Manufacture of Azo, Disazo, and Polyazo Colouring Matters with Phenylen and Toluylen-oxamic Acid.
Year: 1895

page_text: Date of Application, 20th Nov., 1895
Complete Specification Left. 5th Aug., 1896-Accepted, 5th Sept., 1896
[Communicated from abroad by Dr. PAUL REMY, of Farbwerk Friedrichsfeld,
Mannheim, Germany.]
Manufacture of Azo, Disazo, and Polyazo Colouring Matters with
Phenylen and Toluylen-oxamic Acid.
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:-
Oxamic acids appear hitherto not to have been employed for the manufacture of
colouring matters. Phenylen oxamic acid was made known in the Ber. d. Chem.
Ges. vol. VII p. 1261. Toluylen oxamic acid appears not to have been prepared
or described hitherto.
It is prepared in the same manner as phenylen oxamic acid, and forms a slightly
yellow powder which is hardly soluble even in boiling water, but is easily soluble
in alkalies, in particular with slight excesses thereof, and it coincides otherwise
with phenylen oxamic acid.
Favourable results have hitherto generally only been obtained with the use of
the m. acids.
Colouring matters have been obtained that dye both wool and, directly,
cotton.
As the initial substance for the process may be taken the acids themselves, but
particularly valuable products are obtained if the acids are coupled with a diamine,
for instance benzidine, tolidine or dianisidine, or their sulpho-acids. For this
there may be coupled either two acid molecules with one diamine, or one acid
molecule and one amido or phenol sulpho acid with one diamine.
In the substance produced the free am do groups can be farther diazotised.
The oxalic acid can remain in the colouring matter, or it can be split off in order to
render also the amido-group bound thereby available for farther diazotising.
It serves therefore in the various modes of carrying out the new process,
either only as protective group, which, in the first diazotising protects the second
group, and is then separated or it forms a permanent component of the colouring
matter.
The separation is based on the discovery that the products resulting from the
diazotising can be separated by boiling for some hours with a reflux cooler, in
greatly diluted hydrochloric acid, of about 5° Bc.
In the process in which phenylen- or toluylen-oxamic acid is used as the initial
material, the diazotising is carried out in the usual mauner by means of sodium
nitrite and hydrochloric acid.
If the first azo colouring matters produced with 1-4 naphtbol sulpho acid, are
boiled in greatly diluted hydrochloric acid (about 5° Bé.) for about 3 hours, with
a reflux cooler, the oxalic acid is smoothly split off. The dyestuff acids obtained
are soluble with difficulty in water and can therefore be readily washed. In water

page_text: containing alkali they are readily dissolved, and they are therefore dissolved in
ammoniacal water, and the second diazotising can then be carried out without
difficulty. The coupling of the compounds formed has been effected with :
These colouring matters are however of exceedingly difficult solubility, from
which apparently results their small dyeing power. In particular those prepared 30
with phenylen oxamic acid show very difficult solubility; the colouring matters
produced with toluylen oxamic acid are somewhat more easily soluble.

page_text: Of greater value are on the other han] the mixed azo colouring mit ers which
are produced with only one molecule of oxamic acid, and which correspond to the
following general formula:

page_text: The process is exactly the same as in Example III, only that in place of
24.6 kilos. of 14 naphthol sulphonate of soda, in this case 24-5 kilos. of naphthionate
of soda is taken.
There is obtained an easily soluble colouring matter, which dres uamordanted
cotton a scarlet red.
EXAMPLE V. DIAMINESULPHONIC ACID + 1 MOL. OXAMIC ACID + 1 MOL.
OXYCARBONIC ACID.
26 4 kilos. benzidine mono sulpho acid are tetrazotised as in Example II. The
tetrazo compound is poured into a solution of 19.4 kilos. toluylen oxamic acid in
about 500 litres of water containing 25 kilos. carbonate of soda, and the mixture is
stirred for about half an hour.
The cold intermediate product is then introduced into a cooled solution of
15-2 kilos. of o-kresotinic acid in about 500 litres water containing about 25 kilos.
carbonate of soda.
The easily soluble colouring matter produred is salted out.
cotton brown.
It dyes unmordanted
All the colouring matters obtained by the above examples have the property of
becoming farther diazotised and coupled on the fibre. The dyes thus produced
upon the fibre are distinguished by their fastness against acids, alkalies, and
washing, and they are also considerably more light-proof.

page_text: It has been found that also the meta-mononitrobenzidine and the meta-mono-
nitrotolidine can be used with phenylen or toluylen oxamic acid for the production
of valuable mixed azo colouring matters which though not suitable for dyeing
cotton, give on wool dyes of great permanency against washing, fulling, acids,
alkalies and sulphur.
22.9 kilos. meta mono nitro benzidine are tetrazotised in the known manner and
then added to a solution of 19.4 kilos. toluylen oxamic acid and 25 kilos. carbonate
of soda in about 600 litres water.
The intermediate product separates as a yellow brown precipitate. The mass is
stirred for half an hour and the intermediate product is poured into a solution of
24-6 kilos. of 14 naphtho sulphonate of soda and 25 kilos. of carbonate of soda in
about 600 litres of water, when a fine red colouring matter is produced. The mass
is then stirred for about an hour and allowed to stand for about 12 hours; it is
then heated to from 30° to 40° C., and again allowed to stand some hours, the
partially separated colouring matter is completely salted out, pressed, dried, and if
necessary again washed and dried.
It can be fixed both on unmordanted and on chromed wool and dyes the
same red.
If in place of the 22.9 kilos. meta mono nitro benzidine 25-7 kilos. meta mono
nitro tolidine be used, there is obtained a colouring matter of a dark red
brown tint.
It has furthermore been found that the above described colouring matters of
the formula
can be converted into new valuable colouring matters by diazotising the free
amido group and binding with an amine or phenole, or their sulpho or carbon
acids.
The new colouring matters produced correspond to the general formula
ich
represents an amido or phenole sulpho acid, R₁ an amine or phenole or
their sulpho or carbon acids.
The process will be understood from the following examples:
EXAMPLE I. COUPLING WITH AN AMINE.
72.8 kilos. of the colouring matter obtained from 1 mol. dianisidine, 1 mol.
toluylen oxamic acid and 1 mol. 14 naphthol sulpho acid, are dissolved in about
2000 litres water, and under cooling, 18 diazotised in the known manner with 7 kilos.
nitrite and 30 kilos. hydrochloric acid (20° Bé.).
The diazo compound which is obtained after about half an hour's stirring, is
added to a solution of 12.2 kilos. of m-toluylendiamine and about 30 kilos. calcined
carbonate of soda, which is also cooled. The mass is stirred for some time and is
allowed to stand till the next day under occasional stirring; it is then heated to
about 40° to 50° C., is allowed to stand for some hours, and lastly the colouring
matter is precipitated with dilute acid or salt; in the first case there is obtained
the dyestuff acid, which is easily converted into an alkali salt; in the latter
case the easily soluble soda salt is obtained. The colouring matter dyes
unmordanted cotton blue black.

page_text: EXAMPLE II. COUPLING WITH AN AMIDO SULPHO ACID.
667 kilos. of the colouring matter obtained from 1 mol. benzidine, 1 mol. naph-
thionic acid and 1 mol. toluylen oxamic acid are dissolved in about 1500 litres
water, cooled and diazotised with 7 kilos. nitrite and 30 kilos. hydrochloric
acid (20° Bé.). The mass is stirred for half an hour and the diazo compound
produced is added to a solution of 17.3 kilos. sulphanilic acid and about 25 kilos.
carbonate of soda in about 300 litres water. The farther treatment is the same as
in Example I. The colouring matter dyes unmordanted cotton direct brown.

page_text: admit of a farther treatment, the free amido group of the oxamic acid being
diazotised and coupled with an amine or phenole or their sulpho or carbon acids;
by treatment with dilute acid for some hours at the reflux cooler the oxalic acid
rest is split off, and new colouring matters are produced which fix well on
unmordanted cotton, and which are particularly stable against acid and alkali as
also against washing and light. All these colouring matters can be farther
diazotised and coupled on the fibre, and the permanence against washing and light
is thereby considerably increased.
The colouring matters thus produced correspond to the general formula:
Πυριστικ
411
their sulpho or carbon acids.
The following examples will explain the process.
EXAMPLE I. R IS AN AMIDO SULPHO ACID; R₁ IS ALSO AN AMIDO SULPHO
ACID, AND IN THIS CASE = R.
The colouring matter from 1 mol. benzidine, 1 mol. of naphthoic acid
1 mol. toluylen oxamic acid and 1 mol. naphthionic acid which corresponds to
the formula :
ATTL
the free dye acid.
This is filtered, well washed and dried, and can be at once used in this condition
for dyeing, by dissolving it with an addition of some alkali in which it is very
readily soluble. A subsequent conversion of the dye acid into the soda salt offers
no difficulty. The colouring matter dyes unmordanted cotton blue red.
EXAMPLE II. R IS A PHENOL SULPHO ACID; R, 18 ALSO A PHENOL
SULPHO ACID AND IN THIS CASE = = R₁.
The colouring matter from 1 mol. dianisidine 1 mol. 1 : 4 naphthol sulpho acid,

page_text: 1 mol. toluylen oxamic acid and 1 mol. 1 : 4 naphthol sulpho acid corresponding to
the formula:
is treated in exactly the same manner as in Example I. The separation product
obtained dyes unmordanted cotton direct blue.
EXAMPLE III. R IS A PHENOLE SULPHO ACID, R¹ AN AMINE.
The colouring matter from 1 mol, dianisidine, I mol. 1: 4 naphthol sulpho
acid, 1 mol. toluy lenoxamic acid and 1`mol. m-toluylendiamine, corresponding to
the formula :
OCH
CH
is subjected to the treatment with dilute hydrochloric acid described in Example 1,
and the farther treatment is the same as there described.
The separation product obtained dyes uumordanted cotton direct blue black.
EXAMPLE IV. R IS A PHENOL-SULPHO ACID, R' A PHENOLE.
The colouring matter from 1 mol. o-tolidine 1 mol. 1:4 naphthol-sulpho
acid, 1 mol. toluylen-oxamic acid, and 1 mol. a naphthol, which corresponds to the
formula:
CH.

page_text: EXAMPLE V. R IS AN AMIDO-SULPHO ACID, R₁ AN OXYCARBON ACID.
The colouring matter from 1 mol. benzidine 1 mol. naphthionic acid, 1 mol. toluylen
oxamic acid and 1 mol. ẞ oxynaphthoic acid, corresponding to the formula:
NH
CH,
5 is treated with dilute hydrochloric acid and is farther treated as in Example I.
The separation product obtained dyes unmordanted cotton direct blue red.
In conclusion the following table is given of the colouring matters prepared up
to the present time according to this process:

page_text: Lastly the above described colouring matters obtained by splitting off the
oxalylgroup, which correspond to the general formula:
AT
AT
D
BIKHII.
The solution is well cooled and is diazotised in the known manner with 6 kilos.
nitrite and 24 kilos. hydrochloric acid (20° Bé.). The diazo compound separates
completely. After stirring for an hour the diazo compound is added to a solution
of 2 kilos. ẞ naphthol and 10.5 kilos. soda lye (about 36° Bé.) with about
200 litres water.
The mass is stirred for some time, and is allowed to stand for 24 hours with
occasional stirring, and the colouring matter is salted out, or it is precipitated as
free dye acid with dilute hydrochloric acid. The colouring matter is then filtered,
washed, pressed and dried.

page_text: EXAMPLE II. COUPLING OF THE OXALIC ACID SEPARATION PRODUCT
WITH A PHENOLE SULPHO ACID.
40 kilos. of the separation product of the colouring matter from 1 mol. dianisidine,
1 mol. 1:4 naphthol sulpho acid, I mol. toluylen oxamic acid, and 1 mol. m-toluylen-
diamine which corresponds to the formula:
EXAMPLE III. COUPLING OF OXALIC ACID SEPARATION PRODUCT WITH
AN AMIDO SULPHO ACID.
48 kilos. of the separation product of the colouring matter from 1 mol. benzidine
1 mol. naphthionic acid 1 mol. toluylen oxamic acid and 1 mol. phenole, which
corresponds to the formula:
CH;
are dissolved in about 1600 litres of water containing alkali. The cooled solution
is diazotised with 6 kilos. nitrite and 24 kilos. hydrochloric acid. After stirring
for half an hour the separated diazo compound is added to a solution of 13-5 kilos.
of metanilic acid, and about. 24 kilos. carbonate of soda with about 600 litres of
water. The farther treatment is as in Example 1.
The colouring matter dyes unmordanted cotton violet.
2

page_text: EXAMPLE IV COUPLING OF THE OXALIC ACID SEPARATION PRODUCT
WITH AN OXY CARBON ACID.
51 kilos. of the separation product of the colouring matter from 1 mol. benzidine
1 mol. naphthionic acid, 1 mol. toluylen oxamic acid and 1 mol. resorcine,
corresponding to the formula:
are dissolved in about 1800 litres of water with addition of alkali.
The cooled solution is diazotised with 6 kilos. nitrite and 24 kilos. hydrochloric
acid.
After stirring for half an hour the separated diazo compound is added to a
cooled solution of 10.5 kilos. salicylic acid and about 24 kilos. carbonate of soda,
in about 600 litres of water.
The farther treatment is the same as in Example I. The colouring matter
dyes unmordanted cotton violet.
All the colouring matters producible according to this process are easily
soluble; some of them are so soluble that they cannot be subjected to washing.
In this case they are dried, washed with a little cold water or greatly diluted
hydrochloric acid, and again dried.
The free dye acids separated by means of acid can be better washed, but of
these also some are very easily dissolved.
The following is a tabular statement of the colouring matters prepared up to the
present time according to the above process.
1:4 naphthol
sulpho acid
1:4 naphthol blue
sulpho acid
3 naphtholdi-
ẞ naphthol
"
sulpho acid
m-toluylen
diamine
a naphthol
ẞ naphtholdi-
sulpho acid R
1:4 naphthol
sulpho acid
"
39

page_text: 1:4 naphthol
sulpho acid
ẞnaphtholdi-
sulpho acid R
m-toluylen
diamine
a naphthol
β
2
1:4 naphthol
sulpho acid
ẞ naphtholdi-
sulpho acid R
m-toluylen
diamine
1:4 naphthol vio
sulpho acid
a
naphthol
"
ẞ naphtholdi-
sulpho acid R
وو
1:4 naphthol
sulpho acid
""
3 naphthol
ẞ naphtholdi-
sulpho acid R
ẞnaphtholdi-
sulpho acid G
naphthionic
acid
re
viol
"
bl
re
2
"
re
"
$9
m-phenylen
diamine
a naphthol
β
"
sulphanilic
acid
"
phenole
metanílic
acid
vio
resorcine
salicylic acid
"
Boxynaphthoic 3 naphthol-
blu
acid
disulpho acid
re
Balicylic acid
1:4 naphthol
re
sulpho acid

page_text: Manufacture of Azo, Disazo, and Polyazo Colouring Matters with
Phenylen and Toluylen-oxamic Acid.
1 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 :-
Oxamic acids appear hitherto not to have been employed for the manufacture of
colouring matters. Phenylen oxamic acid was made known in the Ber. d. Chem.
Ges. vol. VII. p. 1261. Toluylen oxamic acid appears not to have been prepared
or described hitherto.
It is prepared in the same manner as phenylen oxamic acid, and forms a slightly
yellow powder, which is hardly soluble even in boiling water, but is easily soluble
in alkalies, in particular with slight excess thereof, and it coincides otherwise with
phenylenoxamic acid.
Favourable results have hitherto generally only been obtained with the use of
the m-acids.
Colouring matters have been obtained that dye both wool and directly, cotton.
As the initial substance for the process may be taken the acids themselves, but
particularly valuable products are obtained if the acids are coupled with a diamine,
for instance benzidine, tolidine or dianisidine or their sulpho acids. Likewise
other para-diamines may be employed for instance p-phenylendiamine. For this
there may be coupled either two acid molecules with one diamine, or one acid
molecule and one amido or phenol or their sulpho or carbon acids with one
diamine.
In the substance produced the free amnido groups can be farther diazotised.

page_text: The oxalic acid can remain in the colouring matter or it can be split off in
order to render also the amido group bound thereby available for farther
diazotising.
It serves therefor in the various modes of carrying out the new process, either
only as a protective group which in the first diazotising protects the second amido
group, and is then separated or it forms a permanent component of the colouring
_matter.
The separation is based on the discovery that the products resulting from
the diazotising can be separated from the rest of oxalic acid by boiling them
for some hours with a reflux cooler, in greatly diluted hydrochloric acid of
about 5° Bé.
In the process in which phenylen or toluylen oxamic acid is used as the initial
material, the diazotising is carried out in the usual manner by means of sodium
nitrite and hydrochloric acid.
If the first azo colouring matters produced with 1.4 napthol sulpho acid, are
boiled in greatly diluted hydrochloric acid (about 5° Bé.) for about 3 hours with a
reflux cooler, the oxalic acid is smoothly split off. The dyestuff acids obtained are
soluble with difficulty in water and can therefore be readily washed. In water
containing alkali they are readily dissolved, and they are therefore dissolved in
ammoniacal water, and the second diazotising can then be carried out without
difficulty. The coupling of the compounds formed has been effected with:

page_text: If the diamine be bound with 2 molecules of one of the said oxamic acids, colouring
matters are obtained which correspond to the following formula :-
NH.
The colouring matters are however of exceedingly difficult solubility from which
apparently results their small dyeing power. In particular those prepared with
phenylen oxamic acid shew very difficult solubility, the colouring matters produced
with toluylen oxamic acid are somewhat more easily soluble.
Of greater value are on the other hand the mixed azo colouring matters which
are produced with only one molecule of oxamic acid, and which correspond to the
following general formula:-
in which R represents an amine or phenole or their sulpho or carbon acids.
Also these mixed colouring matters are partially of very difficult solubility. But
the solubility of all colouring matters produced according to (a) and (b) is considerably
increased by the addition of some alkali.
Instead of the simple diamines can also be used their mono and di-sulpho acids
and these give good results particularly with colouring matters prepared according
to formula (a), in so far as the colouring matters are then more readily soluble in
water, and apply readily to the fibre.
Thus a useful brown colouring matter is obtained by coupling one molecule of
tetrazo diphemyl mono sulpho acid with two molecules of toluylen oxamic acid.
But also the almost quite insoluble mixed diazo colouring matters which are
produced according to formula (b) with the use of amines and some oxycarbon
acids, become soluble it, instead of the simple diamines their sulpho acids are
employed.
Thus for instance the colouring matters from benzidine, toluylenoxamic acid and
one of the following bodies ẞ-oxynaphthoic acid, o-kresotinic acid, m-toluylen-
diamine a and ẞ naphthylamine, and some others, are practically quite insoluble,
but they become useful al S soon as the sulpho acids of the diamines are
employed.
The
process for the preparation of the diazo colouring matters will be under-
stood from the following examples.
EXAMPLE I. DIAMINE + 2 MOLECULES OF OXAMIC ACID.
18.4 kilos. benzidine are dissolved in about 600 litres water and 58.2 kilos. hydro-
chloric acid (20° Bé.) and are diazotised with 14 kilos. nitrite. The solution is well
cooled and brought to about 1000 litres, and is poured into a solution of 38.8 kilos.
toluylen oxamic acid in about 1000 litres water containing 50 kilos. carbonite of
soda. The colouring matter at once separates as a light brown powder which is
filtered and washed. It is almost insoluble even in hot water, but is partially
dissolved in alkaline water, and can then be directly fixed on the fibre; it dyes
unmordanted cotton yellowish brown to orange.
If instead of 2 molecules toluylen oxamic acid 2 molecules phenylenoxamio

page_text: It has been found that also the meta mono nitrobenzindine and the meta mono-
nitrotolidine can be used with phenylen or toluylen oxamic acid for the production
of valuable mixed azo colouring matters which though not suitable for dyeing
cotton, give on wool dyes of great permanency against washing, fulling, acids,
alkalies and sulphur.
229 kilos. meta mono nitro benzidine are tetrazotised in the known manner and
then added to a solution of 19.4 kilos. toluylen oxamic acid and 25 kilos. carbonate
of soda in about 600 litres water.
The intermediate product separates as a yellow brown precipitate. The mass is
stirred for half an hour and the intermediate product is poured into a solution
of 24.6 kilos. of 14 naphtho sulphonate of soda and 25 kilos. of carbonate of soda
in about 600 litres of water, when a fine red colouring matter is produced. The
mass is then stirred for about an hour and allowed to stand for about 12 hours; it
is then heated to from 30° to 40° C., and again allowed to stand some hours, the
partially separated colouring matter is completely salted out, pressed, dried, and if
necessary again washed and dried.
It can be fixed both on unmordanted and on chromed wool and dyes the
same red.
If in place of the 22.9 kilos. meta mono nitro benzidine 25.7 kilos. meta mono
nitro tolidine be used, there is obtained a colouring matter of a dark red brown
tint.
It has furthermore been found that the above described colouring matters of the
formula
promote supo acid, a ne or
репоте от
their sulpho or carbon acids.
The process will be understood from the following examples.
EXAMPLE I. COUPLING WITH AN AMINE.
72.8 kilos. of the colouring matter obtained from 1 mol. dianisidine, 1 mol.
toluylen oxamic acid and mol. 14 naphthol sulpho acid, are dissolved in about
2000 litres water, and under cooling, is diazotised in the known manner with 7 kilo3.
nitrite and 30 kilos. hydrochloric acid (20° Bé.).
The diazocompound which is obtained after about half an hour's stirring, is added
to a solution of 12.2 kilos. of m-toluylendiamine and about 30 kilos. calcined
carbonate of soda, which is also cooled. The mass is stirred for some time and is
allowed to stand till the next day under occasional stirring; it is then heated to
about 40° to 50° C., is allowed to stand for some hours, and lastly the colouring
matter is precipitated with dilute acid or salt; in the first case there is obtained
the dyestuff acid which is easily converted into an alkali salt, in the latter case the
easily soluble soda salt is obtained. The colouring matter dyes unmordanted cotton
blue black.

page_text: EXAMPLE II. COUPLING WITH AN AMIDO SULPHO ACID.
66-7 kilos. of the colouring matter obtained from 1 mol. benzidine, 1 mol.
naphthionic acid and 1 mol. toluylen oxamic acid are dissolved in about 1500 litres
water, cooled and diazotised with 7 kilos. nitrite and 30 kilos. hydrochloric acid
(20° Bé.). The mass is stirred for half an hour and the diazo compound produced
is added to a solution of 17.3 kilos. sulphanilic acid and about 25 kilos. carbonate
of soda in about 300 litres water. The farther treatment is the same as in
Example I. The colouring matter dyes unmordanted cotton direct brown.

page_text: admit of a farther treatment, the free amido group of the oxamic acid being
diazotised and coupled with an amine or phenole or their sulpho or carbon acids;
by treatment with dilute acid for some hours at the reflux cooler the oxalic acid
rest is split off, and new colouring matters are produced which fix well on
unmordanted cotton, and which are particularly stable against acid and alkali as
also against washing and light. All these colouring matters can be farther
diazotised and coupled on the fibre, and the permanence gainst washing and light
is thereby considerably increased.
The colouring matters thus produced correspond to the general formula :
their sulpho or carbon acids.
The following examples will explain the process :
EXAMPLE I. R IS AN AMIDO SULPHO ACID; R₁ IS ALSO AN AMIDO
SULPHO ACID, AND IN THIS CASE
= R.
The colouring matter from 1 mol. of benzidine, 1 mol. of naphthionic acid,
1 mol, toluylen oxamic acid and 1 mol. naphthionic acid which corresponds to the
formula:
There is produced a heavy fine powder that precipitates readily, which
represents the fice dye acid.
This is filtered, well washed and dried, and can be at once used in this condition
for dyemg, by dissolving it with an addition of some alkali in which it is very
readily soluble. A subsequent conversion of the dye acid into the soʻla salt offers
no difficulty. The colouring matter dyes unmordanted cotton blue re 1.

page_text: 1 mol. toluylen oxamic acid and 1 mol 1:4 naphthol sulpho acid corresponding to
the formula :
OCH
is treated in exactly the same manner as in Example I. The separation product
obtained dyes unmordanted cotton direct blue.
EXAMPLE III. R IS A PHENOLE SULPHO ACID, R' AN AMINE.
The colouring matter from 1 mol. dianisidine, 1 mol. 1:4 naphthol sulpho acid.
1 mol. toluylen oxamic acid and 1 mol. m-toluylendiamine, corresponding to the
formula:
OCH
5
CH₂
CH,
is subjected to the treatment with dilute hydrochloric acid described in Example I,
and the farther treatment is the same as there described.
The separation product obtained dyes unmordanted cotton direct blue black.
EXAMPLE IV. R IS A PHENOL-SULPHO ACID, R¹ A PHENOLE.
The colouring matter from 1 mol. o-tolidine 1 mol. 1:4 naphthol-sulpho acid,
1 mol. toluylen-oxamic acid, and mol. a naphthol, which corresponds to the
.formula:

page_text: EXAMPLE V. R IS AN AMIDO-SULPHO ACID, R, AN OXYCARBON
ACID.
The colouring matter from 1 mol. benzidine 1 mol. naphthionic acid, 1 mol.
toluylen oxamic acid and 1 mol. ẞ cxynaphthoic acid, corresponding to the
formula:

page_text: Lastly the above described colouring matters obtained by splitting off the oxalyl
group, which correspond to the general formula:

page_text: The mass is stirred for some time, and is allowed to stand for 24 hours with
occasional stirring, and the colouring matter is salted out, or it is precipitated as
free dye, acid with dilute hydrochloric acid. The colouring matter is then filtered,
washed, pressed and dried.
It dyes unmordanted cotton blue.
EXAMPLE II. COUPLING OF THE OXALIC ACID-SEPARATION PRODUCT
WITH A PHENOLE SULPHO ACID.
40 kilos. of the separation product of the colouring matter from mol.
dianisidine, 1 mol. 1:4 naphthol sulpho acid, 1 mol. toluylen oxamic acid, and
1 mol. m-toluylendiamine which corresponds to the formula:
OCH3
-
OH
CH—N = N — C₁H‚—SO₂H
NH,
NH,
N = NCH, _N
=
-
N C.H, NH,
CH,
CH,
CH3
OCH,
are dissolved in about 1600 litres of water, with addition of the necessary quantity
of alkali.
The cooled solution is diazotised with 8 kilos. nitrite and 32 kilos. hydrochloric
acid (20° Bé.). The intermediate product separates out. After stirring for half
an hour, the diazo compound is added to a solution of 20 kilos. R salt and about
16 kilos. calcined carbonate of soda in about 600 litres water.
The farther treatment is the same as in Example I. The colouring matter dyes
unmordanted cotton blue.
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TIT
CARRY THA
AB
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PRODUCT
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TIT
DATION PRODUCT
WITH AN AMIDO SULPHO ACID.
48 kilos. of the separation product of the colouring matter from 1 mol. beuzidine,
1 mol. naphthionic acid 1 mol. toluylen oxamic acid and 1 mol. phenole, which
corresponds to the formula:
-
C.H NN - C₁H₂
NH2
SO,H
NH,
CH-N=N-CHN-N - CHOH
2

page_text: for half an hour the separated diazo compoun is added to a solution of 13.5 kilos.
of metanilic acid, and about 24 kilos. carbonate of soda with about 600 litres of
water. The farther treatment is as in Example I.
The colouring matter dyes unmordanted cotton violet.
5 EXAMPLE IV. COUPLING OF THE OXALIC ACID SEPARATION PRODUCT
WITH AN OXY CARBON ACID.
51 kilos. of the separation product of the colouring matter from 1 mol. benzidine,
1 mol. naphthionic acid, 1 mol. tuluylen oxamic acid and 1 mol. resorcine,
corresponding to the formula:
are dissolved in about 1800 litres of water with addition of alkali.
The cooled solution is diazotised with 6 kilos. nitrite and 24 kilos. hydrochloric
acid.
After stirring for half an hour the separated diazo compound is added to a cooled
solution of 10-5 kilos. salicylic acid and about 24 kilos. carbonate of soda, in about
600 litres of water.
The farther treatment is the same as in Example 1. The colouring matter dyes
unmordanted cotton violet.
All the colouring matters producible according to this process are easily soluble;
some of them are so soluble that they cannot be subjected to washing.
In this case they are dried, washed with a little cold water or greatly diluted
hydrochloric acid, and again dried.
The free dye acids separated by means of acid can be better washed, but of these
also some are very easily dissolved.
The following is a tabular statement of the colouring matters prepared up to the
present time according to the above process:
1:4 naphthol
sulpho acid
ẞ naphtholdi-
sulpho acid
m-toluylen
diamine
a naphthol
1:4 naphthol blue
sulpho acid
ẞ naphthol
naphtholdi-
sulpho acid R
1:4 naphthol
sulpho acid
"
""
"

page_text: ẞ naphthol
1:4 naphthol
sulpho acid
ẞ naphthol-
disulpho acid R
m-toluylen
diamine
a naphthol
"
1:4 naphthol
sulpho acid
3 naphtholdi-
sulpho acid R
rn-toluylen
diamine
m-phenylen
diamine
ẞnaphtholdi- blue
sulpho acid R
1:4 naphthol violet
sulpho acid
a naphthol
"
ẞnaphtholdi- red
sulpho acid R
"
1:4 naphthol
sulpho acid
"
ẞ naphthol
violet
""
blue
red
"
ẞnaphtholdi-red
sulpho acid R
"
G
"
a naphthol
"
phenole
resorcine
naphthionic
acid
sulphanilic
acid
"
وو
metanilic acid violet
salicylic acid
"
3 oxynaphthoic ẞnaphtholdi-blue
acid
salicylic acid
o-kresotime
red
sulpho acid
1:4 naphthol red
sulpho acid
"
"
acid
m-toluylen
diamine
sulpho acid
metanilic acid
naphthionic
acid
1:4 naphthol
sulpho acid
ẞ naphthol
"
"1
resorcine
"
"
"
violet
phenole
Boxynaph-
thoic acid
o-kresotinic
acid
ẞ naphtholdi-
sulpho acid R
1:4 naphthol
sulpho acid R
ẞnaphtholdi- blue
sulpho acid R
"
"

page_text: Having now particularly described and ascertained the nature of my said inveu-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The use of phenylen- and toluylen-oxamic acid in the production of colouring
matters substantially as described.
2. As new products, the colouring matters resulting from the use of phenylen
and toluylen oxamic acid, and corresponding to the herein stated formula.
3. In the production of the colouring matters referred to in the preceding claims,
the process of separating the oxalic acid remainder by means of dilute hydrochloric
acid, substantially as described.
4. The special processes for the production of wool and cotton dyes, characterized
by the coupling of a diamine with 1 or 2 molecules of phenylen- or toluylen-
oxamic acid by means of single or multiple diazotisation, with or without coupling
with other constituents of colouring matters, as described, and with or without
separation of the oxalic acid.
Dated this 5th day of August 1896.
ABEL & IMRAY,
Agents for the Applicant.