The Manufacture of a New Sulphonic Acid of the Naphthalene Series and of Colouring Matters therefrom.
Year: 1898

page_text: Date of Application, 28th May, 1898
Complete Specification Left, 28th Nov., 1898-Accepted, 28th Jan., 1899
PROVISIONAL SPECIFICATION.
The Manufacture of a New Sulphonic Acid 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 amidonaphthol sulphonic acid-gamma can be easily converted
into an acetylamidonaphthol sulphonic acid by heating it, for example, for some
time, with an excess of glacial acetic acid in presence of a dehydrating agent, prefer-
ably anhydrous sodium acetate.
If this new acetylamidonaphthol sulphonic acid be combined with diazo or with
tetrazo compounds, valuable diazo or tetrazo colouring matters are obtained. Our
new acetylamidonaphthol sulphonic acid-gamma is of special value for use in the
production of colouring matters which cannot, or only with great diffi-
culty, be produced from the amidonaphthol sulphonic acid-gamma itself. For
example, very valuable direct colouring matters may be produced from our new acid
in the following manner:-
Diazoparanitraniline, diazoparanitro-orthotoluidine or diazoparanitronaphthyl-
amine are combined in the usual manner either in the presence of a solution of
sodium carbonate or a carbonated alkali, with the new acetylamidonaphthol sul-
phonic acid-gamma. In the nitroazo colouring matters thus produced, the nitro
group is then reduced to the amido group in the well known manner, for example
by means of alkaline sulphides, and amidoazo colouring matters are obtained
having the following general formula:-
.
in which R represents the benzene or naphthalene nucleus.
If these amidoazo colouring matters are treated with nitrous acid; diazo com-
pounds result which readily combine with amines diamines amidophenols
amidonaphthols amidonaphthalene sulphonic acids amidonaphthol sulphonic acids
and the like, forming direct colouring matters which vary in shade from blue to
black.
These colouring matters still contain the acetyl group in the nucleus of the
"

page_text: by means of alkaline sulphides, and amidoazo colouring matters are obtained
which have the following general formula:-
in which R represents the benzene or naphthalene nucleus.
If these amidoazo colouring matters are treated with nitrous acid, diazo com-
pounds result which readily combine with amines, diamines, amidophenols,
amidonaphthols amidonaphthalene sulphonic acids amidonaphthol sulphonic acids
and the like, forming direct colouring matters which vary in shade from blue to
black.
These colouring matters still contain the acetyl group in the nucleus of the
amidonaphthol sulphonic acid-gamma, and it may be split off by saponification,
for example by treatment with hot dilute solution of caustic soda."
Ple. tha sanonified colouring matter having the general formula:-
(in which R, represents the benzene or naphthalene nucleus and R one of the above
mentioned colour producing agents,) possess a greater intensity and dye tints
darker than the original colouring matters. The shades produced on the fibre may
be diazotised and developed with suitable developers, producing dark blue to deep
black tints which are distinguished by their fastness to milling and to light.
The following examples illustrate in what manner we may carry our invention
into practice.
EXAMPLE I.
Production of the acetylamidonaphthol sulphonic acid-gamma.
25 kilos of amidonaphthol sulphonic acid-gamma is mixed with the same weight
of anhydrous sodium acetate and about three times its weight of glacial acetic
acid. The mixture is then boiled under a reflux condenser until a removed sample
is no longer diazotisable. The excess of acetic acid is then distilled off and the
readily soluble residue is dissolved in water. The solution thus obtained may be
directly used for the production of colouring matters after the strength has been
ascertained by titration, for example with diazobenzene, in the usual manner.
The new acetylamidonaphthol sulphonic acid-gamma may be separated either by
evaporation of the solution to crystallisation, or by acidifying the concentrated
The acetylamidonaphthol
solution with hydrochloric acid, when it crystallises out.
sulphonic acid-gamma, is, in distinction to the unacetylated amidonaphthol sul-
phonic acid-gamma, very easily soluble in water.
Colouring matters may be produced from the acetylamidonaphthol sulphonic
acid-gamma as follows:-
EXAMPLE II.
Production of a colouring matter by combining one molecule of tetrazodiphenyl
with one molecule of acetylamidonaphthol sulphonic acid-gamma and one molecule
of amidonaphthol disulphonic acid H, in alkaline solution.
18.4 kilos of benzidine is tetrazotised in the usual manner with 14.2 kilos of

page_text: amidoalpha,naphthol beta,sulphonic acid-gamma, which consists in acetylating
beta,amidoalpha,naphthol betagsulphonic acid-gamma with suitable acetylating
agents, substantially as set forth.
2. The hereinbefore described process for the production of azo and tetrazo
colouring matters, which consists in combining diazo or tetrazo bodies with acetyl-
amidonaphthol sulphonic acid-gamma, substantially as set forth.
3. The herein before described process for the production of mixed tetrazo colour-
ing matters which consists in combining one molecular proportion of a tetrazo
derivative of a paradiamine such as benzidine tolidine dianisidine ethoxybenzidine
diamidodiphenylamine diamidostilbene disulphonic acid and the like, with one
molecular proportion of acetylamidonaphthol sulphonic acid and with one molecular
proportion of an aromatic amine, diamine, phenol, oxyphenol, amidophenol as well
as their sulphonic and carboxylic acids, substantially as set forth.
4. The herein before described process for the production of direct disazo colour-
ing matters derived from paraphenylenediamine or its homologues or naphthylene-
diamines, which consists in diazotising paranitraniline or paranitrorthotoluidine
or nitronaphthylamines (preferably alpha alpha,nitronaphthylamine), combining
the resulting diazo bodies with acetylamidonaphthol sulphonic acid-gamma,
reducing the so obtained nitrazo dye-stuffs with suitable reducing agents (prefer-
ably alkaline sulphides), to amido colouring matters, rediazotising the product and
combining the resulting diazo compounds with aromatic amines diamines amido-
phenols amidophenolethers as well as their sulphonic and carboxylic acids, sub-
stantially as set forth.
5. The herein before described process for the production of direct disazo colouring
matters which consists in saponifying the acetyl colouring matters produced as
described in the fourth claim, for example by heating them with dilute caustic
soda solution, substantially as set forth.
6. As a new article of manufacture, beta acetylamidoalpha naphthol beta-
sulphonic acid-gamma, produced by acetylating beta,amidoalpha naphthol beta-
sulphonic acid-gamma, substantially as set forth.
7. As a new article of manufacture, an almost insoluble azo colouring matter pro-
duced by the combination of diazo) or tetrazo bodies with acetylamidonaphthol
sulphonic acid-gamma, substantially as set forth.
8. As a new article of manufacture, the mixed tetrazo colouring matters produced
by the combination in equi-molecular proportions of a tetrazo derivative of a para-
diamine with acetylamidonaphthol sulphonic acid and an aromatic amine diamine
phenol oxyphenol amidophenol as well as their sulphonic and carboxylic acids,
substantially as set forth.
9. As a new article of manufacture, direct disazo colouring matters produced by
diazotising paranitraniline paranitrorthotoluidine or (preferably alpha,alpha)
nitronaphthylamine, combining the diazo bodies with acetylamidonaphthol sul-
phonic acid-gamma, reducing the product to an amidoazo body, rediazotising it
and combining it with aromatic amines diamines amidophenols amidophenolethers
as well as their carboxylic and sulphonic acids, substantially as set forth.
10. As a new article of manufacture, direct disazo colouring matters produced
by diazotising paranitraniline paranitrorthotoluidine or (preferably alpha,alpha,)
nitronaphthylamine, combining the diazo body with acetylamidonaphthol sulphonic
acid-gamma, reducing the product to an amidoazo body, rediazotising it, combining
it with aromatic amines diamines amidophenols amidophenolethers as well as their
carboxylic and sulphonic acids, and finally saponifying the product, substantially
as described.
T: 05th day of November An 1898