Improvements in the Manufacture of Intermediate Products and Colouring Matters therefrom.
Year: 1898

page_text: Date of Application, 27th May, 1898
Complete Specification Left, 27th Feb., 1899-Accepted, 22nd Apr., 1899
Improvements in the Manufacture of Intermediate Products and
Colouring Matters therefrom.
We, READ HOLLIDAY & SONS LIMITED, of 11, Cambridge Buildings, Upperhead
Row, Manufacturing Chemists, JOSEPH TURNER, of Spink Field Road, Birkby, Chemist,
and HARRY DEAN, of Greenhead Road, Chemist, all in Huddersfield, in the County
of York, do hereby declare the nature of this invention to be as follows:-
In the Specifications of our Applications for Letters Patent Nos. 13999 dated June
8th 1897 and 11736 dated May 24th 1898 we have referred to the preparation of
chlor naphthylamine sulphonic acids by nitration and reduction of chlor naphthalene
sulphonic acids 1:4 and 1 : 5.
The said acids possess the following constitutions
We have now found that by means of the diazo reaction they may be converted
into the corresponding chlor-naphthol sulphonic acids, which when combined with the
various diazo and tetrazo compounds yield colours which are for the most part bluer
than the corresponding colours made from the unchlorinated naphthol sulpho
acids 1:4, 1:5 or 1:8. We have further found that by heating with caustic soda
solution of about 30° Be. under pressure the chlorine may be removed from the the
above mentioned chlor naphthylamine and chlor naphthol sulphonic acids leaving the
sulpho groups intact.
In this manner we obtain the corresponding amido oxy naphthalene sulphonic
acids and dioxynaphthalene sulphonic acids, which are found to be valuable for the
production of colouring matters by combination with diazo or tetrazo compounds.
We have also found that in addition to the above named substances certain other
chlorine derivatives of naphthalene and naphthylamine sulphonic acids yield valuable
products when treated in a similar manner. The chlor naphthylamine disulphonic
acid 18:36 yields by means of the diazo reaction the corresponding chlor
naphthol disulphonic acid. If the said chlor naphthylamine disulphonic acid or
chlor naphthol disulphonic acid be heated with caustic alkalies as previously
described for the chlor naphthylamine mono sulphonic acids, the amido naphthol
disulphonic acid 1:8:3:6 and the dioxy naphthalene disulphonic acid 1:8:3:6
are obtained respectively. Further by heating the chlor naphthalene trisulphonic
acids 18:3: 6 or 1: 8:4:6 with caustic alkalies under pressure the correspond-
ing dioxynaphthalene disulphonic acids are obtained.

page_text: The intermediate products thus obtained are to be used for the manufacture of
colouring matters.
Improvements in the Manufacture of Intermediate Products and
Colouring Matters therefrom.
We, READ HOLLIDAY & SONS LIMITED, of 11, Cambridge Buildings, Upperhead
Row, Manufacturing Chemists, JOSEPH TURNER, of Spink Field Road, Birkby,
Chemist, and HARRY DEAN, of Greenhead Road, Chemist, all in Huddersfield, in the
County of York, do hereby declare the nature of this invention and in what inanner
the same is to be perforined, to be particularly described and ascertained in and
by the following statement :-
In the Specifications of our Applications for Letters Patent Nos. 13999 dated
June 8th 1897.and 11736 dated May 24th 1898, we have referred to the
preparation of chlor naphthylamine sulphonic acids by nitration and reduction of
chlor naphthalene sulphonic acids 1 : 4 and 1: 5.
The said acids possess the following constitutions
We have now found that by means of the diazo reaction they may be
converted into the corresponding chlor-naphthol sulphonic acids, which when
combined with the various diazo and tetrazo compounds yield colours which are
for the inost part bluer than the corresponding colours made from the unchlorinated
naphthol sulpho acids 1 : 4, 1: 5, or 1: 8. We have further found that by heating
with caustic soda solution of about 30° Be. under pressure the chlorine may be
removed from the above mentioned chlor naphthylamine and chlor naphthol sulphonic
acids leaving the sulpho groups intact.
In this manner we obtain the corresponding amido oxy naphthalene sulphonic
acids and dioxynaphthalene sulphonic acids, which are found to be valuable for the
production of colouring matters by combination with diazo or tetrazo compounds.
We have also found that in addition to the above nained substances certain other
chlorine derivatives of naphthalene and naphtylamine sulphonic acids yield
valuable products when treated in a similar manner. The chlor naphthylamine
disulphonic acid 1: 8: 3: 6 yields by means of the diazo reaction the corres-
ponding chlor naphthol disulphonic acid. If the said chlor naphthylamine
disulphonic acid or chlor naphthol disulphonic acid be heated with caustic
alkalies as previously described for the chlor naphthylamine mono sulphonic acids,
the amido naphthol disulphonic acid 1: 8: 3: 6 and the dioxy naphthalene
disulphonic acid 1: 8: 3: 6 are obtained respectively. Further by heating the
chlor naphthalene trisulphonic acids 1: 8: 3: 6 or 1: 8: 4: 6 with caustic
alkalies under pressure the corresponding dioxy napthalene disulphonic acids are

page_text: 100 parts of chlor naphtylamine sulphonic acid 1: 8:5-NH: Cl: SO₂H are con-
verted in the usual manner into the diazo compounds and slowly added to a boiling
solution of 10% sulphuric acid and boiling continued until evolution of nitrogen
ceases. The chlor naphtol sulpho acid may be separated or the solution made
alkaline and used direct for the manufacture of dyestuffs.
1
In a similar manner we prepare the corresponding chlor naphtol sulphonic acids
from the chlor naphtylamine sulphonic acids 1:5:8 NH, CI: SO,H, the
1: 8:4 NH, Cl: SO, H and 1:4:8 NH, Cl: SO₂H also from the chlor
naphtylamine disulphonic acids 1:8:3:6
:
.
-
NH, : CL: SO,H: SO,H
and
100 parts chlor naphtalene trisulphonic acid 1:8:3:6 are heated in an autoclave
with 300 parts caustic soda lye 35° Be. to a temperature of from 200 to 250° C. for
a few hours. On cooling the melt is acidified with hydrochloric acid and boiled until
free from SO,, the solution is then allowed to cool and the dioxynaphtalene disulpho
acid separates out in the form of a yellowish white crystalline precipitate.
similar manner we prepare the dioxynaphtalene disulphonic acid 1: 8:4:6 from the
corresponding chlor naphtalene trisulphonic acid.
:
:
In a
Further we may prepare the following dioxynaphtalene monosulphonic acids
viz. 18: 5-OH OH: SO,H,-18: 4-OH OH: SO₂H, and the 1:5:8-
OH OH: SO,H from the chlor naphtol mono-sulphonic acids 1: 8:5-OH : CI: SO₂H,
-184-OH Cl: SO,H, and the 1:5:8-OH: CI: SO₂H.
:
Also the dioxy-
naphtalene disulphonic acids 1 : 8:3:6-OH OH: SO,H: SO₂H, and 1: 8:4: 6-
OH OH: SO,H: SO,H from the chlor naphtol disulphonic acids 18:36-
OH: CI: SO,H: SO,H and 1:8:4:6-OH: CI: SO₂H: SO₂H, by heating with caustic
alkalies as above described.
We do not limit ourselves to the precise details given in the above examples since
these can be varied to a considerable extent without altering the nature of our
invention

page_text: 25.8 kilos. chlor naphtylamine sulphonic acid 1:8: 4 are converted into the diazo
compound and run into an alkaline solution containing 32 kilos. dioxy naphtalene
disulphonic acid 1:8:3:6.
After standing a few hours the dyestuff is isolated in the usual manner. The
colouring matter so prepared dyes wool bluish red shades which change to deep
shades when treated with bichromate of potash.
19.7 parts of amido azo benzene is diazotised and the diazo compound added to a
slightly acid solution of 24 parts of amido naphtol mono sulphonic acid 1:8:4—
NH, OH: SO,H.
When the formation of the azo compound is complete an excess of sodium carbonate
is added and the diazo solution from 20-8 parts chlor aniline sulphonic acid run in.
The dye stuff separates out and may be filtered pressed and dried.
EXAMPLE 10.
20-8 parts chloraniline sulphonic acid are diazotised and the diazo solution added
to a slightly acid solution of 24 parts of amido naphtol mono sulphonic acid
1:8:5 NH: OH: SO₂H, as soon as the formation of the intermediate compound
is complete an excess of sodium carbonate is added and the diazo solution from
26 parts of chlor naphtylamine sulphonic acid run in. The dye stuff may be
separated from the deep blue black solution by the addition of salt and filtered
pressed and dried.
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
claim is:
1. The production of the chlornaphtol sulphonic acids from, the chlor naphtyl-
amine sulphonic acid NH, SO,H: Cl-1:8: 5, the chlor naphtylamine sulphonic
acid NH, SO,H: Cl 158, the chlor naphtylamine sulphonic acid
-

page_text: NH, SO,H: Cl 185, the chlor naphtylamine sulphonic acid NH, SO,H: Cl
-
-
1:58, the chlor naphtylamine sulphonic acid NH, SO,H: Cl - 1: 8:4 the
chlor naphtylamine sulphonic acid NH, SO,H: Cl
lamine disulphonic acids NH, : C1 : SOH: SOH
SO,H 18:4: 6.
-
-
1:4:8 also the chlor naphty-
18:36 and NH, : Cl : SO₂H :
2. The production of amido naphtol mono sulphonic acids or amido naphtol di-
sulphonic acids by heating the above mentioned chlor naphtylamine sulphonic acids
with caustic alkalies as herein before described.
3. The production of dioxynaphtalene mono or disulphonic acids by heating the
above mentioned chlor naphtol sulphonic acids with caustic alkalies as herein before
described.
4. The production of the dioxynaphtalenė disulphonic acids 1: 8:3:6 and
18:46 by heating the chlor naphtalene trisulphonic acids 1: 8:3:6 or
1846 with caustic alkalies as hereinbefore described.
5. The production of colouring matters by combining diazo or tetrazo compounds
with the above mentioned chlor naphtol mono sulphonic acids or by combining
tetrazo bodies with one molecule of any of the above chlor naphtol mono sulphonic
acids and one molecule of other amines, phenols, amido phenols, their sulpho or
carbo acids.
6. The production of dyestuffs by combining one molecule of a diazotised amine,
or diazotised amido sulpho acid, or their nitro derivatives with one molecule of amido
naphtol monosulphonic acid 1: 8:4, or 1: 8: 5, or amido naphtol disulphonic
acid 18:36 in acid solution and subsequently combining another molecule of the
diazo compound of any of the chlor amido sulpho acids referred to in Claim 1 in
alkaline solution.
7. The production of intermediate products and colouring matters therefrom as
set forth in the preceding claims.
Dated the 27th day of Thabanu 1000
WM. BROOKES & SON,
55/56, Chancery Lane, London, Agents for the Applicants.