Production of New Disazo Coloring- Matters.
Year: 1893

page_text: .Date of Application, 13th Mar., 1893
Complete Specification Left, 12th Dec., 1893-Accepted, 13th Jan., 1894
PROVISIONAL SPECIFICATION.
The Production of New Disazo Coloring- Matters.
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:-
The object of this invention is the production of coloring matters deriving from
a new acid which is obtained from the amidonaphtoldisulpho acid H, described in
Cassella's British Patent No. 17421, by substituting alkyl or benzyl in the place
of one of the hydrogens of its amido group. The new acid is consequently a
hydroxyldisulpho derivative of the monoalkyl-alpha-naphtylamine.
prepared for instance in the following manner :
It can be
36 kilos. sodium salt (neutral) of amidonaphtoldisulpho acid H are heated in a
closed vessel together with 11 kilos. ethyl-bromide and 60 kilos. calcium carbonate
and some diluted alcohol of 50% during 20 hours to 60 deg. C. From the neutral
solution the calcium carbonate is eliminated by filtration and the liquid is then
acidulated with 12 kilos. muriatic acid. A small quantity of acid separates
unchanged. The filtered solution is concentrated by evaporation.
ethylamido-naphtoldisulpho acid H is precipitated by cooling in the shape of fine
colorless needles.. This new acid is easily soluble in water, less so in strong
alcohol. Treated with nitrous acid, it is transformed into nitrosamine which is
easily soluble and. behaves about the same as an alphanaphtolsulpho acid.
The mono-
In an analogous manner the methyl or benzyl derivatives are obtained. The
a a monoalkyl-amidonaphtol 2 B disulpho acid is of, great technical value.
Combined in alkaline solution with the tetrazo derivatives of p. diamines such as
benzidine, tolidine, diamidoethoxydiphenyle, diamidodiphenolether etc., it produces
blue dye-stuffs of a very pronounced greenish tint which dye unmordanted cotton.
These dye-stuffs differ essentially from the products which are obtained by
treating with halogen alkyls and an alkali, those disazo derivatives of 'amidonaphtol-
disulpho acid H which are obtained in acid solution and contain a free, hydroxyl
group. (The analogous disazo derivatives of this acid obtained in alkaline solution,
are not altered by the same treatment.) The disazo dye-stuffs are either obtained, by
combining in alkaline solution one molecule of the tetrazo eompound with two
molecules of the alkyl-amidonaphtoldisulpho acid or by uniting one-molecule of the
acid with one molecule of the tetrazo compound and then combining the resulting
intermediate body with amines or phenols. As the technical value of the deriva-
tives of the alkyl-amidonaphtoldisulpho acid principally consists in their greenish
blue shade,such products are preferably selected as second components, as produce
blue or blueish black dye-stuffs, as for instance amidonaphtoldisulpho acid -H,
amidonaphtal-gamma-sulpho acid, 14 alphanaphtolsulpho acid, dioxynaphtałene-
sulpho acid S.
1.
The following examples explain the process:-
Example 1. 18.4 kilos. benzidine are diazotised in the known manner and the
tetrazo compound is introduced at 0 degree C. into a solution of 83-kilos. a, ethyl-
amido a naphtol ẞ, ẞ, disulpho acid and 53 kilos. soda in about 1000 litres water.
From the dark blue solution the dye-stuff is precipitated with common salt. Dried
it forms a shiny bronzy mass. It dyes unmordanted cotton in a soda bath a pure
blue.
Example. 2. The tetrazo compound from 18.4 kilos. benzidine is at 0 degree C.
kilos soria in 400 litres water.
bl.. intended into
solution of A
.

page_text: Immediately afterwards and while well stirring, a neutral solution of 37 kilos.
a ethyl-amido a naphtol ẞ, ẞ, disulpho acid is added. The resulting intermediate
body separates at once in the form of a blue black precipitate. A neutral solution
of 24 kilos. gamma-amidonaplitolsulpho acid is then added. The intermediate
body dissolves first, then the dye-stuff separates in the form of a dark colored
precipitate. It dyes unmordanted cotton a blue black.
Tolidine, diamidoethoxydiphenyle, diamidodiphenolether may be used in the
place of benzidine with the same result. The nature of the alkyl group having
no influence on the properties and shades of the dye-stuffs, it results that in place
of the ethyl compound the methyl or benzyl compounds may be applied equally
well.
Dated this 13th day of March 1902
COMPLETE SPECIFICA FION.
The Production of New Disazo Coloring Matters.
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 :-
The object of this invention is the production of coloring matters deriving from
a new acid which is obtained from the amidonaphtoldisulpho acid H describe! in
Cassella's British Patent No. 1742", by substituting alkyl or benzyl in the place
of one of the hydrogens of its amido group. The new acid is consequently a
hydroxyl-disulpho derivative of the monoalkylalpha-naphtylamine.
prepared for instance in the following manner :-
It can be
36 kilos. sodium salt (neutral) of amidonaphtoldisulpho acid I are heated in a
closed vessel together with 11 kilos. ethyl-bromide and 60 kilos. calcium carbonate
and some diluted alcoliol of 50 % during 20 hours to 60 dog. C. From the
neutral solution the calcium carbonate is eliminated by filtration and the liquid is
then acidulated with 12 kilos muriatic acid. A small quantity of acid H separates
unchanged. The filtered solution is concentrated by evaporation.
The mono-
ethylamido-naphtoldisulpho acid H is precipitated by cooling in the shape of fine
colorless needles. This new acid is easily soluble in water, less so in strong
alcohol. Treated with nitrous acid, it is transformed into nitrosamine which is
easily soluble and behaves about the same as an alphanaphtolsulpho acid.
In an analogous manner the methyl or benzyl derivatives are obtained. The
a a monoalkyl-amidonaphtol B. ẞ, disulpho acid is of great technical value.
Combined in alkaline solution with the tetrazo derivatives of p. diamines such as
benzidine, tolidine, diamidoethoxydiphenyle, diamidodiphenolether etc., it produces
blue dyestuffs of a very pronounced greenish tint which dye unmordanted cotton.
These dye-stuffs differ essentially from the products which are obtained by
treating with halogen alkyls and an alkali, those disazo derivatives of amido-
paphtoldisulpho acid H which are obtained in acid solution and contain a free
hydroxyl group. (The analogous disazo derivatives of this acid obtained in
alkaline solution, are not altered by the same treatment.)
The disazo dye-stuff's are either obtained by combining in alkaline solution one
molecule of the tetrazo compound with two molecules of the alkyl-amidonaphtol-
disulpho acid or by uniting one molecule of the acid with one molecule of the
tetrazo compound and then combining the resulting intermediate body with amines
or phenols. As the technical value of the derivatives of the alkyl-amidonaphtol-
disulpho acid principally consists in their greenish blue shade, such products are
preferably selected as second components as produce blue or blueish black dye-

page_text: stuffs, as for instance amidonaphtoldisulpho acid H, amidonaphtol-gamma-sulpho
acid, 14 alphanaphtolsulpho acid, dioxynaphtalenesulpho acid S.
The following examples explain the process:
Example 1. 184 kilos. benzidine are diazotised in the known manner and the
tetrazo compound is introduced at 0 degree C. into a solution of 80 kilos.
aethylamido a naphtol ẞ ẞ, disulpho acid and 53 kilos. soda in about 1000 litres
water. From the dark blue solution the dye-stuff is precipitated with common
salt. Dried it forms a shiny bronzy mass. It dyes unmordanted cotton in a soda
bath a pure blue.
Example 2. The tetrazo compound from 184 kilos. benzidine is at 0 degree C.
quickly introduced into a solution of 42 kilos. soda in 400 litres water. Immediately
afterwards and while well stirring, a neutral solution of 37 kilos. a, ethyl-amido
a, naphtol B Bẞ, disulpho acid is added. The resulting intermediate body separates
at once in the form of a blue black precipitate. A neutral solution of 24 kilos.
gamma-amidonaphtolsulpho acid is then added. The intermediate body dissolves
first, then the dye-stuff separates in the form of a dark colored precipitate. It
dyes unmordanted cotton a blue black.
Tolidine, diamidoethoxydiphenyl, diamidodiphenol-ether may be used in the
place of benzidine with the same result. The nature of the alkyl group having
no influence on the properties and shades of the dye-stuffs, it results that in
place of the ethyl compound the methyl or benzyl compounds may be applied
equally well.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, 1 declare that what I
claim is :-
1. The production of monoalkylated amidonaphtoldisulpho acid substantially as
described.
2. The production of disazo coloring matters by combining one molecule of a
tetrazo compound of a para diamine with two molecules of alkylamidonaphtol-
disulpho acid H, substantially as described.
3. The production of disazo coloring matters by combining one of the diazo-
groups of a tetrazo compound of a para diamine with alkylamidonaphtoldisulpho
acid H, and the other diazo-group with an amine or a phenol, such as a naphtol-
sulpho acid, y amidonaphtolsulpho acid, amidonaphtoldisulpho acid H, substantially
as described.
4. The new coloring matters hereinbefore described.
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