The Manufacture and Production of New Colouring-matters, and of New Intermediate Products related thereto.
Year: 1898

page_text: The Manufacture and Production of New Colouring-matters, and of
New Intermediate Products related thereto.
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Badische Anilin and Soda Fabrik, of
Ludwigshafen-on-Rhine, in the German Empire,) to be as follows:-
My foreign correspondents have discovered that several new intermediate products
can be obtained by the condensation of aldehydes with meta-diamines, and with
meta-diamines and a primary aromatic amine and that these intermediate products,
on suitable treatment with a primary aromatic amine, are converted into valuable
new colouring matters, which appear to be particularly suitable for dyeing leather
yellow.
The production of certain of the intermediate products and of the colouring-
matters can be united into one operation, if desired.
The aldehydes which my foreign correspondents especially recommend for use are
formaldehyde and benzaldehyde, and the course of reaction, and the nature of the
intermediate products obtained appear to be different according to the aldehyde
used, but the colouring matters finally obtained resemble one another in their
general properties.
Similar colouring matters can be obtained by suitably melting together the
tetra-ainido-ditolyl methane of the Letters Patent 17,971 of 1889 with an aromatic
amine.
The following examples will serve to illustrate the nature of this invention which
L
The manto are be reight.
PRODUCTION OF AN INTERMEDIATE PRODUCT BY THE CONDENSATION OF ONE MOLECULAR
ONE MOLECULAR
FORMALDEHYDE AND
PROPORTION OF META-
PROPORTION OF
TOLUYLENE-DIAMINE.
Mix about 112 parts of meta-toluylene-diamine (in the form of a fine powder) with
Wherein the greater part of the meta-toluylene-
2,000 to 3,000 parts of water.
diamine will dissolve. Add whilst stirring, 77 parts of a solution of formaldehyde
(containing about 39 per cent. aldehyde). A new intermediate product is at once
formed and begins to separate out, the solution becoming milky. Continue stirring
for a few hours. Then collect the intermediate product by filtering, wash with water,
press, and dry by warming up to 60 degrees Centigrade.
Obtained in this way, the new intermediate product is an amorphous white powder,
insoluble in water and very slightly soluble in alcohol, ether or benzene.
If, in the above example, meta-phenylene-diamine be used instead of meta-
toluylene-diamine, the reaction takes place in a similar manner and the new
intermediate product obtained has similar properties.

page_text: PRODUCTION OF A COLOURING MATTER FROM THE INTERMEDIATE PRODUCT OF EXAMPLE 3 4
WITH THE AID OF PARA-TOLUIDINE.
Dissolve about 48 parts of the intermediate product of Example 3 in 300 parts of
pat-toinidine, at a temperature of 160 degrees. Raice the temperature of the
inigture to about 180 degrees to 180 Aegrees Canthgrade, and tir, at this temperature

page_text: for about 2 hours. Then dilute the melt with about 1,500 parts of water, and distil
off the para-toluidine by means of steam. Allow the solution to cool and then filter
it and add to it about 120 parts of sodium nitrate solution (M-125).
Re-dissolve and again
The colouring-matter separates out as a resinous mass.
precipitate with about 25 parts of sodium nitrate solution. In this way the colouring-
inatter is obtained as a brown powder.
The colouring-matters obtained according to both the foregoing examples appear to
be identical with each other. In each case the colouring matter is easily soluble in
water, the solution being a reddish-yellow with green fluorescence. It dyes leather
or cotton mordanted with tannin, orange-yellow shades. The base can be precipi-
tated by alkali. It is insoluble in ether.
Instead of para-toluidine, or para-toluidine-salt, used in the foregoing example,
other aromatic amines can be used, for instance, beta-naphthylamine.
PRODUCTION OF AN INTERMEDIATE PRODUCT FROM THAT OF THE LAST PRECEDING
EXAMPLE AND PARA-TOLUIDINE.
Dissolve about 21 parts of the intermediate product of Example 7 in about
80 grammes of para-toluidine, heating on the water bath, and add about 24 parts of
para-toluidine-hydro-chlorate. Stir the mixture for twenty minutes then intro-
duce the thick brownish paste which has formed in the mixture, with about
500 parts of water, into a vessel suitable for distilling and add about 15 parts of
caustic soda lye (containing about 35 per cent. NaOH). Distil off the para-toluidine
by means of steain.
The new intermediate product remains behind as a grey-yellow powder. It is
readily soluble in acetone, benzene and alcohol, and almost insoluble in ligroine.

page_text: PRODUCTION OF COLOURING-MATTER FROM THE INTERMEDIATE PRODUCT OF EXAMPLE 7.
Dissolve about 200 parts of the intermediate product of Example 7 in about 900
parts of para-toluidine, heating to a temperature of about 100 degrees Centigrade.
Add to this melt about 400 parts of para-toluidine-hydro-chlorate. Stir the mixture
for about ten hours whilst maintaining a temperature of about 130 to 160 degrees
Centigrade. Then pour the melt into from 3,000 to 4,000 parts of water and distil
off the para-toluidine by means of steam. The solution remaining behind contains a
resinous mass which collect and boil out with water repeatedly. The new colouring-
matter crystallises out from the solutions thus obtained which may be poured
together.
Before crystallising and whilst the solution is still hot remove any pitchy matter
which may separate out.
In a similar manner the same colouring-matter can be prepared from the
intermediate product of Example 8.
Instead of meta-toluylene-diamine, in the reaction with benzaldehyde, meta-
phenylene-diamine can be employed and analogous intermediate products and
colouring matters be obtained, though the yield of colouring matter appears to be
best when meta-toluylene-diamine is used.
Dated this 21st day of September 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Colouring-matters, and of
New Intermediate Products related thereto.
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of London, Patent
Agent, do hereby declare the nature of this invention (which has been communi-
cated to me from abroad by the Badische Anilin & Soda Fabrik, of Ludwigshafen-on-
Rhine, in the German Empire,) and in what manner the same is to be per-
formed to be particularly described and ascertained in and by the following
statement:-
My foreign correspondents have discovered that several new intermediate products
can be obtained by the condensation of aldehydes with meta-diamines, and with meta-
diamines and a primary aromatic amine, and that these intermediate products, on
suitable treatment with a primary aromatic amine, are converted into valuable
new colouring-matters, which appear to be particularly suitable for dyeing leather
yellow.
The production of certain of the intermediate products and of the colouring matters
can be united in one operation, if desired.
The aldehydes which my foreign correspondents use are formaldehyde and benzal-
dehyde, and the course of reaction, and the nature of the intermediate products
obtained appear to be different according to the aldehyde used, but the colouring-
matters finally obtained resemble one another in their general properties.
Similar colouring-matters can be obtained by suitably melting together the tetra-
amido-ditolyl-methane of the Letters Patent 17971 of 1889, with an aromatic
amine.
The following examples will serve to illustrate the nature of this invention, which
is, however, not confined to these examples. The parts are by weight :-

page_text: PRODUCTION OF AN INTERMEDIATE PRODUCT BY THE CONDENSATION OF ONE MOLECULAR
PROPORTION OF FORMALDEHYDE AND ONE MOLECULAR PROPORTION OF META-
TOLUYLENE-DIAMINE.
Mix about 122 parts of meta-toluylene-diamine (in the form of a fine powder) with
about 2000 to 3000 parts of water, wherein the greater part of the meta-toluylene-
diamine will dissolve. Add, whilst stirring, 77 parts of a solution of formaldehyde,
(containing about 39 per cent. aldehyde). A new intermediate product is at once
formned, and begins to separate out, the solution becoming milky. Continue stirring
for a few hours. Then collect the intermediate product by filtering, wash with water,
press and dry.
Obtained in this way the new intermediate product, is a white powder, insoluble in
water and very slightly soluble in alcohol, ether or benzene.
If, in the above example, meta-phenylene-diamine be used instead of meta-
toluylene-diamine, the reaction takes place in a similar manner and the new inter-
mediate product obtained has similar properties.
PRODUCTION OF A NEW INTERMEDIATE PRODUCT FROM ONE MOLECULAR PROPORTION OF
FORMALDEHYDE AND TWO MOLECULAR PROPORTIONS OF META-TOLUYLENE-DIAMINE,
IN ALKALINE SOLUTION.
Mix together 122 parts of meta-toluylene-diamine and 20 parts of caustic soda lye
(containing about 35 per cent. NaOH) and 50 parts of alcohol. Heat the mixture on
the water-bath, and add about 39 parts of an aqueous solution of formaldehyde (con-
taining about 39 per cent. aldehyde). An energetic reaction takes place, and the
liquid boils spontaneously. Maintain the temperature for about half-an-hour, then
distil off the alcohol, and wash with water the oil which remains. The product thus
obtained can be at once used for further treatment, without any previous purification.
It is a stiff oily body, readily soluble in alcohol and chloroform, but only slightly
soluble in ether and ligroin.
If, in the foregoing example, the diamine and aldehyde be mixed in neutral solu-
tion, a mixture of the intermediate product of Example 1 with tetra-amido-ditolyl-
inethane is obtained, and in acid solution the latter is obtained as the sole product,
as has already been described in Letters Patent No. 17971, of 1889.
THE CONVERSION OF THE NEW INTERMEDIATE PRODUCT OF EXAMPLE 1 INTO A
FURTHUR INTERMEDIATE PRODUCT BY TREATMENT WITH PARA-TOLUIDINE.
Dissolve about 40 parts of the intermediate product of Example 1 in about 150 parts
of para-toluidine, by heating them together on the water-bath and add about 43 parts
of para-toluidine-hydrochloride. Stir the mixture until the mass, while still hot,
solidifies to a thick paste. This usually takes about twenty minutes. Introduce the
mixture into a suitable vessel for distilling, containing about 750 parts of water, and
make the mixture alkaline by adding about 60 parts of caustic soda lye, (containing
about 35 per cent. NaOH). Distil off the para-toluidine by means of steam. The
residue, after distillation, is a yellowish, coarsely granular powder, insoluble in hot
water. Collect by filtration, wash with water, press and dry.
If, in this example, other aromatic amido bodies be used instead of para-toluidine
(for instance, meta-xylidine or aniline) a similar intermediate product is obtained.

page_text: PRODUCTION OF A COLOURING-MATTER FROM THE INTERMEDIATE PRODUCT OF
EXAMPLE 1 AND PARA-TOLUIDINE.
Dissolve about 50 parts of this intermediate product in 300 parts of para-toluidine,
by stirring together at 100 degrees Centigrade. Then add about 200 parts of para-
toluidine-hydrochloride, and raise the temperature to about 150 to 160 degrees Centi-
grade. Maintain this temperature for from 1 to 2 hours. Then mix the hot melt
with about 1000 parts of water, and distil off the para toluidine by means of steam.
Filter the residue hot, and to the filtered solution add 100 parts of saturated sodium
nitrate solution. The colouring-matter separates out as a resinous mass. To purify
it redissolve it and reprecipitate it with sodium nitrate solution. This purification
can be repeated, if necessary.
PRODUCTION OF A COLOURING-MATTER FROM
TETRA-AMIDO-DI-TOLYL-METHANE,
LETTERS PATENT No. 17971, 1889 AND BETA-NAPHTHYLAMINE.
OF
Dissolve about 75 parts of the said tetra-amido-di-tolyl-methane in about 350
parts of beta-naphthylamine, at a temperature of 150 degrees Centigrade, and add
about 150 parts of beta-naphthylamine hydrochloride. Heat the mixture for about
2 hours at a temperature of about 170 degrees ('entigrade. Then extract the melt with
about 3000 to 4000 parts of water, acidified with about 300 parts of hydrochloric acid,
(containing about 35 per cent. IICI). Filter hot, to separate a large quantity of beta-
naphthylamine hydrochloride. Allow the filtrate to cool. Add a little common salt

page_text: solution. A further quantity of beta-naphthylamine-hydrochloride is precipitated.
Filter again, and then add sufficient common salt to precipitate the colouring-matter.
Redissolve the colouring-inatter several times, and reprecipitate with common salt in
order to purify it from beta-naphthylamine.
The colouring-matter is a reddish-brown to dark-brown powder, readily soluble in
water, and it dyes tannin mordanted cotton a pure yellow.
Similar colouring-matters result if, instead of beta-naphthylamine, other amines (for
instance, para-toluidine) be used.
PRODUCTION OF AN INTERMEDIATE PRODUCT FROM THAT OF EXAMPLE 8 AND PARA-
TOLUIDINE.
Dissolve about 21 parts of the intermediate product of Example 8 in about 80 parts
of para-toluidine, heating on the water-bath, and add about 24 parts of para-toluidine-
bydrochloride. Stir the mixture for twenty minutes, then introduce the thick
brownish paste which has formed in the mixture, with about 500 parts of water, into a
vessel suitable for distilling, and add about 15 parts of caustic soda lye (containing
about 35 per cent. NaOH). Distil off the para-toluidine by means of steam.
The new intermediate product remains behind as a grey-yellow powder. It is
readily soluble in acetone, benzene and alcohol, and almost soluble in ligrion.
PRODUCTION OF A COLOURING-MATTER FROM THE INTERMEDIATE PRODUCT OF
EXAMPLE 8.
Dissolve about 200 parts of the intermediate product of Example 8 in about 900
parts of para-toluidine, heating to a temperature of about 100 degrees Centigrade.
Add to this melt about 400 parts of para-toluidine-hydrochloride. Stir the mixture
for about ten hours, whilst maintaining a temperature of about 130 to 160 degrees
Centigrade. Then pour the melt into from 3000 to 4000 parts of water, and distil off
the para-toluidine by means of steam. The solution remaining behind contains a
resinous mass and is to be collected and repeatedly boiled out with water. The new
colouring-matter crystallises out from the solutions thus obtained which may be
poured together.
Before crystallising, and whilst the solution is still hot, remove any pitchy matter
which may separate out.
In a similar manner the same, or similar, colouring-matter can be prepared from
the intermediate product of Example 9.
Instead of meta-toluylene-diamine, in the reaction with benzaldehyde, meta-
phenylenediamine can be employed, and analogous intermediate products and
colouring-matters be obtained, though the yield of colouring-matter appears to be
best when meta-toluylene-diamine is used.

page_text: Having now particularly described and ascertained the nature of the said invention
and in what manner the same is to be performed I declare that what I
claim is
1. The production of new intermediate colouring-matter products by the action of
one molecular proportion of formaldehyde on one molecular proportion of an aromatic
meta-diamine, substantially as herein before described.
2. The production of new intermediate colouring-matter products by the action of
one molecular proportion of formaldehyde on two molecular proportions of an aromatic
meta-diamine in the presence of an aqueous solution of an alkali, substantially as
herein before described.
3. The production of intermediate colouring-matter products by heating the
products of Claim 1 with a primary aromatic amine and the hydrochloride of the said
primary aromatic amine; substantially as herein before described.
4. The production of intermediate colouring-matter products by the action of one
molecular proportion of benzaldehyde on one molecular proportion of an aromatic
meta-diamine; substantially as herein before described.
5. The production of intermediate colouring matter products by heating the
products of Claim 4 with a primary aromatic amine and the hydrochloride of the said
amine; substantially as herein before described.
6. The manufacture of colouring matters, which dye leather and tannin mordanted
cotton yellowish shades, by heating the intermediate products of Claim 1 with a
primary aromatic amine and the hydrochloride of the said amine; substantially as
hereinbefore described.
7. The manufacture of colouring matters, which dye leather and tannin mordanted
cotton yellowish shades, by heating the intermediate product of Claim 2 with a
primary aromatic amine and the hydrochloride of the said amine; substantially as
hereinbefore described.
8. The manufacture of colouring matters, which dye leather and tannin mordanted
cotton yellowish shades by heating the intermediate products of Claim 4 with a
primary amine and the hydrochloride of the said amine; substantially as hereinbefore
described.
9. The manufacture of colouring-matters, which dye leather and tannin mordanted
cotton yellowish shades, by heating tetra-amido-ditolyl-methane with beta-naphthyl-
amine and beta-naphthylamine-hydrochloride, or with para-toludine and the hydro-
chloride thereof; substantially as hereinbefore described.
10. The manufacture and production of the new intermediate products and colour-
ing-matters in the manners set forth in the several examples hereinbefore given.
11. As new articles of manufacture the intermediate products and colouring-matters
such as can be obtained substantially as hereinbefore described.
Dated this 19th day of June 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.