New Processes for Producing Polyazo-dye-stuffs fro n Amidonaphtol- sulpho Acids.
Year: 1894

page_text: New Processes for Producing Polyazo-dye-stuffs fro n Amidonaphtol-
sulpho Acids.
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
Empe of Germany,) do hereby declare the nature of this invention to be as
follows .-
-
In the British Application No. 9529 dated May 15th 1894 two groups of dye-
stuffs are described which are produced from the tetiazo compounds obtainable
from Y
amidonaphtolsulpho acid according to the processes of Patent No. 19330.
The first group comprises dyestuffs which are formed by combining these tetrazo
bodies with an additional molecule of y amido-naphtolsulpho acid and one molecule
of another amine on phenole. In this process the last molecule of y amidonaphtol-
sulpho acid cau be replaced by a molecule of another amidonaphtolsulpho acid or a
molecule of a naphtolsulpho or naphtylaminesulpho acid, as last components meta-
diamines are used to advantage for these combinations.
'
The second group comprises dyestuffs for the production of which the intermediate
body-p. diamine-y acid-y acid-is first diazotised and then combined with two
molecules of a component In this process one of the two molecules of y acid may
be replaced by a molecule of another amidonaphtolsulpho acul the azo derivatives
of which are diazotisable, as for example the a₁ a amidovaplitol ß² ß¸ disulpho acid
or the Ba, amidonaphtol ẞ, 3, disulpho acid Also in these cases metadiannes
are used to advantage as last components All dyestuffs thus produced dye
unmoidanted cotton direct black and resemble in general the combinations previously
described
DYESTUFFS FROM ONE MOLECULE OF A PARADIAMINE, ONE MOLECULE
ONE MOLLOULE OF ANOTHER AMIDO-
YAMIDONAPHTOLSULPHO ACID,
NAIHTOLSULPHO ACID AND ONE MOLECULE OF A METADIAMINE.
As paradiamines especially suitable p. phenylenediamine, diamidodiphenylamine,
dianisidine, diamidoethoxydiphenyle, toldme are used. Of the amidonaphtolsulpho
acids foi ustance the per-deivatives give good results.
Example The tetrazoazo compound produced according to Example I in
Application No. 9529" from one molecule tetrazodiphenylamine and one molecule
amido-
y amidonaphtolsulpho acid is brought together with one molecule of
naphtol B B disulpho acid in a solution kept alkaline with carbonate of soda. An
Intermediate body of a black color is instantly formed which combined with one
molecule m. phenylenediamine produces a dyestuff which separates in the form of a
dark precipitate. It dyes unmordanted cotton bluish black.
If another of the above named paladiamines is used, similar products are obtained.
Instead of the disulpho acid an amidonaphtolinonosulpho acid as for instance the
aa amidonaphtol a, sulpho acid may be used with the same result.

page_text: •
DYESTUFFS FROM ONE
MOLECULE OF A PARADIAMINE, ONE
7 AMIDONAPHTOLSULPHO ACID, ONE MOLEOULE OF A
ACID AND ONE MOLECULE OF A METADIAMINE.
MOLECULE
NAPITOLSULPHO
The paradiamines named under No. I are likewise here suitable.
Of the sulpho acids the following give good results.
B naphtol B and B monosulpho acids, 3 naphtol & disulpho acid, a, naphtol
as and a monosulpho acids.
Example. The tetrazoazo compound produced according to Example 2 of
Application No. 9529 from one molecule of p. phenylendiamine and one molecule
Yainidonaphtolsulpho acid is brought together with one molecule of ẞ, naphtol
Basulpho acid in a solution kept alkaline with carbonate of soda. The intermediate
body of a violet black color which is instantly produced reacts easily with ono
molecule of m. phenylenediamine and thus forms a dyestuff which dyes unmordanted
cotton a deep black."
Analogous results are obtained by the application of other naphtolsulpho acids.
DYESTUFIS
PROM ONE MOLECULE OF A P. DIAMINE, ONE MOLLCULE OF
Y AMIDONAPHTOLSULPHO ACID, ONE MOLECULE NAPHTYLAMINESULPHO
ACID AND ONE MOLEOULE OF A METADIAMINE,
The
The best results are obtained by using the paradiamines named under No. I and
B, naphty lamine ẞs or B, sulpho acid, a, naphtylamine as, a Ba monosulpho acid as
well as of naphty laminiedisulpho acid R, a uaphtylamine disulpho acid
dyestuffs only differ with regard to their solubility. They all dye unmordanted
cotton deep black.
Example The tetrazoazo compound obtained according to Example 3 of Patent
No. 193300 from one molecule diamidoethoxydiphenyle and one molecule y amido-
naphtolsulpho acid is mixed in a solution of acetic acid with the solution of the
sodium salt of one molecule of a₁ a naphtylaminesulpho acid After several hous
the intermediate body is completely formed, then a solution of one molecule of
m phenylenediamine is added and afterwards the mixture 18 Faturated with a soda
solution, thus separating the sodium salt of the dyestuff.
DYESTUFFS FROM ONE MOLECULE OF A PARADIAMINE, ONE MOLECULE OF
Y AMIDONAPHTOLSULPHO ACID, ONE MOLECULE OF ANOTHER AMIDO-
NAPITOLSULPHO ACID AND TWO MOLECULES OF A METADIAMINE
The process corresponds to the one descubed in Example 2 of Application
No. 9529. Best results are obtained with the paradiamines named under No. I,
and as amidonaphtolsulpho acids which may replace the hrst or the second molecule
of y amidonaphtolsulpho acid in this process the a₁ a amidonaphtol ẞ, B, or
Ba disulpho acid and the ß, a, amido naphtol ẞ, ẞ, disulpho acid may for instance
be used.
Example: The tetrazoazo compound obtained according to Example 1 of
Application No 9529 from one molecule teti azodiphenylamine and one molecule
yamidonaphtolsulpho acid is combined in a solution hept alkaline with carbonate
of soda, with one molecule B₁, amidonaphtol B, ẞ, disulpho acid, the intermediate
body is immediately formed, its difhcultly soluble tetrazo derivative is then formed
by acidulating the mixture with muatic acid and adding one molecule of nitrite
of sodium.
If this is introduced into a solution kept alkaline with carbonate of

page_text: soda, of two molecules metaphenylenediamine, a dyestuff is formed which dyes
unmoidanted cotton deep black.
By using the known substitutes for the substances named in this example, dye-
stuffs of the same properties are obtained.
DY ESTUFFS OBTAINED BY USING ẞ AMIDONAPHTOLDISULPHO ACID INSTEAD
ON Y AMIDONAPH POLSULPITO AOID FOR THE PURPOSES OF THE PRESENT
INVENTION,
Valuable dyestuffs may be obtained, if in some of the processes forming the object
of the present invention, the y amidonaphtolsulpho acid 18 according to Patent
6972 replaced by the ß amidonaplitoldisulpho acid which is produced by heating
ẞ naphtylaminetrisulpho acid with caustic alkalies
Example 20 kilus diamidodiphenylamine are teli azotised and quickly brought
together with a solution of 32 kilos. ß amidonaphtoldisulpho acid kept alkaline by
means of carbonate of soda. To the thus forined intermediate body a weakly
alkaline solution of 25 kilos. y amidonaphtolsulpho acid 13 directly added
The
dyestuff 18 formed immediately. It dyes unmordanted cotton a bluish black
Example 11. By ticating the intermediate body obtained as above described
from one molecule tetrazodiphenylamine and one molecule of 3 amidonaphtol-
disulpho acid in acid solution with one molecule of nitrous acid a tetrazonzo
compound is formed which like the analogous tetrazoazo compounds described in
the British Application No 9529" can be combined with amines and phenoles.
The following combinations are of special value:
The combination with
2 molecules y amidonaphtolsulpho acid
2
"
in phenylenediamine
2
"
m. toluylenediamine
dyes cotton
-
bluish black
gieenish black
وو
Like all tetrazo compounds the above mentioned new tetrazoazo compound has the
property of forming mixed dyestufłe.
Example The tetrazoazo compound obtained as above described is quickly
brought together with a solution of 24 kilos. y amidonaphtolsulpho acid kept
alkaline by means of carbonate of soda To the thus formed intermediate body a
solution of 11 kilos. m phenylenediamine is added. The dyestuff is formed
immediately It dyes cotton a deep black If in this example the y amidonaphtol-
sulpho acid is for instance replaced by the equivalent quantity of

page_text: COMMER DE PUIFICATION.
New Processes for Producing Polyazo-dye-stuffs from Amido-naphtol-
sulpho Aoids.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a com-
munication to me from abroad by Leopold Cassella and Co, of Frankfort-on-Main,
in the Empne of Germany) do hereby declare the nature of this invention and in
what manner the same 18 to be performed to be particularly described and
ascertained in aud by the following statement.—
In the British Patent No. 9529 dated May 15th 1891 two groups of dye-stuff's
are described which are produced from the tetrazo compounds obtainable from
amidonaphtolsulpho acid according to the processes of Patent No 19330º.
The first group comprises dyestuffs which are formed by combining these tetrazo
bodies with an additional molecule of y amidonapitolsulpho acid and one molecule
of another amine or phenol. In this process the last molecule of y amidonaphtol-
Bulpho acid can be replaced by a molecule of another amido uaphtolsulpho acid
or a molecule of a naphtholsulpho or naphtylaminesulpho acid, as last componente
metadiamines are used to advantage for these combinations.
The second group comprises dyestuffs for the production of which the inter-
mediate body-p-diamine-y acid-y acid-first dinzotised and then combined
with two molecules of a component. In this process one of the two molecules of
Υ acid may be replaced by a molecule of another amido naphtolsulpho acid the
azo derivatives of which are diazotiable, as for example the a, a, amidonaphtol
B, B disulpho acid on the 3, a amulonaphtol ẞ, ẞa disulpho acid. Also in these
cases metadiamines are used to advantage as last components. All dyestuff's thus
produced dye unmordanted cotton direct black and resemble in general the
combinations previously described.
DYESTUFFS FROM ONE MOLECULE OF A PARADIAMINE, ONE MOLECULE
ANOTHER AMIDO-
Y AMIDONAPHTOLBULPITO ACID, ONE MOLICULE OF
NAPHTOLSULPHO-ACID AND ONE MOLECULE OF A METADIAMINE.
As paradiamines especially suitable p phenylene-diamine, dinmidodiphenylainine,
dinusidine, diamidoethoxydiphenyle, tolidine are used. Of the amidonaphtolsulpho
acids for instance the peri-derivatives give good results.
Example. The tetrazoazo compound produced according to Example I in
Patent No. 952994 from one molecule tetrazodiphenylamino and one molecule
y amidonaphtolsulpho acid is brought together with one molecule of a, a, amido-
naplitol B, Ba disulpho acid in a solution kept alkaline with carbonate of soda An
intermediate body of a black color is instantly formed which combined with one
molecule in phenylenediamine produces a dyestuft which separates in the form of a
dark precipitate. It dyes unmordanted cotton bluish black.
If another of the above named paradiamines is used, similar products are
obtained Instead of the disulpho acid an amidonaphtolmouosulpho acid, as for
instance the aa amidonaphtol sulpho acid may be used with the sume result.
DYESTUFFS
II.
FROM ONE MOLICULE OF
A
PARADIAMINE, ONE MOLECULL
Y AMIDONAPHTOLSULPHO ACID, ONE MOLECULE OF A NAPUTOLSULPHO
ACID AND ONE MOLECULE OF A METADIAMINE

page_text: a,
Of the sulpho acids the following give good results.
ẞ, naphtol, and B. Imonosulpho acids, ẞ naphtol & disulpho acid, u, naphtol
iud a monosulpho acids.
Example: The tetrazoazo compound produced according to Example 2 of
Patent No. 9529 from one molecule of p phenylendiamine and one molecule
amidonaphtolsulpho acid is brought together with one molecule of B, naphtol
3, sulpho acid in a solution kept alkaline with carbonate of soda The inter-
mediate body of a violet black color which is instantly produced reacts easily with
one molecule of m. phenylenediamine nud thus forms a dyestuff which dyes
uumordanted cotton a deep black.
Analogous results are obtained by the application of other naphtolsulpho aoids.
DYESTUFFS FROM ONE MOLECULE OF A P. DIAMINE, ONE MOLECULE OF
7 AMIDONAPITOLSULPHO ACID, ONE MOLECULE NAPHTYLAMINESULPHO
AOID AND ONE MOLECULE OF A METADIAMINE.
The best results are obtained by using the paradiamines named under No. 1
and B, naphtylamine 3, or 3. sulpho acid, a naphtylamine as, a 3 monosulpho
acid as well as of 3 naputylaminedisulpho aoid R, a naphtylamine 3 disulpho acid.
The dyestuffs only differ with regard to their solubility. They all dye unmordanted
cotton deep black.
Examplo. The tetrazoazo compound obtained according to Example 3 of Patent
No. 19330 from one molecule diamidoethoxydiphenyle and one molecule y amido-
naphtolsulpho acid is mixed in a solution of acetic acid with the solution of the
sodium salt of one molecule of a, a naphtylaminesulpho acid After several
hours the intermediate body is completely formed, then a solution of one molecule
of m. phenylenediamine is added and afterwards the mixture is saturated with a
soda solution, thus separating the sodium salt of the dyestuff.
DYESTUFFS FROM ONE
MOLECULE OF A PARADIAMINE, ONE MOLECULE
AOID, ONE MOLECULE OF ANOTHER
AMIDONAPITOLSULPHO ACID AND TWO MOLECULES OF A METADIAMINE.
OF
Y
AMIDONAPHTOLSULPHO
The process corresponds to the one described in Example 2 of Patent No. 9529.
Best results are obtained with the paradiamines named under No 1, and as
amidonaphtolsulpho acids which may replace the first or the second molecule of
y amidonaphtolsulpho acid in this process the a, a amidonaphtol ß ß, or
B, a disulpho acid and the ẞ a amidonaphtol B, B, disulpho-acid may for instance
be used.
Example: The tetrazoazo compound obtained according to Example 1 of
Patent No 9529 from one molecule tetrazodiphenylamine and one molecule
7 amidonaphtolsulpho acid is combined in a solution kept alkaline with carbonate
of soda, with one molecule B₁ a amidouaphtol ẞ, ẞ, disulpho acid, the intermediate
body is immediately formed its difficultly soluble tetrazoderivative is then formed
by acidulating the mixture with muriatic acid and adding one molecule of nitrite
of sodium If this is introduced into a solution kept alkaline with carbonate of
soda, of two molecules meta-phenylenediamine, a dyestuff is formed which dyes
unmordanted cotton deep black.
By using the known substitutes for the substances named in this example,
dyestuff's of the same properties are obtained.

page_text: DYFSTUFFS OBTAINED BY USING AMIDONAPHTOL DISULPHO AOID INSTEAD
OF AMIDONAPHTOLSULPHO ACID FOR THE PURPOSES OF THE PRESENT
INVENTION.
Valuable dyestuff's may be obtained, if in some of the processes forming the
object of the present invention, the y-amidonaphtol sulpho acid is according to
Patent No. 6972 replaced by the ẞ ainidonaphtoldisulpho acid which is produced
by heating ẞ naphty lamino trisulpho acid with caustic alkalies.
The
Example 20 kilos. diamidodiphenylamine are teti azotised and quickly brought
together with a solution of 32 kilos. ẞ amidonaphtoldisulpho acid Kopt alkaline by
means of carbonate of soda. To the thus formed intermediate body a weakly
alkaline solution of 25 kilos y amidonaphtolsulpho acid is duectly added
dyestuff is formed immediately. It dyes unmordanted cotton a blush black.
Example II. By treating the intermediate body obtained as above described from
one molecule tetrazodiphenylamine and one molecule of ẞ amidouaphtoldisulpho
acid in acid solution with one molecule of nitrous acid a tetrazoazo compound is formed
which like the analogous tetrazoazo compounds described in the British Patent
No 9529 can be combined with amines and phenoles. The following combinations
are of special value.
Like all tetrazo compounds the above mentioned new tetrazonzo compound bas
the property of forming mixed dyestuffs.
Example The tetinzonzo compound obtained as above described is quickly brought
together with a solution of 24 kilos y amidonaputol sulpho acid kept alkaline by
means of carbonate of soda To the thus formed intermediate body a solution of
11 kilos. m phenylenediamine is added. The dyestuff is formed inediately. It
dyes cotton a deep black. If in this example the y amidonaphtolsulpho acid is for
instance replaced by the equivalent quantity of

page_text: and
In the processes which form the object of the present invention the secondary
intermediate compounds such
as N = N-paradiamme-y acid-y acid and the
analogous compounds can also be produced by a method somewhat different from
the one berebefore described. Instead of hrst combining for instance the teti izo
derivative of a paradiamine with one molecule of y acid, diazotising and coupling
them with the second molecule of y acid, first the diazo derivative of the
may be combined with the second molecule of y acid and afterwards one mole lo
of the tetrazotised paradiamine may be allowed to react on one molecule of the
thus produced azo compound, (7 acid-y acid) The resulting substance will also
in this case be N = N-paradiamine-y acid-y acid. The same method may be
employed for producing the other analogous intermediate compounds mentioned
above in which 7 acid is replaced by other suitable acids
Laving 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. Producing polyazo dyestuffs by combining the tetrazo derivatives of the
intermediate compounds which are obtained by the combination of one molecule of
a paradiamine with one molecule of y amidonaphtolsulpho acid with one molecule
of another amidonaphtolsulpho acid, naphtolsulpho acid or naphtylaminesulpho acid,
and one molecule of a metadiamine substantially as described.
2. Producing polyazo dyestuffs by combining the tetrazo derivatives of the
intermediate compounds which are obtained by the combination of one molecule of
a paradiamine with one molecule of y amidonaphtolsulpho acid with one molecule
of another amidonaphtol sulpho acid, diazotising again and combining with two
molecules of a phenol or an amine such as m. phenylenediamine substantially as
described.
3. Producing polyazo dyestuffs by combining the tetrazo derivative of the
intermediate compound produced from one molecule of the tetra compound of a
paradiamine and one molecule of ẞ amidonaphtoldisulpho acid with one inolecule of
another amidonaphtolsulpho acid (such as y acid), of a naphtolsulpho acid or of a
naphty lamuesulpho acid and combining then either diectly or after further
diazotation with one or two molecules of an amine or a phenol such as m. phenylene-
diamine, y amidonaphtolsulpho acid substantially as described.
4. Producing the intermediate compounds-N = N-paradtamine-A-B [where
A stands for y amidonaphtolsulpho acid or ẞ amidonaphtoldisulpho acid and B for
yamidonaphtolsulpho acid or its equivalent in the process forming the object of
the present invention] by combining one molecule of a tetrazotised paradiamine
with one molecule of the azo compounds obtained by reacting with the diazo
compound of A on B, substantially as described
5. As new articles of manufacture the dyestuffs herein described.