Manufacture of a Novel Diamido-base and of Colouring Matters Amish- from the samė.
Year: 1893

page_text: Date of Application, 7th Apr., 1893
!
Complete Specification Left, 8th Jan., 1894 Accepted, 10th Feb., 1894
PROVISIONAL SPECIFICATION.
..
[Communicated from abroad by THE FARBWERKE vormals MEISTER LUCIUS
AND BRUNING, of Hoechst */ Main, in the Empire of Germany, Chemical
Manufacturers.]
Manufacture of a Novel Diamido-base and of Colouring Matters
Amish-
from the samė.“
I, OLIVER. IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
According to this invention a novel diamido-base which furnishes azo-colouring
matters dyeing cotton directly and of prominent qualities is obtained when benz-
para-nitranilide is nitrated, the trinitro compound thus obtained reduced, and the
formed triamido-derivative condensed.
The invention is carried out for example in the following way :-
The well known benz-para-nitranilide is dissolved in the quintuple quantity of
mono-hydrate and is nitrated by a mixture of fuming nitric acid and mono
hydrate. In this operation there is 'formed a para-trinitro-benz-anilide of the
constitution:

page_text: When the triamido-benz-anilide is heated in racuo to 250° C. one molecule of
water is eliminated and the anilide condensed into the para-diamido-phenyl-benz-
imidazol of the constitution:
This anhydro base is insoluble in water and ether, soluble in alcohol and aceton, 5
its melting point is above 250° C. With mineral acid and nitrite of sodium there
is obtained an easily soluble tetrazo-compound, which easily and promptly
combines with phenoles, naphtholes, phenol-and-naphthol sulphonic and carbonic
acids, with amido-acids etc. etc.
In this manner may be produced for example:
a) Simple colouring matters by combining the tetrazo compound of the para-
diamido-phenyl-benz-imidazol ·
m
"
a-naphtholsulphonic acid of Neville-Winther
a
"
a-naphtholdisulphonic,,
B-naphtholsulphonic
В
33
"
"
B-naphtholdisulphonic,,
> Schöllkopf 1.8
23
German Patent 40571
*,, -Schaffer
,,. German Patent 18027
44079
B-naphtholdisulphonic acid R of German Patent 3229
1
"
"
G
3229
"
"
"
"
"
38281
"
199
"
"
"
22038
B-naphtholtrisulphonic
dioxynaphthaline monosulphonic acid G produced by melting the ẞ naphthol-
disulphonic acid G of the German Patent 3229 with caustic alkalies:
dioxynaphthaline monosulphonic acid of German Patent 42261
dioxynaphthaline monosulphonic acid produced by melting, the a naphthol-
disulphonic acid of German Patent 45776 with caustic alkalies.
dioxynaphthaline-monosulphonic acid produced by melting the a naphthol-
disulphonic acid S of German Patent 40571 with caustic alkalies.
dioxynaphthaline disulphonic acid, produced by melting the ẞ-naphthol-
trisulphonic acid of German Patent 22038 with caustic alkalies.
dioxynaphthaline disulphonic acid produced by melting the naphtho sulton
disulphonic acid of German Patent 56058 with caustic alkalies (chromotrop
acid);
dioxynaphthaline disulphonic acid produced by melting the a-naphthol-
trisulphonic acid of German Patent 10785 with caustic alkalies;
dioxynaphthaline disulphonic acid produced by melting the a-naphthol-
trisulphonic acid prepared by further sulphonation of the a-naphtholdisul-
phonic acid S of German Patent 40571 with caustic alkalies;
naphthionic acid
naphthalidine sulphonic acid.
B-naphthylamine sulphonic acid of Bränner

page_text: hẞ naphthylamine sulphonic acid & produced according to German Patent
27378 by action of ammonia upon the B-naphtholdisulphonic acid G of
German Patent 3229
B-naphthylamine-disulphonic acid R produced according to German Patent
27378 by action of ammonia upon the ẞ-naphtholdisulphonic acid R of
German Patent 3229
amide nanhtholaulahanin anid Griman Dadant 2007
The novel colouring matters are prominent by their great affinity for cotton
fibre, by great fastness to soap and by their not being easily affected by acids.
With regard to shade they are quite up to the so called congo colouring matters
but surpass them in the qualities before mentioned.
"
From the colouring matters described in the application for Letters Patent
No. 10667 of 1892 they differ by dyeing more vivid prettier and much bluer shades
than can be obtained by those,

page_text: EXAMPLE.
a) 112-parts of para-diamido-phenyl-benz-imidazol with the addition, of about
36 parts of hydrochloric acid of 30 per cent. are dissolved in such a quantity of water
that there results a solution of about 10 per cent. strength, and for the diazotising,
this is mixed at a temperature of from 0° to 5° C. with 6.9 parts of nitrite dissolved
in about 35 parts of water.
The tetrazo compound is formed smoothly and remains in solution.
The tetrazo compound thus obtained is caused to flow at 0° C. into a solution of
about 10 per cent. strength.of 15. parts of salicylic acid and 35 parts of soda. The
combination begins immediately and is complete after about 12 hours.. The
formed colouring matter separates already during the operation; it is obtained in
the usual manner and purified.
6). Into the tetrazo, solution of 112, parts of paradiamido-phenyl-benz-imidazol
obtained as described under a) there is caused to flow at 0° C. a solution of about
10 per cent. strength of 12 parts of naphthionate of soda and 45 parts of acetate of
sodium, and the mixture is stirred for from 3 to 4 hours.
-331
The intermediate product thus obtained is caused to flow at this temperature
into a solution of about 10 per cent. strength of 6 parts of resorcine and 35 parts
of soda and the mixture is stirred for about 12 hours longer....The colouring
matter separates during the operation; it is obtained in the usual manner and
purified
Dated this 7th day of Anmil 1893
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of a Novel Diamido-base and of Colouring Matters
from the same.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, 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 :-
According to this invention a novel diamido base which furnishes azo colouring
matters which dye cotton directly, and have special qualities is obtained when
benz-para-nitranilide is nitrated, the trinitro compound thus obtained is reduced
and the formed triamido derivative is condensed.
T1.
The invention is carried out for example in the following way:-
The well known benz-para-nitranilide is dissolved in five times the quantity of
mono-hydrate and is nitrated by a mixture of fuming nitric acid and monohydrate.
In this operation there is formed a para-trinitro-benz-anilide of the constitution:

page_text: It is insoluble in water alcohol or ether, soluble in glacial acetic acid and acetic
ether, on being reduced by means of iron turnings and hydrochloric acid it furnishes
a triamido benzanilide of the constitution :
-4
5 This triamine dissolves in hot water from which it crystallises on cooling, and this
property, can be made use of for recrystallising and purifying it. In hot alcohol
and acetone it is soluble but not in most of the other solvents. Its salts on the
contrary are easily soluble in cold water."
When the triamido-benz-anilide is heated in vacuo to 250° C. one molecule of
water is eliminated and the anilide is condensed into the para-diamido-phenyl-benz-
imidazol of the constitution :
m
» a-naphtholsulphonic acid of Nevile-Winther
"
2 2
"
a
"Schollkopf 1.8
a-naphtholdisulphonic acid of German Patent 40571
B-naphtholsulphonic
В
3 naphtholdisulphonic
"
Schäffer
"
"
"
German Patent 18027
44079
"
"
"3

page_text: "
The novel colouring matters are remarkable by their great affinity for cotton
fibre, by great fastness to soap and by their not being easily affected by acids.
With regard to shade they are quite up to the so called "congo colouring matters'
but surpass them in the qualities before mentioned. From the colouring matters
described in the Specification No. 10667 of 1892 they differ by dyeing tints more
vivid more beautiful and much more blue than can be obtained by those.
EXAMPLE.
a) 11.2 parts of para-diamido-phenyl-benz-imidazol with the addition of about
36 parts of hydrochloric acid of 30 per cent., are dissolved in such a quantity of
water that there results a solution of about 10 per cent. strength, and for diazotising,
this is mixed at a temperature of from 0° to 5° C. with 6.9 parts of nitrite dissolved
in about 35 parts of water.
The tetrazo compound is formed gently and remains in solution.
The tetrazo compound thus obtained is caused to flow at 0° C. into a solution of
about 10 per cent. strength of 15 parts of salicylic acid and 35 parts of soda. The
combination begins immediately and is complete after about 12 hours. The
colouring matter thus formed separates during the operation; it is obtained in the
usual manner, and purified.
b) Into the tetrazo solution of 11°2 parts of para-diamido-phenyl-benz-imidazol
obtained as described under a) there is caused to flow at 0° C. a solution of about
10 per cent. strength of 12 parts of naphthionate of soda and 45 parts of sodium
acetate and the mixture is stirred for from 3 to 4 hours.
The intermediate product thus obtained is caused to flow at this temperature.into-
a solution of about 10 per cent. strength of 6 parts of resorcine and 35 parts of soda
and the mixture is stirred for about 12 hours longer. The colouring matter
separates during the operation; it is obtained in the usual manner and purified.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The manufacture of para diamido-phenyl-benz-imidazol by nitrating the para-
benz-nitranilide, reducing the tri-nitro compound thus produced and condensing the
tri-amido derivative thus formed, substantially as described.
2. The manufacture of colouring matters which dye directly on cotton, by
combining the tetrazo-compound of the para-diamido-phenyl-benz imidazol with
phenoles, naphtholes, phenol and naphthol-carbonic and sulphonic acids with amido-
acids, substantially as described.
3. The para-diamido-phenyl-benz-imidazol manufactured as set forth in the first
claim.

page_text: 4. The colouring matters manufactured as set forth in the second claim, and as
illustrated by the examples hereinbefore given.
Dated this 6th day of January 1894.
ABEL & IMRAY,
Agents for the Applicant.