Manufacture of Sulphonic Acids of the Naphthalene Series, and of Colouring Matters therefrom.
Year: 1898

page_text: Manufacture of Sulphonic Acids of the Naphthalene Series, and of
Colouring Matters therefrom.
We, IVAN LEVINSTEIN, Chemical Manufacturer, RICHARD HERZ, Ph.D., Chemist,
and LEVINSTEIN, LIMITED, Chemical Manufacturers, all of Minshull Street, Man-
chester, in the County of Lancaster, do hereby declare the nature of this invention
to be as follows:-
We have found that a uniform naphthylenediamine sulphonic acid which is a very
valuable raw material for the production of colouring matters, is formed by the re-
duction of the azo colouring matters which result from the combination of diazo
bodies, preferably of diazobenzene, with the alpha,naphthylamine beta,sulphonic acid
or alpha,naphthylamine beta sulphonic acid (Cleve's acids), or a mixture of them,
which are obtained by nitration and subsequent reduction of betanaphthalene mono-
sulphonic acid.
If this naphthylenediamine sulphonic acid be treated with nitrous acid in the
imanner described under Example II of the Specification of Letters Patent No. 2946
dated the 10th February A.D. 1896, there results an amidodiazonaphthalene sulphonic
acid which combines with amines diamines phenols amidophenols oxyphenols both of
the benzene and of the naphthalene series as well as with their known sulphonic and
carboxylic acids, forming valuable amidoazo colouring matters. In these new colour-
ing matters, the second amido group of the naphthylenediamine sulphonic acid,
which remained free in the first diazotisation, may now be diazotised and combined
with amines diamines phenols amidophenols oxyphenols both of the benzene and of
the naphthalene series as well as with their known sulphonic and carboxylic acids, and
produce tetrazo colouring matters which dye unmordanted vegetable fibres in shades
varying from blue to deep black.
The
We have further found that if our naphthylenediamine sulphonic acid is suitably
treated with certain acetylating agents such as acetic anhydride, acetyl chloride, or
strong acetic acid, one of the ainido groups is acetylated, the other remaining free,
and that thus monoacetylnaphthylenediamine sulphonic acid is produced."
acetylnaphthylenediamine sulphonic acid may be otherwise produced. For example,
the azo colouring matters which result from the combination of diazo compounds,
preferably of benzene with alpha,naphthylamine beta,sulphonic acid or alpha,naphthyl-
amine beta sulphonic acid or a mixture of them, obtained by nitration and subsequent
reduction of naphthalene betasulphonic acid may be treated with strong acetylating
agents such as acetic anhydride or acetyl chloride in the presence of anhydrous sodium
acetate. If the thus produced acetylated azo colouring matters be reduced, for
example with iron and acetic acid in the well known manner, acetylnaphthylene-
diamine sulphonic acids are produced.
In the manufacture of colouring matters from these acetylnaphthylenediamine
phonic acids we may, for example, proceed as follows. The acetylnaphthylene-
liamine sulphonic acid is treated with nitrous acid and the resulting diazo compounds
may be combined with amines diamines phenols amidophenols oxyphenols both of
TD 031

page_text: hydrochloric acid and diazotised in the usual manner by a solution of 7.2 kilos. of
sodium nitrite. To this diazo compound, a solution of 14.3 kilos of alphanaphthyl-
amine in 120 kilos. of hydrochloric acid (21° Be.) and 250 litres of water is added
with stirring. After stirring at the ordinary temperature for about 12 hours, the
excess of mineral acid is removed by adding sodium acetate and the mixture is
further stirred for some hours at a temperature of about 40° C. The insoluble colouring
matter is then filtered off and pressed.
Step 2. Rediazotisation of the amidoazo colouring matter produced under Step 1,
and combination thereof with amidonaphthol sulphonic acid-gamma.
The pressed cake of colouring matter produced under Step 1, is made into thin
paste with water and a little ice and is dissolved by adding 15 litres of 33 per cent.
caustic soda solution. To this there is then added a solution containing 7.0 kilos. of
sodium nitrite and the liquid is allowed to run slowly, with stirring, into 50 litres of
hydrochloric acid mixed with ice. Stirring is continued for from 2 to 3 hours, when
the diazotisation is complete. The difficultly soluble diazo compound is then
introduced into a soda solution of 25.0 kilos. of amidonaphthol sulphonic acid-gamma.
Care is taken that during the combination the mass is kept alkaline with soda.
When the combination is finished, the whole is heated to about 90° C. and the
colouring matter is salted out, filtered and pressed.
Step 3. Saponification of the acetyl colouring matter.
The pressed colouring matter resulting from Step 2, is heated with from 6 to 8
times its weight of water to about 90° C. and 80 kilos. of solid caustic soda is
thereupon added and the heating is continued with stirring for an hour or two, when
the saponification is complete. The excess of caustic soda is neutralised with
mineral acid whereby the colour is salted out. It is then filtered off pressed and
dried.
It dies unmordanted cotton a blueish-black, which when diazotised and developed
on the fibre with suitable developers, for instance with betanaphthol or metaphenyl-
enediamine, produces dark blue to deep black shades which are distinguished by their
fastness to milling and to light.
Analogous dye-stuffs are produced if, in this example, the alphanaphthylamine of
Step 1 is replaced by another rediazotisable aromatic amine, amidophenol, amido-
phenolether, or their derivatives, as for example by alpha,beta,amidonaphthol-ether,
or alphabeta, or alpha, beta naphthylamine sulphonic acids. Also, if in Step 2,
the amidonaphthol sulphonic acid-gamma is replaced by another amidonaphthol
sulphonic acid or by dioxynaphthalene sulphonic acids or naphthol sulphonic acids.
Also, if the diazo compound of Example IV, Step 2, instead of being combined with
25 kilos. of amidonaphthol sulphonic acid-gamma, is combined with 25.0 kilos. of
betanaphthol sulphonic acid Schaeffer, in soda solution, and the resulting dye-stuff is
saponified, a colouring matter is obtained which dyes unmordanted cotton blue and
when diazotised and developed on the fibre, with betanaphthol yields bright blue
tints fast to milling and to light.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
olaim is :-
1. The herein before described process for the production of the alpha,alpha-
naphthylenediamine beta,(beta)sulphonic acid which consists in reducing the azo
colouring matters resulting from the combination of suitable diazo bodies, preferably
diazobenzene, with the alpha,beta,-or the alpha,beta,naphthylamine sulphonic acid
or a mixture of them (as obtained by the nitration and subsequent reduction of
betanaphthalene sulphonic acid), substantially as set forth.
2. The hereinbefore described process for the production of monoacetylalpha,alpha-
naphthylenediamine beta,(or beta,) sulphonic acids, by treating the alpha,alpha-
naphthylenediamine beta-or beta sulphonic acid which is produced by reducing the
azo colouring matters resulting from the combination of suitable diazo bodies with
the alphabeta, or the alpha,beta,naphthylamine sulphonic acids or mixtures of
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