Improvements in the Manufacture of Naphthylamine Derivatives and Colouring Matters therefrom.
Year: 1897

page_text: Date of Application, 8th June, 1897
Complete Specification Left, 10th Mar., 1898-Accepted, 7th May, 1898
Improvements in the Manufacture of Naphthylamine Derivatives
and Colouring Matters therefrom.
We, READ HOLLIDAY & SONS LIMITED, Chemical Manufacturers, Huddersfield,
JOSEPH TURNER, Chemist, Spink Field Road, Birkby,. Huddersfield, and HARRY DEAN,
Chemist, Greenhead Road, Huddersfield, all in the County of York, do hereby declare
the nature of this invention to be as follows:-
This invention relates to the manufacture of certain chlorine derivatives of
napthylamine sulphonic acids and colouring matters derived therefrom.
We have found that by nitrating chlor-napthalene sulphonic acid 1:4 there are
obtained two new chlor-nitro napthalene sulphonic acids which on reduction yield the
corresponding chlor-napthylamine sulphonic acids.
These two chlor-napthylamine sulphonic acids probably possess the following con-
stitutions respectively.
Colouring matters can be formed by employing the above mentioned chlor-
napthylamine sulphonic acids in place of the well known 1: 8 or 1:5 napthylamine
5 sulpho acids in combinations with the various diazo and tetrazo compounds the
resulting colouring matters having different properties to the corresponding colours
made with napthylamine sulpho acids 15 or 1 : 8.
Improvements in the Manufacture of Naphthylamine Derivatives
and Colouring Matters therefrom.
We, READ HOLLIDAY & SONS LIMITED, Chemical Manufacturers, Huddersfield,
JOSEPH TURNER, Chemist, Spink Field Road, Birkby, Huddersfield, and HARRY DEAN,
Chemist; Greenhead Road, Huddersfield, all in the County of York, do hereby declare
[Price 8d]

page_text: 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 manufacture of certain chlorine derivatives of
naphthylamine sulphonic acids and colouring matters derived therefrom.
We have found that by nitrating chlor-naphthaline sulphonic acid 1:4 there are
obtained two new chlor-nitro naphthalene sulphonic acids which on reduction yield the
corresponding chlor-naphthylamine sulphonic acids.
These two chlor-naphthylamine sulphonic acids probably possess the following
constitutions respectively.
партму ume surphonic acids m place of the well known 1:8 or 1 : 5 naphthylamine
sulpho acids in combinations with the various diazo and tetrazo compounds the result-
ing colouring matters having different properties to the corresponding colours made
with naphthylamine sulpho acids 1 : 5 or 1: 8.
In order to illustrate the nature of the invention the following examples are given.
EXAMPLE I
100 kilos. chlor-naphthalene sulphonic acid 1: 4 are dissolved in 5 to 6 parts of
sulphuric acid 66° Bé., and nitrated by running in a mixture of 50 kilos. D.O.V., (or
sulphuric acid 66° Bé.) and 36 kilos. nitric acid containing 70 % real Hno, the tem-
perature being kept below 25° C. The mixture is then diluted with water and
reduced by the addition of iron borings and converted into the sodium salt in the usual
way. The two isomeric chlor-naphthylamine sulphonic acids may be separated by
means of the difference of the solubility of their sodium salts. The sodium salt of
the No. I acid being much less soluble than the No. II may be readily separated by
evaporating the solution to crystallizing point and filtering off the No. II acid
remaining in the filtrate. The nitration may also be effected by feeding the chlor-
naphthalene-sulphonic acid into concentrated nitric acid and the nitro compounds
separated by diluting and precipitating with salt.
EXAMPLE II.
Production of a bluish wool black 32.5 parts of naphthylamine disulpho acid in the
form of its acid sodium salt are diazotized in the usual manner and run into a solution
prepared by dissolving 18 parts of a naphthylamine hydrochloride in about 500 parts
of water. When the amido azo compound has completely formed it is further
diazotised by the addition of 7 parts of sodium nitrite and about 30 parts hydro-
chloric acid 21° Bé. The diazo azo compound thus produced is stirred into a
solution of 30 parts of the sodium salt of the chlor-naphthylamine sulphonic acid
No. I to which sodium acetate is added. After standing several hours the colouring
matter is precipitated, filtered off and dried. The colouring matter thus produced
dyes wool from neutral or acid baths fast bluish black shades.

page_text: naphthylamine sulphonic acid No. II in presence of sodium acetate. After standing a
few days the mixture is made alkaline with sodium carbonate and the colouring matter
isolated in the usual manner. It dyes unmordanted cotton bluish red shades.
EXAMPLE IV.
21.2 kilos. of tolidine are converted into the tetrazo compound and run into a
solution containing 28 kilos. of the sodium salt of the chlor-naphthylamine sulphonic
acid No. II in the presence of sodium acetate when the formation of the intermediate
compound is complete a solution containing 35 kilos. of sodium naphthionate 70% is
added. After making alkaline and allowing to stand a few days the formation of
the colouring matter is complete and it is then salted out, filtered, pressed and
dried.
The dyestuff so obtained dyes vegetable fibre fine bluish red shades.
Having now particularly described and ascertained the nature of our said
invention, and in what manner the same is to be performed, we declare that what
we claim is :-
1. The production of two isomeric chlor-naphthylamine sulphonic acids by nitration
and reduction of chlor-naphthalene sulphonic acid 1:4.
2. The production of colouring matters dyeing wool black shades by combining
diazotized amido azo bodies, their sulpho or carbo acids with chlor-naphthylamine
sulphonic acids herein before termed No. I and II.
3. The production of dyestuffs dyeing vegetable fibre without a mordant by com-
bining tetrazo compounds with two molecules of the chlor-naphthylamine sulphonic
acid No. II or with one molecule chlor-naphthylamine sulpho acid No. I or II and
one molecule of other amines, phenols, amido phenols or their sulpho or carbo acids.
4. The production of two isomeric chlor-naphthylamine sulphonic acids and
colouring matters therefrom as set forth in the preceeding claims.
Dated the 10th day of March 1900
WM. BROOKES & SON,
55 and 56, Chancery Lane, London, Agents for the Applicants.