Manufacture of New Colouring Matters derived from Dioxy- diphenylmethan.
Year: 1893

page_text: Manufacture of New Colouring Matters derived from Dioxy-
diphenylmethan.
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN and
ADOLPHE JEAN JAMES D'ANDIRAN, constituting the Firm of L. Durand
Huguenin & Cie. of Basle, Switzerland, Manufacturers, 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 :-
Our present application for Patent has for its object the production of new
colouring matters derived from dioxydiphenylmethan, obtained by the condensation
of formic aldehyde with ordinary phenol in presence of a condensation agent, such,
for instance, as hydrochloric acid.
These colouring matters may be obtained, either by the combination of one
molecule of dioxydiphenylmethan with one molecule of the intermediate products
obtained by the union of equivalent molecules of sulphanilic acid or naphthionic
acid and tetrazodiphenyl, tetrazoditolyl or a tetrazodiphenol ether, or by the
combination of one molecule of dioxydiphenylmethan with two molecules of these
intermediate products.
In the former case colouring matters are obtained containing two "diazo "
groups, whilst in the latter case the colouring matters obtained contain four
diazo" groups.
In this latter case the two molecules of intermediate product may be the
same or different; farther, for one of them may be substituted a simple diazo
body, such as chloride of diazobenzene, diazobenzene sulphonic acid, diazonaph-
thaline sulphonic acid &c., which would furnish colouring matters containing three
times the "diazo" group.
All these colouring matters dye unmordanted cotton in an alkaline bath.
S.I. Colouring matters obtained by the combination of 1 molecule of dioxydi-
phenylmethan with 1 molecule of intermediate product.

page_text: 18.4 kilo. benzidine or 24.4 kilo. dianisidine are dissolved in 600 litres of water
containing 60 kilo. hydrochloric acid at 21° Bé. and diazotised by means of
13.8 kilo. sodium nitrite. The tetrazo compound obtained is poured, care being
taken to agitate, into a solution having 500 litres volume and containing 19.5 kilo.
sulphanilate of soda and 50 kilo. acetate of soda. At the end of 2 or 3 hours
the formation of the intermediate product is completed. This product is then
introduced into a solution of 20 kilo. of the condensation product of formic
aldehyde and of ordinary phenol (dioxydiphenylmethan), 7 kilo. of caustic soda
and 50 kilo. carbonate of soda in 500 litres of water. After leaving the mass
to itself for about an hour, it is boiled, and the colouring matter is precipitated
from it by addition of sea salt. The colouring matter appears, after drying in
the form of a red powder easily soluble in hot water.
By substituting, in this example, for the 19-5 kilo. sulphanilate of soda, 24-5 kilo.
of naphthionate of soda, or by at the same time substituting for the 184 kilo.
benzidine, 21-2 kilo. tolidine, red colouring matters are obtained.
These colouring matters derived from the condensation product of formic
aldehyde and ordinary phenol present, in their chemical reactions, striking
differences from the corresponding colouring matters derived from phenol. The
following table indicates some of these differences.

page_text: louring matter obtained
vith benzidine + sul-
hanilic acid or phenol
Colouring matter obtained
with benzidine + sul-
phanilic acid or dioxy-
diphenylmethan
Cotton dyed with the colouring matter obtained with benzidine, sulphanilic acid
and phenol takes a violet shade by its passage in concentrated hydrochloric acid,
whilst cotton dyed with the corresponding matter from dioxydiphenylmethan, takes,
under the same circumstances, a red brown colour.
S.II. Colouring matters obtained by the combination of 1 molecule of dioxy-
diphenylmethan with 2 molecules of intermediate products.
We attribute to the colouring matter obtained with 1 molecule dioxydiphenyl-
methan, 1 molecule of the intermediate product resulting from the union of
equivalent quantities of tetrazodiphenyl and sulphanilic acid, and 1 molecule of the
intermediate product resulting from the union of equivalent quantities of tetrazo-
diphenyl and naphthionic acid, the following constitution formula :—
= N – CH - CH - N = N - CH
NH
CH,
AT
=

page_text: We shall hereafter give some examples of colouring matters of which the
preceding formulæ constitute types.
1. Colouring matter obtained with one molecule of dioxydiphenylmethan and
two molecules of the intermediate product resulting from the union of equivalent
quantities of tetrazodiphenyl and sulphanilic acid.
18.4 kilo. benzidine are diazotised in the usual way by means of 13.8 kilo. sodium
nitrite and 60 kilo. of hydrochloric acid at 21° Be. The tetrazo compound
obtained is poured into a solution of 19.5 kilo. sulphanilate of soda and 40 kilo.
acetate of soda in 500 litres of water, care being taken to agitate well. The
intermediate product, obtained at the end of 2 or 3 hours, is introduced into a
solution of 10 kilo. dioxydiphenylmethan 3.5 kilo. caustic soda and 50 kilo. carbonate
of soda in 500 litres of water. After leaving the mass to itself for a short time
it is heated to ebullition, and the colouring matter is precipitated by adding sea
salt. This colouring matter appears, after drying, in the form of a red brown
powder, easily soluble in water and dyeing unmordanted cotton in an alkaline bath
a yellow tint.
The solution of the colouring matter in concentrated sulphuric acid has a red
violet colour.
2. Colouring matter obtained with 1 molecule chloride of diazobenzene,
1 molecule dioxydiphenylmethan and 1 molecule of the intermediate product
resulting from the union of equivalent quantities of tetrazo diphenyl and
sulphanilic acid.
The intermediate product prepared as in the preceding case is introduced into
a solution of 20 kilo. dioxydiphenylmethan, 7 kilo. caustic soda, and 40 kilo.
carbonate of soda in 500 litres of water.
After a short time there are added 40 kilo. more of carbonate of soda, and a
solution of chloride of diazobenzene obtained with 9-3 kilo. aniline, 30 kilo. hydro-
chloric acid, and 6-9 kilo. sodium nitrite. After leaving the mass to itself several
hours, the reaction is ended by heating to 60° or 70° C., and the product is filtered.
The new colouring matter obtained cannot be dissolved without great difficulty in
hot water, and is preferably employed in the form of paste. It dyes unmordanted
cotton in an alkaline bath a yellow tint. The dyes obtained with this colouring
matter are distinguished from those obtained with commercial "Congo yellow," by
their resistance to acids and particularly to alkalies.
The solution of the colouring matter in concentrated sulphuric acid presents a
brown colour.
3. Colouring matter obtained with 1 molecule of diazobenzol sulphonic acid,
1 molecule dioxydiphenylmethan and 1 molecule of the intermediate product
resulting from the reaction of equivalent quantities of tetrazodiphenyl and
sulphanilic acid.
In the preparation of this colouring matter, for the 9-3 kilo. aniline in the
preceding example, are substituted 19.5 kilo. sulphanilate of soda. The colouring
matter obtained is very easily soluble in hot water and can only be precipitated
from a neutral solution by large addition of sea salt. When dried, the colouring
matter appears as a deep brown powder, dyeing unmordanted cotton in an alkaline
bath, preferably with addition of sea salt, a yellow tint. The solution of this
colouring matter in concentrated sulphuric acid presents a brown colour.
4. Colouring matter obtained with one molecule of dioxydiphenylmethan, and
2 molecules of the intermediate product resulting from the reaction of equivalent
quantities of naphthionic acid and tetrazodiphenyl.
:
We substitute for the 19.5 kilo. sulphanilate of soda in the preceding example,
24-5 kilo. naphthionate of soda.
The colouring matter dried appears as a deep brown powder with bronze lustre,
easily soluble in hot water; it dyes unmordanted cotton in an alkaline bath a poppy
red tint. Its solution in concentrated sulphuric acid is blue.
5. Colouring matter obtained with 1 molecule of dioxydiphenylmethan and

page_text: 2 molecules of the intermediate product resulting from the reaction of equivalent
quantities of tetrazoditolyle and naphthionic acid.
In the example 1 above given, we substitute for the 18-4 kilo. *benzidine
21.2 kilo. tolidine, and for the 19-5 kilo. sulphanilate of soda, 24.5 kilo. naphthionate
of soda.
The dry colouring matter forms a brown powder with bronze lustre, easily
soluble in hot water; it dyes unmordanted cotton in an alkaline bath a yellowish
red tint. Its solution in concentrated sulphuric acid is blue.
6. Colouring matter obtained with 1 molecule of dioxydiphenylmethan, 1 molecule
of the intermediate product resulting from the reaction of equivalent quantities of
tetrazo diphenyl and sulphanilic acid and 1 molecule of the intermediate product
resulting from the union of equivalent quantities of tetrazo-diphenyl and naphthionic
acid.
The product obtained, according to example 2, by the union of a molecule of
dioxydiphenylmethan with a molecule of the intermediate product derived from
tetrazodiphenyl and sulphanilic acid has added to it 40 kilo. carbonate of soda; to
this mixture is then added the intermediate product obtained with 184 kilo.
benzidine, 60 kilo. hydrochloric acid, 13-5 kilo. nitrite, 24-5 kilo. naphthionate and
40 kilo. acetate of soda. After being left for some time to itself the reaction
product is heated to ebullition and the colouring matter formed is precipitated with
sea salt.
After drying, it forms a deep brown powder easily soluble in hot water and
dyeing unmordanted cotton in an alkaline bath a yellowish red tint. The solution
of this colouring matter in concentrated sulphuric acid gives a grey violet colour.
7. Colouring matter obtained with 1 molecule of dioxydiphenylmethan,
1 molecule of the intermediate product tetrazoditolyl + naphthionic acid, and
1 molecule of the intermediate product tetrazodiphenol methylether + naphthionic
acid.
We first prepare the product obtained with 1 molecule of dioxydiphenylmethan
and 1 molecule of the product tetrazoditolyl + naphthionic acid according to the
process indicated in example 1, by means of 21-2 kilo. tolidine 60 kilo. hydrochloric
acid at 21° Be. 13.8 kilo. nitrite 24.5 kilo. naphthionate and 40 kilo. acetate of soda,
20 kilo. dioxydiphenylmethan, 7 kilo. caustic soda and 40 kilo. carbonate of soda.
To the reaction product we add, after leaving the mass to itself some time, 40 kilo.
carbonate of soda and then the intermediate product tetrazodiphenolmethyl
ether naphthionic acid, obtained by means of 24.4 kilo. dianisidine, 60 kilo.
hydrochloric acid at 21° Be. 13-8 kilo. nitrite, 24.5 kilo. naphthionate and 40 kilo.
acetate of soda. After a short time the whole is heated to ebullition, and the
colouring matter, precipitated by adding sea salt, forms when dried a deep brown
powder and dyes unmordanted cotton in an alkaline bath a Bordeaux red tint.
The solution of the colouring matter in concentrated sulphuric acid has blue
colour.
8. Colouring matter obtained with 1 molecule of chloride of diazonaphthaline,
I molecule of dioxydiphenylmethan, and 1 molecule of the intermediate product
tetrazoditolyl naphthionic acid.
To the product, tetrazoditoly! + dioxydiphenylmethan + naphthionic acid
obtained in the preceding example, we add 40 kilo. carbonate of soda and then a
solution of chloride of diazonaphthaline obtained by means of 14-3 kilo. a-naphthyl-
amine, 30 kilo. hydrochloric acid and 69 kilo. sodium nitrite.
After the reaction has lasted several hours at ordinary temperature, we heat
to 60° or 70° C. to terminate it, and we then precipitate the colouring matter by
adding sea salt. This colouring matter dried forms a deep brown powder easily
soluble in hot water, and dyeing unmordanted cotton in an alkaline bath a
yellowish red tint. Its solution in concentrated sulphuric acid gives a blue colour.
9. Colouring matter obtained with 1 molecule of a-diazonaphthaline sulphonic
acid, 1 molecule of dioxydiphenylmethan, and 1 molecule of the intermediate product
tetrazoditolyl naphthionic acid.

page_text: We substitute for the 14.3 kilo. a-naphthylamine of the preceding example
5 kilo. naphthionate of soda. The colouring matter obtained appears in the form
deep brown powder, easily soluble in hot water, and dyeing unmordanted cotton
an alkaline bath a yellowish red tint. Its solution in concentrated sulphuric acid
a blue colour.
Having now particularly described and ascertained the nature of our said
ention and in what manner the same is to be performed, we declare that what we
im is:-
The manufacture of new colouring matters by the combination of 1 molecule
dioxydiphenylmethan with 1 molecule of one or other of the intermediate
ducts obtained by the combination of the following bodies:-
:-
(a) 1 molecule of tetrazodiphenyl + 1 molecule of sulphanilic acid :
(b) 1 mol. tetrazodiphenyl + 1 mol. naphthionic acid :
(c) 1 mol. tetrazoditolyl + 1 mol. naphthionic acid :
(d) 1 mol. tetrazodiphenol ether derived from dianisidine + 1 mol. sulphanilic
acid :
(e) 1 mol. tetrazodiphenol ether derived from dianisidine + 1 mol. naphthionic
acid.
The manufacture of new colouring matters by the combination of 1 molecule
dioxydiphenylmethan with 2 molecules of one or other of the following
lies:-
1 molecule tetrazodiphenyl + 1 mol. sulphanilic acid :
1 mol. tetrazodiphenyl + 1 mol. naphthionic acid :
1 mol. tetrazoditolyl + 1 mol. naphthionic acid:
3. The manufacture of new colouring matters by the combination of 1 molecule
dioxydiphenylmethan with-
(a) 1 mol. chloride of diazobenzene and 1 mol. of the intermediate product
resulting from the union of 1 mol. tetrazodiphenyl and 1 mol. sulphanilic
acid:
(b) 1 mol. diazobenzene sulphonic acid and 1 mol. of the intermediate product
under (a) resulting from the union of 1 mol. tetrazodiphenyl and 1 mol.
sulphanilic acid :
(c) mol. of the intermediate product resulting from the union of 1 mol.
tetrazodiphenyl and 1 mol. sulphanilic acid, and 1 mol. of the intermediate
product resulting from the union of 1 mol. tetrazodiphenyl and 1 mol.
naphthionic acid :
(d) i mol. of the intermediate product resulting from the union of 1 mol.
tetrazoditolyl and 1 molecule naphthionic acid, and 1 mol. of the intermediate
product resulting from the union of 1 mol. tetrazodiphenolmethyl ether and
1 mol. naphthionic acid :
(e) 1 mol. chloride of diazonaphthaline and 1 mol. of the intermediate product
resulting from the union of 1 mol. tetrazoditolyl and 1 mol. naphthionic
acid:
(f) 1 mol. a-diazonaphthaline sulphonic acid and 1 mol. of the intermediate
product resulting from the union of 1 mol. tetrazoditolyl and 1 mol.
naphthionic acid.
1. As new products the colouring matters obtained according to the processes
forth in Claims 1, 2 and 3.
Dahin 0th d... of Mr. 1000
ABEL & IMRAY,
Agents for the Applicants.