A New Group of Basic Coloring Matters and Means for Producing the same.
Year: 1892

page_text: Date of Application, 8th Dec., 1892
Complete Specification Left, 7th Sept., 1893-Accepted, 4th Nov., 1893
PROVISIONAL SPECIFICATION.
A New Group of Basic Coloring Matters and Means for Producing
the same.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a com-
munication to me from abroad by Leopold Cassella & Co., of Frankfort on Main,
in the Empire of Germany, Manufacturing Chemists,) do hereby declare the
nature of this invention to be as follows:-
This invention has for its object the production of new dye-stuffs of the azo-series
which in consequence of the presence of a basic group, will dye cotton, with the aid
of tannin mordants. The new dye-stuffs do not show the sensibility to the action
of acids of analogous bodies hitherto known.
A difference in the shade between the base and the salts has been observed. in
basic azo-dyes which contain the basic group, (for instance the dimethylamido
group) in the aromatic nucleus with which the azo group is combined, as for
instance with amidoazobenzole, methyl orange. If, however, the dimethylamido
group
is not in the nucleus but in a lateral methyl group, the change from base. to
salt loses its influence on the absorption of light. If, for instance, p. amidobenzyl
dimethylamine: (CH3)2N - CH, CH-NH2, is diazotised and combined
with beta-naphthol, a dyestuff results of the shade of the analogous azo derivative
from p. toluidine, which forms an easily soluble chlorhydrate having exactly, the
same orange color as the free base.
This observation also opens a way to make azo colors soluble in water without
changing their properties. In the following I describe the simplest application of
the invention.
The start may be from the different isomeric modifications of amidobenzyldialkyl-
amine, which are easily obtainable. If p. nitrobenzylchloride and dimethylamine
are brought together, a reaction quickly takes place, which is terminated when the
product is soluble in diluted acid without residue. The p. nitrobenzyldimethylamine
is distinguished by the property of its salts to crystallize, especially the salt of the
The solutions of
chlorhydrate; the reduction is carried out by the known means.
p. amidobenzyldimethylamine can be used directly for producing the dyestuffs. In
the place of the pure para-compound the start may be from the mixture of the
various isomers, which is obtained by uitration of benzylchloride (Kumpf, Liebig's
Annales, page 240, Noelting, Berichte der Deutschen Chemischen Gesellschaft,
vol. XVIII, page 385). Or benzylchloride and dimethylamine are first condensed
(V. Meyer, Berichte der Deutschen Chemischen Gesellschaft, X, page 310), then the
dimethylbenzylamine is dissolved in 3 parts of sulphuric acid and one equivalent of
nitric acid (mixed with sulphuric acid) is added whilst cooling. The nitration
results in nearly quantitative proportion. By this process the various isomers are
formed simultaneously, but principally the para-compound.
:
The following example may illustrate the method of producing the dyestuffs.
15 kilograms of amidobenzyldimethylamine are dissolved with 40 kilograms
muriatic acid and whilst cooling 7 kilograms nitrite are added; the easily soluble
diazo-compound is formed immediately and is allowed to run into the diluted
solution of 14.5 kilograms beta-naphthol dissolved in 4 kilograms hydrate of soda
and 40 kilograms soda; the dyestuff separates completely in the form of orange
colored flakes which unite to a shining tarry mass; the dyestuff is then isolated,
dissolved in 12 kilograms of muriatic acid and 200 litres water and the chlorhydrate
is precipitated from the solution with common salt. It is obtained in the form of a
tarry mass with a greenish reflection, it is easily soluble in water with an orange

page_text: COMPLETE SPECIFICATION.
A New Group of Basic Coloring Matters and Means for Producing
the same.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a com-
munication to me from abroad by Leopold Cassella & Co., of Frankfort on Main, in
the Empire of Germany, Manufacturing Chemists,) do hereby declare 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 has for its object the production of new dye-stuffs of the azo
series which in consequence of the presence of a basic group, will dye cotton, with
the aid of tannin mordants. The new dye-stuffs do not show the sensibility to the
action of acids of analogous bodies hitherto known.
A difference in the shade between the base and the salts has been observed in
basic azo dyes which contain the basic group, (for instance the dimethylamido
group) in the aromatic nucleus with which the azo group is combined, as for
instance with amidoazobenzole, methyl orange. If, however, the dimethylamido
group is not in the nucleus but in a lateral methyl group, the change from base to
salt loses its influence on the absorption of light. If, for instance, p. amidobenzyl-
dimethylamine (CH3)2N - CH, CH. - NH,, is diazotised and combined
with beta-naphthol, a dyestuff results of the shade of the analogous azo derivative
from p. toluidine, which forms an easily soluble chlorhydrate having exactly the
same orange color as the free base.
-
This observation also opens a way to make azo colors soluble in water without

page_text: changing their properties. In the following I describe the simplest application of
the invention.
.
The
The start may be from the different isomeric modifications of amidobenzyldialkyl-
amine, which are easily obtainable. If p. nitrobenzylchloride and dimethylamine
are brought together, a reaction quickly takes place, which is terminated when the
product is soluble in diluted acid without residue. The p. nitrobenzyldimethyl-
amine is distinguished by the property of its salts to crystallize, especially the salt
of the chlorhydrate; the reduction is carried out by the known means.
solutions of p. amidobenzyldimethylamine can be used directly for producing the
dyestuffs. In the place of the pure para-compound the start may be from
the mixture of the various isomers, which is obtained by nitration of benzylchloride
(Kumpf, Liebig's Annales, page 240, Noelting, Berichte der Deutschen Chemischen
Gesellschaft, vol. XVIII, page 385). Or benzylchloride and dimethylamine are
first condensed (V. Meyer, Berichte der Deutschen Chemischen Gesellschaft, X,
page 310), then the dimethylbenzylamine is dissolved in 3 parts of sulphuric acid
and one equivalent of nitric acid (mixed with sulphuric acid) is added whilst
cooling. The nitration results in nearly quantitative proportion. By this process
the various isomers are formed simultaneously, but principally the para-compound.
The following example may illustrate the method of producing the dyestuffs.
15 kilograms of amidobenzyldimethylamine are dissolved with 40 kilograms
muriatic acid and whilst cooling 7 kilograms nitrite are added; the easily soluble
diazo-compound is formed immediately and is allowed to run into the diluted
solution of 14.5 kilograms beta-naphthol dissolved in 4 kilograms hydrate of soda
and 40 kilograms soda; the dyestuff separates completely in the form of orange
colored flakes which unite to a shining tarry mass; the dyestuff is then isolated,
dissolved in 12 kilograms of muriatic acid and 200 litres water and the chlorhydrate
is precipitated from the solution with common salt. It is obtained in the form of a
tarry mass with a greenish reflection, it is easily soluble in water with an orange
color and dyes cotton treated with tannin the same shade. The dyeings are fast to
washing and light.
•
In an exactly analogous way the combination with other phenols and with amines
may be obtained of which the following are of special value.
The dyestuff from diazobenzyldimethylamine

page_text: :.
diazotised again and basic tetrazo dyestuffs can be produced from these diazoazo-
compounds by combining the same with phenols or amines.
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 is:
1. The production, as herein set forth, by the action of diazobenzyle-alkylamines
upon phenols or amines, of basic azo dyestuffs containing the basic group in a
nucleus lateral to the aromatic nucleus with which the azo group is combined.
2. The production as herein set forth of basic azo dyestuffs by the action of para
or ortho diazobenzyle-dialkylamines upon phenol, resorcine, diphenylaminė; m-oxy-
diphenylamine, m-ethoxydiphenylamine, diphenyl-m. phenylenediamine, ditolyle-
m. phenylenediamine, the alpha or beta-naphthylamines, the monoethyl-alpha or beta-
naphthylamines, the phenyl alpha or beta-naphthylamines, alpha or beta-naphthol,
the dioxynaphthalines."
3. As new manufactures the new basic azo dyestuffs herein set forth.