Improvements in the Production of Naphtholtrisulphonic Acid, Naphtholtrisulphonic Monamide Dioxynaphthalindisulphonic Acid, and the Colouring Matters Derived therefrom.
Year: 1890

page_text: Date of Application, 14th June, 1890
Complete Specification Left, 13th Mar., 1891-Accepted, 18th Apr., 1891
Communicated from abroad by Dr. HERMANN KOCH, Marburg, in the German
Empire.]
Improvements in the Production of Naphtholtrisulphonic Acid,
Naphtholtrisulphonic Monamide Dioxynaphthalindisulphonic
Acid, and the Colouring Matters Derived therefrom.
I, OLIVER IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Fellow of the Institute of Patent Agents, do hereby declare
the nature of this invention to be as follows :-
According to the present invention, there is produced, by nitration, from
naphthalintrisulphonic acid, which is obtained by sulphonisation of naphthalin, a
nitronaphthalintrisulphonic acid, which, by reduction, furnishes a novel naphthyl-
aminetrisulphonic acid. This acid can be converted by treatment with nitrous
acid and subsequent boiling with acidulated water into a naphthsultondisulphonic
acid, that is to say, a novel naphtholtrisulphonic acid.
For the nitration of the naphthalintrisulphonic acid my foreign correspondent
proceeds for example as follows:
The naphthalintrisulphonate of sodium is dissolved in the quadruple quantity of
concentrated sulphuric acid; to this solution (or to the product of sulphonisation
obtained directly from naphthalin and fuming sulphuric acid) is added by degrees
the necessary quantity of concentrated nitric acid, and then, in order to complete
the reaction, the whole is heated on a water-bath."
The product thus obtained is diluted with water and there is then added, while
heating, the necessary quantity of iron chips. After the reduction is completed
it is sursaturated with lime and the liquid filtered off from the gypsum is
evaporated.
The novel naphthylamintrisulphonic acid is distinguished from the two isomers
before produced, by not showing any fluorescence in alkaline solution and by
forming a non-colored diazo compound, whereas the diazo compounds of its two
isomeric acids are colored vellow.
The best way of producing the novel naphtholtrisulphonic acid is in the form
of its sodium salt by sursaturating largely the solution of the sodium salt of the
new naphthylamintrisulphonic acid with sulphuric acid, adding the necessary
quantity of nitrite, boiling until the development of nitrogen ceases, then sur-
saturating with lime until alkaline reaction, filtering off, adding soda, filtering
again and evaporating the filtrate on cooling down the salt, will separate from
the concentrated solution in the form of small needles.
If however after the decomposition of the diazo compound the not too largely
diluted liquid, not sursaturated with a base (lime) but still acid, is left to repose,.
there will crystallise out after some time the neutral sodium salt of the naphtsulton-
disulphonic-neil C
(SO,Na).
This salt is in form of small needles, united to bases and does not show any
fluorescence in aqueous solution. Treated with concentrated ammonia it is con-
ZOU

page_text: This novel naphtsultondisulphonic acid on treatment with hot diluted alkalies or
acids, furnishes the novel naphtholtrisulphonic not heretofore known.
If the said naphtsultondisulphonic acid or one of its salts is treated with
ammonia, there is formed, as already stated, a salt of a novel naphtholtrisulphonic
monamide.
The process may be carried out for example, as follows: 100 parts of napht-
sultondisulphonate of sodium are mixed at ordinary temperature with from 200
to 300 parts of aqueous ammonia of 20 per cent.; a quarter of an hour afterwards
there will have formed a clear light-yellow colored solution and the neutral
ammonia sodium salt of the naphtholtrisulphonic monamide will be produced.
There may also be employed alcoholic ammonia or gaseous ammonia.
The neutral ammonia-sodium salt is precipitated from its solution by means of
alcohol in the form of a citrine powder and may be obtained in pure state by
repeated dissolving in water and precipitating by means of alcohol.
If its concentrated aqueous solution is acidulated with hydrochloric acid and
left to repose, there crystallises out after a short time the neutral sodium salt of
OH
the amide having the formlua C₁HSO,NH, in white moss-like formations.
(SO,Na)
The neutral sodium salt is of very easy solubility in water without coloring it
at all. A cold aqueous solution of the same is not colored by the addition of
ferric-chloride solution.
When however the solution is boiled, the ammonia escapes, yellow coloration
sets in and ferric chloride will now give it a blue tint, (reaction of the corre-
sponding naphtholtrisulphonic acid) a proof that by the boiling with water
naphtholtrisulphonic acid has been reformed while ammonia escaped. With alkali
the re-formation goes on rapidly and completely.
If the naphtholtrisulphonic acid mentioned above or its anhydride (the napht-
sultondisulphonic acid) under certain conditions is heated with caustic alkalies
until a sample dissolved in water shows a strong violet fluorescense, there will have
been formed a dioxynaphthalindisulphonic acid.
Example: 500 parts of solid caustic soda are melted in an open vessel with a
small quantity of water, heated to from 180° to 210° C. and then are added by
degrees 300 parts of naphtholtrisulphonate or naphtsultondisulphonate of sodium.
On the adding of such portion, foaming will set in; when the whole quantity of
the salt has been added, the mass is heated for a short time to from 220° to 250º C.,
after which the reaction will be complete.
If an autoclave with a stirrer is used, the melting can be proceeded with at
considerably lower temperatures, for example at from 160 to 190° C. and with a
considerably smaller quantity of caustic soda; for example, with from 150 to 300
parts, the duration of the operation varying in accordance herewith. For the
caustic soda may be substituted any other alkali.
After completion of the melting, the mass is dissolved in water as concentrated
as possible and strongly acidulated whereupon the acid sodium salt of dioxy-
naphthalindisulphonic acid will separate and may be obtained in the usual way.
The formed dioxynaphthalinedisulphonate of sodium after being liberated from the
sulphurous acid, may also be directly employed for further purposes.
The dioxynaphthalindisulphonates are of easy solubility in water, showing
violet fluorescence. As characteristic reactions may be named: the vivid yellow-
green coloration produced by ferric chloride and the orange red coloration produced
by a small quantity of a chloride of calcium solution in its neutral aqueous
solutions. If a larger quantity of the chloride of calcium is added the coloration
will be less and after some time it will disappear completely.
The above mentioned novel sulphonic acids namely the naphtholtrisulphonic acid,
the naphtholtrisulphonic monamide and the dioxynaphthalindisulphonic acid,
submitted to the action of diazo compounds in alkaline, neutral or slightly acid

page_text: solution, furnish azo coloring-matters of great value, with the diazo compounds,
obtained by diazotising:
aniline
amido azonaphthalintrisulphonic acid.
Novel coloring matters dyeing wool blue-black shades are obtained by the
action of the diazo azo compounds prepared by coupling diazo sulphonic acids
with a
naphthylamine and subsequent diazotation, upon the dioxynaphthalindi-
sulphonic acid described above in alkaline or acetic solution.
acid.
Example. Coloring matter from diazonaphthalinazobenzolsulphonic
195 parts by weight of sulphanilate of sodium are dissolved in about 250 parts
by weights of water and thereto are added 25 parts by weight of hydrochloric acid
of 30 per cent, and a solution of 7 parts by weight of nitrite of sodium.
After the diazotising is completed, there is caused to flow under continued
stirring to the cooled diazo compound a hot solution of 18 parts by weight of
hydrochlorate of alpha-naphthylamine in 450 parts by weight of water.
The temperature will rise to from 20 to 30° C. and it is kept at this height for
24 hours. The condensation product will form at once and is purified by dissolving
in soda lye and precipitating by means of hydrochloric acid.
It is cooled down to 0° °C. and there is then added a solution of 7 parts by
weight of nitrite of sodium. The diazo compound formed is caused to act upon

page_text: an alkaline solution or a solution to which some acetate of sodium has bee
added, consisting of 37 parts by weight of dioxynaphthalindisulphonate of sodium
in 300 parts by weight of water.
The coloring matter thus produced, precipitates from the liquid in the form o
a dark powder dissolving in water with deep blue colour and dyeing wool directly
in an acid bath deep blue to blue-black shades, and wool, mordanted with chromi
oxide, blue shades with strong green tint.
For the quantity of sulphanilate of sodium named in the example may be sub
stituted the equivalent quantity of some other amidosulphonic acid.
In accordance with the components chosen, the shades to be obtained and the
degree of solubility of the products vary if for example the alpha-naphthyl
amin disulphonic-acid (Dall) has been used, the shade will be considerably blue
or the tint with chromic oxide will be more greenish.
Of the amido sulphonic acids may be used:
sulphanilic acid,
metanilic acid,
o-toluidine sulphonic acid,
p-toluidine sulphonic acid,
xylidine sulphonic acid,
amidophenolsulphonic acid,
amilocresolsulphonic acid,
naphthylamine sulphonic acid I,
ẞ naphthylamine sulphonic acid III,
a naphthylamine disulphonic acid (Dahl),
B naphthylamine disulphonic acid Y,
ẞ naphthylamine disulphonic acid R,
ẞ naphthylamine trisulphonic acid,
naphthylamine trisulphonic acid,
Bnaphthylamine a disulphonic acid (Freund),
ẞ napthylamine ẞ disulphonic acid (Freund).
Dated this 14th day of June 1890.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Naphtholtrisulphonic Acid,
Naphtholtrisulphonic Monamide Dioxynaphthalindisulphonić
Acid, and the Colouring Matters Derived therefrom.
I, OLIVER IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Fellow of the Institute of Patent Agents, 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 :-
According to the present invention, there is produced, by nitration, from
naphthalintrisulphonic acid, which is obtained by sulphonisation of naphthalin a
nitronaphthalintrisulphonic acid, which, by reduction, furnishes a novel naphthyl-
aminetrisulphonic acid. This acid can be converted by treatment with nitrous
acid and subsequent boiling with acidulated water into a naphthsultondisulphonic
acid, that is to say, a novel naphtholtrisulphonic acid.
For the nitration of the naphthalintrisulphonic acid my foreign correspondent
proceeds for example as follows:
The naphthalintrisulphonate of sodium is dissolved in the quadruple quantity of
concentrated sulphuric acid to this solution (or to the product of sulphonisation
obtained directly from naphthalin and fuming sulphuric acid) is added by degrees
the necessary quantity of concentrated nitric acid, and then, in order to complete
the reaction, the whole is heated on a water bath.

page_text: The product thus obtained is diluted with water and there is then added,
while heating, the necessary quantity of iron chips. After the reduction is com-
pleted it is sursaturated with lime and the liquid filtered off from the gypsum is
evaporated.
The novel naphthylaminetrisulphonic acid is distinguished from the two isomers
before produced, by not showing any fluorescence in alkaline solution and by forming
a non-colored diazo compound, whereas the diazo compounds of its two isomeric
acids are colored yellow.
The best way of producing the novel naphtholtrisulphonic acid is in the form of
its sodium salt by sursaturating largely the solution of the sodium salt of the new
naphthylamint risulphonic acid with sulphuric acid, adding the necessary quantity
of nitrite, boiling until the development of nitrogen ceases, then sursaturating with
lime until alkaline reaction, filtering off, adding soda, filtering again and evaporating
the filtrate; on cooling down, the salt, will separate from the concentrated solution
in the form of small needles.
If however after the decomposition of the diazo compound the not too largely
diluted liquid, not sursaturated with a base (lime) but still acid, is left to repose,
there will crystallise out after some time the neutral sodium salt of the naphth-
at all.
A cold aqueous solution of the same is not colored by the addition of ferric-
chloride solution.
When however the solution is boiled, the ammonia escapes, yellow coloration sets
in and ferric chloride will now give it a blue tint, (reaction of the corresponding
naphtholtrisulphonic acid) a proof that by the boiling with water naphtholtri-
sulphonic acid has been re-formed while ammonia escaped. With alkali the
re-formation goes on rapidly and completely.

page_text: If the naphtholtrisulphonic acid mentioned above or its anhydride (the napht-
sultondisulphonic acid) under certain conditions is heated with caustic alkalies
until a sample dissolved in water shows a strong violet fluorescense, there will have
been formed a dioxynaphthalindisulphonic acid.
Example. 500 parts of solid caustic soda are melted in an open vessel with a
small quantity of water, heated to from 160° C. to 210° C. and then are added
by degrees 300 parts of naphtholtrisulphonate or naphthsultondisulphonate of
sodium.
On the adding of such portion, foaming will set in; when the whole quantity of
the salt has been added, the mass may for security sake be heated for a short time
to from 220° to 250° C., after which the reaction will be complete.
If an autoclave with a stirrer is used, the melting can be proceeded with at con-
siderably lower temperatures, for example at from 160° to 190° C., and with a
considerably smaller quantity of caustic soda; for example, with from 150 to
300 parts, the duration of the operation varying in accordance herewith.
For the caustic soda may be substituted any other alkali.
After completion of the melting, the mass is dissolved in water as concentrated
as possible and strongly acidulated, whereupon the acid sodium salt of dioxy-
naphthalindisulphonic acid will separate and may be obtained in the usual way. If
the acidulation is not strong enough the neutral sodium salt will separate.
The formed dioxynaphthalindisulphonate of sodium after being liberated from the
sulphurous acid may also be directly employed for further purposes.
The dioxynaphthalindisulphonates are of easy solubility in water, showing violet
fluorescence. As characteristic reactions may be named the vivid yellow green
coloration produced by ferric chloride and the orange-red coloration produced by a
small quantity of a chloride of calcium solution in its neutral aqueous solutions. . If
a larger quantity of the chloride of calcium is added, the coloration will be less,
and after some time it will disappear completely.
The above mentioned novel sulphonic acids namely the naphtholtrisulphonic acid,
the naphtholtrisulphonic monamide and the dioxynaphthalindisulphonic acid, sub-
mitted to the action of diazo compounds in alkaline, neutral or slightly acid
solution, furnish azo coloring matters of great value for all, with the diazo
compounds obtained by diazotising:

page_text: diphenylmethan,
-naphthylamine nitrosulphonic acid, obtained by nitrating in sulphuric acid the
a-naphthylamine-monosulphonic acid prepared by heating sodium-naphthionate,
nitro. -naphthylamine, obtained by nitrating the B-naphthylamine in sulphuric
acid, dehydrothiotoluidinesulphonic acid, p-xylidine, amidophenolsulphonic acid.
This fist of bodies capable of being coupled with the new oxynaphthalin
derivatives is not complete, there being left out a great number of bases capable of
being coupled with the same in the form of their diazo compounds.
Novel colouring matters dyeing wool blue-black shades are obtained by the
action of the diazo azo compounds prepared by coupling diazo sulphonic acids with
a naphthylamine and subsequent diazotation, upon the dioxynaphthalin-disulphonic
acid described above in alkaline or acetic solution.
Example. Colouring matter from diazonaphthalin-azobenzolsulphonic acid and
dioxynaphthalin-disulphonic acid.
195 parts by weight of sulphanilate of sodium are dissolved in about 250 parts
by weight of water and thereto are added 25 parts by weight of hydrochloric acid
o: 30 per cent., and a solution of 7 parts by weight of nitrite of sodium.
After the diazotising is completed, there is caused to flow under continued
stirring to the cooled diazo compound a hot solution of 18 parts by weight of
hydrochlorate of alpha-naphthylamine in 450 parts by weight of water.
The temperature will rise to from 20 to 30° C. and it is kept at this height for
24 hours. The condensation product will form at once and is purified by dissolving
in soda lye and precipitating by means of hydrochloric acid.
It is cooled down to 0° C. and there is then added a solution of 7 parts by weight
of nitrite of sodium. The diazo compound formed is caused to act upon an
alkaline solution or a solution to which some acetate of sodium has been added,
consisting of 37 parts by weight of dioxynaphthalin disulphonate of sodium in 300
parts by weight of water.
The colouring matter thus produced, precipitates from the liquid in the form of
a dark powder dissolving in water with deep blue colour, and dyeing wool directly

page_text: n an acid bath deep-blue to blue-black shades, and wool, mordanted with chromic
oxide, blue shades with strong green tint.
For the quantity of sulphanilate of sodium named in the example may be
substituted the equivalent quantity of some other amido sulphonic acid.
:
In accordance with the components chosen, the shades to be obtained and the
degree of solubility of the products vary if for example the alpha naphthylamin
disulphonic acid (Dahl) has been used, the shades will be considerably bluer or the
tint with chromic oxide will be more greenish.
Of the amido sulphonic acids may be used :-
Having now particularly described and ascertained the nature of this inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
1. The production of a novel naphtholtrisulphonic acid or its interior anhydride
a naphthsultondisulphonic acid, by nitration of the naphthalintrisulphonic acid,
reduction of the nitro compound and production of the naphthsultondisulphonic
acid or of the naphthol trisulphonic acid from the novel naphthylaminetrisulphonic
acid by converting it into the diazo compound and boiling the latter with acidulated
water until the development of nitrogen ceases, substantially as described.
2. The production of a naphtholtrisulphonic monamide or of salts of the same
by the action of ammonia in aqueous or alcoholic solution or of ammonia vapour
upon the naphthsultondisulphonic acid referred to in the preceding claim.
3. The production of dioxynaphthalindisulphonates by heating the naphtholtri-
sulphonates or naphthsultondisulphonates above described with caustic alkalies
under or without pressure to temperatures of from 160 to 250° C.
4. The production of azo coloring matters by combining the naphtholtrisulphonic
acid, its monamide and the dioxynaphthalindisulphonic acid referred to in the
preceding claims with diazo bodies, tetrazo-bodies and disazo-bodies.
5. As a new compound the naphthol trisulphonic acid referred to in the first
claim.
6. As a new compound, the naphtholtrisulphonic monamide referred to in the
second claim.
7. As a new compound the dioxynaphthalinedisulphonate referred to in the
third claim.
8. As new compounds the azo-colouring matters referred to in the fourth claim.
Dated this 13th day of March 1891.
ABEL & IMRAY,
Agents for the Applicant.