The Manufacture or Production of Sulpho Acids Derived from Bi-naphthol-3-monosulpho Acid.
Year: 1893

page_text: Date of Application, 12th Sept., 1893
Complete Specification Left, 12th June, 1894-Accepted, 14th July, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Sulpho Acids Derived from
Bi-naphthol-3-monosulpho Acid.
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 or manufacture of sulpho acids
of the naphthalene series.
It is known, that 3-naphthol-8-monosulpho acid F. (B₁-naphthol ẞ monosulpho
acid), when treated with sulphonating agents, is converted into B-naphthol-8-
disulpho acid (B-naphthol ß, ß-disulpho acid), as described in the German Patent
No. 44070. Armstrong and Wynne (see Proceedings of the Chemical Society of
the year 1890, page 127), have proved that the latter acid possesses the following
formula:
No other sulpho product has hitherto been obtained by sulphonating B-naphthol
monosulpho acid, and Weinberg mentions (in the Berichte der Deutschen
Chemischen Gesellschaft, volume 20, page 2911) that under all conditions only the
said disulpho acid would be obtained.
My foreign correspondents have now found that ẞ-naphthol-8-monosulpho acid
can be easily converted by sulphonation into two new sulpho acids, the one of which
is a B-naphtholtrisulpho acid, whilst the other is a 6-naphtholtetrasulpho acid.
These two acids are often formed simultaneously. The process of sulphonation,
however, can be directed in such a manner that either of the two acids is formed
exclusively and in a theoretical amount.
The formation of the tetrasulpho acid is the more noticeable and unexpected, as
it is unknown, up to the present time, that any one has succeeded in introducing
more than three sulpho groups into naphthylamines or naphthols.
The production of the two new sulpho acids is illustrated by the following
examples one and two, the parts mentioned being by weight.
MANUFACTURE OF B-NAPHTHOL-TRISULPHO ACID.
1 part of beta-naphthol-delta-monosulphonate of sodium is introduced into 3 parts
of fuming sulphuric acid (containing 25 per cent. of sulphuric anhydride), and the
mass is allowed to cool. The mixture is then heated at from 80 to 90 degrees
centigrade, until a test portion taken out and poured on ice, and rendered alkaline
by means of sodium carbonate, shews no longer the property of reacting with
diazo compounds to form coloring matters. If this stage be arrived at, the whole
mass is poured on ice, and the resulting solution is neutralised by means of slaked

page_text: lime, care being taken that the liquid is not raised to too high a temperature. The
separated gypsum is then filtered off. The thus resulting filtrate contains the
calcium salt of the new ẞ-naphtholtrisulpho acid, which is converted into the sodium
salt in the well known manner. The solution of the latter sodium salt, after
filtering off the calcium carbonate, is evaporated to dryness.
The B-naphthol-8-monosulpho acid employed in the above example can be
replaced by B-naphthol-8-disulpho acid, in which case a smaller quantity of fuming
sulphuric acid is necessary.
The new B-naphtholtrisulpho acid forms salts which are readily soluble. The
barium salt separates in a gelatinous state when a hot solution thereof is quickly
cooled, and, unlike the barium salt of the ẞ-naphthol-d-disulpho acid, it is easily
soluble in hot water. When its hot solution is slowly cooled, the trisulphonate of
barium separates in a crystallised state, forming microscopical spherical aggregates..
The sodium salt readily dissolves in water, and is precipitated as a white powder
by adding alcohol to the watery solutions. My foreign correspondents have
ascertained by an analytical research, that the above B-naphtholtrisulpho acid
obtainable as described in the foregoing example, really is a naphtholtrisulpho acid,
for they have found, that the B-naphtholtrisulphonate of sodium, when dried at
from 150 to 160 degrees centigrade, contains 15.35 and 15.38 per cent. of sodium,.
in accordance with the formula: CH, (OH) (SO,Na),, which requires 15.33 per
cent. of sodium.
The alkaline solutions of this B-naphthol trisulpho acid shew a strong green
fluorescence. When it is allowed to act on diazo compounds in the presence of
sodium carbonate, colouring matters are not formed. In view of its production
from B-naphthol-&-disulpho acid, my foreign correspondents ascribe the following
composition to this ẞ-naphtholtrisulpho acid, viz. :—
This new acid differs from the single ẞ-naphtholtrisulpho acid hitherto known,
and described in the German Patent No. 22038, which is obvious from the
following:-
New B-naphtholtrisulpho acid :-Its sodium salt is a powder which is soluble in
water with readiness, in alcohol with difficulty. The barium salt dissolves in water
with readiness, and crystallises in a gelatinous state when watery solutions thereof
are quickly cooled. Its alkaline solutions shew a green fluorescence. Ferric
chloride produces a violet colour in its watery solutions. When it is allowed to
act on diazo compounds in alkaline solutions, colouring matters are not produced.
Its composition is probably represented by the following scheme :-

page_text: crystallises in flakes. The alkaline solutions thereof exhibit a very intense green
fluorescence, similar to that produced by fluoresceine. The colour of its solutions
is changed into deep violet on adding ferric chloride. It yields dye stuffs when it
is allowed to act on diazo compounds in alkaline solution. It possesses the following
formula:
PRODUCTION OF NAPHTHOLTETRASULPHO ACID.
20 parts of -naphthol-8-monosulphonate of sodium are introduced into 80 parts
of fuming sulphuric acid containing 40 per cent. of anhydride, and the mass is
cooled. It is then heated at from 120 to 130 degrees centigrade during from
8 to 10 hours. The mass then becomes solid in most cases. It is gradually added
to a large quantity of ice (to check the rising of the temperature), and the resulting
liquid is saturated with lime water (the rise of temperature being checked by an
addition of ice). The solution obtained by filtering off the calcium sulphate is
decomposed by the necessary quantity of sodium carbonate, and after filtering off
the calcium carbonate, the filtrate, which contains the sodium salt of the
betanaphtholtetrasulpho acid, is evaporated to dryness.
It is very characteristic of this new tetrasulpho acid, that its barium salt is soluble
with great difficulty, even in boiling water. This barium salt is precipitated as
a sandy white precipitate on the addition of barium chloride to the hot solutions in
water of the sodium salt, and is very similar to the barium salt of ẞ-naphthol-
8-disulpho acid in a precipitated state. Its sodium salt easily dissolves in water,
and can be obtained in crystals on the addition of alcohol to hot solutions of the
sodium salt. My foreign correspondents have ascertained that the aforesaid
B-naphtholtetrasulpho acid is of the alleged composition, for they have found by
analytical research that the sodium salt of this acid in a dry state contains 16.41
and 16.44 per cent. of sodium, whilst the formula of naphtholtetrasulphonate of sodium
requires 16-66 per cent. of sodium. The alkaline solutions of this acid likewise
exhibit a beautiful and strong green fluorescence with a bluish hue. The tetrasulpho
acid does not yield dye stuffs, when it is allowed to act on diazo products in alkaline
solution. The composition of this ẞ-naphtholtetrasulpho acid very probably is
represented by the following formula:-
35
The last-named tetrasulpho acid can also be obtained by sulphonating ẞ-naphthol-
-disulpho acid, or the aforesaid ẞ-naphtholtrisulpho acid.
The directions given in the above two examples can be varied. For instance,
the fuming sulphuric acid employed in the first example can be replaced by

page_text: sulphuric acid monohydrate. In this case a somewhat higher temperature must be
employed, and the reaction requires a somewhat longer time. Other sulphonating
agents (such as sulphuric acid chlorhydrine or the like) can also be used for the
above purposes.
It is, however, noticeable that if the heating lasts for too long in the case where
the B-naphtholtrisulpho acid is to be produced, or on heating during too short a
time when the B-naphtholtetrasulpho acid is to be formed, mixtures of tri- and tetra-
sulpho acid are obtained. In order to isolate these two acids from the mixture,
the barium salts are prepared, which can easily be separated, as the barium salt of
the B-naphtholtrisulpho acid readily dissolves in water, whilst the B-naphthol-
tetrasulphonate of barium is soluble in water with great difficulty.
The aforesaid new ẞ-naphtholtrisulpho acid and ẞnaphtholtetrasulpho acid can
profitably be employed for producing other sulpho acids of the naphthalene series.
My foreign correspondents have ascertained that the above two naphthol-
sulpho acids (B-naphtholtrisulpho acid and B-naphtholtetrasulpho acid) contain a
sulpho group (viz., that in a or ortho-position to the hydroxylic group) in very loose
combination, and the researches of my foreign correspondents have shewn that this
sulpho group can be split off, on boiling with water or diluted acids. It has been
hitherto unknown, that any ẞ-naphtholsulpho acid had this property. The aforesaid
B-naphtholtrisulpho acid is converted in this manner into ẞ-naphthol-d-disulpho
acid, which possesses the formula :-
TRANSFORMATION OF B-NAPHTHOL a₁ В₂, α, B.-TETRASULPHO ACID INTO
B-NAPHTHOL ẞ, a, B-TRISULPHO ACID.
1 part of naphtholtetrasulphonate of sodium is mixed with from 6 to 10 parts of
muriatic acid (containing 10 per cent. of pure acid), and the mixture is boiled for,
say, one hour in a vessel provided with a reflux condenser. After cooling, the
sodium salt of the new 3 naphtholtrisulpho acid, which is but slightly soluble in
muriatic acid, separates in the state of a white crystalline mass. The crystallised
salt is filtered off, and a further small quantity of the salt can be obtained by
evaporating the filtrate.
It is, however, not necessary to isolate previously the B-naphtholtetrasulpho

page_text: acid in a solid state, but the mixture obtained on sulphonating B-naphthol-8-mono-
sulpho acid, or ẞ-naphthol-8-disulpho acid, as described in the above second
example, can be used directly, that is to say, be boiled after dilution with water, in
order to eliminate the sulpho group in a or ortho position to the hydroxylic group.
Of course, the concentration of the acid employed can vary within wide limits.
The new B-naphthol trisulpho acid differs, by its capability of yielding dye stuffs
when combined with diazo products, from the above B-naphtholtrisulpho acid
(obtainable by sulphonating B-naphtho-8-monosulpho acid or 6-naphthol 8-disulpho
acid), and from the herein before described ẞ-naphtholtetrasulpho acid. From the
said property of the new ẞ naphtholtrisulpho acid it follows that, on heating
B-naphthol a B, a, ß-tetrasulpho acid with water or diluted acids, the sulpho
group in the position a, or ortho to the hydroxylic group is separated. It is
characteristic of the new B-naphtholtrisulpho acid, that the sodium salt thereof
crystallises with great facility, and separates in fine matted needles from a concentrated
watery solution, or from dilute muriatic acid. The alkaline solutions of the acid
exhibit a beautiful green fluorescence. A violet colour appears when ferric chloride
is added to a watery solution of the sodium salt. The barium salt forms a pellucid
gelatine-like mass, which dissolves in cold water with very great difficulty. Even
much diluted hot solutions of the barium salt, on cooling, yield a gelatinous mass,
which is of such a consistence that the vessel containing the gelatine-like mass
may be overturned without its contents being spilt. This ẞ-naphtholtrisulpho acid
can be employed for the production of azo coloring matters.
FOURTH EXAMPLE.
CONVERSION OF NAPHTHOL α, ẞ₂ ẞ. TRISULPHO ACID INTO ẞ-NAPHTHOL-
8-DISULPHO ACID.
A mixture of 1 part of B₁-naphthol a, ẞ, ß, trisulphonate of sodium, and 10 parts
of muriatic acid (containing 10 per cent. of pure acid), is boiled during from
1 to 2 hours in a vessel provided with a reflux condenser. The liquid is neutralised
by means of slaked lime, and after filtering off the calcium sulphate, either barium
chloride is added to the boiling filtrate (the barium salt of the ẞ-naphthol-8-
disulpho acid being thus precipitated), or the said filtrate containing the calcium
salt is mixed with sodium or potassium carbonate, and, after filtering off the calcium
carbonate, the filtrate thus obtained is evaporated.
The conversion of naphthol a ẞ, B. trisulpho acid into B₁ naphthol
BB disulpho acid (so-called B-naphthol-8-disulpho acid) is of special technical
value, as, in the production of the last named B-naphthol-8-disulpho acid according
to the process described in the German Patent No. 44070 (that is to say by
sulphonating B-naphthol-8-monosulpho acid), the above B-naphthol-a₁ B₂ ẞ tri-
sulpho acid is always formed as by-product, by reason of which the amount of
the B-naphthol B, B. disulpho acid hitherto obtained in the above process is a
relatively small one, whilst the process illustrated by the above fourth example
can be easily employed for transforming the trisulpho acid into the required
disulpho acid, and for obtaining the theoretical amount of ẞ-naphthol & disulpho
acid. For this purpose, it is only necessary to dilute the sulphonated mass
obtained according to the process described in the said German Patent No. 44070,
by an addition of a suitable quantity of water, and to boil the resulting mixture for
some time.
It is above mentioned, that the two acids Bi-naphthol a ẞ, B, trisulpho acid,
and B-naphthol a, ẞ, as ẞ, tetrasulpho acid contain one sulpho group (viz., that in a₁
or ortho position to the hydroxylic group) in very loose combination, and that this
sulpho group can be easily separated, for instance, by boiling with water or diluted
acids. Therefore it was unlikely that the said two acids would yield the
corresponding ẞ, naphthylamine sulpho acids by heating with ammonia, without the
sulpho group being separated at the same time.
The researches of my foreign correspondents have now shewn that the said

page_text: transformation can be easily effected when the reaction is caused to take place at
not too high a temperature; for instance, it has been found to be practical to
employ an ammonia liquid (containing 25 per cent. of ammonia), and in the closed
vessel a pressure not rising above 30 atmospheres.
The conversion of the naphtholtrisulpho acid and naphtholtetrasulpho acid into
respectively naphthylamine trisulpho acid and naphthylamine tetrasulpho acid is
illustrated by the following example.
FIFTH EXAMPLE.
PRODUCTION OF ẞ NAPHTHYLAMINE a₁ ẞ, ẞ. TRISULPHO ACID.
1 part of B-naphtholtrisulphonate of sodium (the part is by weight) is mixed with
from 2 to 3 parts of an ammonia solution (containing 25 per cent. of ammonia), and
about part of ammonium chloride. The mixture is heated for 6 hours in a closed
vessel at a pressure of about 28 atmospheres. After cooling, soda lye is added, and
the ammonia in excess is distilled over. The residual liquid is filtered and
acidulated by means of muriatic acid. The acid sodium salt of the new B-naphthyl-
aminetrisulpho acid crystallises from the cooled solution in beautiful bright scales.
It is noticeable, that if the reaction has been allowed to take place at too high
temperature, -naphthylamine-8-disulpho acid is formed simultaneously. The
latter acid can be separated from the B-naphthylamine trisulpho acid by preparing
the sodium or ammonium salt, and isolating the sodium or ammonium salt of the
B-naphthylaminetrisulpho acid, which are readily soluble in water, whilst the
sodium and ammonium salt of the ẞ-naphthylamine-8-disulpho acid are soluble with
..difficulty.
α
The said B-naphthylamine a, B₂ ẞ trisulpho acid can also be produced by heating
the B-naphtholtrisulphonate of sodium in an open vessel, whilst a current of
. ammonia is allowed to pass over.
The B-naphthylamine a, ẞ, ẞ, trisulpho acid possesses the following properties.
Its acid sodium salt very readily dissolves in water, and is separated by adding
common salt or alcohol or muriatic acid to watery solutions thereof. On
evaporating solutions of this acid sodium salt in diluted alcohol, it crystallises in
beautiful bright scales, which my foreign correspondents have subjected to an
analytical research. They found, that the said acid sodium salt, when dried at
from 150 to 160 degrees centigrade, gives off 15-23 and 15.37 per cent. of water, and
that the thus dried acid sodium salt contains 10.27 and 10-32 per cent. of sodium,
which is in accordance with the formula (for the product when not yet dried)--
CH (NH) (SO,H) (SO,Na), +4 H,O, which requires 14-43 per cent. of water,
and with the formula (for the dried product) C₁H. (NH2) (SO,H) (SO,Na),
which requires 10.77 per cent. of sodium. The solutions of the acid and of its salts
shew a bluish fluorescence. The acid barium salt readily dissolves, and can be
salted out from concentrated solutions by saturation with common salt.
The above B-naphthylamine-a₁ B, B-trisulpho acid differs from the single
B-naphthylamine trisulpho hitherto known, and described in the German Patent
No. 27378, as follows:-
The B-naphthylamine-a₁ ẞ, ß trisulpho acid forms an acid sodium salt which
crystallizes in readily soluble scales. Solutions of the acid shew a bluish
fluorescence with a violet hue. Its diazo derivative dissolves with great readiness,
and can be salted out, but with great difficulty. The composition of this acid is
_represented by the following scheme :

page_text: The B-naphthylaminetrisulpho acid described in the German Patent No. 27378
yields an acid sodium salt, which forms needles soluble with readiness. Its solutions.
exhibit an azure fluorescence. The diazo product readily dissolves, and can be.
salted out with facility. The acid possesses the following formula :-
amine
If, in the preceding fifth example, ẞ, naphthol a, ẞ, a, ẞ, tetrasulpho acid is
employed in place of B, naphthol a, ß ß-trisulpho acid, the corresponding ẞ, naphthyl-
ཝ
ẞ, B. tetrasulpho acid is obtained. The acid sodium salt of this.
tetrasulpho acid crystallises from solutions containing common salt, in globular
masses consisting of very fine needles. The neutral sodium salt of the tetrasulpho.
acid remains in needles, on evaporating dilute alcoholic solutions thereof. Watery
solutions of the said tetrasulphonate of sodium exhibit a blue fluorescence.
The aforesaid ẞ-naphthylamine tri- and tetrasulpho acid can be employed for
producing dyestuffs.
My foreign correspondents have found that the above two ẞ. naphthylamine
trisulpho acids (viz., B, naphthylamine a, ẞ. ß. trisulpho acid and ẞ, naphthylamine.
a, Bas B, tetrasulpho acid) shew a chemical behaviour similar to that of the
corresponding B-naphtholtrisulpho acid and B-naphtholtetrasulpho acid, that is to
say, they contain one sulpho group (that which is in a position, or the ortho.
position to the amido group) in such loose combination, that this sulpho group can
also be separated on heating with water or dilute acids, Bi-naphthylamine B, B
disulpho acid, and ẞ-naphthylamine ẞ, a, ẞ trisulpho acid, being formed in this
manner. This conversion is effected in a manner analogous to that described in
the above examples three and four, for the transformation of the corresponding
naphtholsulpho acids.
My foreign correspondents have prepared a new amidonaphthol disulpho acid
by sulphonating ß-naphthylamine-8-disulpho acid (under modified conditions), and.
melting with alkalies the so-formed naphthylamine trisulpho acid.
This new
amidonaphtholdisulpho acid possesses the following formula:-
tetrazo products
The B-naphthylaminetrisulpho acid which my foreign correspondents employ as
initial product in this process, can also be obtained by heating with ammonia the
corresponding ẞ naphtholtrisulpho acid, which results (as described in the above
third example) by sulphonating B-naphthol-8-disulpho acid with an excess of
sulphuric acid, and heating the so-formed ẞ-naphtholtetrasulpho acid with diluted
acids, in order to separate a sulpho group.

page_text: The B-naphthylaminetrisulpho acid obtainable by either of the said operations
possesses the following formula
:-
50 parts of the acid sodium salt of the said ẞ naphthylaminetrisulpho acid are
mixed with 100 parts of soda and 80 parts of water. The resulting mixture is
heated in a closed vessel at from 180 to 240 degrees centigrade, until the
production of dye, on adding diazo products to a solution of a sample rendered
alkaline by means of sodium carbonate, does not increase. At this stage, the
melting mass is acidulated by means of muriatic acid. The amidonaphtholdisulpho
acid then separates in the form of fine white needles, which are filtered off and
pressed after cooling.
The proportions employed in this example can vary within certain limits; the
soda may be partially or totally replaced by potassa.
The new amidonaphtholdisulpho acid forms an acid sodium salt which crystallises
in fine needles soluble in cold water with difficulty, in hot water with readiness.
The solutions thereof shew a blue fluorescence. The acid barium salt dissolves even
in hot water with some difficulty. The diazo compound is readily soluble, and is
salted out by means of common salt in the form of yellow flakes; it assumes a
red brown colour in the presence of alkalies, for instance, sodium carbonate.
solution of the acid sodium salt assumes a deep violet colour on the addition of
ferric chloride and a blue colour on the addition of chloride of lime. The neutral
sodium salt readily dissolves in water, and is precipitated in flakes by means of
✰ common salt.
A
Owing to its properties, the new ẞ, amido as naphthol ẞ, ẞ, disulpho acid differs
from the amidonaphtholdisulpho acid described in the German Patent No. 53023,
and likewise derived from ß-naphthylamine. It is suitable for use for dyeing
purposes.
My foreign correspondents have described in the above examples, some distinct
methods of practically producing the said sulpho acids. Of course they do not
limit themselves to the directions given, as these can be varied, and all methods.

page_text: known and in use for analogous purposes also can be used, the nature of this
invention not being altered by such modifications.
Dated this 12th day of September 1893
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Sulpho Acids Derived from
Beta Naphthol Beta, Monosulpho Acid.
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 or manufacture of sulphonic
acids of the naphthalene series.
It is known that beta naphthol deltamonosulphonic acid F (beta, naphthol beta
monosulphonic acid) is converted by sulphonating agents into beta naphtholdelta
disulphonic acid (beta, naphthol beta, beta, disulphonic acid), as described in the
German Patent No. 44,079. Armstrong & Wynne (see Proceedings of the
Chemical Society of the year 1890, page 127) have proved that this latter acid is
represented by the following formula:
No other sulphonic acid has hitherto been obtained by sulphonating beta-
naphtholdeltamonosulphonic acid, and Weinberg has even stated (in the Berichte
der Deutschen Chemischen Gesellschaft, volume 20, page 2911), that whatever the
conditions, only the said disulphonic acid is obtained.
My foreign correspondents have, however, found that betanaphtholdeltamono-
sulphonic acid can be easily converted by sulphonation into two new sulphonic
acids, one of which is a betanaphtholtrisulphonic acid, the other being a beta-
naphtholtetrasulphonic acid. These two acids are often formed simultaneously,
but the process can be conducted in such a manner that either acid is formed
exclusively, and in theoretical amount. The formation of the tetrasulphonic acid
is the more noteworthy and unexpected, as no one has, up to the present time,
succeeded in introducing more than three sulphonic groups into a naphthylamine or
naphthol.
The production of the two new sulphonic acids is illustrated by the following
Examples A and B, the parts mentioned being by weight.
MANUFACTURE OF BETANAPHTHOLTRISULPHONIC ACID.
1 part of sodium beta naphthol deltamonosulphonate is introduced into 3 parts
of fuming sulphuric acid (containing 25 per cent. of sulphuric anhydride), and the
mass is allowed to cool. The mixture is then heated at from 80 to 90 degrees
centigrade, until, on testing a portion which has been poured onto ice, it is found
to be no longer capable of forming azo-coloring matters.
When this stage is
13

page_text: arrived at, the whole mass is poured onto ice, and the solution is neutralised by
means of slaked lime, care being taken that the liquid is not raised to too high a
temperature. The calcium salt of the new betanaphtholtrisulphonic acid is then
converted into the sodium salt, and the solution of this salt is evaporated to
dryness.
Instead of the betanaphthol delta monosulphonic acid specified in the above
example, betanaphtholdeltadisulphonic acid can be used, in which case a smaller
quantity of fuming sulphuric acid is necessary.
The new betanaphtholtrisulphonic acid forms readily soluble salts. The barium
salt separates in a gelatinous state on quickly cooling hot solutions thereof, and,
unlike barium betanaphtholdeltadisulphonate, is easily soluble in hot water.
When its hot solution is slowly cooled, the barium trisulphonate separates in a
crystalline state in the form of microscopical spherical aggregates. The sodium
salt readily dissolves in water, and is precipitated as a white powder by alcohol.
Alkaline solutions of this betanaphtholtrisulphonic acid show a strong green
fluorescence. In view of the fact that it does not afford azo colors, and of its
production from betanaphtholdeltadisulphonic acid, my foreign correspondents
ascribe the following composition to this betanaphtholtrisulphonic acid, viz.:-
-
The sulphonic group in the alpha ortho position relatively to the hydroxyl
group, is in loose combination, even boiling with dilute mineral acids sufficing to
displace it.
This new
trisulphonic acid differs from the betanaphtholtrisulphonic acid
hitherto known and described in the German Patent No. 22038, in the following
manner :-
In the case of the new beta naphtholtrisulphonic acid (obtainable as described
in the above Example A), the sodium salt is readily soluble in water, but dissolves
in alcohol with difficulty; the barium salt also readily dissolves in water, but
crystallises out in a gelatinous state when the hot solution is quickly cooled.
Alkaline solutions show a green fluorescence. Ferric chloride produces a violet.
color in a solution of the sodium salt. It does not afford coloring matters when
brought into contact with diazo compounds in alkaline solution. Its composition is
probably represented by the following scheme :-
Whereas, in the case of the betanaphtholtrisulphonic acid described in the 35
German Patent No. 22038, the sodium salt is readily soluble in water; the barium
salt dissolves in water with ease, and crystallises in flakes. Alkaline solutions
exhibit a very intense green fluorescence, similar to that produced by fluoresceine.
A solution of its sodium salt assumes a deep violet color on the addition of ferric

page_text: chloride. It yields dye-stuffs when it is allowed to act on diazo compounds in
alkaline solutions. It possesses the following formula :—
UE
20 parts of sodium betanaphtholdeltamonosulphonate are introduced into
80 parts of fuming sulphuric acid containing 40 per cent. of anhydride, which is
kept cool. The mixture is then heated at from 120 to 130 degrees centigrade
during from 8 to 10 hours. The mass then, as a rule, becomes solid.
Sulphonation is complete when azo dye-stuffs are no longer obtainable, and a
sample of the sulphonated mass is found to yield a white sandy barium salt,
difficultly soluble even in boiling water, when mixed with barium chloride. At
this stage, the whole sulphonated mass is gradually added to a large quantity of ice,
and the solution is neutralised with lime. After filtering off the calcium sulphate,
the necessary quantity of sodium carbonate is added, and the solution of sodium
betanaphtholtetrasulphonate is evaporated to dryness.
It is very characteristic of this new tetrasulphonic acid, that its barium salt
dissolves with very great difficulty, even in boiling water; this barium salt is
precipitated on adding barium chloride to a hot solution of the sodium salt as a
sandy white precipitate, very similar to the barium salt of betanaphtholdelta-
disulphonic acid, when in a precipitated state. Its sodium salt easily dissolves in
water, and can be obtained in crystals by adding alcohol to a hot solution of the
sodium salt.
Alkaline solutions of the acid exhibit a beautiful, pronounced bluish-green
fluorescence.
The said tetrasulphonic acid can also be obtained by sulphonating betanaphthol-
deltadisulphonic acid, or the aforesaid betanaphtholtrisulphonic acid.
Like the aforesaid new betanaphtholtrisulphonic acid, the said tetrasulphonic
acid does not possess the power of combining with diazo compounds to form dye-
stuffs, and therefore must also contain a sulphonic group in the "alpha "-ortho-
position relatively to the hydroxyl group. This is also obvious from the fact that,
when heated with dilute mineral acids, the said tetrasulphonic acid easily parts
with the sulphonic group in the "alpha "-ortho-position relatively to the hydroxyl
group, a betanaphtholtrisulphonic acid being thus produced, the sodium salt of
which dissolves with difficulty in dilute muriatic acid, crystallising from the solution
in fine matted needles. The hetanaphtholtrisulphonic acid thus produced differs
from the betanaphtholtrisulphonic acid obtainable as described in the above
Example A, as it combines with diazo compounds to form dye-stuffs. In order to
ascertain the chemical composition of the herein described betanaphtholtetra-
sulphonic acid, my foreign correspondents have converted the last-named beta-
naphtholtrisulphonic acid into the corresponding betanaphthylaminetrisulphonic
acid, by heating it with ammonia under pressure, and from this they have obtained a
naphthalene trisulphonic acid, identical with the naphthalene 2.3.6-trisulphonic
acid (naphthalene B₁ ẞ, ß, trisulphonic acid) described in the Specification of
Letters Patent No. 11865, dated 25th June 1892. This identity was ascertained
by preparing the corresponding naphthalenetrisulphonic chloride which melted at

page_text: from 201 to 202 degrees centigrade, in accordance with the publication of.
Armstrong and Wynne (see Proceedings of the Chemical Society of the year 1893,
page 166), who state that the trisulphonic chloride derived from naphthalene
2.3.6-trisulphonic acid (or naphthalene B₁ ẞ, B-trisulphonic acid) melts at
200 degrees centigrade.
Hence it follows that the aforesaid betanaphtholtrisulphonic acid (obtainable
from the above described betanaphtholtetrasulphonic acid by heating it with dilute
mineral acids) is represented by the formula:
It is noteworthy that on sulphonating betanaphtholdeltamonosulphonic acid, or
betanaphtholdeltadisulphonic acid, or the corresponding betanaphtholtrisulphonic
acid (in order to form a tetrasulphonic acid), the sulphonic group last introduced
takes up the ortho-position relatively to another sulphonic group, a result which is
contrary to the rule given by Armstrong & Wynne for the disulphonic acids of the
naphthalene series, according to which rule sulphonic groups never take up either
a contiguous or a "peri'
or "para" position relatively to a sulphonic group
previously present in the naphthalene derivative. The formation of beta, naphthol
alpha, beta, beta, beta, tetrasulphonic acid, constitutes the first deviation which
has been observed from the said rule of Armstrong & Wynne.
"
The directions given in the above two examples can be varied. For instance, in
place of the fuming sulphuric acid specified in the Example A, monohydrated
sulphuric acid can be used. In this case, the action takes place at a somewhat
higher temperature, and requires a somewhat longer time.
If the heating lasts too long, when the object is to produce the trisulphonic acid,
or too short a time when the beta naphtholtetrasulphonic acid is to be prepared,
mixtures of the said tri- and tetrasulphonic acid are obtained. In order to separate
these two acids, the barium salts are prepared from the mixture; these salts can be
easily separated, as the barium salt of betanaphtholtrisulphonic acid readily
dissolves in water, while barium betanaphtholtetrasulphonate dissolves with great
difficulty.
The aforesaid new betanaphtholtrisulphonic acid and betanaphtholtetrasulphonic
acid can be profitably used in producing other sulphonic acids of the naphthalene
series.
As above mentioned, my foreign correspondents have ascertained that the
said two new naphtholsulphonic acids (betanaphtholtrisulphonic acid and beta-
naphtholtetrasulphonic acid) contain a sulphonic group (viz., that in the alpha-
ortho-position relatively to the hydroxyl group) in very loose combination, and the
researches of my foreign correspondents have shown that this sulphonic group can
be split off by boiling with water or diluted acids. It was hitherto unknown that

page_text: any betanaphtholsulphonic acid has this property.
The afore-mentioned beta-
naphtholtrisulphonic acid is convertel, in this manner, into betanaphtholdelta-
disulphonic acid represented by the formula :-
In order to illustrate the conversion of the said betanaphtholtetrasulphonic acid
and betanaphtholtrisulphonic acid, respectively, into beta naphthol trisulphonic
acid and betanaphtholdeltadisulphonic acid, the two following examples are given,
the parts mentioned being by weight.
TRANSFORMATION OF BETA, NAPHTHOL ALPHA BETA, BETA, BETA TETRA-
SULPHONIC ACID INTO BETA NAPHTHOL BETA, BETA, BETA TRI-
SULPHONIC ACID.
1 part of sodium betanaphtholtetrasulphonate is mixed with from 6 to 10 parts of
muriatic acid (containing 10 per cent. of pure acid), and the mixture is boiled
during, say, one hour in a vessel provided with a reflux condenser. On cooling
the liquid, the solution salt of the new betanaphtholtrisulphonic acid, being but
slightly soluble in muriatic acid, separates in the form of a white crystalline mass.
The crystallised salt is filtered off, and a further small quantity of the salt can be
obtained by evaporating the filtrate.
It is not necessary, however, to previously isolate the betanaphtholtetrasulphonic
acid in a solid state, but the mixture obtained on sulphonating beta naphthol delta
monosulphonic acid, or beta naphthol delta disulphonic acid, as described in the
above Example B, can be directly used, that is to say, it may be boiled after it has
been diluted with water, in order to eliminate the sulphonic group in the alpha-
ortho-position relatively to the hydroxyl group. Of course the concentration of
the acid used may be varied within wide limits.
The new betanaphtholtrisulphonic acid thus produced, differs from the beta-
naphtholtrisulphonic acid obtainable by sulphonating betanaphtholdeltamono-
sulphonic acid, or betanaphtholdeltadisulphonic acid, and from the hereinbefore
described beta naphtholtetra sulphonic acid, inasmuch as it is capable of yielding
azo dyestuffs.
As the new betanaphtholtrisulphonic acid possesses the said property, it follows
that, on heating beta, naphthol alpha, beta, beta, beta, tetrasulphonic acid with
water or diluted acids, the sulphonic group in the "alpha," "ortho " position
relatively to the hydroxyl group, is that which is separated. It is characteristic of
the new betanaphtholtrisulphonic acid, that the sodium salt thereof crystallises
with great facility, separating in fine matted needles from a concentrated aqueous
solution, or from dilute muriatic acid. The alkaline solutions of the acid exhibit a

page_text: beautiful green fluorescence. A violet color is produced when ferric chloride is
added to a solution of the sodium salt. The barium salts forms a pellucid
gelatinous mass which dissolves in cold water with very great difficulty. Even
much diluted hot solutions of the barium salts, when cooled, yield a gelatinous
mass which is of such a consistency that the vessel containing it may be inverted
without the contents being spilt. This betanaphtholtrisulphonic acid can be used
for the production of azo coloring matters.
CONVERSION OF BETA₁ NAPHTHOL ALPHA BETA, BETA, TRISULPHONIC ACID
INTO BETA NAPHTHOL DELTADISULPHONIC ACID.
A mixture of 1 part of sodium beta, naphthol alpha, beta, beta, trisulphonate and
10 parts of muriatic acid (containing 10 per cent. of pure acid) is boiled during
from 1 to 2 hours in a vessel provided with a reflux condenser. The liquid is
neutralised by means of slaked lime, and after filtering off the calcium sulphate,
either barium chloride is added to the boiling filtrate (the barium salt of the beta-
naphthol-delta-disulphonic acid being thus precipitated), or the said filtrate
containing the calcium salt is mixed with sodium or potassium carbonate, and after
precipitating the calcium carbonate the filtrate is evaporated.
The production from beta, naphthol alpha, beta, beta, trisulphonic acid, of beta
naphthol-beta, beta, disulphonic acid (so-called beta-naphthol delta disulphonic
acid), has a special technical value, as in producing the said beta naphthol delta
disulphonic acid according to the process described in the German Patent No. 44079
(that is to say, by sulphonating beta naphthol delta monosulphonic acid), the above
described beta, naphthol alpha beta, beta, trisulphonic acid is always formed as
bye-product, so that the amount of beta, naphthol beta, beta, disulphonic acid
hitherto obtained by the said process, is a relatively small one, whilst the process
illustrated by the above Example D can be easily used in transforming the said
trisulphonic acid into the said delta disulphonic acid, of which it affords the
theoretical amount. For this purpose it is only necessary to dilute the sulphonated
mass obtained according to the process described in the said German Patent
No. 44079 with a suitable quantity of water, and to boil the mixture.
As above mentioned, the two acids: beta, naphthol-alpha, beta, beta, trisulphonic
acid, and betai naphthol alpha, beta, betas beta tetra sulphonic acid containing one
-sulphonic group (viz. that in the "alpha," "ortho" position relatively to the
hydroxyl group) in very loose combination, this latter sulphonic group being easily
.separated, for instance, by boiling with water or diluted acids. Therefore, it was
unlikely, that the said two acids would yield the corresponding beta, naphthylamine
sulphonic acids, when heated with ammonia, without the sulphonic group becoming
separated.
The researches of my foreign correspondents have, however, shown that the said
transformation can be easily effected, particularly when the action is caused to take
place at not too high a temperature; for instance, it has been found to be advan-
tageous to use a solution of ammonia containing 25 per cent. of the gas, and not to
allow the pressure to rise above 30 atmospheres. The process is facilitated by
using ammonium salts together with the ammonia solution."
The conversion of naphtholtrisulphonic acid and naphtholtetrasulphonic acid into
naphthylaminetrisulphonic acid and naphthylaminetetrasulphonic acid, respectively,
is illustrated by the following example.

page_text: 2 to 3 parts of an ammonia solution containing 25 per cent. of ammonia and about.
part of ammonium chloride. The mixture is heated during 6 hours in a closed
vessel, under a pressure of about 28 atmospheres; the contents of the digestor
having been cooled, are mixed with soda lye, and the ammonia is distilled off. The
residual liquid is then filtered, and when not too hot, is acidulated with muriatic
acid. The acid sodium salt of the new beta naphthylamine trisulphonic acid
crystallizes from the solution, as it cools, in beautiful bright scales.
It is noteworthy that if the action has been allowed to take place at too high a
temperature, beta naphthylamine delta disulphonic acid is also formed. In this:
case, the separation of the trisulphonic acid and disulphonic acid can be effected by
utilizing the following properties of the two acids. The sodium salt of the beta
naphthylamine disulphonic acid can be salted out from its neutral solutions by
means of common salt, the sodium salt of the beta naphthylamine trisulphonic acid
remaining dissolved. After filtering off the sodium salt of the said disulphonic
acid, muriatic acid is added to the filtrate, and the acid sodium salt of the
trisulphonic acid thus precipitated is separated by filtration.
The said beta, naphthylamine alpha, beta, beta, trisulphonic acid can also be
produced by heating sodium betanaphtholtrisulphonate in an open vessel, in a
current of ammonia.
The beta, naphthylamine alpha beta, beta, trisulphonic acid possesses the
following properties:-Its acid sodium salt very readily dissolves in water, and is
separated by adding common salt or alcohol, or muriatic acid, to solutions thereof
in water. Ou evaporating dilute solutions of this acid sodium salt in alcohol, it
crystallizes in beautiful bright scales, the composition of which is represented by
the formula:-C₁H, (NH) (SO,H) (SO,Na), + 4 H₂O.
The solutions of the acid and of its salts shew a bluish fluorescence. The acid
barium salt readily dissolves in water, and crystallises in the shape of balls ou
evaporating its solutions.
The said beta, naphthylamine alpha, beta, beta, trisulphonic acid differs from
the beta naphthylamine trisulphonic acid hitherto known and described in the
German Patent No. 27378 as follows:-
Beta, naphthylamine alpha, beta, beta, trisulphonic acid forms an acid sodium.
salt, which crystallizes in very soluble scales; solutions of the acid shew a.bluish
fluorescence with a slight violet hue. Its diazo derivative dissolves with great.
readiness, and can be salted out only with great difficulty. The composition of this.
acid is represented by the following scheme :-

page_text: If, in the preceding Example E, beta, 'naphthol alpha, beta, beta, beta
tetrasulphonic acid is used in place of beta, naphthol alpha, beta, beta, trisulphonic
acid, advantageously at a somewhat lower temperature, the corresponding beta,
naphthylamine alpha, beta, beta, beta, tetrasulphonic acid is obtained.
This naphthylamine tetrasulphonic acid, which is the first naphthylamine
tetrasulphonic acid hitherto produced, is so strong an acid, that my foreign
correspondents have not yet succeeded in obtaining acid salts thereof. The
neutral salts crystallize well, and in some cases exhibit special properties. The
neutral sodium salt crystallizes from dilute alcoholic solutions, forming fine stiff
crystals, and its solution in water shews a violet-blue fluorescence. The neutral
barium salt separates as a sandy powder, on boiling even very dilute solutions, and
when separated, it again dissolves only with great difficulty. The diazo derivative
of this tetrasulphonic acid dissolves with readiness, and can be precipitated by
saturating its solution with common salt. It yields a brownish orange dye-stuff
when it is allowed to act on beta naphthol disulphonic acid R, or salts thereof.
The aforesaid beta naphthylamine tri- and tetrasulphonic acid can be used in
producing dye stuffs.
"
My foreign correspondents have found that the said two beta, naphthylamine
sulphonic acids (viz., beta, naphthylamine alpha, beta, beta, trisulphonic acid, and
beta, naphthylamine alpha, beta, beta, beta, tetrasulphonic acid) correspond in
chemical behaviour with the beta naphthol trisulphonic acid and beta naphthol-
tetrasulphonic acid from which they are derived, that is to say, they contain a
sulphonic group (that which is in "alpha' "ortho" position relatively to the
amido group) so loosely combined that it can be separated by heating with water
or dilute acids, giving rise to beta, naphthylamine beta, beta, disulphonic acid (beta
naphthylamine delta disulphonic acid), and beta, naphthylamine beta, beta, beta
trisulphonic acid. This conversion is effected in a manner analogous to that
described in the above Examples C. and D., illustrating the conversion of the
corresponding naphtholsulphonic acids.
The beta, naphthylamine beta, beta, beta, trisulphonic acid thus produced,
is represented by the formula :—
It possesses the following properties. The acid sodium salt forms lustrous white
matted needles, and easily dissolves in hot, but less easily in cold, water; it is,
however, less soluble than the corresponding acid sodium salts of the isomeric acids.
The neutral sodium salt readily dissolves, and can be salted out by means of
common salt or soda lye. The neutral salts of this acid shew a blue fluorescence.
Its acid barium salt is obtained in flakes which dissolve with difficulty even in
boiling water. When heated with dilute mineral acids, the acid undergoes no
alteration. The diazo compound prepared from the acid sodium salt forms
yellowish needles which dissolve in water with difficulty, and can be salted out by
common salt. A difficultly soluble dye-stuff is formed if the said diazo compound
is allowed to act on the sodium salt of betanaphtholdisulphonic acid R in a solution
rendered alkaline by means of sodium carbonate.
My foreign correspondents have prepared a new amidonaphthol disulphonic acid
by fusing with alkalies the naphthylamine trisulphonic acid possessing the following

page_text: The said betanaphthylaminetrisulphonic acid which my foreign correspondents
use in this process, can also be obtained by heating with ammonia the corresponding
beta naphthol trisulphonic acid formed (as described in the above Example C) by
sulphonating beta-naphthol delta disulphonic acid with an excess of sulphuric acid,
and heating the betanaphtholtetrasulphonic acid so formed with dilute acids in
order to separate a sulphonic group.
The new amidonaphtholdisulphonic acid thus obtainable, probably possesses the
following formula
when combined with diazo or tetrazo compounds. This amido naphtholdisulphonic
acid yields valuable dye-stuffs.
The conversion of the said beta, naphthylamine beta, beta, beta, trisulphonic
acid into the new amidonaphtholdisulphonic acid, is effected by heating it with
alkalies in open or closed vessels, at from about 170 to 250 degrees centigrade,
which process is illustrated by the following example. The parts are by weight.
MANUFACTURE OF BETA₁ AMIDO-BETA NAPHTHOL BETA, BETA, DISULPHONIC
ACID.
50 parts of the acid sodium salt of the said "beta, naphthylamine beta, betaz
beta, trisulphonic acid, are mixed with 100 parts of caustic soda and 80 parts of
water. The resulting mixture is heated in a closed vessel at from 180 to 240 degrees
centigrade, until no increase is observed in the amount of dye-stuff produced on
adding diazo compound to a solution of a sample rendered alkaline by means of
sodium carbonate. At this stage, the mass is acidulated with muriatic acid. The
amidonaphtholdisulphonic acid then separates in the form of fine white needles,
which are filtered off and pressed.
The proportions used in this example can vary within certain limits; the soda
may be partially or totally replaced by potash. The process can also be carried
out in open vessels; in this case, it is advantageous to use more concentrated
alkali-lye.
The new amidonaphtholdisulphonic acid forms an acid sodium salt crystallizing
in fine needles, which dissolves in cold water with difficulty, in hot water with
readiness. The solutions shew a blue fluorescence. The acid barium salt dissolves
even in hot water with some difficulty. The diazo compound is readily soluble,
and is salted out by means of common salt in the form of yellow flakes; it assumes
a red-brown colour in the presence of alkalies, for instance, sodium carbonate.
Solutions of the acid sodium salt assume a deep violet colour on the addition of
ferric chloride, and a blue colour on the addition of chloride of lime. The
neutral sodium salt readily dissolves in water, and is precipitated in flakes by means
of common salt.
The new beta, amido beta, naphthol beta, beta, disulphonic acid differs in its
properties from the amido naphthol disulphonic acid also derived from beta-
naphthylamine as described in the German Patent No. 53023.
My foreign correspondents have described in the above examples several distinct
methods of practically producing the said sulphonic acids. Of course, they dọ not
0

page_text: limit themselves to the directions given, as these can be varied, and all methods
known and in use for analogous purposes can also be used, without. the nature of
this invention being altered by such modifications.
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 by
my foreign correspondents, I declare that what I claim is :-
1. The manufacture or production of beta, naphthol alpha, beta, beta, trisulphonic
acid, by heating beta naphthol delta monosulphonic acid (beta, naphthol beta, mono-
sulphonic acid), or beta naphthol delta bisulphonic acid (beta, naphthol beta, beta
disulphonic acid), or salts thereof, with sulphonating agents.
2. The process for producing betaj naphthol alpha, beta, beta, beta, tetrasulphonic
acid, which process consists either in heating beta naphthol delta monosulphonic
acid, or beta naphthol delta disulphonic acid, or beta, naphthol alpha, beta, beta
trisulphonic acid, with sulphonating agents, or in adding to the crude sulphonated.
product of the process claimed in the foregoing claim, a further quantity of
sulphonating agent, and heating the mixture until the product no longer affords
azo dyes, but yields a white sandy barium salt difficultly soluble even in boiling
water.
3. The separation of beta₁ naphthol alpha, beta, beta, trisulphonic acid, and
beta naphthol alpha₁ beta, beta, beta tetrasulphonic acid, from a mixture
containing these two acids obtained under certain conditions, by sulphonating
beta naphthol delta monosulphonic acid, or beta naphthol delta disulphonic acid,
which separation can be effected by converting the said two acids into barium
salts, and utilizing the different degrees of solubility of these barium salts.
4. The production of beta, naphthol beta, beta disulphonic acid, and betai
naphthol beta, beta, beta, trisulphonic acid, from beta, naphthol alpha, beta,
beta trisulphonic acid, and beta, naphthol alpha, beta, beta, beta tetra
sulphonic acid (or salts thereof), respectively, by heating them with water or
dilute acids.
5. The process for producing beta, naphthylamine alpha, beta, beta, trisulphonic
acid and beta naphthylamine alpha₁ beta, beta, beta, tetrasulphonic acid, or
salts thereof, which process consists in heating beta, naphthol alpha beta, beta
trisulphonic acid, and beta naphthol alpha, beta, betas beta, tetrasulphonic acid
(or salts thereof), respectively, either with ammonia alone, or together with
ammonium salts, at not too high a temperature.
6. The conversion of beta, naphthylamine alpha, beta, beta, trisulphonic acid,
and beta naphthylamine alpha beta, beta, beta, tetrasulphonic acid, or salts
thereof, into beta, naphthylamine beta, beta, disulphonic acid, and beta, naphthyl-
amine beta, beta, beta, trisulphonic acid, respectively, by heating the former
acids, viz., beta, naphthylamine alpha, beta, beta, trisulphonic acid and beta
naphthylamine alpha beta, betas beta, tetrasulphonic acid (or salts thereof),
respectively, with water or dilute acids.
7. The production of a new amidonaphtholdisulphonic acid (which is probably
beta, amido beta naphthol beta, beta, disulphonic acid) by heating beta, naphthyl-
amine beta, beta, beta, trisulphonic acid, or salts thereof, with alkalies at
temperatures from about 170 to 250 degrees centigrade.
8. As new products of manufacture:
(a), Beta, naphthol alpha, beta, beta, trisulphonic acid;
(b) Beta, naphthol alpha, beta, beta, beta, tetrasulphonic acid;
Beta, naphthol beta, beta, beta, trisulphonic acid;
Beta, naphthylamine alpha, beta, beta, trisulphonic acid;
Beta, naphthylamine alpha, beta, beta, beta, tetrasulphonic acid;
Beta naphthylamine beta, beta, beta, trisulphonic acid;
The new amidonaphtholdisulphonic acid, which is probably beta, amido
beta, naphthol beta, beta, disulphonic acid,

page_text: or salts thereof, produced by the processes hereinbefore defined, or by any other
means affording the same result.
Dand thin 11th daw of Tunn 1001
NEWTON & SON,
Agents for the Applicant.

page_text: Date of Application, 12th Sept., 1893
Complete Specification Left, 12th June, 1894-Accepted, 14th July, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Sulpho Acids Derived from
Bi Naphthylamine-ẞ, B. Disulpho Acid.
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 researches of my foreign correspondents have shewn that ẞ naphthyl-
amine-8-disulpho acid, possessing the formula :-
FIRST EXAMPLE.
MANUFACTURE OF ẞ₁ NAPHTHYLAMINE-a₁ ẞ, B. TRISULPHO ACID.
1 part of the acid sodium salt of ẞ naphthylamine-8-disulpho acid, is introduced
into from 3 to 4 parts of fuming sulphuric acid (containing 40 per cent. of sulphuric
anhydride), and the resulting mass is heated for several hours at from 80 to
90 degrees centigrade, until the whole is dissolved and a sample taken out and
diazotised, yields, with betanaphthol disulphonate of sodium (so-called R salt), in
the presence of sodium carbonate, an orange-red coloring matter, which is readily
soluble (it is noticeable that ẞ naphthylamine-8-disulpho acid yields a red dye-
stuff soluble with difficulty). The sulphonated mass is poured on ice, the liquid is
neutralised with lime-water, and the precipitated calcium sulphate is filtered off.
Sodium carbonate is added to the resulting filtrate, until calcium carbonate is no
longer separated. After filtering off the calcium carbonate, the thus obtained
filtrate evaporated, and the resulting concentrated solution of the sodium salt,
when cool, is acidulated by means of muriatic acid.
The sodium salt of the thus formed ẞ naphthylaminetrisulpho acid then crystallises
out in beautiful bright scales.
This naphthylamine trisulpho acid has been proved to be identical with that
ẞ naphthylamine trisulpho acid which results on sulphonating either ẞ3 naphthol-
8-monosulpho acid, or ẞ-naphthol-8-disulpho acid, and subsequently heating with
[Price xd I

page_text: ammonia the formed betanaphtholtrisulpho acid. The latter acid does not re-act.
with diazo products to form colouring-matters, and can be produced from
B₁ naphthol B, ẞ, disulpho acid. Hence it follows, that the said ẞ naphthol-
trisulpho acid possesses the following formula:-
PRODUCTION OF ẞ₁ NAPHTHYLAMINE ẞ. α, ẞ. TRISULPHO ACID.
On heating for a longer period the sulphonated mass obtained as described in the
preceding First Example at from about 120 to 130 degrees centigrade, the
aforesaid B-naphthylamine trisulpho acid is converted into two isomeric trisulpho
acids. The mass is heated, until a test portion (when diazotised, and combined
with the so-called R salt), yields a dyestuff soluble with difficulty. When this
stage is arrived at, the mass is poured on ice, and the liquid is neutralised by means
of slaked lime. After filtering off the calcium sulphate, the filtrate is mixed with
sodium carbonate, and the thus precipitated calcium carbonate is filtered off. The
resulting solution of the sodium salt is acidulated, the acid sodium salt of a
new ẞ-naphthylamine trisulpho acid being thus precipitated, which differs totally
from the acid sodium salt of the above described B₁ naphthylamine a, b, ẞ, trisulpho
acid. The acid sodium salt of the new ẞ3 naphthylaminetrisulpho acid crystallises
in beautiful fine needles, with silky lustre, and dissolves in water less easily than
the acid sodium salt of the above ẞ-naphthylamine a, Bẞ trisulpho acid.
It is noticeable that the mother liquor obtained after filtering off the acid sodium
salt of the new ẞ-naphthylamine trisulpho acid, contains the corresponding salt of
an isomeric trisulpho acid, which is hereinafter described.
The new B-naphthylaminetrisulpho acid obtainable as described in the preceding
Second Example, very probably possesses the following formula :

page_text: This is evident from the fact that the said trisulpho acid is, by diazotising and
subsequently boiling with dilute acids, converted into ẞ-naphthol trisulpho acid,
possessing very probably the following composition :
MANUFACTURE
OF AN
TRISULPHO
ISOMERIC ẞ NAPHTHYLAMINE
(SO-CALLED ẞ-NAPHTHYLAMINE TRISULPHO ACID IV).
ACID
A mixture containing 1 part of ẞ-naphthylamine-d-disulpho acid and 4 parts of
fuming sulphuric acid, is heated during from about 20 to 30 hours at 130 degrees
centigrade. A new ẞ-naphthylamine trisulpho acid is formed as chief product
in this manner, whilst the aforesaid ẞ, naphthylamine ẞ, a, ẞ trisulpho acid, and
Baphthylamine tetra sulpho acid are produced as by-products. In order to
isolate the new ẞ naphthylamine trisulpho acid (so-called ẞ-naphthylamine
trisulpho acid IV), the tetra sulpho acid formed simultaneously is first converted
(by splitting off a sulpho group) into ẞ, naphthylamine ẞ2 a, ß, trisulpho acid,
which conversion is effected by introducing the sulphonated mass into ice water,
diluting with water, and boiling. The resulting solution now contains but two
sulpho acids, which can easily be separated, owing to the difference degrees of
solubility of their sodium salts. For this purpose the solution is neutralised by
means of slaked lime, the calcium sulphate is filtered off, the filtrate is mixed with
sodium carbonate, and after filtering off, the precipitated calcium carbonate, the
resulting solution of the sodium salts is evaporated, and subsequently acidulated
by means of muriatic acid. The acid sodium salt of ẞi naphthylamine 3, a, ẞt
trisulpho acid, is mostly separated in long needles, and the new B-naphthylamine
trisulpho acid IV is isolated from the mother liquor, viz., either by saturating
with common salt, or by rendering alkaline, evaporating, and acidulating again.
4
My foreign correspondents have ascertained by an analytical research, that the
so-called acid IV is a true naphthylamine trisulpho acid, for they have found that
the acid sodium salt, when dried at from 150 to 160 degrees centigrade, contains

page_text: 10.50 and 10-47 and 10.49 per cent. of sodium, in accordance with the formula:
CH. (NH) (SO,H) (SO,Na), which requires 10-77 per cent. of sodium.
The salts of the new acid IV are readily soluble. The acid sodium salt
crystallises in indistinct globular masses from solutions containing common salt,
or from moderately diluted alcohol. The neutral sodium salt crystallises in yellow
needles from alcohol. The solutions of the salts shew a beautiful and strong green
fluorescence. The diazo compound dissolves with great readiness, and can be
salted out by saturating the concentrated solution with common salt. When this
diazo product is allowed to act on the so-called R salt in alkaline solutions, a red
dye stuff soluble with readiness is obtained.
P3 P4 1 TETRASULPHO ACID.
The B-naphthylaminetetrasulpho acid, which results together with two ẞ naph-
thylamine trisulpho acids, on sulphonating ẞ naphthylamine-8-disulpho acid, is
prepared in a practical manner by treating ẞ-naphthylamine ẞ, a B-trisulpho
acid with fuming sulphuric acid.
1 part of naphthylamine ẞ, as ẞ, trisulpho acid is introduced into 5 parts of
fuming sulphuric acid (containing 40 per cent. of anhydride) and the resulting
mixture is heated at from 140 to 150 degrees centigrade, until a sample carefully
poured on ice, diazotised, and coupled with the so-called R salt, yields a brown
colouring matter, soluble with readiness. If this stage be arrived at, the whole
mass is poured on ice (whilst care must be taken that any rise of temperature be
avoided), and the resulting liquid is neutralised with slaked lime, or lime water
(being kept the while at a low temperature). The sodium salt of the tetrasulpho
acid is then prepared in the well known manner. If the sulphonated mass should
have been raised to a somewhat higher temperature before pouring it on ice,
B₁ naphthylamine ẞ, a ẞ trisulpho acid is formed, owing to the separation of a
sulpho group from the tetrasulpho group. These two acids, viz., the tetrasulpho
acid and the trisulpho acid, can easily be separated in a manner analogous to
that described in the above Third Example for the separation of the two isomeric
naphthylamine trisulpho acids, that is to say, the mass, when cold, is acidulated
with muriatic acid, and the thus separated acid sodium salt of the trisulpho acid
is filtered off; the resulting filtrate is rendered alkaline again, and then evaporated,
until an addition of muriatic acid to a sample of the cold alkaline solution causes
the separation of the tetrasulpho acid.
At this stage, the whole mass is acidulated with muriatic acid. After about
24 hours, the separated tetrasulpho acid is filtered off, pressed, and dried.
The watery solutions of the acid and neutral salts of this tetrasulpho acid shew
a bluish fluorescence with a violet hue. Its barium salt is soluble with readiness.
Its diazo compound is of a yellow colour, and dissolves with great readiness. The
tetrasulpho acid is readily converted (on heating with dilute acids) into ẞ₁ naph-
thylamine ß, a, ß, trisulpho acid, a sulpho group being split off in this process. By
reason of this property, my foreign correspondents ascribe to the above tetra sulpho
acid the following formula, viz. :-

page_text: Of course, the fuming sulphuric acid employed in the above examples can be
replaced by analogous agents, such as sulphuric acid, chlorhydrine, or the like.
Dated this 17th day of October 1893.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Sulpho Acids Derived from
Beta-naphthylamine-beta, Beta-disulpho Acid.
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 researches of my foreign correspondents have shown, that the beta-
naphthylamine-delta-disulphonic acid represented by the formula :
can be converted, by treatment with sulphonating agents, into several new poly-
sulphonic acids, and that, according as the process is effected at lower or higher
temperatures, four different products are formed, viz. three naphthylamine
trisulphonic acids, and one naphthylamine-tetrasulphonic acid.
According to the researches of my foreign correspondents, when treated with
sulphonating agents (such as fuming sulphuric acid), the aforesaid beta-naphthyl-
amine-delta-disulphonic acid (beta-naphthylamine-beta,-beta-disulphonic acid)
is first converted into beta-naphthylamine-alpha, beta, beta, trisulphonic acid;
having the formula :—
"
On further heating the trisulphonic acid thus formed with fuming sulphuric acid,
the said trisulphonic acid is changed into two isomeric trisulphonic acids, the
sulphonic group in the "alpha," position being split off, and re-introduced, on the
one hand, into the "alpha," position, and, on the other hand, into the "beta,
position, beta-naphthylamine-beta, alpha, beta, trisulphonic acid and beta,
naphthylamine beta, beta, beta-trisulphonic acid, represented respectively by the
formula:

page_text: The researches of my foreign correspondents have further shewn that, when the
last-named trisulphonic acid (beta-naphthylamine-beta, beta, beta, trisulphonic
acid) is further acted on by the fuming sulphuric acid present in the sulphonated
mass, it is partially converted into a tetrasulphonic acid, viz., beta,-naphthylamine-
-alpha, beta, betas beta, tetrasulphonic acid, represented by the formula
MANUFACTURE OF BETA₁-NAPHTHYLAMINE-ALPHA BETA, BETA-TRISULPHONIC
ACID.
1 part of the acid sodium salt of beta-naphthylamine-delta-disulphonic acid
(beta,-naphthylamine-beta, beta, disulphonic acid) is introduced into from 3 to
4 parts of fuming sulphuric acid (containing 40 per cent. of sulphuric anhydride),
and the resulting mass is heated during several hours at from 80 to
90 degrees centigrade, until the whole is dissolved, and a sample is found to yield
a readily soluble brownish orange-red colouring matter, when diazotised and
coupled with the betanaphthol disulphonate of sodium, known as R-salt, in the
presence of sodium carbonate, unlike the beta-naphthylamine-delta-disulphonic
acid, which yields a difficultly soluble red dye-stuff.
The sulphonated mass is poured onto ice, and the liquid is neutralised with milk
of lime, care being taken that the temperature is not raised too high.
The calcium salt thus prepared having been converted into the sodium salt, the
solution is concentrated by evaporation and, when cool acidulated with muriatic
: acid.
The sodium salt of the beta-naphthylaminetrisulphonic acid thus produced
⚫ crystallises out in beautiful bright scales, which readily dissolve in water.
According to the researches of my foreign correspondents, this beta-naphthyl-
amine trisulphonic acid is identical with the beta-naphthylamine trisulphonic acid
which is formed on sulphonating either beta-naphthol-delta-monosulphonic acid, or
beta-naphthol-delta-disulphonic acid, and subsequently heating the beta-naphthol-
trisulphonic acid thus produced with ammonia.
As the said acid does not form azo colouring-matters, and can be produced from
beta-naphthol-beta, beta-disulphonic acid, it follows, that it may be represented
by the following formula :-

page_text: Consequently the beta-naphthylamine trisulphonic acid obtainable as described in.
the preceding example is represented by the following formula :—
PRODUCTION OF BETA1-NAPHTHYLAMINE-BETA, BETA3 BETA TRISULPHONIC
ACID.
On heating during a longer period (during, say, from 20 to 30 hours) at about-
130 degrees centigrade, a mixture containing one part of beta-naphthylamine--
delta-disulphonic acid, and from 3 to 4 parts of fuming sulphuric acid (containing
40 per cent. of anhydride), the betai-naphthylamine-alpha,-beta, beta-trisulphonic
acid, which is first produced, is converted into two isomeric trisulphonic acids.
The mass is heated until the aforesaid beta-naphthylamine-alpha, beta, beta-
trisulphonic acid is no longer distinguishable, that is to say, until a test portion.
(when diazotised and combined with so-called R-salt) yields a partially soluble.
dye-stuff.
When this stage is arrived at, the mass is poured onto ice, and the liquid is.
neutralised with slaked lime, care being taken that the temperature of the liquid.
is not raised.
After filtering off the calcium sulphate, the filtrate is mixed with sodium
carbonate, and the precipitated calcium carbonate is filtered off.
The solution of the sodium salt thus obtained having been evaporated until its.
bulk is reduced to about 6 litres (in case the parts are kilos. by weight), and.
acidulated, an acid sodium salt of beta-naphthylamine-beta, beta, beta.
trisulphonic acid, having the formula :—C₁₁(NĦ₂) (SOH) (SON), +3 H₂O,"
is precipitated.
10
After several hours, this acid sodium salt is filtered off, and the filtrate is
rendered neutral, or moderately alkaline, and evaporated until the volume is about
from 3 to 4 litres, when the parts are kilos. by weight.
The beta-naphthylamine tetrasulphonic acid can be precipitated from the liquid
either by adding common salt, and cooling, or by adding a hot solution prepared
from 04 parts of crystallised barium chloride, and heating to boiling. The barium
salt of the beta-naphthylamine tetrasulphonic acid is thus perfectly precipitated.
and can be separated by filtration.
The mother liquor contains beta-naphthylamine-beta, alpha, beta-trisulphonic acid,.
which can be precipitated by adding muriatic acid, the liquid being advantageously
previously concentrated, and allowed to stand some time after mixing it with
the acid.
As above mentioned, the beta, naphthylamine-beta, beta, beta, trisulphonic acid,.
is formed from the beta-naphthylamine-alpha, beta, beta trisulphonic acid which
is first produced from the beta naphthylamine-delta-disulphonic acid originally
used. Consequently, the said beta, naphthylamine-beta, beta, beta, trisulphonic
acid can also be obtained from beta-naphthylamine-alpha, beta, beta trisulphonic
acid and fuming sulphuric acid, or the like; if, for instance, 1 part of the acid
sodium salt of beta, naphthylamine-alpha,-beta, beta trisulphonic acid is heated
with 3 parts of fuming sulphuric acid (containing 25 per cent. of anhydride) at
from 130 to 140 degrees centigrade, in the manner described in the foregoing
Example B.

page_text: The aforementioned beta, naphthylamine trisulphonic acid is identical with the
beta,-naphthylamine beta, beta, beta, trisulphonic acid produced by my foreign
correspondents in another way, viz., by heating beta, naphthylamine-alpha1-beta,
beta, beta, tetrasulphonic acid, or salts thereof, with water or dilute acids.
MANUFACTURE OF BETA,, NAPHTHYLAMINE-BETA, ALPHA, BETA4
TRISULPHONIC ACID.
A mixture containing 1 part of beta-naphthylamine-delta-disulphonic acid, and
from 3 to 4 parts of fuming sulphuric acid (containing 40 per cent. of sulphuric
anhydride) is heated during from about 20 to 30 hours at 130 degrees centigrade,
as mentioned in the preceding Example B.
Beta-naphthylamine beta, alpha, beta trisulphonic acid, together with the
above described beta,-naphthylamine-beta, beta3 beta4 trisulphonic acid, and beta,
naphthylamine tetrasulphonic acid, are thus produced.
In order to isolate the beta-naphthylamine beta, alpha, beta, trisulphonic acid,
the tetrasulphonic acid which is formed simultaneously, is first converted, by the
removal of a sulphonic group, into beta, naphthylamine-beta, alpha, beta-
trisulphonic acid, the which conversion is effected by introducing the sulphonated
mass into ice water, diluting with water, and boiling.
The solution now contains but two sulphonic acids, which can easily be
separated, owing to the different degrees of solubility of their sodium salts.
For this purpose the solution of the sodium salts is evaporated until the volume
is about from 5 to 6 litres, in case the parts are kilos. by weight, and is then
acidulated with muriatic acid.
The acid sodium salt of beta-naphthylamine beta, betas beta-trisulphonic acid
separates in long needles, and is filtered off.
The beta-naphthylamine beta, alpha, beta-trisulphonic acid is then isolated from
the mother-liquor, viz., either by saturating with common salt, or by previously
rendering alkaline, evaporating, and acidulating.
The said beta-naphthylamine-beta, alpha, beta, trisulphonic acid possesses the
following properties:-The acid sodium salt dissolves with very great readiness in
water, and crystallizes in indistinct globular masses from solutions containing
common salt, or from dilute alcoholic solutions.
The neutral sodium salt dissolves with great readiness, and can be obtained in
fine yellow needles by crystallising it from dilute alcoholic solutions. The solutions
of the neutral salts exhibit a beautiful and intense green fluorescence.
The acid barium salt readily dissolves, and separates in indistinct flakes.
When heated with dilute mineral acids, the acid undergoes no alteration.
The diazo compound obtainable from the acid sodium salt dissolves with great
readiness, and can be salted out, by means of common salt, from its not too dilute
solutions.
A red, easily soluble dyestuff is obtained on allowing the said diazo compound
to act on heta-naphtholdisulphonate of sodium (so-called R-salt) in a solution
rendered alkaline by means of sodium carbonate.
The acid is represented by the following formula :-

page_text: The aforesaid beta-naphthylamine tetrasulphonic acid, which is formed together
with the above-mentioned two beta naphthylamine trisulphonic acids, viz., betai
naphthylamine-beta, beta, beta, trisulphonic acid and beta, naphthylamine-beta,-
alpha,-beta, trisulphonic acid, on sulphonating beta-naphthylamine-delta-disulphonic
acid, may be prepared in a practical manner by heating beta-naphthylamine-beta,
beta, beta-trisulphonic acid with fuming sulphuric acid, as is illustrated by the
following example. The parts are by weight.
PRODUCTION OF BETA-NAPHTHYLAMINE-ALPHA BETA2 BETA, BETA-TETRA-
SULPHONIC ACID.
1 part of beta, naphthylamine-beta, beta, beta, trisulphonic acid, or of its acid
sodium salt, is introduced into from 3 to 4 parts of fuming sulphuric acid
(containing 40 per cent. of anhydride), and the resulting mixture is heated at from
120 to 140 degrees centigrade, until a sample carefully poured onto ice, diazotised,
and coupled with the so-called R-salt, yields a brown, readily soluble colouring-
matter.
When this stage is arrived at, the whole mass is poured onto ice (care being
taken to prevent any rise of temperature), and the resulting liquid is neutralised
with slaked lime, being kept the while at a low temperature. The sodium salt
If the
of the tetrasulphonic acid is then prepared in the well-known manner.
sulphonated mass should have been raised to a somewhat higher temperature before
pouring it on ice, beta, naphthylamine beta, beta, beta trisulphonic acid is
re-formed, owing to the separation of a sulphonic group from the tetrasulphonic
acid which is first formed.
These two acids, viz., the tetrasulphonic acid and the last-named trisulphonic
acid, can be easily separated in a manner analogous to that described in the above
Example C for the separation of the two isomeric naphthylamine trisulphonic acids,
that is to say, when cold, the solution of the sodium salts is acidulated with
muriatic acid, and the acid sodium salt of the trisulphonic acid which separates, is
filtered off.
The filtrate is then rendered alkaline by means of sodium carbonate, and
evaporated, until, on adding muriatic acid to a sample of the cold alkaline solution,
the tetrasulphonic acid separates.
At this stage the whole mass is acidulated with muriatic acid, and after about
24 hours, the separated tetrasulphonic acid is filtered off, pressed, and dried.
According to the researches of my foreign correspondents, the beta, naphthyl-
amine tetrasulphonic acid obtainable is described in the preceding Example D, is
identical with the beta, naphthylamine-alpha, beta, beta, beta, tetrasulphonic acid
obtained by my foreign correspondents in another way, viz., by heating beta₁
naphthol-alpha, beta, beta, bеta tetrasulphonic acid with ammonia alone, or in
presence of ammonium salts.
In the above Examples A, B, C, and D, my foreign correspondents have
described distinct methods of producing the naphthylamine poly-sulphonic acids
hereinbefore defined. Naturally, they do not limit themselves to the directions
therein given, as these can be varied within certain limits.
The strength of the fuming sulphuric acid, that is to say, the percentage of
sulphuric anhydride therein, can also vary within certain limits. The temperature
used can also vary, in which case the relative quantities of the several acids are
alone altered.
The said beta-naphthylamine poly-sulphonic acids can be used for producing
dye-stuffs.

page_text: 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 process for producing beta,-naphthylamine-alpha, beta, beta, trisulphonic
acid, which process consists in heating beta-naphthylamine-delta-disulphonic acid
(beta-naphthylamine-beta, beta,-disulphonic acid), or salts thereof, with fuming
sulphuric acid, until the formation of the said beta,-naphthylamine-alpha, beta,
beta, trisulphonic acid is completed, which is known to be the case when a sample
taken from the sulphonated mass, and diazotised, yields a brownish-orange azo
dye-stuff, when mixed with the sodium salt of beta-naphthol disulphonic acid R.
2. The production of a mixture containing varying quantities of beta-naphthyl-
amine-beta-alpha, beta, trisulphonic acid, beta, naphthylamine-beta, beta, beta
trisulphonic acid, and beta, naphthylamine alpha, beta, betas beta, tetrasulphonic
acid, by heating beta-naphthylamine-delta-disulphonic acid (beta-naphthylamine-
beta, beta, disulphonic acid), or beta-naphthylamine-alpha, beta, beta, trisulphonic
acid, or salts thereof, with sulphonating agents, until the beta-naphthylamine-
alpha, beta, beta, trisulphonic acid is no longer to be distinguished.
3. The separation of the beta, naphthylamine-beta-alpha, beta, trisulphonic acid,
beta-naphthylamine-beta, beta,-beta, trisulphonic acid, and beta,-naphthylamine
alpha, beta, beta, beta. tetrasulphonic acid, from the mixture obtainable as
described in the foregoing second claim, which separation can be effected by
utilising the different degrees of solubility of the sodium salts, or barium salts, of
the said three acids.
4. The separation of beta-naphthylamine beta, alpha, beta, trisulphonic acid,
and beta, naphthylamine-beta, beta, beta, trisulphonic acid, from the mixture
obtainable as described in the preceding second claim, which process can be effected
by pouring the said mixture into water, and boiling the liquid, in order to convert
beta-naphthylamine-alpha, beta, beta, beta, tetrasulphonic acid into beta, naphthyl-
amine-beta, beta, beta, trisulphonic acid, and by subsequently separating the beta-
naphthylamine-beta, alpha, beta, trisulphonic acid, and beta, naphthylamine-beta,
beta, beta trisulphonic acid, by utilising the different degrees of solubility of the
sodium or barium salts of these two acids.
5. The production of beta, naphthylamine alpha, beta, beta, beta, tetrasulphonic
acid, by heating beta, naphthylamine-beta, beta, beta, trisulphonic acid, or salts
thereof, with fuming sulphuric acid.
6. As new product of manufacture, the beta-naphthylamine-beta,-alpha, beta
trisulphonic acid, or salts thereof, produced by the processes hereinbefore described,
or by any other means affording the same result.
Dated this 11th day of June 1891
NEWTON & SON,
Agents for the Applicant.

page_text: Date of Application, 12th Sept., 1893
Complete Specification Left, 12th June, 1894-Accepted, 14th July, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany].
The Manufacture or Production of a₁-naphthylamine-ẞ₁ as ẞ,-trisulpho
Acid and of other Sulpho Acids Derived 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:-
My foreign correspondents have found, that the hitherto unknown ai-naphthyl-
amine-ß, as B-trisulpho acid of the composition :
can be obtained by treating the a, naphthylamine-a, B-disulpho acid (described in
the German Patent No. 69555) with sulphonating agents. The sulpho group is
taken up in the position ortho to the amido group (that is to say, in the position ẞ1),
which is obvious from the fact that the same a-naphthylamine trisulpho acid can
also be obtained by sulphonating the a,-naphthylamine B₁ a, disulpho acid (described
in the German Patent No. 56563).
The production of this new a-naphthylamine-ß, α, ẞ trisulpho acid is illustrated
11
TY
PRODUCTION OF
a1
NAPHTHYLAMINE ẞ₁ α, ẞ, TRI-SULPHO ACID.
4
50 parts of the acid sodium salt of a₁-naphthylamine-ẞ₁ as disulpho acid (described
in the German Patent No. 56563), or of a naphthylamine a ẞ disulpho acid
(described in the German Patent No. 69555) are introduced into 150 parts of
fuming sulphuric acid (containing 40 per cent. of anhydride). The resulting
mixture is then heated at from 120 to 130 degrees centigrade during about
10 hours. The sulphonated mass, which mostly becomes solid, is introduced into
ice water, and the liquid is saturated with lime-water. After filtering off the
precipitated calcium sulphate, the filtrate, which contains the calcium salt of the
formed a-naphthylamine trisulpho acid, is treated with sodium carbonate, in order
to convert the said calcium salt into the sodium salt, and the solution of the latter
in water is evaporated. The concentrated hot solution is then acidulated, and, on
cooling, the acid sodium salt is separated in crystals.
It is known that a₁ naphthylamine ẞ₁ a disulpho acid is prepared by sulphonating
1

page_text: α
naphthylamine ẞ₁ sulpho acid, for which reason this last named acid can also be
used in place of a, naphthylamine 8, a, disulpho acid employed in the above First
Example. The ai naphthylamine B₁ as ß, trisulpho acid can also be produced by
sulphonating acetyl-a₁ amido a, sulpho acid, which, under the influence of
sulphonating agents, is first converted into acetyl-a₁-naphthylamine as ẞ. disulpho
acid, as described in the German Patent No. 69555.
The sulphuric acid (containing 40 per cent. of anhydride) employed in the above
First Example can be replaced by fuming sulphuric acid containing more or less
anhydride. The quantities of sulphuric acid to be employed are merely varied
thereby. In place of fuming sulphuric acid. other agents acting in a similar manner
may be used (such as sulphuric chlorhydrine or the like.
The new a-naphthylamine B₁ as ẞ trisulpho acid possesses the following
properties Its salts are soluble with great readiness. The acid sodium salt forms
fine needles (aggregated in globular form and readily soluble), and can be salted
out from its solutions by means of common salt or muriatic acid. The acid barium
salt is obtained in fine white needles, which readily dissolve in hot water, but less
readily in cold water. The watery solutions of the acid and its salts shew a
beautiful green fluorescence. The diazo compound forms fine needles, which readily
dissolve, and can be salted out by means of common salt.
My foreign correspondents enumerate hereinafter the properties of the new acid
in comparison with those of the two known naphthylamine trisulpho acids.
The a-naphthylamine trisulpho acid described in the German Patent No. 22545
yields an acid sodium salt which forms bright white needles soluble with readiness.
The solutions of its salts exhibit a pure blue fluorescence, and the diazo derivative
of the acid is of a clear yellow colour, and dissolves with readiness. The acid
possesses the following formula :-
The a-naphthylamine trisulpho acid described in the German Patent No. 5605$
forms an acid sodium salt, which results in fine colourless needles, soluble with
readiness. The solutions of the salts of this acid shew a weak green fluorescence. 30
The diazo product of the acid is colourless, and soluble with readiness. The
composition of the acid is represented by the following formula :-
The new a
naphthylamine tri-sulpho acid, obtainable as described in the foregoing
First Example, yields an acid sodium salt which forms fine white needles (matted, 3
and aggregated in globular form), and is soluble with readiness.
The watery
solutions of the salts of this acid shew a green fluorescence, and the diazo derivative

page_text: of the acid results in clear yellow needles, which readily dissolve. The acid-
possesses the following formula :-
The last named new a-naphthylamine-ß₁ a, ẞ trisulpho acid can be profitably
employed for the production of dye stuffs and other new sulpho acids of the
naphthalene series. The researches of my foreign correspondents have shown,
that the said trisulpho acid can, by melting with alkalies, be converted into a new
valuable amido naphthol disulpho acid, the amido group undergoing no alteration.
This conversion is illustrated by the following example; the parts are by
weight
TRANSFORMATION OF a1 NAPHTHYLAMINE B₁ as B. TRISULPHO ACID INTO
a1 AMIDO as NAPHTHOL B₁ ẞ DISULPHO ACID.
100 parts of the acid sodium salt of the said a naphthylamine trisulpho acid, are
mixed with 100 parts of potassa and 100 parts of water. The resulting mixture is
heated in a closed vessel at from 180 to 200 degrees centigrade, until a sample of
the melting mass no longer shews an increase of amido naphthol disulpho acid, which
is distinguishable by the fact that the quantity of dye-stuff formed from the
amidonaphthol disulpho acid, and a diazo product, no longer increases. At this
stage, the whole mass is acidulated, the new amido naphthol disulpho acid being
thus precipitated in needles soluble with difficulty.
The new amido naphthol disulpho acid shews the following properties:-The
acid sodium salt is soluble in hot water with moderate facility, and dissolves in
cold water with greater difficulty; it crystallises in needles, and can be salted out
The neutral sodium salt
by adding common salt to watery solutions thereof.
The acid barium salt.
dissolves with great readiness, and cannot be salted out.
dissolves in cold water with difficulty, and in hot water with readiness. Watery
solutions of the salts of this amidonaphtholdisulpho acid shew a blue fluorescence.
The diazo derivative is soluble, and is separated as an orange red mass of crystals
by means of common salt. When the diazo product is added to alkalies, or solutions
of sodium carbonate, a beautiful azure colour results, but which is unstable, and turns
into orange. A solution of the acid sodium salt assumes a claret-red colour on the
addition of ferric chloride, whilst chloride of lime causes a yellow colour therein.
The aforesaid amido naphthol disulpho acid probably possesses the following
formula

page_text: This acid (owing to its property and composition) differs from all hitherto
known amido naphtholdisulpho acids, and can be profitably employed for the
production of dye-stuffs.
Dated this 17th day of October 1893.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Alpha Naphthylamine-beta
Alpha, Beta, Trisulpho Aoid and of other Sulpho Acids
Derived 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 :-
My foreign correspondents have found, that the hitherto unknown alpha,
naphthylamine-beta, alpha, beta, trisulphonic acid of the composition
can be obtained by heating alpha, naphthylamine-alpha, beta, disulphonic acid
(described in the German Patent No. 69555) with sulphonating agents. The
sulphonic group is introduced into the ortho position relatively to the amido group
(that is to say, in the position beta₁), which is obvious from the fact that the same
alpha-naphthylamine trisulphonic acid can be obtained by sulphonating alpha1
naphthylamine-beta, alphas disulphonic acid (described in the German Patent
No. 56563).
The production of this new alpha, naphthylamine-beta, alpha, beta, trisulphonic
acid is illustrated by the following example. The parts are by weight.
PRODUCTION OF ALPHA₁ NAPHTHYLAMINE BETA, ALPHA, BETA
TRISULPHONIC ACID.
50 parts of the acid sodium salt of alpha, naphthylamine beta, alpha3 disulphonic
acid (described in the German Patent No. 56,563), or of alpha naphthylamine
alpha, beta, disulphonic acid (described in the German Patent No. 69,555) are
introduced into 150 parts of fuming sulphuric acid containing 40 per cent. of
sulphuric anhydride. The mixture is then heated at from 120 to 130 degrees
centigrade during about 10 hours. The sulphonated mass, which usually becomes
solid, is introduced into ice-water, and the liquid is saturated with lime, the calcium
salt having been converted into the sodium salt, the solution is evaporated and
the concentrated hot solution is then acidulated. On cooling the liquid, the acid
sodium salt separates in crystals.

page_text: It is known that alpha, naphthylamine-beta, alpha, disulphonic acid is prepared
by sulphonating alpha, naphthylamine-beta, sulphonic acid, for which reason this
last-named acid can also be used in place of alpha, naphthylamine-beta, alpha,
disulphonic acid used in the foregoing Example A for producing alpha, naphthyl-
amine-beta, alpha, beta, trisulphonic acid. The latter acid can also be produced
by sulphonating acetyl alpha amido-naphthalene alpha, sulphonic acid, which,
when subjected to the influence of sulphonating agents, is first converted into acetyl-
alpha, naphthylamine alphas beta, disulphonic acid, as described in the German
Patent No. 69,555.
The sulphuric acid containing 40 per cent. of anhydride used in the preceding
Example A, can be replaced by fuming sulphuric acid containing more or less
anhydride. The quantities of sulphuric acid, and the temperature, are merely
varied thereby. In place of fuming sulphuric acid, other agents acting in a similar
manner may be used, such as sulphuric chlorhydrin or the like.
The new alpha, naphthylamine beta, alpha, beta, trisulphonic acid possesses the
following properties:-Its salts dissolve in water with great readiness. The acid
sodium salt forms fine needles, which aggregate in globular forms, and are readily
soluble; it can be salted out from its solutions by means of common salt or muriatic
acid. The acid barium salt is obtained in fine white needles, which readily dissolve
in hot water, but less readily in cold water. Solutions of the acid and its salts in
water shew a beautiful green fluorescence. The diazo compound of this trisulphonic
acid forms fine needles, which readily dissolve, and can be salted out by means of
common salt.
My foreign correspondents enumerate hereinafter the properties of the new acid
in comparison with those of the two naphthylamine trisulphonic acids known up to
the present time.
The alpha naphthylamine trisulphonic acid described in the German Patent
No. 22545, yields an acid sodium salt crystallizing in bright white needles, which
dissolve in water with readiness. Solutions of its salts exhibit a pure blue
fluorescence. Its diazo derivative is of a clear yellow colour, and dissolves in
water with readiness. This acid is represented by the formula :-
The alpha naphthylamine trisulphonic acid described in the German Patent
No. 56058, affords an acid sodium salt which crystallizes in fine colourless, readily
5 soluble needles. Solutions of the salts of this acid shew a weak green fluorescence.
The diazo derivative of the acid is colourless, and readily dissolves. The com-
position of the acid is represented by the following formula:-

page_text: The new alpha_naphthylamine trisulphonic acid obtainable as described in the
foregoing Example A, yields a readily soluble acid sodium salt, which crystallizes
in fine white needles, matted and aggregated in globular form. Solutions of the
salts of this acid shew a green fluorescence. Its diazo derivative forms clear
yellow needles, which readily dissolve in water. The acid is represented by the
following formula
The last-named new alpha, naphthylamine-beta, alpha, beta, trisulphonic acid
can be profitably used in producing dye-stuffs and other new sulphonic acids of the
'naphthalene series.
The researches of my foreign correspondents have shown that the said
trisulphonic acid can be converted into a new valuable amidonaphthol disulphonic
acid by the action of alkalies, the amido group undergoing no alteration. This
.conversion is illustrated by the following example. The parts are by weight.
TRANSFORMATION OF ALPHA₁ NAPHTHYLAMINE BETA, ALPHA BETA TRI-
SULPHONIC ACID INTO A NEW AMIDO NAPHTHOL DISULPHONIC ACID.
The
100 parts of the acid sodium salt of alpha, naphthylamine-beta, alpha, beta
trisulphonic acid are mixed with 100 parts of potash and 100 parts of water.
mixture is heated in a closed vessel capable of withstanding pressure at from
180 to 200 degrees centigrade, until the amount of amidonaphthol-disulphonic acid
reaches a maximum which is ascertained by noting the quantity of dyestuff
obtainable from a sample of the beated mixture and a diazo compound. At this
stage the whole mass is acidulated, the new amido naphthol di-sulphonic acid being
thus precipitated in difficultly soluble needles.
The potash used in the preceding Example B can be replaced by soda, or
mixtures of potash and soda. The fusion can also be carried out in open vessels ;
in the latter case a more concentrated alkali-lye, or solid alkali, can be used.
The new amido naphthol disulphonic acid has the following properties: The
acid sodium salt dissolves in hot water with moderate facility, but less readily in
cold water. It crystallizes in needles, and can be salted out by adding common
salt to watery solutions thereof. The neutral sodium salt dissolves with very great
readiness, and cannot be salted out. The acid barium salt dissolves in cold water
with difficulty, in hot water with less difficulty. Watery solutions of the salts of
this amidonaphthol disulphonic acid shew a blue fluorescence. The diazo derivative
is soluble, and is separated as an orange-red mass of crystals by means of common
salt. When the diazo derivative is added to alkalies, or solutions of sodium
carbonate, the liquid acquires a beautiful azure colour, which is very unstable,
turning into orange after a short time. A solution of the acid sodium salt assumes
a claret-red colour on the addition of ferric chloride, whilst chloride of lime causes
a yellow colour therein.

page_text: The aforesaid amidonaphthol di-sulphonic acid is probably represented by the-
following formula :-
:—
This acid differs in its properties and composition from all amidonaphthol
disulphonic acids hitherto known, and can be profitably used for the production of
dye-stuffs.
Having now particularly described and ascertained the nature of this inven-
tion and in what mauner the same is to be performed, as communicated to me from.
abroad, I declare that what I claim is :-
1. The process for producing alpha, naphthylamine-beta, alpha, beta, trisulphonic
acid, which process consists in treating alpha, naphthylamine beta, monosulphonic.
acid, alpha, naphthylamine beta, alpha, disulphonic acid, alpha, naphthylamine
alpha, beta, disulphonic acid, or aceto alpha, naphthylamine alpha, sulphonic acid,.
or salts thereof, at elevated temperatures, with fuming sulphuric acid, or other
sulphonating agents acting in the same manner.
2. The production of a new amidonaphthol disulphonic acid (which is probably
alpha, amido alpha, naphthol beta, beta, disulphonic acid), by melting with alkalies
at elevated temperatures the alpha, naphthylamine-beta, alpha, beta, trisulphonic
acid, or salts thereof.
3. As new products of manufacture :-
a) alpha, naphthylamine-beta, alpha, beta, trisulphonic acid;
6) the new amidonaphthol disulphonic acid (probably alpha, amido alpha,:
naphthol beta, beta, disulphonic acid),
or salts thereof, produced by the processes hereinbefore defined, or by any other
means affording the same result.
Dated this 12th day of June 1894.
NEWTON & SON,
Agents for the Applicant..

page_text: Date of Application, 12th Sept., 1893
Complete Specification Left, 12th June, 1894-Accepted, 14th July, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Sulpho Acids Derived from
Naphthalene-a₁ ẞ₂ az (or as ß α) Trisulpho Acid, or analogous
Sulpho Acids.
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:-
It is described in the German Patents No. 56058 and 67563, that, on nitrating
naphthalene-a, ß, B-trisulpho acid, the nitro group replaces the hydrogen atom in
the position peri to the a-sulpho group, the nitro naphthalene a, ß, B, trisulpho
acid being thus formed.
My foreign correspondents have nitrated the naphthalene-a₁ ß, a: (or a, ẞ a)
trisulpho acid, and they have found that likewise a perinitro naphthalene
trisulpho acid is formed. It is obvious that the perinitro naphthalene trisulpho
acid thus formed could possess either of the following two formulæ, viz. :-
The researches of my foreign correspondents have now shown, that the former
formula belongs to the above nitro naphthalenetrisulpho acid derived from
naphthalene a, as trisulpho acid, for this nitro acid is, by reduction, converted
into a a-naphthylamintrisulpho acid, which by diazotisation and subsequently
boiling with diluted sulphuric acid, yields a naphthosultone disulpho acid, which is,
by melting with alkalies, transformed into a-naphtholtrisulpho acid. The latter
acid was found to be not identical with a-naphtholtrisulpho acid S (described in the
Specification of English Letters Patent No. 3397 of 1890, and obtainable by
sulphonating a-naphthol-&-disulpho acid of the German Patent No. 40571),
this a naphtholtrisulpho acid S possessing the following formula :

page_text: My foreign correspondents have proved that the a-naphtholtrisulpho acid S is of
the said composition, in the following way :-
a) The a-naphthol-&-disulpho acid possesses the formula (see Armstrong &
Wynne, Proceedings of the Chemical Society, 1890, page 126):-
b) The a-naphtholtrisulpho acid S does not possess the ability to combine with
diazo products; hence it follows, that the hydrogen atoms in the positions ortho
and para to the hydroxylic group are substituted.
c) When the sodium salt of the a-naphtholtrisulpho acid S is dissolved in
concentrated sulphuric acid, and this sulphuric solution, when cooled, is mixed
with the calculated quantity of nitric acid, the brilliant yellow described in the
German Patent No. 40571 is formed, which possesses the following formula :-
.
above mentioned composition.
α
If the nitronaphthalenetrisulpho acid obtained from naphthalene a₁₂ as-trisulpho
acid had the composition represented by the latter of the above two nitro formulæ,
the naphtholtrisulpho acid derived from this a-nitro-naphthalene-B₁ a, a, trisulpho
acid must be identical with a-naphthol trisulpho acid S. But this is not the case,.
and therefore the nitro trisulpho acid obtained from naphthalene a₁ B₂ as-trisulpho
acid possesses the former of the two nitro formula above given.
α
The production of the said a, nitro naphthalenetrisulpho acid, its conversion into
the corresponding naphthylaminetrisulpho acid, naphthosultone disulpho acid, and
naphtholtrisulpho acid, are illustrated by the following three examples, the parts
being by weight.
FIRST EXAMPLE.
MANUFACTURE OF a₁ NITRO α, ẞ₁ α. TRISULPHO ACID.
The naphthalene a ẞ, as trisulpho acid (or naphthalene as ẞs a trisulpho acid)
which is employed as initial product, is described in the German Patent No. 70296.
It can also be prepared more simply by heating naphthalene ai a, disulpho acid
with fuming sulphuric acid, according to the process described in the German
Patent No. 38281. For the latter purpose, 100 parts of the sodium salt of the
naphthalene disulpho acid, in a finely powdered state, are stirred into 300 parts of
fuming sulphuric acid (containing 20 per cent. of anhydride). The temperature
rises to from about 60 to 80 degrees centigrade during this operation. The mass is

page_text: then slowly heated to 130 degrees centigrade, whilst being well agitated.
Whilst the disulphonate of sodium employed is not dissolved by the sulphuric acid
at temperatures lower than 125 to 130 degrees, this dissolution suddenly takes place
at the said temperature, and the disulpho acid is then converted into naphtha-
lene a₁
B, as trisulpho acid. It is characteristic of the latter acid, that, on diluting
a sample of the sulphonated mass with water, and saturating with common salt,
no crystallization of the naphthalene a a-disulphonate of sodium readily
distinguishable takes place.
The sulphonated mass is treated in the usual manner with lime water, sodium
carbonate, and the like, in order to prepare the trisulphonate of sodium, the solution
of which is finally evaporated to dryness. However, it is not necessary to isolate
the so formed naphthalene trisulpho acid, but the solution thereof may be directly
employed for the manufacture of the a-nitronaphthalene trisulpho acid. For this
purpose, the sulphonated mass is mixed with such a quantity of ice, that the
resulting liquid, at 15 degrees centigrade, shows a specific gravity corresponding to
from 63 to 66 degrees Baumé. The liquid is then cooled down to 5 degrees
centigrade, and whilst it is well stirred, the calculated quantity of nitric acid
(viz., 1 molecular proportion of nitric acid for 1 molecular proportion of naphthalene
disulpho acid employed), mixed with concentrated sulphuric acid, is allowed to flow,
at from 5 to 10 degrees centigrade, into the said liquid. After pouring into water,
the liquid is neutralised by means of slaked lime. The precipitated calcium sulphate
is filtered off, and sodium carbonate is added, in order to precipitate the calcium.
After filtering off the calcium carbonate, the filtrate is concentrated by evaporation.
At a certain degree of concentration, the sodium salt of nitronaphthalenetrisulpho
acid separates in a crystalline state. This sodium salt readily dissolves in water.
PRODUCTION OF a₁ NAPHTHYLAMINE a2 ẞs as TRISULPHO ACID.
In order to produce this amido acid, it is not necessary to isolate previously the
above nitro acid. The solution of the calcium salt of the nitro acid, obtainable as
described in the foregoing First Example, can be employed practically, after diluting
the same with water. The reduction is effected in the usual manner, for instance,
with iron in moderately acid solution. The liquid resulting after reduction is
rendered alkaline again by means of lime water; the precipitate is filtered off, and
the filtrate is evaporated. After acidulating, the acid salt of the amidosulpho acid
separates in needles from the concentrated solution. It dissolves in water very
readily. Its alkaline solutions show an intense green fluorescence. If it is distilled
with slaked lime, a-naphthylamine is formed. The diazo compound derived from
this a-naphthylaminetrisulpho acid is soluble with readiness.
CONVERSION OF α-NAPHTHYLAMINE a, ẞ, a-TRISULPHO ACID INTO α₁ а-NAPH-
THOSULTONE-a2 ß,-DISULPHO ACID AND α-NAPHTHOL-a, ẞ, a.-TRISULPHO
ACID.
42-6 parts of the acid a, naphthylamine a, ẞ, a-trisulphonate of sodium are
dissolved in 150 parts of water. After adding 15 parts of sulphuric acid (at
60 degrees Baumé), the naphthylaminetrisulpho acid is diazotised by introducing a
solution prepared by dissolving parts of sodium nitrite in 35 parts of water.
The liquid is slowly heated, and finally boiled, until the disengagement of nitrogen
ceases. The naphthosultone disulpho acid is in the resulting solution. As it
cannot be readily isolated, it is transformed, in the well known manner, into the
sodium salt of naphtholtrisulpho acid, the solution of which is evaporated to
dryness.

page_text: The new naphtholtrisulpho acid, when combined with diazo compounds, yields
azo dye stuffs.
My foreign correspondents have prepared a new a₁ amido-a-naphthol-a, ß,-disulpho
anid of the formula
by nitrating naphthalene-a, ẞ, a-trisulpho acid, reducing the so-formed nitro
product, and melting with alkalies the a-naphthylamine trisulpho acid thus
obtained. They have ascertained this formula in the following manner:-On
nitrating the said naphthalene-a, ß, as-trisulpho acid, two a-nitrotrisulpho acids
would result is
a
A nitro acid of the latter of these two formulæ (when reduced, diazotised, and
boiled with diluted acids) yields, as above mentioned, a naphthol-ẞ₁ α, a-trisulpho
acid (so-called a-naphtholtrisulpho acid S., and obtainable by sulphonating
a-naphthol a, a-disulpho acid). The naphtholtrisulpho acid resulting from the
aforesaid naphthalene-a, ẞ, a trisulpho acid, is found not to be identical with
naphtholtrisulpho acid S. Hence it follows, that the nitro acid obtained from
naphthalene-a ẞ2 a, trisulpho acid possesses the former of the two formulæ
amido-
above given, and the amido acid derived therefrom must be an αι
naphthalene-a, ß, a-trisulpho acid. The latter acid is, by melting with alkalies,
converted into a amido-a-naphthol-a, ẞ, disulpho acid, which follows from the
fact stated by my foreign correspondents, that this amidonaphtholdisulpho acid, by
heating with diluted alkalies, is transformed into a₁ a-dihydroxynaphthalene-
disulpho acid, ammonia being disengaged in this process.
The following example is given in order to illustrate the production of this new
amidonaphtholdisulpho acid.
FOURTH EXAMPLE.
PRODUCTION OF α-AMIDO-a-NAPHTHOL-a, ẞ, DISULPHO ACID.
200 parts of a-naphthylamine-a, ẞ, a-trisulphonate of sodium are mixed with
300 parts of soda and 120 parts of water. The resulting mixture is heated in a
closed vessel at from 170 to 175 degrees centigrade, until a sample dissolved in
water shows a bluish-violet fluorescence, and an increase in the formation of the dye,
in alkaline or acetic solution, with diazo compounds, no longer distinguishable.
After cooling, the mass is acidulated by means of muriatic acid. The amido-
naphtholdisulpho acid gradually separates in fine long needles, which represent the
acid sodium salt. When filtered off, they can be directly employed for producing
dye stuffs.

page_text: The above melting process can also be effected in open vessels.
The new amidonaphtholdisulpho acid can be employed for the production of
dye-stuffs.
The researches of my foreign correspondents have also shown that a new
dihydroxynaphthalene sulpho acid, which corresponds to the last named amido-
naphtholdisulpho acid, can be obtained by nitrating naphthalene-a, ẞ, a-trisulpho
acid, reducing the resulting nitro product, diazotising the so-formed amidotrisulpho
acid, boiling the diazo derivative with dilute acids, and subsequently melting
with alkalies. The dihydroxynaphthalene disulpho acid possesses the following
formula
The last mentioned composition is obvious from the following:-On nitrating
naphthalene-a ẞ, a, trisulpho acid, two mononitronaphthalenetrisulpho acids would
be formed, which would further yield the following naphtholsulpho acids, viz. :-
PRODUCTION OF α, a DIHYDROXYNAPHTHALENE a, ẞ, DISULPHO ACID FROM
a NAPHTHOL a, ẞ, u-TRISULPHO ACID.
200 parts of the sodium salt of a₁-naphthol a, ẞs a-trisulpho acid, are mixed with
300 parts of soda and 120 parts of water. The resulting mixture is heated in a
closed vessel, at from 170 to 180 degrees centigrade, until a test portion taken out
exhibits a bluish-green fluorescence characteristic of the new dihydroxynaphtha-
lene disulpho acid, and the formation of dye no longer proceeds on allowing diazo
derivatives to act on the sample in solutions acidulated by means of acetic acid.
After cooling, the mass is moderately acidulated by means of muriatic acid. The
sodium salt of the thus formed dihydroxynaphthalene disulpho acid separates after
some time from the concentrated solution in fine needles.

page_text: Of course, the a-naphtholtrisulpho acid employed in the preceding. Fifth Example
can be replaced by the corresponding naphthosultone disulpho acid, and the melting
process can also be carried out in open vessels.
This new dihydroxynaphthalene disulpho acid, when combined with diazo
products, yields dye-stuffs which produce shades possessing a clearness and.brightness
at least equal to that produced by the corresponding coloring matters derived: from
a a dihydroxynaphthalene B2 B3. disulpho acid. The new coloring. matters also
are distinguishable by their property of yielding extremely even shades.
The production of the last named as a dihydroxyuaphthalene B, ẞ, disulpho
acid, by melting with alkalies a₁-naphthol B, ẞ, a, trisulpho acid, or the correspond-
ing sultone, at from 170 to 250 degrees centigrade, is described in the German
Patent No. 67563. It is not mentioned in the Specification of this Patent in what
manner the melting process proceeds at higher temperatures, and how the first-
formed a a-dihydroxynaphthalene B, B, disulpho acid is further altered. It could
not at all be foreseen whether a trihydroxynaphthalene monosulpho acid would
result, or if, in accordance with the action of alkalies on ẞ-naphtholdisulpho acid R
and dihydroxynaphthalene mono sulpho acid R (as described in the German Patent
No. 57525), trihydroxynaphthalene or dihydroxynaphthalene mono sulpho acid,
or dihydroxynaphthalene, would be formed, sulpho groups being separated in
:this case.
My foreign correspondents have found that melting alkalies act in another
manner on the above a₁ a dihydroxynaphthalene B, ẞ, disulpho acid than is the
case when dihydroxynaphthalene monosulpho acid is employed, and that tri-
hydroxynaphthalene mono sulpho is exclusively formed, whilst sulpho groups are
not separated.
Of course the production of this new trihydroxynaphthalene mono sulpho acid,
can be effected by heating a₁ naphthol ẞ, ẞs a trisulpho acid, or the corresponding
sultone, with alkalies, at temperatures rising above 250 degrees centigrade.
The following example is given, in order to illustrate the production of the said
trihydroxynaphthalene monosulpho acid, the parts being by weight:-
SIXTH EXAMPLE.
CONVERSION OF a NAPHTHOL-ẞ, ẞз α, TRISULPHO ACID, INTO TRIHYDROXY-
NAPHTHALENE MONOSULPHO ACID.
A mixture of 1 part of a₁ naphthol B, ẞ, atrisulphonate of potassium, and
2 parts of potash, is heated at from 310 to 320 degrees centigrade, until dihydroxy-
naphthalene disulpho acid no longer separates, on acidulating samples of the melted
mass with muriatic acid. When this stage is arrived at, the whole mass is then
dissolved in dilute muriatic acid, and the solution thus obtained is allowed to stand.
The acid potassium salt of the formed trihydroxynaphthalene monosulpho acid
separates slowly in fine white needles.
Of course the melting process also can be carried out in closed vessels under
pressure.
The so-formed acid potassium salt readily dissolves in pure water.
Its watery
.solutions assume a dull color, on the addition of ferric chloride, whilst chloride of
lime produces therein a yellowish brown color, which slowly disappears on adding
an excess of chloride of lime.
The neutral salts of the trihydroxynaphthalene sulpho acid readily dissolve in
water, and the resulting water solutions show a greenish-blue fluorescence.
The new trihydroxyuaphthalene monosulpho acid can be employed for the
production of coloring matters.
Dated this 17th day of October 1893.
NEWTON & SON,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
The Manufacture. or Production of Sulpho Acids Derived from:
Naphthalene α1 Bas (or as ẞ3 a₁) Trisulpho Acid, or analogous.
Sulpho Acids.
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 :-
It is stated in the German Patents Nos. 56058 and 67563, that on nitrating
naphthalene alpha, beta, beta, trisulphonic acid, the nitro group displaces the
hydrogen atom in the "peri" position relatively to the alpha, sulphonic group, a
perinitronaphthalenetrisulphonic acid, riz., the alpha, nitronaphthalene alpha,.
beta beta, trisulphonic acid being thus formed.
My foreign correspondents have nitrated naphthalene alpha₁ beta, alpha,.
trisulphonic acid, and have found that again, in this case, a perinitronaphthalene-
trisulphonic acid is formed. It is obvious that the perinitronaphthalenetrisulphonic
acid thus formed could have either of the following two formulæ, viz. :—
My foreign correspondents have ascertained that the aforesaid alphanaphthol--
trisulphonic acid S has the formula mentioned as is hereinafter described :-
a) The alpha naphthol delta disulphonic acid possesses, according to Armstrong &

page_text: b) The alphanaphtholtrisulphonic acid S. does not possess the ability to combine
with diazo products; hence it follows that the hydrogen atoms in the relative 5
positions "ortho" and " ' para to the hydroxylic group are substituted.
"
c) When the sodium salt of the alphanaphtholtrisulphonic acid S is dissolved in
concentrated sulphuric acid, and this sulphuric solution, after being cooled, is
mixed with the calculated quantity of nitric acid, the “brilliant yellow" described
in the German Patent No. 40571 is formed, which possesses the following 1
From the preceding points a, b, and c, it follows that alphanaphtholtrisulphonic
acid S is of the above mentioned composition.
If the nitronaphthalenetrisulphonic acid obtainable from naphthalene alpha,
beta, alpha,, or alpha, beta, alpha, trisulphonic acid, had the composition represented
by the latter of the above two nitro formulæ, the naphtholtrisulphonic acid derived
from this alpha, nitro naphthalene beta, alpha, alpha, trisulphonic acid must be
identical with alphanaphtholtrisulphonic acid S. But this is not the case, and
therefore the nitrotrisulphonic acid obtained from naphthalene alpha, beta, alpha,
trisulphonic acid, or naphthalene alpha, beta, alpha, trisulphonic acid possesses the
former of the two nitro formulæ above given.
The production of the said alpha, nitro naphthalenetrisulphonic acid, its
conversion into the corresponding naphthylaminetrisulphonic acid, and the production
of the corresponding naphthosultone disulphonic acid and naphtholtrisulphonic
acid, are illustrated by the following Examples A, B, and C, the parts being by
weight.
MANUFACTURE OF ALPHA1
NITRONAPHTHALENE
TRISULPHONIC ACID.
ALPHA, BETA, ALPHA
The naphthalene alpha, beta, alpha; trisulphonic acid which is used as initial
product, is described in the German Patent No. 70296. It can also be prepared
in a simpler manner, by heating naphthalene alpha, alpha, disulphonic acid with
fuming sulphuric acid, according to the process described in the German Patent
No. 38281. For the latter purpose, 100 parts of the sodium salt of the naphthalene
alpha, alpha, disulphonic acid in a finely powdered state are stirred into 300 parts

page_text: of fuming sulphuric acid containing 20 per cent. of anhydride. The temperature
rises to from about 60 to 80 degrees centigrade during this operation. The mass is
then slowly heated to 130 degrees centigrade, and well agitated the while. The
disulphonate does not dissolve in the sulphuric acid at temperatures lower than
125 to 130 degrees, but suddenly dissolves at the said temperature, viz., 130 degrees
centigrade, and is then converted into naphthalene alpha, beta, alpha, trisulphonic
acid. It is characteristic of the latter acid that, on diluting a sample of the
sulphonated mass with water, and saturating with common salt, no crystallisation
of the naphthalene alpha, alpha, disulphonate of sodium, which would be readily
distinguishable, takes place.
The sulphonated mass may be treated in the usual manner with milk of lime, &c.,
and the solution of the sodium salt of the naphthalene alpha, beta, alpha, tri-
sulphonic acid may be evaporated to dryness. However, it is not necessary to
isolate the trisulphonic acid, but the solution thereof may be directly used for the
manufacture of the nitro trisulphonic acid.
For this purpose, the sulphonated mass is mixed with such a quantity of ice that the
liquid has a specific gravity corresponding to from 63 to 66 degrees Baumé at 15 degrees
centigrade. The liquid having been cooled down to 5 degrees centigrade, the
calculated quantity of nitric acid (viz., 1 molecular proportion of nitric acid for
1 molecular proportion of the naphthalenedisulphonic acid used), mixed with con-
centrated sulphuric acid, is stirred into it at from 5 to 10 degrees centigrade. It
is then poured into water, and the liquid is neutralised with slaked lime; the
precipitated calcium sulphate is filtered off, and sodium carbonate is added to the
filtrate the calcium carbonate having been separated, the filtrate is concentrated
by evaporation. At a certain degree of concentration, the sodium salt of a₁ nitro-
naphthalene alpha, beta, alpha, trisulphonic acid separates out in a crystalline state.
This sodium salt readily dissolves in water.
PRODUCTION OF ALPHA₁ NAPHTHYLAMINE ALPHA, BETA, ALPHA
TRISULPHONIC ACID.
In order to produce this amido acid, it is not necessary to previously isolate the
last-named nitrotrisulphonic acid. The solution of the calcium salt of this alpha,
nitronaphthalene alpha, beta, alpha, trisulphonic acid, obtainable as described in
the foregoing Example A, can be used, after diluting it with water. The reduction
is effected in the usual manner, for instance, with iron in moderately acidulated
solution. When reduction is complete, the liquid is rendered alkaline by means of
lime, the precipitate is filtered off, and the filtrate is evaporated. On acidulating
the concentrated solution, the acid calcium salt of the amido naphthalenetri-
sulphonic acid separates in needles. The acid calcium salt of alpha, naphthyl-
amine alpha, beta, alpha, trisulphonic acid dissolves in water very readily. The
alkaline solutions of the acid show an intense green fluorescence. If it is distilled
with slaked lime, alpha-naphthylamine is formed. The diazo compound derived
from this alpha naphthylaminetrisulphonic is readily soluble.
45 CONVERSION OF ALPHA, NAPHTHYLAMINE ALPHA, BETA, ALPHA, TRISULPHONIC
ACID, INTO ALPHA ALPHA NAPHTHOSULTONE ALPHA, BETA, DISULPHONIC
ACID AND ALPHA, NAPHTHOL ALPHA, BETA, ALPHA TRISULPHONIC ACID.
42-6 parts of the acid sodium salt of alpha, naphthylamine alpha, beta, alpha
trisulphonic acid are dissolved in 150 parts of water. After adding 15 parts of
50) sulphuric acid (at 60 degrees Baumé), the naphthylaminetrisulphonic acid' is
diazotised by introducing a solution prepared by dissolving 7 parts of sodium
B

page_text: nitrite in 35 parts of water. The diazo compound which separates in white needles
on saturating the liquid with common salt, is filtered off, and then stirred into
150 litres (in case the parts are kilos. by weight) of sulphuric acid (containing
50 per cent. of pure acid). The liquid mixture is heated nearly to the boiling
point, until the diazo compound is no longer distinguishable. On allowing the
fiquid thus obtained to stand for some time at a low temperature, fine needles
separate consisting of the sodium salt of alpha, alpha, naphthosultone alpha, beta 3
disulphonic acid. This sodium salt dissolves with great readiness.
If the naphthosultone disulphonic acid, or its salts, are treated with alkaline
hydroxides or carbonates, the corresponding alpha, naphthol alpha, beta, alpha.
trisulphonic acid is obtained, which can easily be combined with diazo compounds
to form dye-stuffs.
My foreign correspondents have prepared a new alpha, amido alpha, naphthol
alpha, betas disulphonic acid of the formula :-
The composition above given for the said amidonaphtholdisulphonic acid, is
obvious from the fact that, according to the reasearches of my foreign corre-
spondents, the said amidonaphtholdisulphonic acid is converted, by heating it with
diluted alkalies, into an alpha, alpha, dihydro-oxynaphthalene disulphonic acid,
ammonia being disengaged during this process.
The following example is given, in order to illustrate the production of this
new amidonaphthol disulphonic acid. The parts are by weight.
PRODUCTION OF ALPHA₁ AMIDO-ALPHA NAPHTHOL ALPHA, BETA;
DISULPHONIC ACID.
200 parts of alpha, naphthylamine alpha, beta, alpha, trisulphonate of sodium,
are mixed with 300 parts of caustic soda and 120 parts of water. The mixture
is heated in a closed vessel capable of withstanding pressure at from 170
to 175 degrees centigrade, until a sample dissolved in water shews a blue
fluorescence, and no further increase is observed in the amount of dye formed on
mixing it in alkaline or acetic solution with diazo compounds.
When the cooled mass is acidulated with muriatic acid, long fine needles of the
acid sodium salt of alpha, amido alpha, naphthol alpha, beta, disulphonic acid
gradually separate.
The fusion process can also be effected in open vessels, and the temperature can
vary within from about 150 to 220 degrees centigrade.
This amidonaphtholdisulphonic acid possesses the following properties. The
acid sodium salt forms long fine needles, which dissolve with readiness even in cold
water. Solutions of its acid salts shew a bluish-violet fluorescence which turns
into greenish blue on the addition of alkalies. When treated with nitrous acid,
the acid, or salts thereof, are converted into a very soluble diazo compound,
which can be salted out by means of common salt in fine yellow needles; these

page_text: assume a dull bluish-violet colour when brought into contact with a solution of
sodium carbonate.
The new amidonaphthol disulphonic acid can be used for the production of
dye-stuffs.
The researches of my foreign correspondents have further shown, that a new
alpha, alpha, dihydroxynaphthalene disulphonic acid can be obtained by diazotising
the aforesaid alpha, naphthylamine alpha, beta, alpha, trisulphonic acid, boiling
the diazo derivative with diluted acids, and subsequently fusing the alpha,
naphtholtrisulphonic acid, which thus forms, with alkalies.
The dihydroxynaphthalene disulpho acid thus produced is represented by the
following formula :-
PRODUCTION OF ALPHA ALPHA, DIHYDROXYNAPHTHALENE ALPHA, BETA,
DISULPHONIC ACID, FROM ALPHA, NAPHTHOL-ALPHA, BETA ALPHA
TRISULPHONIC ACID.
At
200 parts of the sodium salt of alpha, naphthol alpha, beta, alpha, trisulphonic
The mixture is
acid are mixed with 300 parts of soda and 120 parts of water.
heated in a closed vessel capable of withstanding pressure, at from 170 to
180 degrees centigrade, until a test portion no longer affords an increased amount
of azo dye, when acted on by diazo derivatives in presence of acetic acid.
this stage, the mass is cooled, and then moderately acidulated with muriatic acid.
The sodium salt of the alpha, alpha, dihydroxynaphthalene alpha, beta, disulphonic
acid thus formed, separates after some time from the concentrated solution in fine
needles.
According to the researches of my foreign correspondents, the alpha naphthol-
trisulphonic acid used in the preceding Example can be replaced by the equivalent
quantity of the corresponding alpha, alpha, naphthosultone-alpha, beta, disulphonic
acid, and the fusion can also be carried out in open vessels.
The new alpha, alpha dihydroxynaphthalene alpha, beta, disulphonic acid
possesses the following properties. Its alkaline salts dissolve with readiness.
The disodium salt crystallises in fine needles from saturated solutions of common
When the acid or
salt. The alkaline solutions shew a weak blue fluorescence.
its salts are treated with nitrous acid, a nitroso compound is formed which
possesses an intense yellow colour, and can be salted out in fine yellow needles
from its solutions, by means of common salt. When combined with diazo products,
the acid or its salts yield dye-stuffs which produce shades distinguished by their
clearness and brightness. The new colouring matters also possess the valuable
property of yielding extremely even shades.
The new alpha, alpha, dihydroxynaphthalene alpha, beta, disulphonic acid differs
from the isomeric alpha, alpha, dihydroxynaphthalene beta, beta, disulphonic acid.

page_text: The production of the last-named alpha, alpha, dihydroxynaphthalene beta,
beta, disulphonic acid, by fusing alpha, naphthol beta, beta, alpha, trisulphonic
acid, or the corresponding sultone, with alkalies, at from 170 to 250 degrees
centigrade, is described in the German Patent No. 67563. It is not mentioned in
this Patent in what manner the melting process proceeds at higher temperatures,
and how the alpha, alpha, dihydroxynaphthalene beta, beta, disulphonic acid which
is first formed, is further altered.
My foreign correspondents have now found that fused alkalies act on the
aforesaid alpha, alpha, dihydroxynaphthalene-beta, beta, disulphonic acid in such a
manner as to convert it exclusively into the trihydroxynaphthalene monosulphonic
acid represented by the following formula :-
Of course, the production of this new trihydroxynaphthalene monosulphonic acid
can also be effected by heating alpha, naphthol beta, beta, alpha, trisulphonic acid,
or the corresponding sultone, with alkalies at temperature rising above 250 degrees
centigrade.
The following example is given in order to illustrate the production of the
said trihydroxynaphthalene monosulphonic acid, the parts being by weight:
-
.
CONVERSION OF ALPHA, NAPHTHOL BETA BETA ALPHA TRISULPHONIC
ACID INTO ALPHA ALPHA BETA, HYDROXYNAPHTHALENE BETA; MONO-
SULPHONIC ACID.
A mixture prepared from 1 part of potassium alpha, naphthol beta, beta, alpha,
trisulphonate, and 2 parts of potash, is heated at from 310 to 320 degrees
centigrade, until dihydroxynaphthalene disulpho acid no longer separates on
acidulating samples of the melted mass with muriatic acid.
At this stage the whole mass is dissolved in diluted muriatic acid, and the solution
thus obtained is allowed to stand. The acid potassium salt of the alpha, alpha
beta, trihydroxynaphthalene betas monosulphonic acid very slowly separates in
fine white needles.
Of course the melting can also be carried out in closed vessels under pressure.
The acid potassium salt thus formed readily dissolves in pure water. Its
solutions assume a dull colour on the addition of ferric chloride, whilst chloride of
lime produces therein a yellowish-brown colour, which slowly disappears on adding
an excess of chloride of lime.
་
The neutral salts of the trihydroxynaphthalene monosulphonic acid very
readily dissolve in water, and the resulting watery solutions shew a greenish-blue
fluorescence.
The new trihydroxynaphthalene monosulphonic acid can be used for the
production of colouring matters.
Having now particularly described and ascertained the nature of this invention
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 alpha, nitronaphthalene alpha, beta, alpha trisulphonic

page_text: acid, by nitrating naphthalene alpha, beta, alpha, trisulphonic acid or salts.
thereof.
2. The process for producing alpha, naphthylamine alpha, beta, alpha, tri-
sulphonic acid, which process consists in reducing alpha, nitro alpha, betas.
alpha, trisulphonic acid or salts thereof.
3. The conversion of alpha, naphthylamine alpha, beta, alpha trisulphonic acid,
into alpha, alpha, naphthosultone alpha, beta, disulphonic acid, by diazotising
alpha, naphthylamine alpha, beta, alpha, trisulphonic acid, or salts thereof, and
heating the diazo product with water or dilute acids.
4. The production of alpha, naphthol alpha, heta, alpha, trisulphonic acid, by
heating alpha alpha, naphthosultone alpha, betas disulphonic acid, or salts
thereof, with alkalies.
5. The process for producing alpha, amido alpha, naphthol alpha, betas.
disulphonic acid, by fusing alpha, naphthylamine alpha, beta, alpha, trisulphonic
acid, or salts thereof, with alkalies, at temperatures varying from about 150 to 220
degrees centigrade.
6. The production of alpha, alpha, dihydroxynaphthalene alpha, beta, disulphonic
acid, by fusing alpha, naphthol alpha, beta, alpha, trisulphonic acid, or alpha,
alpha, naphthosultone alpha, beta, disulphonic acid, or salts thereof, with alkalies,.
at temperatures varying from about 150 to 250 degrees centigrade.
7. The process for producing alpha, alpha, beta, trihydroxynaphthalene beta..
monosulphonic acid, which process consists in heating alpha naphthol beta,.
beta, alpha, trisulphonic acid, alpha, alpha, naphthosultone beta, beta, disulphonic
acid, alpha alpha, dihydroxynaphthalene beta, beta, disulphonic acid, or salts.
thereof, with alkalies, at temperatures above 250 degrees centigrade.
8. As new products of manufacture:
a) alpha, nitronaphthalene alpha, beta, alpha, trisulpbonic acid;
b) alpha, naphthylamine alpha, beta, alpha, trisulphonic acid;
c) alpha, alpha, naphthosultone alpha, beta, disulphonic acid
d) alpha, naphthol alpha, beta, alpha, trisulphonic acid;
;
e) alpha, amido alpha, naphthol alpha, beta, disulphonic acid;
f) alpha, alpha, dihydroxynaphthalene alpha, beta, disulphonic acid;
9) alpha, alpha, beta, trihydroxynaphthalene-betas monosulphonic acid;
or salts thereof, produced by the processes hereinbefore defined, or by any other
means affording the same result.
T
1001