Improvements in the Manufacture of Colouring Matters of the Alkylated Induline Series.
Year: 1894

page_text: Date of Application, 19th Mar., 1894
Complete Specification Left, 11th Dec., 1894-Accepted, 12th Jan., 1805
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters of the
Alkylated Induline Series.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of the said invention (which has
been communicated to me from abroad by The Badische Anilin & Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows:-
In the Specification of Letters Patent Nos. 10138, 10138A, 10138B and 10138c
of 1892 and in the Provisional Specifications of the applications for Letters Patent
Nos. 17572, 18374 and 18925 of 1893, I have described a new class of colouring-
matters which may be regarded as related to the indulines and eurhodines. The
present invention relates to improved methods of manufacturing dyes of this
class.
The improvement consists in the use of an ortho-nitro-compound of the general
Thus for
(where R represents an alkyl, or phenyl group or the like) in the production of the
5 said colouring matters instead of starting from an ortho-diamido-compound or an
ortho-amido-azo-body as described in the Specifications referred to.
instance beta-methyl-homo-eurhodine (see Example 14 of 10138) can be obtained
by condensing alpha-naphthylamine with ortho-nitro-methyl-paratoluidine
O instead of effecting a condensation of alpha naphthylamine with the azo compound
derived from sulphanilic acid and monomethyl para-toluidine as described in the
example cited above..
This reaction is capable of very general application so that various colouring-
matters of the new class can be obtained. by condensing alpha-naphthylamine, or
5 mono-alkylated or phenylated alpha naphthylamines and the like with ortho-nitro-
amines.
To further illustrate the nature of this invention I give the following examples
without however limiting myself to these as the methods of operating can be

page_text: of the hydrochloric acid used, then raise the temperature to about one hundred
and sixty to one hundred and eighty degrees Centigrade and maintain this heat
till the nitro-body has nearly disappeared. Dissolve the melt in very dilute
hydrochloric acid (one quarter per cent. HCI) filter and allow the filtrate to cool,
then precipitate the colouring matter base with caustic soda. Test a portion of
this with acetic acid, if it is not completely soluble in this solvent it contains
phenyl eurhodine. To purify dissolve the whole mass as far as possible in
one per cent. acetic acid and filter. The filtrate contains the desired alpha-
phenyl-beta-methyl eurhodine, precipitate with caustic soda and collect in the
usual way.
In a similar way alpha-phenyl-beta-ethyl eurhodine can be obtained by using the
nitro-ethyl-toluidine instead of the methyl compound.
Dated the 19th day of March 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, Loudon, Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters of the
Alkylated Induline Series.
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-ou-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 :-
In the Specifications of Letters Patent Nos. 10138, 10138A, 10138B, and 101380
of 1892 and Nos. 17572, 18374 and 18925 of 1893, I have described a new class of
colouring matters which may be regarded as related to the indulines and eurhodines.
The present invention relates to improved methods of manufacturing dyes of this
class.
The improvement consists in the use of an ortho-nitro-compound of the general
(where R represents an alkyl, or phenyl group or the like) in the production of the
said colouring matters instead of starting from an ortho-diamido-compound or an
ortho-amido-azo body as described in the Specifications referred to. Thus for
instance beta-methyl-homo-eurhodine (see Example 14 of 10138) can be obtained
by condensing alpha-naphthylamine with ortho-nitro-methyl-paratoluidine

page_text: instead of effecting a condensation of alpha-naphthylamine with the azo-compound
derived from sulphanilic acid and monomethyl-para-toluidine as described in the
example cited above.
This reaction is capable of very general application so that various colouring-
matters of the new class can be obtained by condensing alpha-naphthylamine or
mono-alkylated or phenylated alpha naphthylamines and the like with ortho-nitro-
amines.
To further illustrate the nature of this invention and the manner in which it is
carried into practical effect I give the following examples without however limiting
myself to these as the methods of operating can be largely varied without departing
from the nature of the invention. The parts are by weight.
EXAMPLE 1.
Mix together about fourteen parts of alpha-naphthylamine, about ten parts of
alpha-naphthylamine-hydrochlorate, about sixteen parts of nitro-methyl-ortho-
toluidine CH, CH, NO, NHCH, (1:3:4), and about five parts of chloride of
zine and heat the mixture to a temperature of about one hundred and seventy to
one hundred and eighty degrees Centigrade. Maintain this heat for say about four
hours. To determine the progress of the reaction withdraw test-portions of the
melt from time to time and treat them with ether. Unchanged nitro-compound
dissolves therein giving a yellow solution and when no further diminution in the
quantity of nitro-body present can be observed the operation is interrupted.
Extract the melt by boiling with very dilute hydrochloric acid (containing say
one per cent. HCI) and filter. The solution contains the beta-methyl-eurhodine.
Precipitate this by adding common salt solution, filter and press. The crude
product thus obtained usually contains some eurhodine formed by the splitting off
of the alkyl group in the melt. To purify dissolve the press-cakes by stirring with
cold water and then adding hot water, filter and allow to cool, then add a slight
excess of ammonia and stir for about half an hour, filter and wash the precipitate
with hot water. The non-alkylated eurhodine remains on the filter while the
ammoniacal solution contains the beta-methyl-eurhodine. Add common salt
solution, whereby this body is precipitated in the form of hydrochloric acid salt.
Filter press and dry.
In an analogous manner beta-ethyl-eurhodine can be obtained, by using nitro-
ethyl-toluidine CH, CH, NO, NHC,H, (1:3:4) instead of the methyl-com-
Found specified in the foregoing example. In this case I prefer when extracting
the melt to use dilute hydrochloric acid containing one quarter per cent. HCl and
to precipitate the colouring-matter with a solution of chloride of zinc instead of
common salt. Beta-ethyl-eurhodine and the methyl compound give similar shades
of colour but the former is more readily soluble in water.
EXAMPLE 2.
amines.
To further illustrate the nature of this invention and the manner in which it is
carried into practical effect I give the following examples without however limiting
myself to these as the methods of operating can be largely varied without departing
from the nature of the invention. The parts are by weight.
EXAMPLE 1.
Mix together about fourteen parts of alpha-naphthylamine, about ten parts of
alpha-naphthylamine-hydrochlorate, about sixteen parts of nitro-methyl-ortho-
toluidine C.H, CH, NO, NHCH, (1:3:4), and about five parts of chloride of
zinc and heat the mixture to a temperature of about one hundred and seventy to
one hundred and eighty degrees Centigrade. Maintain this heat for say about four
hours. To determine the progress of the reaction withdraw test-portions of the
melt from time to time and treat them with ether. Unchanged nitro-compound
dissolves therein giving a yellow solution and when no further diminution in the
quantity of nitro-body present can be observed the operation is interrupted.
Extract the melt by boiling with very dilute hydrochloric acid (containing say
one per cent. HCl) and filter. The solution contains the beta-methyl-eurhodine.
Precipitate this by adding common salt solution, filter and press. The crude
product thus obtained usually contains some eurhodine formed by the splitting off
of the alkyl group in the melt. To purify dissolve the press-cakes by stirring with
cold water and then adding hot water, filter and allow to cool, then add a slight
excess of ammonia and stir for about half an hour, filter and wash the precipitate
with hot water. The non-alkylated eurhodine remains on the filter while the
ainmoniacal solution contains the beta-methyl-eurhodine. Add common salt
solution, whereby this body is precipitated in the form of hydrochloric acid salt.
Filter press and dry.
In an analogous manner beta-ethyl-eurhodine can be obtained, by using nitro-
ethyl-toluidine C.H, CH, NO, NHC,H, (1:3:4) instead of the methyl-com-
Found specified in the foregoing example. In this case I prefer when extracting
the melt to use dilute bydrochloric acid containing one quarter per cent. HCl and
to precipitate the colouring-matter with a solution of chloride of zinc instead of
common salt. Beta-ethyl-eurhodine and the methyl compound give similar shades
of colour but the former is more readily soluble in water.
EXAMPLE 2.
Mix together about eighteen parts of methyl-alpha-naphthylamine, about sixteen
parts of nitro-methyl-toluidine (1:3:4), about five parts of hydrochloric acid
(containing about thirty two per cent. HCl) and about five parts of chloride of
zinc. Heat the mixture slowly, and whilst stirring well, to,about one hundred to
one hundred and five degrees Centigrade in order to expel the water of the hydro-
chloric acid, and then raise the heat to about one hundred and seventy, to one
hundred and eighty degrees Centigrade until nearly all the nitro-body has
disappeared. Work up the melt as described in Example 1.
The alpha-beta-dimethyl-eurhodine is obtained in the form of its hydrochloric
acid salt.

page_text: Mix together about -twenty-eight parts of phenyl-alpha-naphthylamine about
sixteen parts of nitro-methyl-toluidine about five parts of hydrochloric acid (con-
taining about thirty two per cent. HCl) and about five parts of chloride of zinc.
Heat first slowly, and whilst stirring thoroughly, to a temperature of about one
hundred to one hundred and five degrees Centigrade. Stir, in order to drive off
the water of the hydrochloric acid used, then raise the temperature to about one
hundred and sixty to one hundred and eighty degrees Centigrade and maintain
this heat till the nitro-body has nearly disappeared. Dissolve the melt in very
dilute hydrochloric acid (one quarter per cent. HCI) filter and allow the filtrate to
cool, then precipitate the colouring-matter-base with caustic soda. Test a portion
of this with acetic acid if it be not completely soluble in this solvent it contains
phenyl-eurhodine. To purify, dissolve the whole mass as far as possible in
one per cent. acetic acid and filter. The filtrate contains the desired alpha-
phenyl-beta-methyl-eurhodine. Precipitate with caustic soda and collect in the
usual way
In a similar way alpha-phenyl-beta-ethyl-eurhodine can be obtained by using
the nitro-ethyl-toluidine instead of the methyl compound.
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 I
claim is :-
1. The manufacture of colouring-matters of the alkylated induline series by
the condensation of the ortho-nitro-compounds herein before defined with alpha-
naphthylamine or monoalkylated or phenylated alpha-naphthylamines and
the like.
2. The manufacture of colouring-matters of the alkylated induline series in the
manners herein before described in the several Examples 1. 2. and 3.
Dated this 10th day of December 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, Londou, W.C., Agents.