of water, and the resulting solution is mixed with half a part of sodium
nitrite, dissolved in a small quantity of water. The liquid is slowly acidulated by
means of acetic acid, and the so-formed quinone sulpho acid is precipitated as
sodium salt, by adding common salt. This sodium salt forms yellow crystals.
The naphthoquinone sulpho acid thus produced, is identical with the naphtho-
quinone alpha sulpho acid mentioned by O. N. Witt and H. Kaufmann in the
Berichte der Deutschen Chemischen Gesellschaft, volume 24, page 3163.
In a similar manner as the sodium nitrite employed in the last named example,
analogous oxidising agents can also be used, such as, for example, the halogens and
the like.
If, in the preceding example, in place of betanaphthohydroquinone sulpho acid,
the corresponding quantity of betanaphthohydroquinonethiosulpho acid is used, the
analogous betanaphthoquinonethiosulpho acid results.
The above named derivatives of betanaphthohydroquinone or betanaphtho
quinone, can easily be converted into new dye stuffs according to the researches of
my foreign correspondents, viz., by condensing them with nitroso compounds in or
without the presence of thiosulphuric acid or salts thereof.
If, for example, the watery solution of betanaphthoquinone sulpho acid is hented
with a molecular proportion of nitroso derivative, in presence of thiosulphuric acid,
the formation of the dye stuff begins after a short time.
The production of these coloring matters is explained in the following example,
the parts being by weight:—
COLORING MATTER FROM BETANAPHTHOQUINONE SULPHO ACID, AND
NITROSOETHYBENZYLANILINE SULPHO ACID.
27.5 parts of betanaphthoquinone sulphonate of potassium, are dissolved in 50 times
its weight of water, and a concentrated solution of 26 parts of sodium thiosulphate
is added to the first formed liquid. Whilst the solution is kept cool, it is
acidulated by means of acetic acid. The original intense yellow color disappears
after a short time. 31.5 parts of nitrosoethylbenzlaniline sulpho acid are then
added, and the resulting liquid mixture is heated on the water bath, until the
bluish-violet, color (which the reaction mixture soon assumes) does not further
increase in intensity.
The new dye stuff can easily be separated by adding common salt, and is isolated
by filtering off. It represents a mass with metallic lustre. It easily dissolves in
hot water, with bluish-violet color, and produces pure blue and bright shades on
wool previously mordanted with chromium salts. The resulting shades are
absolutely fast against the action of fulling, and possess a great degree of fastness

page_text: .
against the action of light. The new dye stuff likewise can be employed with
advantage for printing on cotton material.
In place of nitrosoethylbenzylaniline sulpho acid, other nitroso compounds, such
as nitroso derivatives of benzlaniline sulpho acid, methylbenzylanilinesulpho acid,
dibenzylanilinedisulpho acid, and the like, can be used without materially altering
the mode of working explained in the last example.
If nitrosodimethylaniline, or nitrosodiethylaniline, or nitrosodiphenylamine, or
other nitroso compounds containing no sulpho groups are employed, similar dye
stuffs result, which only differ from the former by being less soluble in water.
The betanaphthoquinone sulpho acid used in the above last example, can be
replaced by betanaphthohydroquinone sulpho acid, without materially altering the
mode of working explained in the last named example.
:
The production of dye stuffs by means of beta-naphthohydroquinone sulpho acid,
is explained in the following example, the parts being by weight :-
DYE-STUFF FROM BETANAPHTHOHYDROQUINONE SULPHO ACID AND NITROSO-
ETHYLBENZYLANILINE SULPHO ACID.
:
27.5 parts of betanaphthohydroquinone sulphonate of potassium are dissolved in
a solution prepared by dissolving 26 parts of sodium thiosulphate in about
500 parts of water, and the resulting solution, after cooling, is mixed with
31-5 parts of finely powdered nitrosoethylbenzylaniline sulpho acid, whilst the
mixture is well agitated. After the whole is dissolved, the liquid is heated at
100 degrees centigrade, until the formation of the dye stuff, which soon begins, is
complete. The isolation of the colouring matter thus produced is effected in the
same manner as described in the last named fourth example.
The nitrosoethylbenzylaniline sulpho acid employed in the foregoing fourth
example, can of course be replaced by other nitroso compounds, similar results
being thus obtained.
.
If the above named naphthohydroquinone sulpho acid, or naphthoquinone sulpho
acid, is allowed to act on nitroso compounds, without the presence of this sulphuric
salts, dye stuffs are obtained, which differ from those produced in the manner
illustrated by the foregoing fourth and fifth examples.
According to the further researches of my foreign correspondents, colouring
matters, which are analogous to those obtained by means of the processes explained
in the foregoing fourth and fifth examples, resuit, if the above named thiosulpho
acids, viz., betanaphthohydroquinone thiosulpho acid and betanaphthoquinone thio-
sulpho acid, are heated with molecular proportions of nitroso compounds in watery
An addition of thiosulphuric salts, or the like, is not necessary in
solutions.
this case.
All the colouring matters herein before defined, and derived from the above named
derivatives of betanaphthoquinone, or betanaphthohydroquinone, are particularly
adapted for dyeing wool mordanted with metallic salts. They can likewise be
employed for printing on cotton. The shades produced by means of these colouring
matters possess great fastness against fulling; and against the action of light.
Dated this 13th day of January 1893.
NEWTON & SON,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
The Production or Manufacture of Derivatives of Betanaphtha-
hydroquinone, or Betanaphthaquinone, and of Colouring
Matters therefrom.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
The present invention relates to the production of derivatives of beta-naphtha
hydroquinone or beta naphtha quinone.
My foreign correspondents have found that the action of sulphurous acid used in
the state of an acid salt on beta naphtha quinone, is totally different from that
which takes place when an aqueous solution of sulphurous acid is used. In the
latter case, beta naphtha hydroquinone is formed as described by Liebermann and
Jacobson, in Liebig's. Annalen, volume 211, page 58. If, however, beta naphtha-
quinone is introduced into from two to three times its weight of a concentrated cold
solution of sodium bisulphite, the quinone is first dissolved, producing a yellowish-
brown coloured liquid. After a short time, the liquid sets to a jelly like mass of
colourless crystals, probably an addition compound formed by the union of the
quinone with sodium bisulphite. These crystals, however, are very unstable, and
after a time become dissolved, and eventually another product separates in fine
needles of a rather yellowish colour. This latter substance, unlike the former, is
very stable, and is the sodium salt of beta naphtha hydro quinone sulpho acid.
When considerable quantities of quinone are introduced into the solution.
of sodium bisulphite, heat is spontaneously evolved, and the separation of the
immediate product above referred to does not take place, the sodium salt of the
naphtha hydroquinone sulpho acid alone crystallising out.
According to the researches of my foreign correspondents, it is most advantageous
to isolate the beta naphtha hydroquinone sulpho acid in the form of potassium salt,
as this salt is only slightly soluble in cold water. In order to obtain this potassium
salt after the action has taken place, an excess of potassium chloride is added to the
liquid the potassium salt then separates in beautiful large crystals.
The production of beta naphtha hydroquinone sulphonate of potassium is described
in the following example. The parts are by weight.
FIRST EXAMPLE.
PRODUCTION OF THE POTASSIUM SALT OF BETA NAPHTHA HYDROQUINONE
SULPHO ACID.
10 parts of beta naphthaquinone (in the form of a paste containing 30 per cent. of
pure quinone) are gradually stirred into 30 parts of a solution of sodium bisulphite
(specific gravity 1:4); when the quinone is dissolved, the mixture is allowed to
stand during several hours, and a small quantity of insoluble matter having been
filtered off, the filtrate is mixed with a concentrated solution of 7:5 parts of
potassium chloride. The separation of the potassium salt of the beta naphtha
hydroquinone sulpho acid soon begins, and is complete after some time.
The potassium salt obtained in this manner, and separated by filtering off, is
sufficiently nearly pure for most purposes. It is obtained in a pure state by
recrystalising it from a solution of sodium bisulphite.
Whereas the sodium salt forms fine needles easily soluble even in cold water, the
potassium salt is easily soluble in hot water, but only slightly soluble in cold water,
separating from the solution, as it cools, in beautiful brilliant prismatic crystals.
The beta naphtha hydro quinone sulpho acid obtained in such or an analogous

page_text: way, is easily transformed into the corresponding beta naphthaquinone sulpho acid
by means of suitable oxidising agents.
=
On adding soda lye to a solution of the hydro quinone sulpho acid, or its salts, a
brownish coloured liquid is obtained, which assumes a red colour, when allowed to
stand during some time exposed to the air. If concentrated solutions are employed,
the sodium salt of beta hydroxyalpha naphthaquinone (O: OH: 0 1:2:4)
separates in deep red coloured crystals.
Hence it follows, that the beta naphtha hydroquinone sulpho acid prepared in
the manner described, is the alpha, beta, naphthahydroquinone-alpha, monosulpho
) acid represented by the formula :
This latter substance has already been obtained in another way by O. N. Witt
and H. Kaufmann, viz., from alphanaphtholmonosulpho acid (1:4), as briefly
mentioned in the Berichte der Deutschen Chemischen Gesellschaft, volume XXIV.,
page 3163.
1
Instead of the sodium bisulphite prescribed in the above first example, other
soluble acid sulphites can be used, and the mode of working described in the said
example can likewise be varied.
My foreign correspondents have found that alpha, beta, naphtha hydroquinone-
alpha, monosulpho acid (1: 2-dihydroxynaphthalene-4-monosulpho acid) may, with
advantage, be used as a photographic developer. This developer acts very rapidly,
even when used with alkaline carbonates, almost instantaneously bringing out the
finest details, even in the shadows. The image but gradually gains in intensity as
the development is continued, and it is therefore easy to control the degree of
development.
In this respect, the said substance is advantageously distinguished from the other
naphthalene derivatives hitherto known and in use for photographic purposes (such
as eikonegen and the like). It unites the advantages of the latter with those of
hydroquinone, and it is particularly adapted for use as a developer in instantaneous
photography.
My foreign correspondents have further found that the thiosulphates exert an
action on beta naphtha quinone analogous to that of acid sulphites. A well
characterised derivative of beta naphtha hydro quinone containing sulphur, is
obtained by allowing moderately acidulated solutions of thiosulphates to act on
molecular quantities of beta naphthaquinone.
In order to illustrate the process for producing this new derivative of beta
[naphtha hydroquinone, the following example is given. The parts are by weight.
SECOND EXAMPLE.
DIHA AATHIA
HIDROQUINUAL
THIUSULTHO
AUID
1:6 parts of beta naphtha quinone having been thoroughly mixed with 10 parts
of water, a solution of 2:5 parts of sodium thio sulphate in 10 parts of water is
added, and subsequently 3 parts of acetic acid (containing 20 per cent. of pure
acid). The quantities employed of these ingredients correspond to molecular
proportions. The beta naphtha quinone is rapidly dissolved, and a small quantity

page_text: of insoluble matter having been filtered off, a clear, slightly brownish coloured
liquid is obtained, containing the new naphtha hydro quinone derivative.
If the solution is saturated with common salt, the sodium salt of the new product
separates, after some time, in fine grayish needles.
My foreign correspondents find that it is more advantageous to precipitate the
new compound in the form of potassium salt, as this latter is less readily soluble,
viz., by adding potassium chloride (in place of common salt) to the liquid. The
potassium salt then separates in beautiful crystals.
The
The sodium salt of the new acid is readily soluble, even in cold water, while the
potassium salt easily dissolves in hot water, but with difficulty in cold water.
potassium salt separates from concentrated hot solutions, on cooling, in anhydrous
beautiful long needles or prismatic crystals. It may easily be purified by re-
crystallising from water, which is advantageously mixed with a small quantity of
sulphurous acid.
My foreign correspondents represent this salt by the formula
OXIDATION OF THE BETA NAPHTHA HYDRO QUINONE SULPHO-ACID INTO
BETA NAPHTHA QUINONE SULPHO ACID.
1 part of the potassium salt of the above described naphtha hydro quinone
sulpho acid (alpha, beta, naphthahydro quinone-alpha,-mono sulpho acid) is
dissolved in about 10 parts of water, and the resulting solution is mixed with a
concentrated solution, in water, of half a part of sodium nitrite. The liquid
having been cooled by the addition of ice, is gradually acidulated by means of

page_text: acetic acid. The nitrous acid thus disengaged very quickly effects oxidation of
the hydroquinone salt, and the greater part of the potassium salt of the resulting
beta naphtha quinone sulpho acid separates in yellow crystals. A further quantity
thereof is precipitated by the addition of common salt.
The naphtha quinone sulpho acid thus produced is identical with the naphtha
quinone alpha sulpho acid mentioned by O. N. Witt and H. Kaufinann, in the
Berichte der Deutschen Chemischen Gesellschaft, volume 24, page 3163.
Other oxidizing agents can be used in a similar manner, such as, for example,
the halogens and the like.
According to the researches of my foreign correspondents, this naphtha quinone
sulpho acid is an eminently "active" substance, the sulpho group therein contained
being easily displaced by other groups. Owing to its possessing the last named
property, my foreign correspondents have succeeded in preparing a totally new
series of valuable dye stuffs from the said naphthaquinone sulpho acid, and then,
if nitroso derivatives of secondary or tertiary aromatic amines are allowed
to act on alpha, beta, naphthaquinone-alpha-sulpho acid in the presence of
thiosulphates, and most practically in presence of weak acids, dye-stuffs are formed,
owing to the sulpho group becoming displaced, and the nitrogen of the nitroso
group becoming bound to the naphthalene nucleus in its place. A so-called thiazine
nucleus is formed in this manner, the benzene and naphthalene nucleus becoming
connected by sulphur derived from the thiosulphate employed. For instance, on
employing nitroso dimethylaniline, a product results to which my foreign corre-
spondents ascribe the following formula :-
COLOURING MATTER FROM THE BETA NAPHTHA QUINONE SULPHO
AND NITROSOMETHYLBENZYLANILINE BULPHO ACID.
ACID
27:5 parts of betanaphthaquinone sulphonate of potassium are dissolved in
50 times its weight of water, and 36 parts of acetic acid (containing 33 per cent.).
A concentrated solution of 50 parts of sodium thiosulphate and 32 parts of the
sodium salt of nitrosomethylbenzylaniline sulpho acid are then added, and the
resulting liquid mixture is heated to boiling.
The formation of dye stuff begins after a short time, the liquid mixture assuming
a blue colour; as the boiling is continued, the new dye-stuff begins to separate in
crystals exhibiting a dark bronze-like lustre. As soon as this separation no longer
increases in amount, the colouring matter is filtered off, washed with cold water, and
dried. It is sufficiently nearly pure, and can be directly used for dyeing.
The dry substance exhibits a bronze-like lustre. It dissolves very slightly in
cold water; more readily in hot water; forming a pure blue coloured liquid,
especially in the presence of a small quantity of acetic acid. It is dissolved by
concentrated sulphuric acid, a greenish yellow coloured solution being obtained,
B

page_text: which becomes blue on adding water, the dye-stuff acid then separating out in
blue flakes. On adding concentrated soda lye to the aqueous solution of this
colouring matter, the basic sodium salt thereof is precipitated. The dye-stuff
produces pure and bright blue shades on wool mordanted with chromium salts.
The shades thus produced are distinguished by their eminent fastness, withstanding
both fulling and exposure to light, and are not inferior to the shades obtained by
means of the known alizarin dye-stuffs, but are even superior to them in purity
and brightness. The new dye-stuff can also be advantageously employed for
printing on cotton or wool.
If, in the above example, nitrosoethylbenzylaniline sulpho acid is employed in
place of nitrosomethylbenzylaniline sulpho acid, a colouring matter is produced
which only very slightly differs from the aforesaid dye stuff. The product
obtained from nitrosodibenzylaniline disulpho acid possesses a materially greater
solubility. The colouring matters obtainable from nitroso-mono-benzylaniline sulpho
acid, or nitroso diphenylamine mono sulpho acid, are distinguishable by their some-
what redder shades. (The last named nitrosodiphenylamine mono sulpho acid can
easily be prepared by treating the nitroso-amine of diphenylamine mono sulpho acid
with alcoholic muriatic acid.)
Other nitroso-derivatives of secondary or tertiary aromatic amidosulpho acids
can also be used in the said process. The colouring matters thus obtainable are
sufficiently soluble, and therefore can be directly employed for dyeing or printing
purposes.
If nitrosodimethylaniline, nitrosodiethylaniline, nitrosomono methylaniline, nitro-
somonomethyl orthotoluidine, or other nitroso derivatives of secondary or tertiary
aromatic amines destitute of sulpho group, are used in the process illustrated by
the above fourth example, products result which are but very slightly soluble, or
are insoluble in water, and therefore must be subsequently treated with sulphonating
agents, in order to obtain valuable dye-stuffs.
For instance, operating in accordance with the process illustrated by the above
fourth example, using 27:5 parts of beta naphtha quinone sulphonate of
potassium, 18:6 parts of nitrosodimethylaniline hydrochloride, 50 parts of
sodium thiosulphate, and 36 parts of acetic acid (containing 33 per cent. of pure
acid) a product is obtained which separates in reddish-brown crystals, that can
be purified by recrystallisation from nitrobenzene, phenol, quinaldine, or similar
solvents. It separates from quinaldine in pure needles or scales exhibiting bronze-
like lustre. It is insoluble in water, and is dissolved only with difficulty by other
solvents. In order to render it soluble, the dried product is introduced into
4 times its weight of fuming sulphuric acid (containing 25 per cent. of anhydride),
and the mixture is heated at from 80 to 100 degrees centigrade, until a sample
entirely dissolves in hot water containing a small quantity of sodium acetate,
forming a pure blue coloured liquid. When this stage is arrived at, the mixture
is poured on ice water; the precipitated dye stuff sulpho acid is then filtered
off, and converted into its sodium salt by means of sodium acetate. The sodium
salt thus obtained dissolves only with difficulty in cold water, but with greater
readiness in hot water, especially after adding a small quantity of acetic acid.
The colouring matter produces, on wool mordanted with chromium salts, blue
shades differing by a somewhat green tinge from the shades obtained by means of
the dye-stuff's hereinbefore defined.
-
The corresponding dye stuff from nitrosodiethylaniline, yields shades which
are still greener, whilst the colouring matters produced by means of nitroso-
nitrosomono, methylaniline,
derivatives of alkylated, amines (such, ag
nitrosomonomethylortho toluidine, or the like) in general yield redder and less
bright shades.
My foreign correspondents have also found, that the herein described alpha,
beta, naphthahydroquinone-alpha, sulpho acid, can be employed- in place of the
alpha, beta, naphthaquinone sulpho acid for the production of dye-stuffs, and
the researches of my foreign correspondents have shown, that the colouring

page_text: matters thus obtainable are identical with the corresponding dye-stuffs from alpha₁
beta, naphtho quinone sulpho acid.
DYE STUFF FROM BETA NAPHTHAHYDROQUINONE SULPHO ACID AND NITROSO-
METHYLBENZYLANILINE SULPHO ACID.
27:5 parts of betanaphthahydroquinone sulphonate (alpha, beta₁-naphthahydro-
quinone alpha,-sulphonate) of potassium, are dissolved in a solution prepared by
dissolving 50 parts of sodium thiosulphate in about 1500 parts of water. A
concentrated solution of 32 parts of nitrosomethylbenzylaniline sulphonate of
sodium, acidulated by means of 36 parts of acetic acid (containing 33 per cent.
of pure acetic acid), is added, and the liquid mixture is heated to boiling. The
formation of dye soon begins, and the dye-stuff separates in crystals. Boiling is
continued until the formation of dye no longer increases.
When this stage is
arrived at, the dye-stuff is filtered off and dried. It is identical with the
colouring matter obtained from nitrosomethylbenzylaniline sulpho acid and beta
naphthaquinone sulpho acid.
In place of nitrosomethylbenzylaniline sulpho acid, other nitroso derivatives
derived from nitroso compounds of secondary-or tertiary-aromatic amido sulpho
acids can be employed, dye stuffs being thus obtained which are also identical
with the corresponding colouring matters from beta naphthaquinone sulpho acid
(alpha, beta, naththaquinone alpha, sulpho acid).
If unsulphonated nitroso-derivatives of secondary or tertiary aromatic amines
are used, products are formed which are insoluble, or soluble with difficulty,
which, by subsequent treatment with sulphonating agents, are converted into
valuable dye-stuffs, by means of the process hereinbefore illustrated for the
corresponding products from unsulphonated nitroso compounds and ẞ naphtha-
quinone sulpho acid.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me
from abroad, I declare that what I claim is :—
1. The production of salts of alpha, beta, naphthahydroquinone-alpha,-mono-
sulpho acid by treating beta naphthaquinone with solutions of alkaline bisulphites,
and subsequently precipitating the resulting naphthahydroquinone sulpho acid in
the form of its salts.
2. The process for producing salts of alpha, beta, naphtha hydro quinone
thiosulpho acid, by treating betanaphthaquinone with solutions of thio sulphates,
or with solutions of sulphur in alkaline sulphites, and subsequently precipitating
the resulting alpha, beta, naphthahydroquinone thiosulpho acid in the form of its
salts.
3. Conversion of salts of alpha, beta, naphthahydroquinone-alpha,-mono,
sulpho acid, into salts of alpha, beta, naphthaqui none-alpha,-mono sulpho acid
by a treatment with suitable oxidising agents.
4. The process for producing colouring matters, which process consists in
allowing nitroso derivatives of secondary or tertiary aromatic amines, or substituted
amines, to act, in the presence of thio sulphates, on salts of alpha, beta, naphtha-
quinone alpha, mono sulpho acid, or alpha, beta, naphthahydroquinone-alpha,-
mono sulpho acid, and subsequently treating the resulting products with
sulphonating agents, in case they are found to be insoluble, or soluble only with
difficulty in water,

page_text: 5. The production of dye-stuffs by acting with nitroso derivatives of methyl-
benzylaniline sulpho acid, ethylbenzylaniline sulpho acid, monobenzylaniline sulpho
acid, dibenzylaniline disulpho acid, diphenylamine mono sulpho acid, or methyl-
diphenylamine mono sulpho acid, on salts of alpha, beta, naphthaquinone-alpha,
mono sulpho acid, or alpha, beta, naphthahydroquinone alpha, mono sulpho acid
in the presence of thio sulphates.
6. The manufacture of colouring matters by acting with nitroso-derivatives of
dimethylaaniline, diethylaaniline, monomethylaniline, monoethylaniline, mono-
methyl-ortho-toluidine, or monoethyl-ortho-toluidine, on salts of alpha, beta,
naphthaquinone-alpha,-mono sulpho acid, or alpha, beta, naphthahydroquinone-
alpha,-mono sulpho acid, in the presence of thio sulphates, and subsequently
sulphonating the resulting products.
7. As new products of manufacture :-
a) alpha beta, naphtha hydroquinone thiosulphonic salts obtainable by
b) the new colouring matters
means of the
processes
hereinbefore defined, or by any other process affording the same result.
8. The employment of alpha, beta, naphthhydroquinone alpha, mono sulpho
acid, in the form of its soluble salts, as a photographic developer.
Dated this 10th day of October 1893.
NEWTON & SON,
Agents for the Applicant.