Manufacture of New Bases applicable for the Production of Substantive Cotton Dyes.ROM
Year: 1892

page_text: COMPLETE SPECIFICATION.
[Communicated from abroad by the firm of L. DURAND HUGUENIN & Co., of
Bâle, Switzerland, Manufacturers.]
Manufacture of New Bases applicable for the Production of
Substantive Cotton Dyes.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery Lane
in the County of London, Consulting Engineer aud 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 :-
This invention relates to the manufacture of new bases by condensation of
benzidine or tolidine or a diamido diphenole ether, as for example dianisidine,
with formalde-hyde or a phenylendiamine as for example meta phenylendiamine.
These new bases are intended to serve for the production of substantive cotton
dyes.
I. CONDENSATION PRODUCT FROM TOLIDINE AND FORMALDEHYDE.
For the production of this new condensation product the following process is
employed. 21-2 kilos tolidine and 24.8 kilos basic tolidine hydrochlorate are
incorporated with 10 kilo alcohol to form a thick paste and to this are added
7.5 kilos of formaldehyde solution of 40 p.c.
The mass is allowed to stand for twelve hours when it assumes by degrees a
greyish green colour; it is then heated for twelve hours on a water bath. The
melt first becomes thinly liquid, and then gradually thickens to a resinous con-
sistency, and at the end of the operation it forms a tough pitch like green mass,
which after cooling, solidifies and is easily pulverised.
The reaction product is treated with rather more than the theoretical quantity
of hot sulphuric acid; the new base is thereby completely dissolved while the
tolidine which remained unaffected by the reaction, is separated by filtration as a
salt that dissolves with difficulty.
From the sulphate solution the base is precipitated by carbonate of soda as a
light green resinous mass that quickly solidifies.
The new base begins to liquefy at from 60° to 65° cent. and is completely melted
at 85 to 90° C., it is easily soluble in alcohol, only slightly soluble in benzole, and
almost insoluble in ether; its hydrochlorate and sulphate are readily soluble in
water.
The probable constitution formula of the new body may be assumed to be:

page_text: II. CONDENSATION PRODUCT FROM BENZIDINE AND FORMALDEHYDE.
For the production of the condensation product from benzidine and formaldehyde
the following process is employed.
184 kilos of benzidine and 22 kilos of basic benzidine hydrochlorate are
incorporated with sufficient alcohol to produce a thick paste, and this is added to
7.5 kilos of formaldehyde solution of 40 p.c. The mass is then left for 12 hours,
whereby it solidifies and assumes a light yellow colour; it is then heated for
12 hours to 100° C. or more.
The melt forms a tough resin-like greenish yellow mass, which, on cooling,
becomes hard and brittle.
The reaction product is treated with rather more than the theoretical quantity of
diluted hot sulphuric acid; the new base is thereby completely dissolved, while the
benzidine which is not affected by the reaction is separated by filtration as sulphate
of difficult solution.
From the sulphate solution the base is precipitated by alkalies, in the form of a
light yellow flocculent precipitate.
The new base melts between 84° to 100° C., it is slightly soluble in hot alcohol,
but almost insoluble in benzole and ether; its sulphate or hydrochlorate is easily
soluble in water.
By treating the sulphate solution with nitrite, a diazo compound is obtained that
dissolves with difficulty in water, and which forms, for example, with naphthyl-
amine-sulphonic acids substantive cotton dyes.
III. CONDENSATION PRODUCT FROM DIANISIDINE AND FORMALDEHYDE.
The condensation product from dianisidine and formaldehyde may be prepared
as follows.
24.4 kilos of dianisidine and 28 kilos of basic dianisidine hydrochlorate are
incorporated with a sufficient quantity of alcohol to form a thick paste and this is
then added to 7-5 kilos of a formaldehyde solution of 40 p.c. After standing for a
day at ordinary temperature it is heated on a water bath for 12 hours. The melt
obtained forms a viscous dark coloured mass which, after cooling, frequently does
not solidify for some time. The treatment of the reaction product takes place in
the same way as described under II.
The new base melts between 75° and 90° C. it dissolves in alcohol and benzole,
and is almost insoluble in ether.
Its sulphate or hydrochlorate is easily soluble in water.
From the solutions of its salts the base is precipitated by alkalies, in the form of
light grey resinous floccules which soon solidify and assume a darker colour. On
treating the hydrochlorate solution with nitrite, there is obtained a diazo compound
that can be used for the production of substantive cotton dyes.
IV. CONDENSATION PRODUCT FROM TOLIDINE AND METAPHENYLENDIAMINE.
For producing this condensation product the following process is employed.
12 kilos metaphenylendiamine are heated to 180° C., and to the melted diamine
are then added gradually and under stirring, 10 kilos of basic tolidine hydrochlorate;
the temperature of the mass is then raised to 280° C. and is maintained at that
temperature for 3 hours.
The reaction, which is shewn by the evolution of ammonia will be completed at
the end of the three hours heating to 280° C.
.
The melt, which hardens on cooling, is pulverised and is washed with warm
water in order to remove the diamine which has not entered into the reaction; it is
then dissolved in hot diluted hydrochloric acid, and the small quantity of tolidine
still present being precipitated by means of sulphuric acid, the solution is filtered.
By the addition of soda lye to the hydrochlorate solution the free base will be

page_text: precipitated as a yellowish brown resinous mass which, after a time will become
quite solid, and when pulverised will form a brownish yellow powder.
The diluted alcoholic solution of the new base possesses a strong green
fluorescence; the base is only slightly soluble in ether and benzole.
The hydrochlorate and sulphate of the new base readily dissolve in water and
the free base is dissolved from their solutions by means of alkalies.
It is not possible to crystallise the base. It separates from each of its solvents
as a resinous mass having no constant melting point but which begins to melt below
100° C. and is entirely melted at 110° C.
The base can be readily diazotised according to the usual method, and forms a
diazo-compound which is only partially soluble in water.
The nitrite consumed corresponds to the following formula.
The existence of two amido groups is also demonstrated by the fact that the
diazotised base forms for example with naphthylaminsulpho acids, substantive
cotton dyes.
The course of the reaction of the metaphenylendiamine upon tolidine may be
represented as follows.
V. CONDENSATION PRODUCT FROM BENZIDINE AND META PHENYLENDIAMINE.
The production of this condensation product from benzidine and meta phenylen-
diamine is best effected in the same way as described under IV for the
preparation of the condensation product of tolidine with metaphenylendiamine.
The condensation product of benzidine and metaphenylendiamine is precipitated
from its acid solutions by means of the addition of alkalies as a light chocolate
brown precipitate, which darkens on drying, forming a dark red brown powder,
which melts between 47° and 57°.
The new base is easily soluble in alcohol, slightly soluble in benzole and almost
insoluble in ether.
The bydrochlorate and sulphate are easily soluble in water.
The solutions, in particular those of the free base, are distinguished by strong
green fluorescence.
VI. CONDENSATION PRODUCT FROM DIANISIDINE AND METAPHENYLEN-
DIAMINE.
The production of this condensation product is effected in the same manner as
described under IV.
The condensation product of diansidine and metaphenylendiamine is precipitated
from its acid solutions by the addition of alkalies as a dark chocolate brown
precipitate which when dried, given a dark brown powder that melts between 80°
and 100° C.
The
The new base is soluble in alcohol, slightly soluble in ether and almost insoluble
in benzole. The hydrochlorate and sulphate are easily soluble in water.
solutions possess a strong green fluorescence.
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. Process for the manufacture of new bases applicable for the production of

page_text: substantive cotton dyes by the condensation of tolidine or benzidine or a diamido-
diphenole-ether, as for example diansidine, with formaldehyde or a phenylendiamine
as for example metaphenylendiamine, substantially as described.
2. As a new manufacture, the herein described bases obtained by the process
referred to in the preceding claim.
3. The use of the new bases herein described for the production of substantive
cotton dyes.
Dated this 17th day of May 1809
ABEL & IMRAY,
Agents for the Applicant