The Production of Phenylamidooxynaphtaline Sulpho Acid and of Coloring Matters Deriving therefrom.
Year: 1894

page_text: Date of Application, 8th June, 1894
Complete Specification Left, 7th Mar., 1895-Accepted, 13th Apr., 1895
The Production of Phenylamidooxynaphtaline Sulpho Acid and
of Coloring Matters Deriving therefrom.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communi-
cation to me from abroad by Leopold Cassella and Co., of Frankfort-on-Main, in
the Empire of Germany,) do hereby declare the nature of this invention to be
as follows:-
My correspondents have found that the amido group in the amidonaphtolsulpho
acids can be phenylated by observing suitable conditions without the hydroxyl or
the sulpho group taking part in the reaction and, especially acids in which the
hydroxyl group stands in the a position, can easily, and in theoretical quantity, be
transformed into their phenyl derivatives.
As a typical example of such an acid the y-amidonaphtolsulpho acid may be
considered. If this acid is heated with aniline or its homologues in presence of
means of condensation such as hydrochlorate of aniline, an acid of the following
constitution is formed:
Favorable proportions for the production are the following:
25 kilos. y-amidonaphtolsulpho acid and 25 kilos. hydrochlorate of aniline are
dissolved in 100 kilos. aniline and the solution is cautiously heated up to 160° C. :
this temperature is maintained for 4 to 5 hours. The termination of the reaction
is ascertained in the following manner:
To a sample, an excess of diluted acid is added, the resulting precipitate is filtered
off, washed and distributed in acidulated water, some nitrite of soda is added and
tben the solution is tested, whether an alkaline solution of R salt still produces a
color reaction. As soon as a color reaction can no longer be noticed in a sample,
the melt is allowed to run into a solution of 120 kilos. muriatic acid of 21° Bé.
and 500 litres water. The phenylamidooxynaphtalinesulpho acid separates; it is
filtered off and washed out with water.
The acid thus obtained is almost perfectly pure; it forms colorless small needles.
It is difficultly soluble in water. If the acid is suspended in acidulated water
and nitrite of soda is added, it is transformed into oxynaphtylphenylnitrosamine-
sulpho acid which is easily soluble in water. In alkalies the acid dissolves by
forming easily soluble salts. It easily reacts like the non-phenylated acid with
diazo- and tetrazo-compounds forming valuable dye-stuffs which generally are more
difficultly soluble and darker in shade than the corresponding derivatives of the
non-phenylated acid. The symmetrical dye-stuffs which are formed from one
molecule of a paradiamine and two molecules of the acid, are for most purposes
not sufficiently soluble. Especially valuable are the mixed dye-stuffs from one
molecule of a paradiamine, one molecule of phenylamidonaphtolsulpho acid and one
molecule of an amine or a phenol; their shade and solubility vary according to the

page_text: nature of the latter. Common to all derivatives of the phenylamidonaphtolsulpho
acid is their great intensity, their remarkable fastness to light and as a typical
property their behaviour towards nitrous acid. The azo derivatives of the
phenylamidonaphtolsulpho acid formed.in alkaline solution contain a free phenyl-
amido group, thus differing materially in this respect from the known azo
derivatives of phenyl-3-naphtylamine. By the action of nitrous acid the hydrogen
of the imido group is substituted by the nitroso group, and nitrosamine dye-stuffs are
formed which latter are difficultly soluble. If they are produced on the fibre
itself, they are completely fixed. Consequently for the dye-stuffs of this new group
a simple treatment with nitrous acid is sufficient for fixation, whilst the analogous
dye-stuffs from the non-phenylated amidonaphtolsulpho acid require, besides the
nitrite bath, a second developing bath containing naphtol etc.
The process for producing these new dye-stuffs is illustrated by the following
examples:
Example I. 92 kilos. benzidine are tetrazotised in the known manner and
combined in alkaline solution by the addition of soda with 7-6 kilos. salicylic acid,
thus forming the intermediate body. Then a solution of 16 kilos. y-phenyl-
. amidonaphtolsulpho acid is added. The yellow color of the intermediate body
changes at once into a brown one. The mixture is left standing for 24 hours,
boiled again and filtered. The dye-stuff dyes unmordanted cotton a dark brown.
Example:II: 12.2 kilos. dianisidine are tetrazotised. The solution of the tetrazo
compound is mixed with a solution of 12.2 kilos. of an as-naphtolsulpho acid,. then
it is allowed to run into a cold soda solution. To the intermediate body thus
formed a solution of 16 kilos. phenyl-y-amidonaphtolsulpho acid is added. A dark
blue precipitate is formed. After 12 hours it is heated to the boiling point and
filtered. The dye-stuff dyes unmordanted cotton a blackish blue.
Likewise analogous combinations may be produced. As a matter of course it is
indifferent in which succession the components are brought to reaction. Instead of
benzidine or dianisidine other paradiamines, such as tolidine, ethoxybenzidine,
p. phenylenediamine, etc. may be used. Besides those second components already
mentioned, y-amidonaphtolsulpho acid, amidonaphtoldisulpho acid H and naphtionic
acid are found to be especially suitable. The dyeing properties of some com-
binations are shown in the following table:

page_text: The Production of Phenylamidooxynaphtaline Sulpho Acid: and
of Coloring Matters Deriving therefrom.
1, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communi-
cation to me from abroad by Leopold Cassella and Co., of Frankfort-on-Main, in
the Empire of Germany) 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:—
My correspondents have found that the amido group in the amidonaphtolsulpho
acids can be phenylated by observing suitable conditions without the hydroxyl or
the sulpho group taking part in the reaction and, especially acids in which the
hydroxyl group stands in the a position, can easily, and in theoretical quantity, be
transformed into their phenyl-derivatives.
As a typical example of such an acid the y-amidonaphtolsulpho acid mayi be
considered.
If this acid is heated with aniline or its homologues in presence of means of
condensation such as hydrochlorate of aniline, an acidiof the following constitution
is formed.
Favorable proportions. for the production are the following.
25 kilos. y-amidonaphtolsulpho acid and 25 kilos. hydrochlorate of aniline are
dissolved in 100 kilos. aniline and the solution is cautiously heated up to 160° C. ;
this temperature is maintained for 4 or 5 hours: The termination of the reaction
is ascertained in the following manner:-
To a sample, an excess of diluted acid is added, the resulting precipitate is
filtered off; washed and distributed- in acidulated-water, some nitrite of soda is
added and then the solution is tested, whether an alkaline solution of a salt of
beta-naphtoldisulpho acid R still produces a color reaction. As soon as a color
reaction can no longer be noticed in a sample, the melt is allowed to run into a
solution of 120 kilos. muriatic acid of 21° Bé, and 500 litres water.
The phenyl-
amidooxynaphtalinesulpho acid separates; it is filtered off and washed out with
water...
The acid thus obtained is almost perfectly pure; it forms colorless small needles.
It is difficultly soluble in water. If the acid is suspended in acidulated/water and
nitrite of soda is added, it is transformed into oxynaphtylphenylnitrosaminesulpho
acid which is easily soluble in water. In alkalies the acid dissolves .by forming
easily soluble salts. It easily reacts like the non-phenylated acid with diazo- and
tetrazo-compounds forming valuable dye-stuffs which generally are more difficultly
soluble and darker in shade than the corresponding derivatives of the non-phenylated
acid. The symmetrical dye-stuffs which are formed from one molecule of a para-
diamine and two molecules of the acid, are for most purposes not sufficiently soluble.
Especially valuable are the mixed dye-stuffs from one molecule of a paradiamine, one
molecule of phenylamidonaphtolsulpho acid and one molecule of an amine or a

page_text: phenol; their shade and solubility vary according to the nature of the latter.
Common to all derivatives of the phenylamidonaphtolsulpho acid is their great
intensity, their remarkable fastness to light and as a typical property, their
behaviour towards nitrous acid. The azo derivatives of the phenylamidonaphtol-
sulpho acid formed in alkaline solution contain a free phenylamido group, thus
differing materially in this respect from the known azo derivatives of phenyl-
B-naphtylamine. By the action of nitrous acid the hydrogen of the imido group is
substituted by the nitroso group, and nitrosamine dye-stuffs are formed which latter
are difficultly soluble. If they are produced on the fibre itself, they are completely
fixed. Consequently for the dyestuffs of this new group a simple treatment with.
nitrous acid is sufficient for fixation, whilst the analogous dye-stuffs from the non-
phenylated amidonaphtolsulpho acid require, besides the nitrite bath, a second
developing bath containing naphtol etc.
The process for producing these new dye-stuffs is illustrated by the following
examples:
Example I. 9-2 kilos. benzidine are tetrazotised in the known manner and combined
in alkaline solution by the addition of soda with 7.6 kilos. salicylic acid, thus forming
the 'intermediate body. Then a solution of 16 kilos. y-phenyl-amidonaphtolsulpho
acid is added. The yellow color of the intermediate body changes at once into a
brown one.
The mixture is left standing for 24 hours, boiled again and filtered.
The dye-stuff dyes unmordanted cotton a dark brown.
Example II. 12.2 kilos. dianisidine are tetrazotised. The solution of the tetrazo
compound is mixed with a solution of 12.2 kilos. of as a₂-naphtolsulpho acid, then it
is allowed to run into a cold soda solution. To the intermediate body thus formed a
solution of 16 kilos. phenyl-y-amidonaphtolsulpho acid is added. A dark blue
precipitate is formed. After 12 hours it is heated to the boiling point and
filtered. The dye-stuff dyes unmordanted cotton a blackish-blue.
Likewise analogous combinations may be produced. As a matter of course it
is indifferent in which succession the components are brought to reaction. Instead
of benzidine or dianisidine other paradiamines, such as tolidine, ethoxybenzidine,
p. phenylenediamine, etc. may be used. Besides those second components already
mentioned, y-amidonaphtolsulpho acid, amidonaphtoldisulpho acid H and naphtionic
acid are found to be especially suitable. The dyeing properties of some combinations
are shown in the following table:

page_text: Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The process for the manufacture of phenylated amidonaphtolsulpho acids or
their homologues substantially as described.
2. The production of azo colouring matters from phenylated amidonaphtolsulpho
acids or their homologues substantially as described.
3. As new articles of manufacture the phenyl-gamma-amidonaphtolsulpho acid
above described and the azo colouring matters deriving therefrom.
Dated this 18th day of February 1895.
SYDNEY PITT.