Production of a New Trioxynaphtaleae and Dyestuff's Deriving therefrom.
Year: 1898

page_text: Date of Application, 27th Dec., 1898
Complete Specification Left, 26th Sept. 1899-Accepted, 28th Oct., 1899
PROVISIONAL SPECIFICATION
PROTIONAL DREVIFICATION
The Production of a New Trioxynaphtaleae and Dyestuff's Deriving
therefrom.
I, ROBERT BOLTON RANSFORD, Gentleman, of 41, Waldegrave Road, Upper Nor-
wood, in the County of Surrey, do hereby declare the nature of this invention
(which has been communicated to me from abroad by Leopold Cassella and Com-
pany, of Frankfort-on-Main, in the Empire of Germany,) to be as follows.-
If the 2.3.8 trioxynaphtalene 6 sulpho acid, which 18 obtained by melting the
2 naphtol 3.6.8. trisulpho acid with alkalis, be heated with water to higher tem-
peratures, it looses its sulpho group and is transformed into a new trioxynaph-
talene, very valuable for the manufacture of dyestuffs, of the following con-
stitution
It is produced for instance as follows ·
27 5 kilos trioxynaphtalene sulphonate of soda are heated with 98 hilos sul-
phuric acid of 66° Bé and 200 litres water in an autoclave for 5 hours to 210°--
220° C. By evaporating and cooling the solution, the ti1oxynaphtalene 18
obtained in the form of small needles of a light brownish colou
The 23.8 trioxynaphtalene melts at 1640-165° C, it is fairly easily soluble
in water, very easily in alcohol and ether In benzol and chloroform it 18
scarcely soluble The alkaline solution is coloured dark brown by the oxygen of
the air; perchloride of 11on produces an intense blue colouration. When treated
with acetic acid anhydride and some acetate of sodium, the 2.3 8. trioxynaphtalene
18 transformed into a triacetyl-combination, which is obtained in fine needles,
melting at 125°-126° C.
The new trioxynaphtalene is of great technical value in consequence of the
property of some of its azo derivatives of yielding fast dyeings on metallic mor-
danta For this purpose it is essential to combine it with the diazo compounds
in such a manner that the latter enter only in relation to the alpha hydroxyl
group This may be done by working in a weak acid solution. In this case
both betahydroxyl groups are left free and the colours obtained are consequently
capable of forming lakes with metallic mordanta
If for instance disazobenzol is allowed to react on trioxynaphtalene in a weak
acetic acid solution, a difficultly soluble brown dyestuff is obtained, which behaves

page_text: exactly like alizarine dyestuffs and may be fixed absolutely fast both on chrome-
moidanted cotton and wool
The dyeings are perfectly even (level), fast to acids, to potting and to light
Hitherto azodyestuffs possessing such properties were unknown and consequently
this discovery is of great importance
Of course the nature of the disazo body used for the combination greatly in-
fluences the shade and the solubility of the dyestuff It has been found that
generally speaking only the dyestuffs obtained from unsulphonated disazo bodies
and disazo carbonic acids yield dyestuffs of absolute fastness on cotton, whilst
on wool the fastness to milling is not or only very little impaired by the pre-
sence of one and sometimes also of two sulpho groups according to the weight
of the molecule of the component, as the effect of the sulpho groups on the
solubility is compensated by the energetic fixing power of the lake forming
hydroxyl groups
The method is therefore not limited to the selection of cortain
components, but 18 a general one
The following examples illustrate the same.
EXAMPLE I
138 kilos metanitianiline are disazotised and added to the solution of 18 kilos
of 238 trioxynaphtalene containing an excess of acetate The formation of
the dyestuff begins at once. After 12 hours the solution is heated to about
50° C, neutralised with some soda, and the complete separation effected by
addition of common salt
The dyestuff is best used in the form of a paste On cotton mordanted with
chrome or iron salts fast brown dyeings are obtained and likewise on wool mor-
danted with ohrome.
EXAMPLE II.
224 kilos naphtionic acid are diazotised and the diazo compound introduced
into the solution of 18 kilos 2.38 toxynaphtalene containing an excess of
acetate After 12 hours the mass is heated to about 50° C. and the dyestuff
precipitated with common salt It is easily soluble in hot water, the solution is
On
In an
of a dark red colour, which is tuined to a violet by the addition of soda
mordanted cotton or wool fast dark brown dyeings are obtained
analogous manner the combinations from other diazo bodies are produced.
which all yield brown to black shades
Dated this 27th day of December 1898
The Production of a New Trioxynaphtalene and Dyestuffs Deriving
therefrom.
I, ROBERT BOLTON RANSFORD, Gentleman, of 41, Waldegrave Road, Upper Nor-
wood, in the County of Surrey, do hereby declare the nature of this invention
(which has been communicated to me from abroad by Leopold Cassella and Com-
pany, of Frankfort-on-Main, in the Empue of Germany,) and in what
manner the same is to be performed, to be particularly described and ascertained
in and by the following statement:-
If the 2.3.8 trioxynaphtalene 6 sulpho acid, which is obtained by melting the
naphtol 3.68 trisulpho acid with alkalis, be heated with water to higher tem-

page_text: peratures, (my correspondents believe that the temperature should exceed 160° C.,)
it loses its sulpho group and is transformed into a new trioxynaphtalene, very
valuable for the manufacture of dyestuffs, of the following constitution: —
It is produced for instance as follows.
27 E kilos trioxynaphtalene sulphonate of soda are heated with 9.8 kilos sul-
phuric acid of 66° Bé and 200 lities water in an autoclave for 5 hours to 210°-
220° C By evaporating and cooling the solution, the trioxynaphtalene is
obtaired in the form of small needles of a light brownish colour.
The 2.3.8. trioxynaphtalene melts at 164°-105° C; it is fairly easily soluble
in water, very easily in alcohol and ether. In benzol and chloroform it is
scarcely soluble The alkaline solution is coloured dark brown by the oxygen of
the air; perchloride of non produces an intense blue colouration. When treated
with acetic acid anhydide and some acetate of sodium, the 23 8. trioxynaphtalene
is transformed into a triacetyl-combination, which is obtained in fine needles,
melting at 125°-126° C
The new trioxynaphtalene is of great technical value in consequence of the
property of some of its azo derivatives of yielding fast dyeings on metallic mor-
dants For this purpose it is essential to combine it with the diazo compounds
in such a manner that the latter enter only in relation to the alpha hydroxyl
group. This may be done by working in a weak acid solution
In this case
both betahydroxyl groups are left free and the colours obtained are consequently
capable of forming lakes with metallic moidants
If for instance diazobenzol is allowed to react on trioxynaphitalene in a weak
acetic acid solution, a difficultly soluble brown dyestuff is obtained, which behaves
exactly like alizarine dyestuffs and may be fixed absolutely fast both on chrome-
mordanted cotton and wool
The dyeings are perfectly even (level), fast to acids, to potting and to light.
Hitherto azodyestufts possessing such properties were unknown and consequently
this discovery is of great importance
Of course the nature of the diazo body nsed for the combination greatly in-
fluences the shade and the solubility of the dyestuff It has been found that
generally speaking only the dyestuffs obtained from unsulphonated diazo bodies
and diazo carbonic acids yield dyestuffs of absolute fastness on cotton, whilst
on wool the fastness to milling is not on only very little impaired by the pre-
sence of one and sometimes also of two sulpho groups according to the weight
of the molecule of the component, as the effect of the sulpho groups on the
solubility is compensated by the energetic fixing power of the lake forming
hydroxyl groups The method is therefore not limited to the selection of certain
components, but is a general one
The following examples illustrate the same.
EXAMPLE I
13 8 kilos metanitraniline are diazotised and added to the solution of 18 kilos
of 238 trioxynaphtalene containing an excess of acetate The formation of
the dyestuff begins at once. After 12 hours the solution is heated to about
50° C, neutralised with some soda, and the complete separation effected by
addition of common salt
The dyestuff is best need in the form of a maste On cotton moulanted with

page_text: chrome or iron salts fast brown dyeings are obtained and likewise on wool mor-
danted with chrome.
EXAMPLE II.
22.4 kilos naphtionic acid are diazotised and the diazo compound introduced
into the solution of 18 kilos 2.3.8 toxynaphtalene containing an excess of
acetate. After 12 hours the mass is heated to about 50° C. and the dyestuff
precipitated with common salt It is easily soluble in hot water, the solution 18
of a dark red colour, which is turned to a violet by the addition of soda. On
mordanted cotton or wool fast dark brown dyeings are obtained
In an
analogous manner the combinations from other diazo bodies are produced, which
all yield brown to black shades
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed I declare that what
I claim 18:
1. The production of the 23.8. trioxynaphtalene by heating the 238 trioxy-
naphtalene sulphonic acid with water substantially as described.
2 The production of colouring matters by combining one molecule of a diazo-
compound with one molecule of 238 trioxynaphtalene substantially as herein-
before described.
3. The new trioxynaphtalene and the new dyestuffs deriving therefrom
TL 041 1