IMPROVEMENTS IN COLOURING MATTER
Year: 1883

page_text: PROVISIONAL SPECIFICATION left by Frank Wirth at the Office of the
Commissioners of Patents on the 16th July 1883. A communication from
Heinrich Baum, chemist, a person resident at Höchst on the Main, Germany
FRANK WIRTH of the firm of Wirth and Company, Patent Solicitors at Frankfort
on the Main, in the Empire of Germany, "IMPROVEMENTS IN COLOURING MATTER."
[a communication from Heinrich Baum, chemist, a person resident at Höchst on
the Main, Germany]
This Invention relates to improvements in the production or manufacture of
two isomeric alphanaphthol monosulpho acids from alpha-naphthol and in the pro-
duction or manufacture of azo colors therefrom.
The object of this Invention is the production of new azo colors and the novelty
consists in the production and separation of two alphanaphtholmonosulpho acids
and also the mode of action on diazo substances or bodies.
I will first describe the production and separation of the sulpho acids. When
treating alphanaphthol with an equal weight or up to double the weight of con-
centrated or fuming sulphuric acid at any temperature and in any manner, a
mixture is almost always obtained of sulpho acids, which mixture together with
diazò bodies, yields only a small percentage of useful azo colors. The reason of this
is that the alphanaphthol as compared with the Beta naphtol forms a very constant
and with difficulty, soluble alphanaphthyl sulphuric acid (a C, H, O SO, H)
which in the presence of hydrated sulphuric acid becomes sulphurized, and then by
further heating yields an alphanaphtholdisulpho acid which is useless for the pro-
duction of azo colors. The formation of this alphanaphthyl sulphuric acid may
however be prevented if an opportunity is offered to the alphanaphthol to combine
with sulphuric anhydride in acid solution, which at the same time protects the
hydroxyl group. The Inventor has found that the organic fatty acids, and
especially acetic acid, are excellent means for fulfilling these conditions. The alpha-
naphthol is dissolved in its own up to double 'its' weight of acetic anhydride and
heated to 60° to 70° C; the theoretical quantity of sulphuric anhydride, either as
гр
-

page_text: such or in the form of strong fuming sulphuric acid, or in the form of monochlor-
hydrine sulphuric acid, is then put into the aforesaid alphanaphthol solution;
hereby is obtained a mixture of two isomeric alpha-naphthol-monosulpho acids
which yield the theoretical quantity of azo dyes a proof that the formation of
alphanaphthyl sulphuric acid is avoided. The two monosulpho acids thus obtained
are then separated in the form of their salts of barium. The barium salt of the
one quite new acid is insoluble in cold water, that of the other is soluble in every
proportion.
The following example will illustrate it-144 kilogrammes alphanaphthol is
dissolved in its own, to double the weight of anhydrous acetic acid at 100° C.
When cooled down to 60° C, 100 kilogrammes of fuming sulphuric acid containing
80 per cent anhydride, or 116.5 kilogrammes chlorhydrine of sulphuric acid, or 80
kilogrammes of sulphuric anhydride are put into the solution while avoiding a rise
of temperature above 75° C. Lastly, the mixture is exposed to the temperature of
50° to 60° C for 5 to 6 hours. The so obtained mass is then poured into 5 times
its own bulk of water whereupon a quantity of barium carbonate is added sufficient
to fix the sulphuric acid as well as the sulpho acid formed. When the fuming acid
is used the hydrated sulphuric acid may be separated by its combining with lime
in the form of gypsum. The sulpho acids formed may then, by adding the theoretical
quantity of carbonate of barium (98.5 kilogrammes) be transformed into the barium
salts. The acetic acid is recovered from the so obtained solution by distillation
and the lye boiled down until crystals begin to form on the surface, and then
allowed to cool. Hereby is obtained the barium salt of a heretofore unknown new
alphanaphthol sulpho acid. The separated salt is filtered off and washed out with
a little water. This barium salt is tolerably soluble in hot water but scarcely at
all soluble in cold water. With chloride of iron it forms a violet red solution
which quickly turns brown and the ammoniacal solution fluoresces a pure blue.
The mother liquor contains the barium salt of the isomeric sulpho acid and is there-
fore directly boiled down till it is dry. This sulpho àcid which yields an easily
soluble barium salt is identical with that isolated by Schäffer (Berliner Berichte
1869 page 93) and with that by R. H. Nevile and A. Winther (Berliner Berichte
1880 page 1949) which alpha-naphthol-monosulpho acid was obtained from naph--
thylaminsulpho acid. With chloride of iron it gives a bluish green shade which
becomes greener by heat and its. diluted ammoniacal solution shows a pure violet
fluorescence. Instead of barium salt a strontium salt may be applied.
The next part of this Invention consists in the production of azódyes, the sulpho
acid of the alpha naphthol yielding salts which are soluble with difficulty, yield no
useful dyes with diazo compounds of aromatic hydrocarbons. But with sulpho
acids and carbon acids and' their sulpho acids, it yields beautiful and valuable, casily
crystallized dyes.
The following example illustrates the production of dyes from the barytic
salts of the hardly soluble sulpho acid.
A dye from diazo benzol sulpho acid and the difficultly soluble barium salt of
the new alphanaphtholmonosulpho acid, for instance 29 kilogrammes of the hardly
soluble barium salt, are dissolved in 100 kilogrammes of water, and to the solution
is added 5.3 kilogrammes of soda or the corresponding quantity of carbonate of
potash or carbonate of ammonia and the precipitated carbonate of barium is filtered
off. The filtrate is then mixed with 5 kilogrammes of lime in the form of milk of
lime and cooled by means of ice. To this solution is now added a solution of, 184
kilogrammes of diazo-benzol-sulpho acid obtained by well known methods. The
dark red solution is heated and filtered, and after the surplus dissolved lime has
been neutralised by muriatic acid it is separated by common.salt. The dye comes
out as a strongly red powder, and after it has been recrystallised from a concen-
trated aqueous solution, it may be obtained in red crystals which show a brilliant
blue surface lustre.
یا

page_text: Ine aye is remarkable for its very considerable coloring
and cotton and for its appearing a decided yellow color by refracted light while by
reflected light it appears, comparatively speaking, reddish orange.
I claim further the following combinations of this sulpho-acid with the following
Diazo acids:-
1. With Diazotolħolsulph-oacid
.Dye Red-orange
2.
"
3.
4.
5.
6.
7.
8.
9.
"
رو
"
"
"
"
"
Diazooxytoluolsulpho-acid
Diazoorthoanisolsulpho-acid
Diazoorthophenetolsulpho acid
Diazobenzolmonosulpho-acid
Diazoazobenzoldisulpho acid
Diazoalphanaphthalinesulpho-acid
Diazobetanaphthalinsulpho-acid
»
Bright red with a shade of
yellow (Ponceau)
"3
Bright red with a shade of
blue (Ponceau)
” (same as 3)
כן
Carmine red.
"
"
33
"
Red Ponceau.
"
Diazobetanaphtholethylethersulphio-acid,
Diazobenzoic acid
Bluish red.
Violet.
orange yellow
Diazocinnamic acid
10.
"
11.
Diazotoluic acid
"
12.
">
13.
"
Diazonaphthoic acid.
14
"
Diazooxynaphthoic acid
:
33
»
orange
rod
"
red violet
"
"3.
violet with brown tint.
The coloring matters, which form easily soluble Barium salts, are prepared in
the same way as those which form difficultly soluble Barium salts The easily
soluble Baryta salt yields with the Diazo compounds of the aromatic carburetted
hydrogens, as well as with carbon and sulpho acids and their ethers, very valuable
dyes. The coloring matters from sulphoacid with the Diazocompounds are, when
in a neutral condition, very difficultly soluble. Those of the sulpho or carbon
acids of the Diazo compounds are very easily soluble. Further it is advisable to
prepare the ammonium salt only by the action of Diazo compounds. The following
will serve as an explanation.-
29 kilogrammes of the Barium salt are dissolved in 100 kilogrammes of water.
5.3 kilogrammes soda or its equivalent of carbonate of potash, or better still of
carbonate of ammonia, are added and then filtered. 5 kilogrammes of lime in the
form of milk of lime are then added. To this solution, kept cool by means of ice,
14 kilogrammes of Diazo benzol chloride are added in solution. The liquid acquires
a yellow color and the coloring matter separates from it as an orange-yellow paste.
The coloring matter is then dissolved by heating with 5.3 kilogrammes soda, and,
after filtration, again thrown down with common salt and by neutralizing the
excess of alkali. It separates as a fiery orange-yellow powder and can be obtained
in the crystalline form by dissolving in hot water and allowing the solution to
cool. It dissolves with difficulty in water and colors wool and silk a fiery yellow-
orange.
I further claim the following combinations of this sulpho acid with Diazo bodies
in the manner above described―

page_text: 9 Dye with Diazobenzolsulphoacid
دو
10
22
"
"
11
12
13
14
15
し
23
"
+16
17
18
"
د,
"
"
"
L
"
Diazotoluolsulphoacid
Diazoxylolsulphoacid.
Diazodiphenylsulphoacid
Diazoanisolsulphoacid
Diazophenetolsulphoacid
Diazobenzolsulphoacid
Diazobenzoldisulphoacid
a Diazonaphthalinesulphoacid
B Diazonaphthalinesulphoacid
Diazobenzoic acid
Diazotoluicacid
Yellow-orange
Orange
Red orange.
Ponceau with blue tint
Ponceau with red tint.
"
"
"
Ponceau with blue tint
Carmoirsine red
Bluish red
Ponceau.
Orange yellow
»
"
•
20.
21
22
23
24
25
20.
27
28
29
30
31
32
"
"
"
23"
"
"
"
"
دو
"
"
"}
"
"
>>
"
"
"
L
"
"
"
33
"
"
Diazocinnamicacid
Ponceau
Diazonaphthoicacid
Diazoxynaphthoicacid
Diazobenzoicacidethylether
Diazotoluicacidethylethor
Diazocinnamicacidethylether
Diazonaphthoic acid ethylether
Diazooxynaphthoicacid methylether
,,Diazonaphtholmethylether
Orthodiazoanisol
Orthodiazophenetol
Diazoparacresolmethylether
Brownish violet
"
"
Orange
Orange
Fiery Ponceau
Violet
"
Ponceau with blue tint
"
Red with blue tint