The Production of New Acetnaphtylene-diamine-sulpho Acids and of Coloring Matters Derived therefrom.
Year: 1893

page_text: Date of Application, 14th Aug., 1893
Complete Specification Left, 11th May, 1894-Accepted, 16th June, 1894
PROVISIONAL SPECIFICATION.
The Production of New Acetnaphtylene-diamine-sulpho Acids and
of Coloring Matters Derived therefrom.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communi-
cation 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:-
By nitration of the acetylcompound of naphtionic acid Nietzki and Zübelen
(Berichte der Deutschen Chemischen Gesellschaft XXII page 451) have obtained
a nitro acid which by reduction gave the eulpho acid of the acetic combination
of an a, naphtylenediamine. My foreign correspondents have ascertained that, if
instead of naphtionic acid, a ß, or a, ß, naphty laminesulpho acid is subjected to an
analogous treatment, sulpho acids of the acetic combination of an as naphtylene-
diamine are obtained which in contrast to the above mentioned isomeric acid are of
great technical value.
In particular new disazo dye-stuff's are obtainable from a, a, acetnaphtylene-.
diamine ẞ (or ẞ4) sulpho acid, containing the group:
From the above formula it is evident that the position of the various groups
remains the same, whether the sulpho group is placed in the ẞ, or ẞ position.
Consequently it is of no importance for the technical production of the new acids,
whether one starts from the pure ai ẞ, (or a, ß.) naphtylaminesulpho acid or from
a mixture of these two.
The acetylation of the a₁ 3 and a₁ ẞ, naphtylaminesulpho acid may be carried
out successfully by treating the dry sodium salts of the acid during some time with
an excess of glacial acetic acid. After the latter has been separated by distillation,
the acetylated acids are obtained in a shape directly suitable for technical purposes.
The nitration may f.i. be carried out as follows:-
265 kos. of the mixed acetnaphtylaminesulpho acid are dissolved in 1300 kos.
sulphuric acid and while cooling 160 kos. of a mixture of nitric and sulphuric acid,
containing 43% HNO3 are introduced. The mixture is left standing for a short
time, then diluted to 3000 litres by adding ice and water, then the sodium salts of
the nitro acids are precipitated by addition of 500 kos. common salt.
These are easily soluble in pure water. The salt of the a, ẞ, acid crystallises in
the shape of needles, that of the a, ẞs acid in the shape of rhombic tablets.
Characteristic of the nitro acids is that they can be easily saponified with mineral
acids. The as a nitronaphtylamine ẞ sulpho acids thus produced dye wool in an
acid bath a greenish yellow, similar to naphtol yellow.
The reduction of the nitroacetnaphtylaminesulpho acids is best executed in the
following manner:
31 kos. nitro acid are introduced gradually into a boiling mixture of 50 kos. iron
shavings, 100 litres water and 3 kos. acetic acid 50%. As soon as the liquid loses

page_text: its color, the dissolved iron is precipitated with soda. Then the liquid is filtered
and the a, a, acetnaphtylenediaminesulpho acid is precipitated from the filtrate by
the addition of 20 kos. muriatic acid.
The a, a, acetnaphtylamine ẞ, sulpho acid as well as the B. sulpho acid are very
difficultly soluble even in warm water. Both crystallise in needles. If treated
with nitrous acid, acetamidodiazonaphtalenesulpho acids result. They are of a
yellow color, very difficultly soluble in water, and react very easily with amines
and phenoles.
The new a, a, acetnaphtylenediaminesulpho acids combine also with diazo and
tetrazo bodies.
The new acids can be used for the production of dye-stuffs in the following
manner:
Disazo dye-stuffs can be produced by saponifying the azo combinations of the
aa, amidoacetnaphtalidsulpho acid, diazotising again and combining a second
time. Two cases have bere to be distinguished: if the first combination was done
with a phenol, a diazo-azo compound is obtained by the second diazotation, from
which disazo dye-stuffs of the simple constitution:
-
(a₁)
- N=N
CH, SO,H
-
R'
- N - N R¹¹
-
are produced; if however the first combination was accomplished with a diazotisable
amine, a tetrazo-azo compound is obtained by the second diazotation, which gives
dye-stuffs of the following constitution :
AT
D
AT
DI
C₁, H, SO,H
(N = NR¹.
I.
Example. 302 kos. a, a, amidoacetnaphtalid ẞ, sulpho acid are diazotised
with 7 kos. nitrite and 24 kos. muriatic acid. The diazo compound separates
after some time as a difficultly soluble powder of a weak yellowish color. If the
same is introduced into an alkaline solution of 25 kos. a, a, naphtolsulphonate of
sodium, the dye-stuff forms immediately; the separated dye-stuff is filtered off and
boiled with 500 litres of 10 % soda lye, until a sample mixed with acetic acid shows
a pure blue-violet color. Then it is acidulated with muriatic acid and at a
temperature of 0° C. 7 kos. nitrite are added. After a few hours the dye-stuff will
be found to be completely transformed into the difficultly soluble diazo compound
of a brown color. If the same is introduced into the alkaline solution of 38 kos.
ẞ naphtoldisulpho acid R, after it has been left standing for a short time, the
formed dye-stuff separates as a dark blue precipitate. It dyes wool in an acid bath
a deep blue.
Analogous dye-stuffs are obtained, if in the place of a, a, naphtolsulpho acid
other components as f.i. salicylic acid, ẞ naphtol, ẞ, naphtol ẞ, sulpho acid,
a, a dioxynaphtalene a, sulpho acid, are used. In the place of -naphtoldisulpho
acid phenoles as well as amines can be used, especially a, as naphtolsulpho acid,
Ba, amidonaphtol ẞ, sulpho acid (y), a, as amidonaphtol ẞ, ẞ, disulpho acid (H),
a, a dioxynaphtalene ß, B,-disulpho acid, m. phenylenediamine.

page_text: CARPMAEL & Co.,
Agents for the Applicant.

page_text: The Production of New Acetnaphtylene-diamine-sulpho Acids and
of Coloring Matters Derived therefrom.
1, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communi-
cation 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 :-
By nitration of the acetyl compound of naphtionic acid Nietzki and Zübelen
(Berichte der Deutschen Chemischen Gesellschaft XXII page 451) have obtained
a nitro acid which by reduction gave the sulpho acid of the acetic combination
of a, a, naphtylenediamine. My foreign correspondents have ascertained that, if
instead of naphtionic acid, a, ß, or a B. naphtylaminesulpho acid is subjected to an
analogous treatment, sulpho acids of the acetic combination of a, ag naphtylenediamine
are obtained which in contrast to the above mentioned isomeric acid are of great
technical value.
The acetylation of the a₁ ẞ, and a₁ 34 naphtylaminesulpho acid may be carried
out successfully by treating the dry sodium salts of the acid during some time with
an excess of glacial acetic acid. After the latter has been separated by distillation,
the acetylated acids are obtained in a shape directly suitable for technical purposes.
The nitration may for instance be carried out as follows :-
265 kos. of the mixed acetnaphtylaminesulpho acid are dissolved in 1300 kos.
sulphuric acid and while cooling 160 kos. of a mixture of nitric and sulphuric acid,
containing 43% HNO, are introduced. The mixture is left standing for a short
time, then diluted to 3000 litres by adding ice and water, then the sodium salts of
the nitro acids are precipitated by addition of 500 kos. common salt.
These are easily soluble in pure water. The salt of the ai ẞ, acid crystallises in
the shape of needles, that of the ai ẞ, acid in the shape of rhombic tablets.
Characteristic of the nitro acids is that they can be easily saponified with mineral
acids. The a₁ as nitronapbtylamine ẞ sulpho acids thus produced dye wool in an
acid bath a greenish yellow, similar to naphtol yellow.
The reduction of the nitroacetnaphtylaminesulpho acids is best executed in the
following manner :-
31 kos. nitro acid are introduced gradually into a boiling mixture of 50 kos. iron
shavings, 100 litres water and 3 kos. acetic acid 50%. As soon as the liquid
loses its color, the dissolved iron is precipitated with soda. Then the liquid is
filtered and the a₁ a, acetnaphtylenediaminesulpho acid is precipitated from the
filtrate by the addition of 20 kos. muriatic acid.
The a, a, acetnaphtylamine 3, sulpho acid as well as the ẞ, sulpho acid are very
difficultly soluble even in warm water. Both crystallise in needles. If treated with
nitrous acid, acetamidodiazonaphtalenesulpho acids result. They are of a yellow
color, very difficultly soluble in water, and react very easily with amines and
phenoles.
The new at a acetnaphtylenediaminesulpho acids combine also with diazo and
tetrazo bodies.
The new acids can be used for the production of dye-stuffs in the following
manner :
Disazo dye-stuffs can be produced by saponifying the azo combinations of the
amidoacetnaphtalidsulpho acid, diazotising again and combining a second time.
Two cases have here to be distinguished: if the first combination was done with a
a1 a,

page_text: -
– NH,
Example. The diazo compound of 30.2 kos. a₁ a, amidoacetnaphtalid B, sulpho
acid produced as indicated under II is combined with a naphtylamine. The
product is dissolved in 500 litres water and 4 kos. caustic soda, then 7 kos. nitrite
are added to the solution which is then allowed to run into 36 kos. diluted muriatic
acid which is kept cold. The diazo compound separates in brown, very difficultly
soluble flakes. If the diazo compound is brought into an alkaline solution of
27 kos. B, a, amidonaphtol ẞ, sulpho acid, the formation of dyestuff takes place at
once. The difficultly soluble dark colored precipitate is filtered off and boiled
with 1000 litres of 10% soda lye, until the pure blue color of a diluted sample
does not change any more under the influence of acetic acid.
By neutralising the liquid the dye-stuff precipitates. It dyes wool and cotton a
blueish black.
Analogous dye-stuffs are obtained, if in this example naphtylamine is replaced by
either a 3 or a ẞ, naphtylaminesulpho acid, as ẞ, amidonaphtolether.
Instead of y amidonaphtolsulpho acid other amidonaphtol-sulpho acids, as for
instance B, B3 disulpho acid (H), a, a, amidonaphtol a, sulpho acid, or also
naphtolsulpho acids, as for instance ai a acid may be used.
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 acetnaphtylenediaminesulpho acids from the alpha 1
beta 3 or alpha 1 beta 4 naphtylaminesulpho acid substantially as described.
2. The production of azo dye-stuffs by combining the diazotised acetnaphtylene-
diaminesulpho acids bereinbefore described with phenols or amines, saponifying the
acetyl-group, diazotising or tetrazotising again and combining with phenols or
amines substantially as described.
3. The production of azo dye-stuffs by combining the diazotised acetnaphtylene-
diaminesulpho acids herein before described with diazotisable amines (such as alpha
naphtylamine, gamma amidonaphtolsulpho acid etc.) immediately diazotising again,
combining then with phenols or amines and finally saponifying the acetyl-group.
4. The new dyestuffs or coloring matters hereinbefore described.
Dated this 2nd day of May 1894
SYDNEY PITT.