Production of New Blueish-black Coloring Matters.
Year: 1889

page_text: Date of Application, 13th May, 1889
Complete Specification Left, 11th Feb., 1890-Accepted, 22nd Mar., 150
PROVISIONAL SPECIFICATION.
The Production of New Blueish-black Coloring Matters.
1. SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communication
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 :-
-
The tetrazo-compounds the combinations of which with naphtols or their sulphoacids
form the object of the British patent No. 92148 can also be combined with the
substituted metadiamines and meta-amidophenoles thus producing black coloring
matters which are of great technical value in consequence of their fastness to milling
and their shades; some of them have also affinity to unmordanted cotton.
In the following I give some examples in order to demonstrate more clearly the
nature of my invention and the manner in which it is to be performed.
1st Example I combine the diazo-compound of 34-7 kilos. of a naphtylamine
disulphonate of sodium with an aqueous solution of 18 kilos. of a naphtylamine
chlorhydrate and transform the violet amidoazo body into the tetrazo-compound
by adding 7 kilos. of nitrite of soda. This tetrazo compound I pour into an alcoholic
solution of 16 kilos. tetramethyltoluylenediamine containing an equivalent quantity
of acetate of sodium. The coloring matter is almost entirely dissolved and crystal-
lises after evaporation of the alcohol. The dyestuff dyes wool in neutral bath con-
taining common salt a blueish black.
:
2nd Example I combine the tetrazo-compound obtained as indicated in the
above example in acid solution with 16 kilos. of diethyl-m-phenylenediamine.
The acid of the new coloring matter is precipitated after a short time, and is
separated by filtration. The dyestuff dies wool in neutral bath a black of greenish
blue shade.
3rd Example: If I use for the combination an alcoholic solution of 29 kilos. of
dibenzyle-m-phenylenediamine, I obtain a solution of a deep blue tint out of which the
new coloring matter is separated by adding water after evaporating the alcohol. It
similarly to the preceding one.
4th Example I cause the tetrazo-compound obtained as per 1st example, to run
into an alcoholic solution of 25 kilos. of diphenyl-u-phenylenediamine, or of 28 kilos.
ditolyl-m-phenylenediamine. The acid of the new coloring matter separates at once
forming a crystalline precipitate. After a short time it is filtered, it dyes wool
in acid or neutral bath a blueish black and unmordanted cotton a deep blue.
5th Example: If an alcoholic solution of 39 kilos. of diethyldiphenyl-m-
phenylenediamine is used, I likewise obtain an acid, which separates easily. The
dyestuff dyes wool in acid or neutral bath from grey to black.
6th Example: The alcoholic solution of 35 kilos. of a dinaphtyl-m-phenylenediamine
serves to form a dyestuff dyeing wool in acid or neutral bath a blueish black of great
fastness.
The substituted amidophenols which are best suitable for my purposes, are tho
m-oxydiphenyleamine, the m-oxymethyldiphenylamine and the ethers and homologues
of these bodies.
7th Example: The tetrazo-compound prepared as indicated in the 1st Example I
combine in alkaline solution with 18 kilos. m-oxydiphenyleamine (monophenyle-m-
amidophenole) the dyestuff is formed immediately and precipitated by the usual-
means; it dyes wool in neutral or acid bath a black of reddish shade, but of great
strength; it shows a remarkable affinity to unmordanted cotton.
The
8th Example. In the same manner this combination can be performed with
21 kilos. of in-oxyethyle-diphenyleamine (phenyle-ethyle-m-amidophenole).
dyestuff resembles the foregoing one, but it is of a more blueish shade,

page_text: :
9th Example In the same manner 1 combine the alcoholic solution of 28 kilos.
meta-ethoxyparatolyle-phenyleamine (paratolyl-m-amidophenetole) which yields a
solution of a dark blue shade, from which the dyestuff is separated in small crystals;
it resembles the ono formed by the 7th example and has a great affinity to the
cotton fibre.
In all the examples I have used the same tetrazo-compound deriving from
alpha-naphty lanine disulphonic acid. Instead of the latter I can likewise use the
sulpho acids of aniline, toluidine, xylidine, benzidine its homologues and amidostilbene
combining these in the known inanner with a-naphtylamine and then with the
substituted amidophenole or the metadiamines.
Dated this 13th day of May 1889.
CARPMAEL & Co.,
Agents.
COMPLETE SPECIFICATION.
The Production of New Blueish-black Coloring Matters.
1, SYDNEY PITT, of Sutton in the County of Surrey, Gentleman, (a communication
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 :—
their
The tetrazo-compounds the combinations of which with naphtols or
sulphoacids form the object of my correspondents British Patent No. 92145 can
also be combined with the substituted metadiamines and meta-amido-phenoles thus
producing black coloring matters which are of great technical value in consequence
of their fastness to milling and their shades, some of them have also affinity to
unmordanted cotton.
In the following I give some examples in order to demonstrate more clearly the
nature of the Invention and the manner in which it is to be performed.
1st Example: Combine the diazo-compound of 34.7 kilos. of a-naphtylaminedisul-
phonate of sodium with an aqueous solution of 18 kilos. of a-napthylamine chlorhydrate
and transform the violet amido azo body into the tetrazo compound by adding 7 kilos.
of nitrite of soda. This tetrazo-compound pour into an alcoholic solution of 16 kilos.
tetramethyltoluylenediamine, containing an equivalent quantity of acetate of sodium.
The coloring matter is almost entirely dissolved and crystallises after evaporation
of the alcohol. The dyestuff dyes wool in neutral bath containing common salt a
blueish black.
2nd ExampleCombine the tetrazo-compound, obtained as indicated in the above
example in acid solution with 16 kilos. of diethyl-m-phenylenediamine. The acid of
the new coloring matter is precipitated after a short time and is separated by
filtration. The dyestuff dyes wool in neutral bath a black of greenish blue
shade.
3rd Example-If for the combination an alcoholic solution of 29 kilos. of
dibenzole-m-phenylenediamine is used then a solution of a deep blue tint is obtained
out of which the new coloring matter is separated by adding water after evaporating
the alcohol. It dyes similarly to the preceding one.
4th Example: If an alcoholic solution of 39 kilos. of diethyldiphenyl-m-
phenylenediamine is used, an acid is likewise obtained which separates easily. The
dyestuff dyes wool in acid or neutral bath from grey to black.
5th Example: The alcoholic solution of 35 kilos. of a dinaphtyl-m-phenylenediamine
serves to form a dyestuff dyeing wool in acid or neutral bath a blueish black of "
great fastness.
The substituted amidophenols which are best suitable for these purposes are the
m-oxydiphenyleamine, the m-oxymethyldiphenylamine and-the ethers and homologues
of these bodies.

page_text: 6th Example: The tetrazo-compound prepared as indicated in the 1st example is
combined in alkaline solution with 18 kilos. m-oxydiphenyleamine (monophenyle-
m-amidophenole) the dyestuff is formed immediately and precipitated by the usual
means; it dyes wool in neutral or acid bath a black of reddish shade, but of great
strength; it shows a remarkable affinity to unmordanted cotton.
7th Example:-In the same manner this combination can be performed with
The
21 kilos. of m-oxyethyle-diphenyleamine (phenyle-ethyle-m-amidophenole).
drystuff resembles the foregoing one, but it is of a more blueish shade.
8th Example: In the same manner combine the alcoholic solution of 28 kilos.
meta-ethoxy-paratolyle-phenyleamine (paratolyl-m-amidophenotole) which yields a
solution of a dark blue shade, from which the dyestuff is separated in small crystals ;
it resembles the dyestuff formed according to the 7th example and has a great
affinity to the cotton fibre.
In all the examples the same tetrazocompound deriving from alpha-naphtylamine
disulphonic acid has been used. Instead of the latter likewise may be used the
sulpho acids of aniline, toluidine, xylidine, benzidine its homologues and amidostilbene
combining these in the known manner with a naphtylamine and then with the
substituted amidophenoles or metadiamines.
I would remark that I am aware of the recently published Specification No. 4825
in the year 1889 and I make no claim to the Invention described in the said
Specification and the claiming clauses of my Specification are to be read subject to
this disclaimer.
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 production of new blueish black coloring matters by combining one of the
diazo-azo-compounds obtained by the general process described in the Specifica-
tion No. 9214 in the year 1885 (consisting in reacting with diazosulphoacids upon
a-naphtylamine and diazotizing again) with a substituted metadiamine or meta-
amidophenol.
.
2. The production of new blueish black coloring matter substantially in the manner
herein described.