Improvements in the Manufacture or Production of Indulines or Induline-like Dye Stuffs.
Year: 1889

page_text: Date of Application, 27th Feb., 1889
Complete Specification Left. 26th Nov., 1889-Accepted, 4th Jan., 1890
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture or Production of Indulines or
Induline-like Dye Stuffs.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this Invention, which has been
communicated to me from abroad by Farbenfabriken vormals Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany, to be as follows:-
My foreign correspondents have ascertained that indulines in water can be formed
by melting together amidoazo benzene hydrochloride with aniline hydrochloride. It
is found however that as the temperature required to form this new substance is too
high, the amount of product resulting from the decomposition of the materials
employed is too small to admit of this process being employed with advantage in
practice.
My foreign correspondents have now discovered a process by means of which
molecular quantities of hydrochlorides of amido azo compounds and aniline hydro-
chloride can be converted into induline soluble in water and the present invention
consists in the first place in causing these substances to react upon one another in the
presence of glycerine whereby chinoline derivatives known by their odour appear to
result with separation of water.
This process may be illustrated by the following example-One part of amido azo
benzene hydrochloride and two parts of aniline hydrochloride are mixed with two parts
of glycerine and this mixture is heated in the first place to say about 150 degrees
centigrade. The melt which assumes a deep blue colour is afterwards maintained at
a temperature of from say about 170 to 180 degrees centigrade, and a beautiful
greenish blue induline soluble in water is formed. The reaction is known to he
completed when a sample dissolves with a greenish blue colour in diluted hydro-
chloric acid. The thin liquid melt is poured into water, dissolved in hydrochloric
acid and the dye stuff is then salted out of the filtrate in the usual way. The aniline
that has not entered in re-action can be obtained from the filtrate in the known
manner.
It is not necessary to adhere strictly to the quantities or proportions mentioned
in the foregoing example for instance an excess of aniline may be employed. Similar
results can be obtained by employing in place of the aniline hydrochloride the
homologues thereof such as toluidine xylidine and cumidine and amido azo toluol,
amido azo xylol or other like amido azo compounds may be substituted for the amido azo
benzene hydrochloride. When benzidine, diamido, phenyl tolyl and tolidine are
employed in place of the aniline hydrochloride indulines of a green tinge, soluble in
water are obtained in like manner but are much less readily soluble than the dyestuffs
obtained from aniline and its homologues.
My foreign correspondents have further discovered that the dyestuffs soluble in
spirit and known in the trade as nigrosine and aniline black can be converted into
dyestuffs that are soluble in water by melting them with para phenylene diamine.
These new dyestuffs resembling induline are of about the same shade as the original
materials and by means of this process dye stuffs are obtained of from a gray to a
deep blue black colour and readily soluble in water.
This process may be briefly described as follows:-About one part of nigrosine is
beated to from about 170 to 190 degrees centigrade with two parts of para phenylene
diamine until the melt dissolves readily and completely with a clear colour in dilute
hydrochloric acid. After cooling the melt is dissolved in dilute hydrochloric acid and
the dye stuff is salted out of the filtrate. The proportions in the foregoing example
may be varied and but slight differences in the colour result therefrom or from
changing the length of the time allowed for the reaction or raising the temperature.

page_text: A dyestuff dyeing a beautiful deep blue black is obtained by substituting aniline black
for the nigrosine in this example.
When azo benzene is melted with para phenylene diamine in the presence of a
certain quantity of ammonium chloride or sal ammoniac at a temperature of from
about 220 to 240 degrees centigrade a dyestuff soluble in water is obtained which
possesses very strong dyeing power.
One part of azo benzene is melted together with three parts of paraphenylene
diamine and some ammonium chloride and the temperature is gradually raised to
from about 220 to 240 degrees centigrade. When all the azo benzene has disappeared
the melt is poured into water and dissolved in dilute hydrochloric acid. The dyestuff is
separated from the filtrate in the usual way by salting out. The proportions may be
varied in various ways without affecting the result and even the presence of the sal
ammoniac is not absolutely indispensable. In place of the azo benzene the homologues
thereof such as azo toluol and azo xylol or benzene azo toluol may be employed with
the same result:
Azoxy bydrazo compounds also yield with para phenylene diamine induline like
dyestuffs that are soluble in water. Meta phenylene diamine may be employed in place
of the para phenylene diamine and the corresponding toluylene diamine in particular
or xylylene diamine may be substituted for the phenylene diamine.
Greenish blue to blue black induline like dyestuffs can also be obtained by oxidising
meta and para phenylene diamine and the homologues thereof or the substitution
products with weak organic oxydising agents such as chloranil dichloro naphtho
'chinone, chinone and naphtho chinone chlorimide and the like. The process for the
production of this group of new induline like dyestuffs may be illustrated by the
following example. About three parts of para phenylene diamine are heated with
one part of chloranil to about 150 degrees centigrade and the temperature is gradually
raised to from about 170 to 180 degrees. The blue coloured melt acquires a darker
colour and the action is known to be completed when a sample dissolves with a greenish-
blue colour in dilute hydrochloric acid. The melt when cold is ground and freed from
para phenylene diamine which has not entered in reaction by a boiling process, the
dyestuff forming the residuum is dissolved in dilute hydrochloric acid and the dyestuff
is precipitated from the filtrate by common salt.
By heating meta or para nitraniline with aniline hydrochloride or its homologues
with or without the employment of chloride of iron and a product of condensation to
from about 100 to 200 degrees centigrade, a beautiful clear induline like dyestuff
dissolving in dilute hydrochloric acid with a pure blue colour is obtained as before.
The process for the production of this group of new induline like dyestuffs soluble
in water is illustrated by the following example. One part of para nitraniline is
melted together with two parts of aniline hydrochloride and some chloride of iron
and bensoic acid or ammonium chloride and the temperature is raised to from
about 180 to 190 degrees. The result is a readily flowing melt. When a sample
dissolves with a pure blue colour in dilute acid the melt is poured into water dissolved
in dilute hydrochloric acid and the dye stuff is precipitated from the filtrate by means
of salt. The operation occupies about three or four hours.
According as more than two parts of aniline hydrochloride are employed in this
process or this material is replaced by its homologues such as tolnidine, xylidine,
cumidine or mixtures thereof or the para nitraniline is replaced by meta nitraniline
and the substitution products thereof and the process is conducted without employing
the chloride of iron and benzoic acid similar dyestuffs soluble in water are obtained
which differ considerably in their shades of colour. Oxalic acid may be employed in
place of the benzoic acid. When a condensing agent such as chloride of zinc, chloride
of calcium and the like is added to the melts in this process, this has an advantageous
effect on the quantity of dyestuff obtained but the dye itself is somewhat duller.
Dated this 27th day of February 1889.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture or Production of Indulines or
Induline-like Dyestuff.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this Invention which has been
communicated to me from abroad by The Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld in the Empire of Germany and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
My foreign Correspondents have discovered that the dyestuffs soluble in spirit and
known in the trade as nigrosine, aniline black and saffranine can he converted into
dyestuffs which are soluble in water by melting them together with para-phenylene-
diamine. By means of this process dyestuffs are obtained of from a gray to a deep
blue-black colour which are readily soluble in water.
This process may be briefly described as follows-About one part (parts are by
weight) of nigrosine is heated to from about 170 to 190 degrees centigrade with two
parts of para-phenylene-diamine until the melt dissolves readily and completely with
a clear colour in dilute hydrochloric acid-After cooling the melt is dissolved in dilute.
hydrochloric acid and the dye stuff is salted out from the filtrate-The proportions
in the foregoing example may be varied and but slight differences in the colour result
therefrom or from changing the length of the time allowed for the reaction or from
raising the temperature-Dyestuffs dyeing a beautiful deep blue-black are obtained
by substituting aniline black or saffranine for the nigrosine in this example-
Toluylendiamine may be substituted for paraphenylene-diamine with the same
effect.
When azo-benzone is melted with para-phenylene-diamine in the presence of a certain
quantity of ammonium chloride or sal-ammoniac at a temperature of from about 220
to 240 degrees centigrade a dyestuff soluble in water is obtained which possesses very
strong dying powers.
One part of azo-benzene is melted together with three parts of para-phenylene-
diamine and a small quantity of ammonium-chloride and the temperature is gradually
raised to from about 220 to 240 degrees centigrade-When all the azo benzene has
disappeared the melt is poured into water and dissolved in dilute hydrochloric-acid.
The dyestuff is separated from the filtrate in the usual way by salting out. The
proportions may be varied in various ways without affecting the result even a small
quantity of the hydrochloride of para-phenylendiamine can be substituted for the
ammonium chloride-In place of the azo-benzene the homologues thereof videlicet
azo-toluene or benzene-azo-toluene may be employed with the same result.
Azooxy or hydrazo compounds also yield with para-phenylene-diamine induline
like dye stuffs that are soluble in water.
Meta-phenylene-diamine may be employed in place of the para-phenylene-diamine
and the corresponding toluylene-diamine in particular may be substituted for the
phenylene diamine.
Greenish-blue to blue-black induline-like dyestuffs can also be obtained by oxidising
meta and para-phenylenediamine and the homologues thereof or the substitution
products with weak organic oxidising agents such as chloranil, dichloro-naphtho
quinone quinone and naphtho-quinone chlorimide.
The process for the production of this group of new induline-like dyestuffs may be
illustrated by the following example-About three parts of para-phenylene-diamine are
heated with one part of chloranil to about 150 degrees centigrade and the temperature
is gradually raised to from about 170 to 180 degrees centigrade-The blue coloured melt
acquires a darker colour and the action is known to be completed when a sample
dissolves with a greenish-blue colour in dilute hydrochloric acid-The melt when cold
is separated from para-phenylene-diamine which has not entered into reaction bý

page_text: boiling it with water-The dyestuffs forming the residuum is dissolved in dilute
hydrochloric acid and the dyestuff is precipitated from the filtrate by common salt.
By heating meta or para nitraniline with aniline hydrochloride or its homologues
with or without the employment of chloride of iron and a condensing agent to from
about 100 to 200 degrees centigrade beautiful clear induline-like dyestuffs dissolving
in dilute hydrochloric acid with pure blue colours are obtained as before-The
process for the production of this group of new induline-like dyestuffs soluble in water
is illustrated by the following example-One part of para-nitraniline is melted together
with two parts of aniline-hydrochloride and some chloride of iron and benzoic acid
or ammonium chloride and the temperature is at first raised to about 120 degrees
centigrade and maintained at this for one hour then the temperature is slowly
raised to from about 120 to 150 degrees centigrade and after some hours to
150-165 degrees centigrade-The reaction is finished if a sample dissolves easily
with a pure blue colour in dilute acid-The melt is then poured into water made
alkaline and is treated with steam in order to remove any aniline which may not have
taken part in the reaction-The separated dyestuff is dissolved in dilute hydrochloric
acid and the dyestuff precipitated from the filtrate by means of common salt.
According as more than two parts of aniline hydrochloride are employed in this
process or this material is replaced by its homologues such as toluidine, xylidine or
mixtures thereof or the para-nitraniline is replaced by meta-nitraniline and the
substitution products thereof and the process is conducted without employing the
chloride of iron and benzoic acid similar dyestuffs soluble in water are obtained
which differ considerably in their shades of colour-Oxalic acid may be employed
in place of the benzoic acid. When a condensing agent such as chloride of zinc
chloride of calcium or the like is added to the melts in this process it has an
advantageous effect on the quantity of dyestuff obtained but the dye itself is somewhat
duller.
If in this process of manufacturing soluble induline like dye stuffs the secondary or
tertiary amines are substituted for the primary amines only a small quantity of soluble
dyestuff is obtained-My foreign correspondents have however found that the reaction
proceeds perfectly as to the formation of soluble dyestuffs if some hydrochloride of
aniline or toluidine be added to the melt.
New dyestuffs result which are easily soluble in dilute hydrochloric acid with blue
to green-blue colours.
Good results have been obtained by my foreign correspondents by the employment
of the following secondary and tertiary amines, monomethyl-ethyl-benzylamine,
Dimethyl-diethyl-aniline, methyl benzylaniline, ethylbenzylaniline.
The following is an example of how these new dyestuffs can be manufactured.
Example 1 part by weight of meta nitraniline is heated with 2 parts of hydrochloric
acid or 2 parts chloride of iron, 3 parts of hydrochloride of dimethyl-aniline and
5 parts of chloride of zinc from about 2 to 3 hours at about 120 to 130 degrees
centigrade and the temperature is then slowly elevated to say 160 degrees centigrade.
The reaction is finished if a sample dissolves in dilute hydrochloric acid with a
green-blue colour. The resulting melt is then treated as above described.
Having now particularly described and ascertained the nature of the said Inven-
tion and in what manner the same is to be prepared I declare that what
1 claim is-
First The process for the manufacture of Indulines soluble in water by melting
together the dyestuffs known in commerce under the names of Nigrosines, Aniline
black aud saffranine and the azo compounds videlicet Azo-benzene Azotolnene
Benzeneazotolnene Azooxybenzene Azooxytolnene Hydrazobenzene or Hydrazotoluene
or mixtures of them with meta or para-phenylene-diamine, or toluylenediamine in the
presence of Ammonium Chloride at a temperature of 100 to 250 degrees centigrade.
Second-The process for the manufacture of Indulines soluble in water (which is an
oxydising process) by melting together meta or para-phenylene-diamine with weak

page_text: oxidising agents viz.: quinone chloranil Dichlor-naphtho quinone-Naphtho-quinone or
chlorimide with or without the presence of Benzoic or oxalic acid and of a condensing
agent such as chloride of zinc and chloride of calcium at a temperature of 100 to
200 degrees centigrade.
Third The process for the manufacture of Indulines soluble in water by melting
together Nitro-aniline (nitraniline) nitro-toluidine or mixtures of them with hydro-
chloric acid salts of primary amines videlicet, Aniline, toluidine, xylidine or secondary
and tertiary Amines viz.: monomethyl-, ethyl-, benzyl-anilines; dimethyl-, diethyl-,
methylbenzyl-, ethyl benzyl-Anilines, or mixtures of them with or without the
employment of some chloride of iron benzoic acid oxalic acid or ammonium chloride
or both and a condensing agent videlicet chloride of zinc or chloride of calcium at a
temperature of 100 to 250 degrees centigrade.
.
Fourth As new articles of manufacture the products claimed in each of the
foregoing claiming clauses.
1
mabon 1000
J. H. JOHNSON & Co.