Improvements in the Manufacture of a New Amidonaphtolsulphonic Acid and Coloring Matters therefrom.
Year: 1891

page_text: Date of Application, 30th Jan., 1891
Complete Specification Left, 1st Aug., 1891-Accepted, 12th Sept., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of a New Amidonaphtolsulphonic
Acid and Coloring Matters therefrom.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a
communication to me from abroad by Leopold Cassella and Company, of
Frankfort-on-Main, in the Empire of Germany, Chemists,) do hereby declare the
nature of this invention to be as follows:-
I. In the Specification of the British Patent 1534600 there is described the
diamido a naphtalenedisulphonic acid which is obtained by double nitration and
reduction of the naphtalcnedisulphonic acid 2.7 designated by Ebert and Merz by
the letter 'a. This a diamido acid is the primary matter for the process to be
described hereafter.
If the a diamido acid is heated with diluted mineral acids it is decomposed in a
particular way. Losing one of its amidogroups, it is transformed into an
amidonaphtoldisulphonic acid.
This acid hitherto not known is herein named "acid H." Worked under
suitable conditions the reaction gives nearly a quantitative result according to the
formula:

page_text: III. COLORING MATTERS DERIVED FROM TETRAZO-BODIES.
The combinations of two-molecules of acid H, with one molecule of a paradiamine
show blue shades of great purity.
Example: 92 kilogr. benzidine are diazotized and added to an alkaline solution
of 38 kilogr. amidonaphtoldisulphonic acid H. The coloring matter separates in
needles of a metallic reflex,,it dyes unmordanted.cotton.a pure blue.
..
Analogous coloring matters are obtained with tolidine, methylbenzidine,
diamidoethoxydiphenyl, diamidodiphenolether, diamidostilbene and p. phenylene-
diamine.
The tetrazo-derivatives of all these bases combine with one equivalent of the
acid H forming intermediate bodies; which have the property to react with.a
second equivalent of an amine or a phenol. The coloring matters resulting from
this process have the same characteristic qualities as the derivatives of the acid H.
Example I. 21 kilogr. diazotized tolidine are added to an alkaline solution of
38 kilogr. acid H, thus forming the intermediate violet body. 27 kilogr. amido-
naphtolsulphonic acid are added, then allowed to stand during 48 hours at a
temperature of 15° C. The coloring matter thus formed dyes unmordanted cotton
a blueish black. This black is bluer and more easily soluble than diamine black.
which contains two molecules of acid.
Y
Example II: 23 kilogr. diamidoethoxydiphenyl are diazotized and the
intermediate product is formed in alkaline solution with 38 kilogr. acid H, then a
solution of 25 kilogr. a naphtol a sulphonic acid is added. The reaction is
terminated in 24 hours. The coloring matter dyes cotton a deep blue.
In an analogous manner blue coloring matters are obtained by using ẞ naphtol,
dioxynaphtalene and their sulphio acids: the combinations with naphtylamines and
their sulpho acids; the combinations with naphtylamines and their sulpho acids
dye violet shades; the combinations with m. phenylene diamine, phenol and salicylic
acid dye blacks of violet to brown blue shades.
Dated this 30th day of January 1891
COMPLETE SPECIFICATION.
Improvements in the Manufacture of a New Amidonaphtolṣulphonic
Acid and Coloring Matters therefrom.
I, SYDNEY PITT of Sutton, in the County of Surrey, Gentleman, (a
communication to me from abroad by Leopold Cassella and Company, of Frankfort-
on-Main, in the Empire of Germany, Chemists) 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. In the Specification of my British Patent No. 153460 there is described the
diamido a naphtalenedisulphonic acid which is obtained by double nitration and
reduction of the naphtalenedisulphonic acid 2.7 designated by Ebert and Merz by
the letter a. This a diamido acid is the primary matter for the process to be
described hereafter.
If the a diamido acid is heated with diluted mineral acids it is decomposed in a
particular way, Losing one of its amido groups, it is transformed into an
amidonaphtol-disulphonic acid.
This acid, hitherto not known, is herein named "acid H." Worked under
suitable conditions the reaction gives nearly a quantitative result according to the
forinula :
СËH¸(NH₂),(SO₂H),+H₂O=CH¸NH₂OH(SO¸H), + NH¸.
3

page_text: and 10 kilogrammes sulphuric acid during about 6 hours at 110-120° C. Fine
yellowish needles separate from the cooled mass representing the acid ammonia salt
of the acid H, which is difficultly soluble in cold water, it is purified by crystallisa-
tion. Hydrochloric acid may be used in place of sulphuric acid; a suitable
proportion will be 80 kilogrammes of acid (21° Bé.) to each 100 litres of water.
The free acid is difficultly soluble the neutral salts are easily soluble in water. By
nitrous acid the acid H is transformed into its diazoic derivative, which separates
from the solution in the form of fiue yellow needles. Under the influence of
alkalies this diazo-body takes a violet color. The acid H combines with diazo,
tetrazo, etc. bodies. The resulting coloring matters shew chemical properties
analogous to the colors obtained from the y amidonaphtolsulphonic acid. The shades
are mostly very pure. Not only mineral acids, but also solutions of a caustic
alkali such as hydrate of lime, and even pure water can transform the a diamido acid
into the acid H. In these cases the yields are smaller, other products resulting,
besides the acid H, which heated in the presence of mineral acids can be transformed
into the acid H.
Example. 32 kilogrammes of the diamido acid are heated with 10 litres water
and 30 kilogrammes hydrate of lime or 20 kilogrammes caustic soda during about
8 hours at a temperature of 215° C. It is acidulated with hydrochloric acid and the
precipitate is filtered off. In order to transform the product thus obtained into pure
Hacid, it may be heated with mineral acids in the manner described in the first
example.
II. COLORING MATTERS DERIVED FROM DIAZO-BODIES.
The combinations of the acid H with diazo-bodies can be accomplished in
alkaline or weak acid solutions. According to the method of operation two series
of coloring matters are obtained, the shades of which do not much differ.
Example: 93 kilogrammes aniline are diazotised, the diazobenzol is added to the
alkaline solution of 38 kilogrammes acid H, the coloring matter forms immediately
and deposits as a dark green precipitate, it dyes wool in acid bath a reddish blue
perfectly level.
If other diazo compounds are used instead of diazobenzol, coloring matters are
obtained, the shades of which vary from red to violet or black; for instance,
diazotoluols, dioxylol and their sulpho-acids yield products of shades varying from
carmine-red to claret. Diazonaphtalenes and their sulphonated acids yield violet
coloring matters; diazoazobenzol, its homologues and its sulphonated derivatives
and p-nitrodiazobenzol, diazosalicylic acid, yield coloring matters dyeing wool a
blackish violet. The diazo derivatives of those amidoazosulphonic acids which are
obtained by combining diazo sulpho-acids or diazo carbonic'acids with a naphtylamine,
produce blueish and greenish black dyestuffs.
III. COLORING MATTERS DERIVED FROM TETRAZO-BODIES.
The combinations of two molecules of acid H with one molecule of a paradiamine
show blue shades of great purity.
Example. 92 kilog. benzidine are diazotised and added to an alkaline solution
of 32 kilog. amidonaphtoldi-sulphonic acid H. The coloring matter separates in
needles of a metallic reflex, it dyes unmordanted cotton a pure blue.
Analogous coloring matters are obtained with tolidine, methylbenzidine, diamido-
ethoxydiphenyl, diamidodiphenolether, diamidostilbene, and p. phenylenediamine.
The tetrazo-derivatives of all these bases combine with one equivalent of the
acid H, forming intermediate bodies which have the property to react with a second
equivalent of an amine or a phenol. The coloring matters resulting from this
process have the same characteristic qualities as the derivatives of the acid H.

page_text: .
naphtolsulphonic acid are added, then allowed to stand during 48 hours at a
temperature of 15° C. The coloring matter thus formed dyes unmordanted cotton
a blueish black. This black is bluer and more easily soluble than diamine black
which 'contains two molecules of y acid.
Example 11-23 kilog. diamidoethoxydiphenyl are diazotised and the inter-
mediate product is formed in alkaline solution with 32 kilog. acid H; then a
solution of 25 kilog. a naphtol a sulphonic acid is added. The reaction is terminated
in 24 hours. The coloring matter dyes cotton a deep blue.
In an analogous manner blue coloring matters are obtained by using the naphtols
or the dioxynaphtalenes and their sulpho acids; the combinations with naphtyl-
amines and their sulpho acids dye violet shades; the combinations with m. phenylene-
diamine m. toluylendiamine, resorcine, chrysoidine, Bismark-brown, phenol and
salicylic acid dye violet blacks or deep brown shades.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1.) The process of preparing a new amidonaphtol disulphonic acid (H) by
heating the diamidonaphtalene a disulpho acid with diluted sulphuric or hydro-
chloric acid at a temperature of from 100 to 140° C.
2.) The process of heating the diamido a naphtaline disulpho acid with alkaline
substances such as hydrate of lime or caustic soda and of transforming the thus
obtained product into pure acid H by the action of mineral acids.
3.) The process of preparing coloring matters by reacting with diazo compounds
on the acid H in an alkaline or weakly acid solution.
4.) The process of preparing coloring matters by the action of one molecule of
a tetrazo-compound of a paradiamine (such as benzidine tolidine, diamidodiphenol-
ether) upon two molecules of the acid H.
5.) The process of preparing mixed azo colors by combining one molecule of a
tetrazo compound of a paradiamine with one molecule of the acid H and one
molecule of an other amine or phenol or amidophenolic body or their sulpho or
carbonic acids. -
6.) The new substances and coloring matters obtained according to Claim 1 to 5
both inclusive.
Doted this 1st dov of
1001