Improvements in the Manufacture of Colouring Matters related to the Indulines and Eurhodines.
Year: 1894

page_text: Date of Application, 4th June, 1894
Complete Specification Left, 4th Mar., 1895-Accepted. 6th Apr., 1895
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters related to
the Indulines and Eurhodines.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields, in the County of London,
Gentleman do hereby declare the nature of this invention (which has been com-
municated to me from abroad by The Badische Auilin and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows:-
--
This invention consists in improvements in the manufacture of colouring matters
belonging to the new class of dyes described in the Specification of Letters Patent
No. 10138 of 1892 and constitutes in some instances improvements upon the inven-
tion described and claimed under the said Letters Patent.
In Example 14 of the Specification of Letters Patent No. 10138 of 1892 and in
Example 3 of the Specification of Letters Patent No. 10138A the production of
beta-methyl-homo-eurhodine is described. This is obtained by the interaction of
the azodye from sulphanilic acid and mono-methyl-para-toluidine with alpha-
naphthylamine.
My foreign correspondents have found that if mono-alkylated-alpha-naphthyl-
amine be used in a process such as is illustrated by the said examples the eurhodines
alkylated in both the alpha and beta positions are obtained such as alpha-beta-
dimethyl-eurhodine, if methyl-alpha-naphtylamine be used and alpha-ethyl-beta-
methyl-eurhodine if ethyl-alpha-naphtylamine be used and so on.
Further my foreign correspondents have discovered that instead of the amido-
azo-dyes from mono-alkyl-para-toluidine being used as described in the examples
of the aforesaid Specifications the dialkylated azo dyes can be used such for
instance as those from sulphanilic acid and di-methyl- or di-ethyl-para-toluidine.
When using such dialkylated products one alkyl group is expelled in the melt and
the same product is obtained as if the mono-alkylated derivative had been
employed. Hence it is possible to use the amido-azo-product derived from the
combination of a diazo-compound and mixtures of mono- and dialkylated para-
toluidine such as are usually obtained by the alkylation of para-toluidine so that it
is unnecessary to separate these alkylated products from one another.
The dialkylated amido-azo products can of course also be used in the melt with
alkylated alpha-naphthylamine.
Under the term alkyl are included such groups as methyl, ethyl, amyl, benzyl,
and the like.
My foreign correspondents have further discovered that in the improvements in
the process described in the aforesaid prior Specifications as set forth in the
Specification of the application of Benjamin Willcox for Letters Patent
No. 175723 and consisting in the manufacture of beta-methyl-eurhodine by the
interaction of beta-hydroxy-naphtho-quinone-imide and mono-methyl-ortho-toluy-
lene-diamine the process can also be applied to mono-methyl-ortho-phenylene-
diamine and to other mono-alkyl derivatives of ortho-phenylene and toluylene-diamine
by replacing for instance in the example given in the said Specification 17572³ the
mouo-methyl-orthc-toluylene-diamine by the corresponding ethyl derivative or by
the corresponding alkyl derivatives of ortho-phenylene-diamine.
Dated this 4th day of June 1891
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: Improvements in the Manufacture of Colouring Matters related to
the Indulines and Eurhodines.
I, JAMES YATE JOHNSON, of 47 Lincoln's Inn Fields, in the County of
London, Gentleman, 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 Empire of Germany) and in what manuer, the
same is to be performed to be particularly described and ascertained in and by the
following statement
->
This invention consists in improvements in the manufacture of colouring matters
belonging to the new class of dyes described in the Specification of Letters Patent
No. 10138 of 1892 and constitutes in some instances improvements upon the inven-
tion described and claimed under the said Letters Patent.
In Example 14 of the Specification of Letters Patent No. 10138 of 1892 and in
Example 3 of the Specification of Letters Patent No. 10138 the production of
beta-methyl-homo-eurhodine is described: This is obtained by the interaction of
an ortho-azo-dye namely that from sulphanilic acid and mono-methyl-para-toluidine
with alpha-naphthylamine:
.
My foreign correspondents have found that if mono-alkylated-alpha-naphthyl-
amine be used in a process such as is illustrated by the said examples the eurhodines
alkylated in both the alpha- and beta-positions are obtained such as alpha-beta-
dimethyl-eurhodine if methyl-alpha-naphthylamine- be used; and alpha-ethyl-beta-
methyl-eurhodine if ethyl-alpha-naphthylamine be used and so on. In each case it
is merely necessary to follow the directions given in the examples aforesaid but
using the equivalent (quantity of the alkylated aphthylamine instead of the
quantity of the naphthylamine there stated.
Further my foreign correspondents have discovered that instead of the amido-
azo-dyes from mono-alkyl-para-toluidine being used as described in the examples of
the aforesaid Specifications the dialkylated azo-dyes can be used such for instance
as those from sulphanilic acid and di-methyl or diethyl para-toluidine. When using
such dialkylated products one alkyl group is expelled in the melt and the same
product is obtained as if the mono-alkylated derivative had been employed: Hence
it is possible to use the amido-azo-product derived from the combination of a diazo-
compound and mixtures of mono- and di-alkylated para-toluidine such as are usually
obtained by the alkylation of paratoluidine; so that it is unnecessary to separate
these alkylated products from one another.
The dialkylated amido-azo products can of course also be used in the melt with
alkylated alpha-naphthylamine..
My foreign correspondents have further discovered that in the improvements in
the process described in the aforesaid prior Specifications. as set forth in. the
Specification of the application of Benjamin Willcox for Letters Patent
No. 1757293 and consisting in the manufacture of beta-methyl-eurhodine by the
interaction of beta-hydroxy-naphtho-quinone-imide and mono-methyl-ortho-toluylene-
diamine the process can also be applied to mono-methyl-ortho-phenylene-liamine
and to other mono-alkyl-derivatives of ortho-phenylene and toluylene-diamine by
replacing for instance in the example given in the said Specification 1757293 the
mono-methyl-ortho-toluylerfe-diamine by the corresponding ethyl-derivative or by
the corresponding alkyl-derivatives of ortho-phenylene-diamine.
Under the term alkyl are included such groups as methyl; ethyl-amyl, benzyl,
and the like.
To further illustrate the nature of the invention and the manner in which it can
be carried into practical effect I give the following examples of the production of

page_text: certain of the new colouring matters. or dyestuffs but I do not limit myself to the
details which I shall give as it will be evident that they may be varied without
departing from the nature of the invention. The parts are by weight.
PREPARATION OF DIALKYL-EURHODINE FROM MONO-METHYL-ALPHA-NAPH-
THYLAMINE AND THE AMIDO-AZO-COMPOUND FROM A MIXTURE OF MONO
AND DI-ALKYL-PARA-TOLUIDINE.
Heat together about ten parts of the azo-dye obtained by combining, diazo-
sulphanilic-acid and mono- and dimethyl-para-toluidine. with.about. fifty parts of
phenol on the water bath. As soon as the temperature reaches ninety five degrees
Centigrade add about nine parts of mono-methyl-alpha-naphthylamine hydro-
chlorate. After a short time the reaction sets in and the temperature rises above
one hundred degrees Centigrade.. When this again sinks below one hundred degrees
the operation may be regarded as ended. Stir the melt into cold dilute caustic soda
solution to remove the phenol used as the diluent. Collect the crude colouring-
matter which separates out from the alkaline solution. and wash with water, until
the wash-water is only slightly alkaline. Next extract the residue by boiling with
dilute hydrochloric acid, (containing five per cent. real acid,) and precipitate the
dyestuff from the filtered cold solutions by adding one fourth of its volume of
strong hydrochloric acid (containing thirty per cent, real acid). To purify dissolve
the colouring-matter so obtained in fifty times the weight of water, saturate the
cold solution with ammonia, stir for about one hour and filter. Precipitate the
colouring matter from the solution with hydrochloric acid, press and dry. The
hydrochlorate so obtained is readily soluble in water, its solution is not altered by
ammonia.
EXAMPLE 2.
PREPARATION OF BETA-ETHYL-EURHODINE.
Mix together about one hundred and seventy three parts of beta-hydroxy-
naphtho-quinone-imide, about one hundred and thirty six parts of mono-ethyl-ortho-
phenylene-diamine and about one thousand parts of glacial acetic acid and heat the
mixture on the boiling water bath. In order to ascertain when the operation may
be interrupted work up small portions of the melt from time to time in the manner
hereinafter described for the entire mass and continue heating until successive tests
indicate that no further increase occurs in the quantity of beta-ethyl-eurhodine
formed. To isolate the beta-ethyl-eurhodine extract the melt by boiling with
very dilute hydrochloric acid repeating the extraction as long as colouring
matter dissolves. Filter the solutions obtained and add caustic soda solution
to the entire extract. A. precipitate which contains the beta-ethyl-eurhodine
is obtained. Filter and wash with water. Dissolve the residue after washing
in dilute hydrochloric acid, filter the solution and precipitate the beta-ethyl-
eurhodine-hydrochlorate with common salt. Filter and press the red precipitate
of the beta-ethyl-eurhodine-hydrochlorate. In order to more completely purify
the product redissolve in water and add just sufficient ammonia solution to give
a distinct alkaline reaction, a precipitate consisting chiefly of impurity is obtained.
Filter and precipitate the dye which remains in solution with common salt.
The beta-ethyl-eurhodine hydrochlorate so obtained is a red crystalline powder
readily soluble in hot water giving a red solution.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what [
claim is :-
1. The improvement in the manufacture of alkylated induline colouring matters

page_text: consisting in melting together an ortho-azo-dye with mono-alkyl-alpha-naphthyl-
amine substantially as herein before described.
2. The improvement in the manufacture of the alkylated induline colouring
matters consisting in the use of an ortho-azo-dye derived from a mixture of mono
and dialkylated paratoluidine in the melt with alpha-naphthylamine or mono-alkyl-
alpha-naphthylamine substantially as hereinbefore described.
3. The improvement in the manufacture of alkylated induline colouring matters
consisting in the use of an ortho-azo-dye derived from dialkylated paratoluidine
in the melt with alpha-naphthylamine or mono-alkyl-alpha-naphthylamine substan-
tially as described.
4. The improvement in the manufacture of alkylated induline colouring matters
consisting in the use in the melt with beta-hydroxy-naphtho-quinone-imide of mono-
alkyl-ortho-phenylene-diamine and mono-alkyl-ortho-toluylene-diamine derivatives
other than the mono-methyl-ortho-toluylene-diamine (the use of which is described
in Specification No. 17572 of 1893) substantially as hereinbefore described.
5. The improvements in the manufacture of alkylated induline colouring matters
consisting in the production thereof in the manners hereinbefore described in the
examples.
Dated this 4th day of March 1895.
JOHNSONS & WILLCOX,
Agents.