The Manufacture and Production of Naphthalene Sulpho Acids.
Year: 1892

page_text: Date of Application, 25th June, 1892
Complete Specification Left, 22nd Mar., 1893-Accepted, 6th May, 1893
PROVISIONAL SPECIFICATION.
The Manufacture and Production of Naphthalene Sulpho Acids.
I BENJAMIN WILLCOX of 47 Lincolus Inu Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me by The Farbenfabriken vormals Friedrich Bayer & Co. of
Elberfeld in the Empire of Germany) to be as follows:-
R. Leuckart has made the interesting observation that the amido group of
aromatic amines can be easily replaced by the sulphhydryl group (SH) in reacting,
with the so called, xanthogenic salts, on diazotised aromatic amines. At first
xanthogenic acid compounds are formed, which yield, by a further treatment with
alkalies, the sulphhydryl compounds containing the group SH instead of the amido
group of the amine employed (see Journal für Praktische Chemie volume 41
page 181).
In this manner diazotised naphthylamine can be changed into naphthyl-sulph-
hydrate (C,H,SH). As the latter is easily oxidised into the corresponding disulphide
even by the oxygen of the atmosphere, the disulphides are always formed as bye
products in these processes and in reacting with xanthogenic salts on diazo-
naphtalene-mono-sulpho acids, and further treating the xanthogenic acid products
first obtained with alkalies disulphides of the following formula result almost
entirely
My foreign correspondents have now found that these disulphides and analogues
thereof can readily be changed by oxidation into naphthalene disulpho acids and
that most generally the disulphides resulting by treating diazotised naphthylamine-
mono; naphthylamine-disulpho; naphthylamine-tri-sulpho acids etc., or substitution
products thereof with xanthogenic salts, and heating the first formed xanthogenic
compounds with alkalics, yield, by oxidation, naphtalene-di-; naphthalene tri- ;
naphthalene tetra-sulpho acids etc. or substitution products thereof.
Of the substituted naphthylamine sulpho acids the following can be employed;
for example amido-naphthol-sulpho acids, amido-dihydroxy-naphthalene-sulpho
acids, amido-naphtol-ether-sulpho acids, amido-chloro-naphthalene-sulpho acids and
the corresponding bromo- or iodine compounds, amido-nitro-naphthalene-sulpho
acids, amido-nitro-naphthol-sulpho acids, amido-nitro-naphthol-ether-sulpho acids,
amido-nitro-chloro-naphthalene-sulpho acids and the analogous bromo-, or iodine-
substitution products, amido-chloro-, amido-bromo, amido-iodine-naphthol-sulpho
acids and the corresponding naphthol-ether-sulpho acids.
Analogous derivatives of naphthylamine-sulpho acids, containing one, or several.
substitution groups are my foreign correspondents have found likewise capable of
being transformed, in the aforesaid manner, into the corresponding sulpho acids,
containing one sulpho group more than the products used. Amido-naphthalene
carbonic acids, di-amido-naphthalene-sulpho acids and substitution products thereof
can likewise be employed.
On using diamido-naphthalene-sulpho-acids, substituted or not substituted either
the diazo compounds or the tetrazo compounds thereof can be treated with
xanthogenic salts. In the latter case two sulpho groups are at once introduced
into the naphthalene molecule.

page_text: By this method my foreign correspondents have succeeded in readily and
sucressfully obtaining substituted (or not substituted) naphtalene-poly-sulpho acids
which products for the greatest part have not hitherto been prepared or only with
very great difficulty.
7
In order to illustrate this method .the following, example is given, starting from
the disulphide which results by reacting with the potassium salt of ethyl
xanthogenic acid! on diazotised alpha-naphtionic acid andi heating the first formed
alpha-xanthogenic-naphthalene-sulpho acid with alkalies as described in the Journal
für Praktische Chemie volume 41.page 219.
45 kilos of the said naphthalene-sulpho acid disulphide of the formula,:.
•
are dissolved in about 600 litres of water with the addition of.. 15 kilos of sodium
carbonate; a solution of 52 kilos of potassium permanganate in 1000 litres of water.
is then allowed to flow into this liquid which is constantly stirred untiliaclasting
red colour appears. After adding a small quantity of alcohol- and boiling,, the
manganese residue is filtered off-andi the filtrate resulting is neutralised, evaporated,
and mixed with the necessary quantity ofratsolution: of barium chloride or calcium
chloride:
In this manner a sand-liketand very difficultly soluble, precipitate of the barium;
or calcium, salt of the naphthalene-disulpho acid is obtained.
The said barium, or calcium, salt is changed into the sodium salt by boiling with
a solution of sodium carbonate, and the sodium salt thus formed crystallizes out of
the evaporated solution in beautiful leaves soluble with great difficulty.
My foreign correspondents have by melting with alkalies transformed this
naphthalene-disulpho acid into the. known alpha-naphthol-alpha-mono-sulpho
acid (OH SO,H= 14) and thereby proved"that the former is a naphthalene-1.4
-disulpho acid:
In the employment of analogous disulphides obtained from diazotised alpha--and
beta-naphtylamine-mono-sulpho acids by means of: xanthogenic salts, and by
subsequently heating the first produced xanthogenic acid compounds with: alkalies,
the isomeric naphthalene-disulpho acids result in the same manner..
The method likewise can be employed for all those disulphides which are derived
from alpha or beta-naphthylamine-disulpho- or tri-sulpho acids etc..it.. beings only
necessary to use in the foregoing example: instead! of ther disulphide: stated the
corresponding quantity of one of the other disulphides:
On starting from the diazo derivatives of naphthylamine-sulpho acids: substituted;
the analogous substituted naphthalene-disulphio, acids, tri sulpho-tetrasulpho,.acids
etc. are obtained in an analogous manner.
The oxidation of all these disulphides can, my foreign.correspondents have.found,
also be effected by other oxidising agents; employing for example,, instead of
potassium permanganate (MuO), potassium: ferricyanide, hydrogene.superoxide,
or the like, the same results being obtained:.
Dated this 25th day of'June 1892:

page_text: COMPLETE SPECIFICATION.
The Manufacture and Production of, Naphthalene Sulpho Acids.
1, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me from abroad by. Farbenfabriken vorm. Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany) and in what manner the same is to be
performed to be particularly cdescribed and ascertained in and by: the following
statement :-
R. Leuckart has made the interesting observation that the amido group of
aromatic amines can be easily displaced by the sulphhydryl group (SH) by the
action of xanthates on diazotised aromatic amines. At first xanthates are formed
which on treatment with alkalies yield the sulphhydryl compounds containing the
group SH instead of the amide group of the amine employed (see Journal-für
Praktische Chemie volume 41, page 184).
In this manner diazotised naphthylamine can be changed into naphthyl-sulph-
hydrate (CH,-SH). As the latter is easily converted by oxidation into the
corresponding disulphide, even by atmospheric oxygen, the disulphides are always
formed as bye-products in these processes; and on treating diazo-naphthalene-
mono-sulpho acids with xanthates and submitting the resulting xanthates: to. the
action of alkalies, disulphides of the following formula are almost the sole
products—
My foreign correspondents have now found that these disulphides and analogues
thereof.can readily be changed by oxydation into naphthalene 'disulpho-acids and
that the disulphides which generally result on treating 'diazotised naphthylamine-
mono-, naphthylamine-disulpho-; naphthylamine-trisulpho-acids with xanthates,
and treating the .resulting xanthates with alkalies, yield on oxydation, naph-
thalene di-naphthalenetri- or naphthalenetetra-sulpho acids.
The analogues of these disulphides (e.g. sulphhydryl products, and the like
derived from naphthalene sulpho acids) can in a similar manuer be oxidised and
converted into naphthalene poly sulpho acids. Such thio compounds can also be
prepared by acting with salts of thio carbonic acid or with carbon disulphide
and alkalies on the diazo compounds of amido-naphthalene sulpho acids in the
manner described for example by G. Lustig in the Gazzetta. Chimica volume 21,
page 213.
By this method my foreign correspondents..have succeeded in readily obtaining
naphthalene-poly-sulpho acids which for the most part hitherto have either not.
been prepared or only with difficulty.
In order to illustrate this method, the following.example is given, using the
disulphide which is formed by the action of, potassium xanthate .on diazotised
alpha-naphthionic acid. and. heating, the resulting alpha-xanthate naphthalene-
sulpho acid with. alkalies, as described in the Journal für Praktische Chemie,
volume 41, page 219.
i

page_text: TRANSFORMATION OF ALPHA
NAPHTHYLAMINE ALPHA MONOSULPHO ACID
(14) (NAPHTHIONIC ACID) INTO NAPHTHALENE DISULPHO ACID (1: 4).
554 kilos of the potassium salt of the said naphthalene sulpho acid disulphide
of the formula
are dissolved in about 600 litres of water with the addition of 15 kilos of sodium
carbonate; a solution of 52.5 kilos of potassium permanganate in 1000 litres of
water is then allowed to run into this cold liquid (which is constantly stirred)
until it acquires a permanent red colour. After adding a small quantity of
alcohol and boiling, the manganese residue is filtered off and the filtrate is
neutralised with hydrochloric acid, evaporated, and mixed with the necessary
quantity of a solution of barium chloride or calcium chloride.
In this manner a
sandy and very difficultly soluble precipitate of the barium- or calcium, salt of the
naphthalene-disulpho acid is obtained. The said barium-, or calcium, salt is con-
verted into the sodium salt by boiling with a solution of sodium carbonate. The
sodium salt thus formed crystallizes from the filtered and evaporated solution in
beautiful difficultly soluble plates.
:
The sodium salt can also be directly salted out from the concentrated filtrate
obtained after the oxidation of the disulphide has been effected.
By fusing it with alkalies, my foreign correspondents have transformed this
naphthalene-disulpho acid into the known alpha-naphthol-alpha-mono-sulpho acid
(OH SO,H=1: 4) thereby proving that it is a naphthalene 1: 4 disulpho
acid.
Isomeric naphthalene disulpho acids are formed in like manner from the
analogous sulphides or thio compounds obtained for example from diazotised alpha-
or beta-naphthylamine-mono-sulpho acids by means of xanthates or the like, and
subsequently heating the resulting xanthates with alkalies.
The method can be also made use of in the case of all the disulphides or thio
products which are derived from alpha- or beta-naphthylamine-disulpho acids--it
being only necessary to use in the foregoing example instead of the disulphide
stated the corresponding quantity of one of the other disulphides.
In order to illustrate the method of producing a naphthalenetrisulpho acid from
a naphthylamine disulpho acid, the following example is given. The parts are by
weight
75 parts of the bisulphide (obtained for example by acting with xanthates on
diazotised beta naphthylaminedisulpho acid R and subsequently hydrolysing the
product thus formed are oxidised (in a solution rendered alkaline by the addition
of sodium carbonate) with 52 parts of potassium permanganate dissolved in
1000 parts of water, the oxidation being effected in a manner analogous to that
described in the foregoing first example. The liquid is filtered, and the resulting
filtrate is evaporated until the separation of crystals begins; as the liquid cools
the potassium salt of the naphthalene trisulpho acid separates in a crystallised form.
It dissolves with difficulty in solutions of common salt in water and is isolated by

page_text: filtering off and pressing. The salt thus obtained can be easily purified by
recrystallisation from a small quantity of boiling water. When fused with alkalies
it is converted into the so called beta naphtholdisulpho acid R or salts thereof. It
follows from this latter behaviour, that the naphthalene trisulpho acid thus formed
is a naphthalene-2:3: 6-trisulpho acid.
The same general method can be used for the production of naphthalene tetra-
sulpho acids from alpha- or betanaphthylamine trisulpho acids. My foreign
correspondents describe in the following example a practical method of converting
alphanaphthylamine trisulpho acid (NH, SO,H: SO,H: SO,H = 1:3:6:8) into
the corresponding naphthalene tetra sulpho acid. The parts are by weight.
TRANSFORMATION OF ALPHANAPHTHYLAMINE TRISULPHO ACID (NH,: SO₂H.
SO,H: SO, H 1:3:6:8) INTO NAPHTHALENE TETRASULPHO ACID
(SO,H: SO,H: SO,H: SO,H=1:3:6:8).
-
10 parts of the bisulphide formed by the action of potassium xanthate on the
diazotised alphanaphthylamine trisulpho acid and subsequent hydrolysis of the
resulting product are dissolved in 100 parts of water such a quantity of sodium
carbonate being added that the liquid shews an alkaline action. The thus obtained
alkaline solution is mixed with a solution of 5.2 parts of potassium permanganate
in 100 parts of water, and the oxidation is effected in a manner analogous to that
described in the above first example. When the oxidation is complete, the resulting
solution of the sodium salt of the naphthalene tetrasulpho acid is filtered and the
filtrate having been neutralised by means of hydrochloric acid is evaporated, until
a separation of crystals begins on the surface. As the liquid cools the salt of the
naphthalene tetrasulpho acid thus produced separates in crystals. It is filtered off;
pressed and dried. In order to purify it, it may be recrystallised from a small
quantity of water.
When the so formed salt is fused with alkalies the 1: 8-dihydroxynaphthalene
beta disulpho acid (the so called chromotrop acid OH: SO,H: SO,H: OH=
1:3:6:8) or salts of this acid are obtained. Hence it follows that the tetrasulpho
acid produced in the above manner is a naphthalene tetrasulpho acid (SO,H:
SO,H SO,H SO,H=1:3:6:8).
:
:
My foreign correspondents have described in the foregoing three examples
methods of converting a naphthylamine mono sulpho acid, a naphthylamine disulpho
acid and a naphthylamine trisulpho acid respectively into the corresponding
naphthalene polysulpho acids, to wit, naphthalene disulpho acid, naphthalene
trisulpho acid and naphthalene tetra sulpho acid. The production of analogous
naphthalene polysulpho acids in general can be effected in a manner similar
to that described in these examples, but my foreign correspondents, do not
limit themselves to the directions given therein, as these can be varied. For
instance the oxidation may be carried out by means of oxidising agents other than
the potassium permanganate used in the above example. It is also not necessary
to isolate the thio compounds in a pure state, but in most cases the liquids which
result for example on hydrolysing the xanthates or the like, can be directly
employed after removing volatile thio products by boiling the acidulated liquids.
Such or similar modifications do not alter the nature of this invention, as the latter
in general relates to the production of naphthalene poly sulpho acids by oxidising
thio compounds such as are obtainable by the action of salts of xanthic acid or the
like on the diazo compounds of naphthylamine mono sulpho acids, naphthylamine
disulpho acids or naphthylamine trisulpho acids and subsequently bydrolysing the
thus formed thio compounds of naphthalene sulpho acids.
Among the naphthalene-poly-sulpho acids prepared by my foreign corre-
spondents the following are of special value:-naphthalene-1: 2-di sulpho acid

page_text: :
from -alphanaphthylamine' mono sulpho acid (2) of the German Patent
No. 56563, naphthalene-14-disulpho acid from alphanaphthylamine valpha-
monosulpho acid (14), naphthalene-1:8-disulpho acid from alpha-naphthyl-
amine' mono sulpho acid S described in the German Patent No. 40571, naphthalene
-1: 2: 5-trisulpho acid from the alphas naphthylamine disulpho acid to be
obtained in the manner described in the German Patent No. 56563 by sulphonating
the alphanaphthylamine ortho mono"sulpho acid (1:2), naphthalene-1: 26-
trisulpho acid from the disulpho acid which results on further sulphonating beta-
naphthylamine beta monsulpho acid 26 (Proceedings of the Chemical: Society
1890, page130), naphthalene 2:4:8-trisulphonacid from beta naphthylamine.di-
sulpho acid C (NH, SO,H: SO,H=2:4:8), naphthalene-1:3:7-or-2:6:8
-trisulpho acid from beta naphthylamine disulpho acid G (NH, SO,H: SO,H
2:6:8) or from alpha naphthylamine disulpho acid B (NH, SO H: SO H
1.3:7), naphthalene-1: 3: 8-trisulpho acid from alphanaphthylamine epsilon di-
sulpho acid, naphthalene 1:4:8-trisulpho acid from alphanaphthylamine disulpho
acid S. naphthalene 1-47-trisulpho acid from alphanaphthylamine di-
sulpho acid II (NH, SO,H: SO,H=1:14: 6) or from alpha naphthylamine disulpho
acid III. (NH, SO,H: SO,H=1:4:7) of the German Patent No. 41957,
naphthalene 23:6 or 2:3:7-trisulpho acid from betanaphthylamine disulpho
acid R' (NH, SO,H: SO₁H-2:3:6) or from betanaphthylamine disulpho acid: F
(NH, SO, SOH 2:37), naphthalene-1:3:6:8-tetrasulpho acid from
alpha naphthylamine"trisülpho acid (NH, SOH: SOH SO;H=1:3:6:8),
naphthalene 2:36 8-tetrasulpho acid from beta naphthylamine trisulpho acid
of the German Patent No. 27378.
•
:
=
"My foreign correspondents do not limit themselves' to the production of the
naphthalene poly sulpho acids hereinbefore "enumerated, inasmuch as other
naphthalene poly sulpho "acids "can be prepared by means of the above defined
process.
My foreign correspondents have as a matter of course prepared salts of the
naphthalene poly sulpho acids obtained by. means of "the process hereinbefore
explained.
...Having: now particularly described and ascertained the nature of the said inven-
tion and in what: manner the. same is to be performed :Í.declare.. that what I
claim is :-
9.
1. The production of naphthalene poly sulpho acids by treating with oxidising
agents thio derivatives (such as sulphhydryl-compounds and disulphides) produced
from alpha- or beta naphthalene mono-, di- or trisulpho acids and obtainable for
instance by the action of xanthates or salts of thio carbonic acids on the diazo
derivatives of alpha- or betanaphthylamine mono- or polysulpho acids.
2. "The processes of producing; naphthalene-1 2-disulpho acid from alpha
naphthylamine mono sulpho acid (1:2) of the German Patent No. 56563, naphtha-
lene 14-disulpho acid from alpha naphthylamine alpha mono sulpho acid (1:4),
naphthalene 18-disulpho acid' from álpha naphthylamine mono sulpho acid S
described in the German Patent No: 40571; naphthalene-12:5-trisulpho acid
from the alpha naphthylamine disulpho "acid obtainable "as described in the
German Patent No. 56563 by sulphonating the alpha naphthylamine ortho mono-
sulpho acid (12); naphthalene-1:2 : 6-trisulpho acid from the disulpho acid
which is formed by further sulphonating beta naphthylamine beta mono-sulpho
acid 2:6 (Proceedings of the Chemical Society 1890, page 130), naphthalene
-2:4:8 trisulpho acid from beta naphthylamine disulpho acid C (NH,:
SO,H: SO,H=2:4:8), naphthalene-1:3:7-or-2: 6: 8-trisulpho acid from
beta-naphthylamine disulpho acid G (NH, SO,H: SO,H='26:8) or from alpha-
naphthylamine 'disulpho acid B (NH, SO,H: SO,H=1:37), naphthalene-
1:3:8-trisulpho acid from alpha inaphthylamine epsilon disulpho acid, naphtha-
lene-1:4:8-trisulpho acid from alphanaphthylamine disulpho acid S, naphtha-
lene 1'47 trisulpho acid from alphanaphthylamine 'disulpho "acid II (NH, :
:

page_text: -
:
:
SO,H: SO,H 1:46) or from alphanaphthylamine disulpho acid III (NH,
SOH SO H=1:4:7) of the German Patent No. 41957, naphthalene-2:3:6-
or 2:37 trisulpho acid from betanaphthylamine disulpho acid R (NH, SO, H:
SO,H=2:3:6) or from betanaphthylamine disulpho acid F (NH, SO₂H:
SO H 2:3:17), naphthalene 1:3:6:8-tetrasulpho acid from alphanaphthyl
amine trisulpho acid (NH, SO,H: SO,H: SO,H = 1:3:6:8), naphthalene-
2:3:6:8-tetrasulpho acid from betanaphthylamine trisulpho acid of the German
Patent No. 27378,- the which processes consist in oxidising thio compounds
derived from naphthalene mono-, naphthalene di- or naphthalene trisulpho acids
that are formed for instance by acting with salts of xanthic acid, thio carbonic
acid or similar substances or mixtures on the diazo derivatives of the naphthyl-
amine sulpho acids named in this second claiming clause.
3. As new manufactures the new naphthalene disulpho, naphthalene trisulpho
and naphthalene tetrasulpho acids which result on application of the process
hereinbefore defined or which can be prepared in other ways producing the same
effect.
B. WILLCOX.