Improvements in the Production of New Sulphonic Acids Derived from Naphthaline, and of Colouring Matters therefrom
Year: 1895

page_text: Date of Application, 1st May, 1895
Complete Specification Left, 17th Jan, 1896-Accepted, 22nd Feb, 1898
PROVISIONAL SPECIFICATION
[Communicated from abroad by THE ACTIEN GESELLSCHAFT FÜR
ANILIN FABRIKATION, of Berlin, in the Empire of Germany, Chemical
Manufacturers ]
Improvements in the Production of New Sulphonic Acids Derived
from Naphthaline, and of Colouring Matters therefrom
I, CHARLES DENTON ABEL, of No 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention to be as follows
-
I My foreign correspondents have made the observation that the ẞ₁ Bramido-
naphthol-3-monosulphonic acid described in the Specification No 15176 of 1889
may, by the action of fuming sulphuric acid, easily and with very good yield be
transformed into a new amidonaphtholdisulphonic acid possessing the following
constitution
For effecting this transformation the BB-amidonaphthol-6-monosulphonic acid
above mentioned is treated with about three parts by weight of fuming sulphuric
acid (25 per cent anhydride) on the water bath until a sample of the reaction
product is readily soluble in cold water and yields no yellow precipitate on
addition of nitrite When this point is reached, the melt is poured into water
and the lime salt or sodium salt of the new acid is prepared in the well known
manner
If the solution of the neutral sodium salt of the new acid is acidulated with
mineral acids the acid sodium salt crystallises out.
On diazotation the new acid yields a yellow, very readily soluble diazo
compound which, on addition of an excess of soda solution, yields a red solution
The new acid when combined with tetrazodiphenyl yields a violet red colouring
matter, by reacting with diazobenzene on the new acid a brown red colouring
matter is formed.
II My foreign correspondents have further found that the ß, B-amidonaphthol-
Bradisulphonic acid above referred to is by treatment with ammonia under
pressure at a temperature above 150° C, transformed into a new naphthylen-
diamine disulphonic acid. This new acid forms fine colourless needles which are
easily soluble in hot water, and this solution shews a fine blue fluorescence.
The new naphthylendiamine disulphonic acid is capable of combining in
acidulated solution with nitrite of soda, but only with one molecule. The resulting
product does not combine with amines or phenols and therefore has the characteristic
of an azımıdo body

page_text: The new naphthylendiamine disulphonic acid can be combined with one molecule
of a diazo body to form azo colours The combination can be transformed in
alkaline or acetic acid solution
III For one of the sulpho groups in the B₁ ẞ-naphthylenediamine-ẞ3 α-
disulphonic acid first referred to, can easily be substituted the OH group, by
melting the said acid in open or closed vessels with caustic soda at a temperature
between 190° and 200° C
The diamidonaphtholmonosulphonic acid thus formed is insoluble in water and
alcohol
The constitution of this new acid is probably expressed by the following 1
The new naphthylendiamine disulphonic acid can be combined with one molecule
of a diazo body to form azo colours The combination can be transformed in
alkaline or acetic acid solution
III For one of the sulpho groups in the ẞ₁ B-naphthylenediamine-ẞ3 α-
disulphonic acid first referred to, can easily be substituted the OH group, by
melting the said acid in open or closed vessels with caustic soda at a temperature
between 190° and 200° C
The
alcohol
diamidonaphtholmonosulphonic acid thus formed is insoluble in water and
The constitution of this new acid is probably expressed by the following 1
formula
HOBS
HO
00
NH,
NH,
Diazo bodies combine with the new acid in alkaline or acid solution to form
most valuable colouring matters the colours obtained by combination in alkaline
solution are not identical with those which are formed in acid solution, the former 1
dye tints much more red and blue than the products obtained by coupling in an
acid solution and they have moreover much better tinctorial power
Nitrous acid acts on the new diamido-naphthol sulphonic acid in a manner
analogous to its action on naphthylenediamine sulphonic acid forming an azımido
product
with the properties of a naphthol sulphonic acid, which product may be combined
with diazo compounds to form valuable colouring matters
My foreign correspondents have found that the products described above
B-amido-naphthol-3, a disulphonic acid,
B. B,-naphthylendiamine-ẞ, a-disulphonic acid,
B₁ Brdiamido-a-naphtholmonosulphoni acid,
B. Brazımidonaphthol-ag-monosulphonic acid,
can be used for the production of new colouring matters
The said acids can be combined with diazo- or tetrazo-compounds in the
manner well known to chemists The resulting colouring matters are distinguished
by their great fastness against the action of soap, of air, of light, and by their
tinctorial power The tints which the different colours produce on wool or cotton
vary from red to violet and dark blue
Dated this 1st day of May 1895
ABEL & IMRAY,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION
Improvements in the Production of New Sulphonic Acids Derived
from Naphthaline, and of Colouring Matters therefrom
I, CHARLES DENTON ABEL, of No 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered 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
I My foreign correspondents have made the observation that the Bi-3-amido-
naphthol 6-monosulphonic acid described in the Specification No 15176 of 1889,
may, by the action of faming sulphuric acid, easily and with very good yield be
transformed into a new amidonaphtholdisulphonic acid possessing the following
constatation
For effecting this transformation 10 kilos of ẞ, B.-amidonaphthol B.-mono-
sulphonic acid above mentioned are treated with about three parts by weight of
fuming sulphuric acid (25 per cent anhydride) on the water bath until a sample of
the reaction product is readily soluble in cold water and yields no yellow precipitate
on addition of nitrite When this point is reached, the melt is poured into water
and the lime salt or sodium salt of the new acid is prepared in the well known
manner
If the solution of the neutral sodium salt of the new acid is acidulated with
mineral acids the acid sodium salt crystallises out
On diazotation the new acid yields a yellow very readily soluble diazo compound
which, on addition of an
The
excess of soda solution, yields a red solution
new acid when combined with tetrazodiphenyl yields a violet red colouring matter,
by reacting with diazobenzene on the new acid a brown red colouring matter is
formed
Il My foreign correspondents have further found that the ßßamidonaphthol-
Bra-disulphonic acid above referred to is by treatment with ammonia under
pressure at a temperature above 150° C, transformed into a new naphthylen-
diamine disulphonic acid This new acid may for example be prepared as
follows
100 kilos. of B-ẞ, amidonaphthol-ẞra-disulphonic acid are mixed with 200 kilos.
of ammonia liquor contaming 30 per cent NH, and heated from 185° to 190° C
for 8 hours in a closed vessel. The whole is dissolved in water and the excess of
ammonia, being removed by boiling, the solution is acidulated by means of
hydrochloric acid The B₁ B-naphthylenediamine-Be a disulphonic acid crystallises
out from the cold solution and is isolated in the usual way It forms fine colourless
needles which are easily soluble in hot water, and this solution shews a fine blue
fluorescence
The new naphthylendiamine disulphonic acid is capable of combining in
acidulated solution with nitrite of soda, but only with one molecule The resultang

page_text: product does not combine with amines or phenols and therefore has the characteristic
of an azımıdo body
The new naphthylendiamine disulphonic acid can be combined with one molecule
of a diazo body to form azo colours The combination can be effected in alkaline
or acetic acid solution
III For one of the sulpho groups in the ß ß-naphthylenediamine-ß, α-
disulphonic acid first referred to, can easily be substituted the OH group, by
melting the said acid in open or closed vessels with caustic soda at a temperature
between 190° and 200° C
The following is given as an example of process for the production of this new
acid
100 kilos of ẞ-ß-naphthylenediamine-ß a disulphonic acid, 250 kilos of
caustic potash and 25 litres of water are well mixed together and heated in an
open or closed vessel for half an hour at a temperature of from 190° to 200° C
The reaction product is dissolved in 1300 litres of water and the solution 13
rendered acid by addition of hydrochloric acid The diamido-naphthol-sulphonic
acid thus formed crystallises out in the shape of fine slightly coloured Deedles,
is insoluble in water or alcohol
it
The constitution of this new acid is probably expressed by the following
1
Diazo bodies combine with the new acid in alkaline or acid solution to form
most valuable colouring matters, the colours obtained by combination in alkaline
solution are not identical with those which are formed in acid solution the former
dye tints much more red and blue than the products obtained by coupling in an acid
solution and they have moreover much better tinctorial power
Nitrous acid acts on the new diamido naphthol sulphonic acid in a manner
analogous to its action on naphthylenediamine sulphonic acid forming an azımido
product
with the properties of a naphthol sulphonic acid, which product may be combined
with diazo compounds to form valuable colouring matters
My foreign correspondents have found that the products described above
B-amido-B-naphthol-ẞ, a-disulphonic acid,
BB-naphthylendiamine-, a-disulphonic acid,
B₁ B-diamido-a-naphtholmonosulphonic acid,
BB-azımıdo-a-naphthol-3-monosulphonic acid,
can be used for the production of new colouring matters by combining them with
suitable diazo- or tetrazo-compounds. As the production of these colouring

page_text: matters is effected by a series of reactions and systematic operations familiar to
chemists conversant with this branch, my foreign correspondents hereinafter
confine themselves to statement of the typical properties and tints of the colouring-
matters which they have obtained, starting from the initial products above
mentioned
All dyestuffs derived from the acids above mentioned are distinguished by their
great intensity and fastness to the action of washing and light.
The combination-products obtained from diazo-derivatives dye wool, those
prepared by the action of a tetrazo-compound can be fixed also on unmordanted
cotton The tinte vary, owing to the components, from a yellowish-red to a dark
violet blue
Colouring-matters dyeing very dark shades may be obtained by combining two
molecules of a diazo-derivative with one molecule of ß ß-diamido-a-naphthol-
B-monosulphonic acid
The said acids can be combined with diazo- or tetrazo-compounds in the manner
well known to chemists. The resulting colouring matters are distinguished by
their great fastness against the action of soap, of air, of light, and by their
tinctorial power
The tints which the different colours produce on wool or cotton
vary from red to violet and dark blue
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 herenbefore described manufacture of B₁ ẞ, amidonaphthol-ẞ, α-disulpho
acid
2 The herein before described manufacture of ẞ₁ B-naphthylenediamine ß, α-
disulphonic acid
3 The herein before described manufacture of B₁ B-diamido-a-naphthol-ẞ,-
monosulphonic acid
4 The hereinbefore described manufacture of ẞ, Brazımido-a naphthol-ẞr
sulphonic acid
5 The manufacture of azo- and tetrazo-colouring matters derived from the new
acids obtained as set forth in the preceding claim
6 The products as manufactured in Claims 1, 2, 3, 4 and 5
Dated this 13th day of January 1896
ABEL & IMRAY,
Agents for the Applicant.