Year: 1894

page_text: Date of Application, 22nd Feb., 1894
Complete Specification Left, 17th Nov., 1894-Accepted, 22nd Dec., 1894

page_text: compounds and the new naphthylenediaminedisulpho acid dye wool in an acidulated
bath violet red to dark violet tints.
By combining the tetrazo derivatives of paradiamines such as benzidine, tolidine,
diamidodiphenolether, diamidostilbene and the like with two molecules of the new
acid, colouring matters may be obtained which dye unmordanted cotton in an alkaline
or in a salt bath from red to violet.
My foreign correspondents have farther discovered that the new 2: 7 naphthyl-
enediaminedisulpho acid yields, when combined with tetrazo compounds, in the
proportion of one molecule to one molecule, an intermediate product which still
contains one free diazo group and may therefore be combined with one molecule of
another component; the mixed dyes obtained in this way dye unmordanted cotton
tints which, according to the second component introduced, vary from orange to
red, brown, and violet.
The tetrazo colours produced by means of the new 2: 7 naphthylenediamine-
disulpho acid may be re-diazotised on the fibre and combined with phenols, amines,
diamines or amidophenols.
Generally a grey-brown.colour prevails in the tints obtained in this way.
Dated this 22nd day of February 1891
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of a New Naphthylenediaminedisulpho Acid 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 :-
This invention relates to the production of a new disulpho acid of 2: 7-naphtyl-
enediamine by treating 2: 7-dihydroxynaphthalenedisulpho acid with ammonia
under pressure, and of a series of colouring matters prepared by means of this
new acid.
My, foreign correspondents have discovered that 2: 7-dihydroxynaphthalene-
disulpho acid obtained by sulphonation of 2: 7-dihydroxynaphthalene when heated
for a longer time with caustic ammonia in a close vessel may be transformed into a
new naphthylendiaminedisulpho acid according to the equation :
Manufacture of a New Naphthylenediaminedisulpho Acid 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 :-
This invention relates to the production of a new disulpho acid of 2: 7-naphtyl-
enediamine by treating 2: 7-dihydroxynaphthalenedisulpho acid with ammonia
under pressure, and of a series of colouring matters prepared by means of this
new acid.
My foreign correspondents have discovered that 2: 7-dihydroxynaphthalene-
disulpho acid obtained by sulphonation of 2: 7-dihydroxynaphthalene when heated
for a longer time with caustic ammonia in a close vessel may be transformed into a
new naphthylendiaminedisulpho acid according to the equation:
(2). OH
(7) OH
[(2) NH,
(7) NH,
CH
+ 2 NH = CH
+ 2 H₂O
(SO,Na),
·(SO,Na),
The following example may illustrate the production of the new 2: 7-naphthyl-
enediaminedisulpho acid.
50 kilos. of the sodium salt of the 2: 7-dihydroxynaphthalenedisulpho acid-
obtained by sulphonation of 2: 7 dihydroxynaphthalene with sulphuric acid
of 66° Bé. on the water bath- -are heated for about 20 hours with 150 kilos. of
caustic ammonia (of about 23 per cent.) in a close vessel at a temperature of 200°
to'220º C.
:

page_text: The reaction-product is dissolved in water; the solution is boiled in order to
remove the excess of ammonia, and the new acid is precipitated by means of a
mineral acid.
The 27 naphthylenediaminedisulpho acid is sparingly soluble in water and it
forms a sodium salt which is readily soluble in water and may be precipitated from
this solution by the addition of salt. By the action of nitrite the new acid is
transformed into a brownish-red coloured, sparingly soluble tetrazo compound.
My foreign correspondents have discovered that this new acid may be used for
the production of a series of valuable colouring matters by combining the same with
diazo or tetrazo bodies.
•
Moreover the tetrazo compound of the new acid yields, as my foreign corre-
spondents have further discovered, valuable colouring-matters when combined with
phenols, amines, amido-phenols or their sulpho or carbo acids.
The following examples may illustrate the production of these colouring-
matters.
Ex. I. 212 kilos. of tolidine are tetrazotised in the well known manner, the
tetrazo body is added to a solution of 74 kilos. of the sodium salt of the
2: 7-naphthylenediaminedisulpho acid in presence of an excess of sodium acetate.
A brown-red precipitate is formed; the solution is stirred for some time, slightly
heated and made alkaline by means of sodium-carbonate. The colouring-matter is
salted out, filtered off, pressed and dried.
Instead of combining in presence of acetic acid, the combination may also be
effected with the same result in an alkaline solution.
The colouring-matter dyes unmordanted cotton red tints, resisting alkalis and
acids. The colouring-matter also dyes wool in a neutral or slightly acidulated
bath.
The colouring-matter may be rediazotised on the fibre and combined with
phenols, amines and the like, yielding, for instance, if metatoluylendiamine be
employed, in the latter case fast brown tints.
By substituting for the benzidine other para-diamines or their sulpho acids,
colouring matters are obtained, which dye tints from yellowish red to violet-red to
violet.
My foreign correspondents have further discovered that the new 2: 7-naphthyl-
enediaminedisulpho acid yields, when combined with tetrazo compounds in the
proportion of one molecule to one molecule an intermediate product which still
contains one free diazo group and may therefore be combined with one molecule of
another component. The mixed dyes, obtained in this way, dye unmordanted
cotton tints which according to the second component introduced, vary from orange
to red, brown and violet.
Ex. II. 18.2 kilos. of benzidine are diazotised in the well known manner and the
diazo body is added to a solution of 37 kilos. of the sodium salt of the 2: 7-naphthyl-
enediaminedisulpho acid in presence of sodium acetate. As soon as the formation
of the intermediate product is completed the solution is acidulated and a solution
of 14.3 kilos. of a-naphthylamine in hydrochloric acid is added. The mixture is
stirred for 12 hours, finally slightly heated, and the colouring-matter is transformed.
into its sodium salt in the usual manner. The colouring matter dyes wool.and
unmordanted cotton in red tints. The dyed cotton may equally be rediazotised and
developed on the fibre, yielding for instance with meta-toluylendiamine a fast black
brown tint.
In an analogous manner, other mixed tetrazo colouring-matters are prepared.
The formation of the intermediate product may also be effected with the same
result in an alkaline solution. According to the second component introduced,
these mixed colouring-matters dye tints varying from orange to red, brown and
violet.
"
The new acid may also be combined with simple diazo bodies, such for instance
as those derived from aniline, its homologues and its analogues, nitraniline, the
daphthylamines, the sulpho and carbo acids of these substances and the like. The

page_text: products obtained dye wool in an acidulated bath in tints varying from orange red
to violet red.
Ex. III. 93 kilos. of aniline are diazotised in the well known manner, the diazo
body is added to an alkaline solution of 31.8 kilos. of the 2: naphthalenediamine-
disulpho acid. The colouring-matter obtained dyes wool red-orange tints. By
substituting for the aniline a-naphthylamine a red-violet dye is obtained.
My foreign correspondents may also produce dyestuffs with this new acid by
combining it with the diazo compounds of such amido bodies as belong to the series
of thioamido-compounds, as for instance, dehydrothiotoluidine, dehydrothioxylidine,
primuline base and the like, or sulpho acids of these compounds. In this way dyes
are obtained producing on unmordanted cotton yellowish-red to red tints.
The new acid also yields colouring-matters when combined with diazotised
amidoazo bodies, such for instance as amidoazobenzene and the so-called mixed
amidoazo bodies and also the sulpho acids of these products.
The colouring-matters derived from such amidoazo compounds and the new acid
dye wool in an acidulated bath red to dark violet tints.
Ex. IV. 19-7 kilos. of amido-azo-benzene are converted into diazo-azo-benzene
in the well known manner and the diazo compound is combined with 34 kilos. of
2:7 naphthylendiaminedisulpho acid in alkaline solution; the colouring matter
obtained dyes wool in an acidulated bath a red tint.
1
As already mentioned, my foreign correspondents have discovered, that the
tetrazo compound of the new acid yields valuable orange, red, brown and violet
colouring matters when combined with phenols, amines, amidophenols or their
sulpho or carbo acids; these colouring matters dye wool in an acidulated bath and
possess a marked affinity for vegetable fibre.
Ex. V. 31-8 kilos. of the 2: 7-naphthylenediaminedisulpho acid are tetrazotised
in the well known manner, the tetrazo body is added to an alkaline solution
28-8 kilos. of 3 naphthol. The formation of the colouring matter is almost
immediately completed and the dyestuff is filtered off, pressed and dried. It dyes
wool red tints of great intensity and purity which are fast to soap and
fulling.
By substituting for the B-naphthol resorcine, a colouring matter producing
yellow-brown tints is obtained; if meta-toluylendiamine is used, an orange dye is
formed whilst the dye derived from a-naphthylamine dyes orange-brown tints, that
obtained with amidonaphtholmonosulpho acid y dyes red brown tints.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of a 2: 7 naphthylenediaminedisulpho acid by heating the
27-dioxynaphthalinedisulpho acid or its salts with ammonia under pressure.
2. The herein described process for the production of colouring matters by
combining two molecules of 2: 7 naphthylendiaminedisulpho acid in an alkaline or
weakly acidulated solution with one molecule of the tetrazo compounds of para-
diamines such as benzidine, ortho-tolidine, diamidophenyltolyl, diamidodiphenyl-
ether, diamidostilbene or alkyloxybenzidine.
3. The herein described process for the production of mixed azo colours by
combining one of the two diazo groups of the tetrazo derivatives of the para-
diamines mentioned in the preceding claim in an alkaline or weakly acidulated
solution with the 2: 7 naphthylinediaminedisulpho acid and combining the other
diazo-group with an amine or diamine, a phenol, an amidophenol or their sulpho
and carbo acids.
4. The herein described process for producing azo-colouring-matters derived
from 2: 7-naphthylendiaminedisulpho acid by combining the new acid in an
alkaline or weakly acidulated solution with the diazo compounds of amido bodies,
such as aniline, nitraniline, the toluidines, xylidines, anisidines, naphthylamines,
amidonaphtol ethers or their sulpho or carbonic acids, dehydrothiotoluidine;

page_text: dehydrothioxylidine, primuline and the other members of the series of thioamido
compounds, amidoazobenzene its homologues and its analogues and their sulpho
acids.
5. The herein described process for the production of azo-colouring-matters by
combining one molecule of the tetrazo body of the new acid with two molecules of
an amine, phenol, amidophenol or their sulpho or carbo acids, including the mixed
colouring matters.
6. The 2: 7-naphthylenediaminedisulpho acid manufactured as set forth in
Claim 1.
7. The colouring-matters produced by the processes set forth in the Claims 2, 3, 4
and 5.
Dated this 17th day of November 1894
ABEL & IMRAY,
Agents for Applicant.