Improvements relating to the Manufacture of a New Class of Basic Dyestuffs or Colouring Matters and of Sulpho-acids thereof, and of Materials and Intermediate Products relating thereto.
Year: 1892

page_text: Date of Application, 27th May, 1892
Complete Specification Left, 27th Mar., 1893-Accepted, 29th Apr., 1893
PROVISIONAL SPECIFICATION.
Improvements relating to the Manufacture of a New Class of Basic
Dyestuffs or Colouring Matters and of Sulpho-acids thereof, and
of Materials and Intermediate Products relating thereto.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this 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:-
:―
This invention relates principally to the manufacture of a new class of basic dye-
stuffs or colouring matters which are derived from the so-called eurhodines and their
analogues and which in their chemical constitution closely resemble the indulines.
They may indeed be regarded as indulines in which one or more phenyl- (or sub-
stituted phenyl-) group is replaced by hydrogen or by an alkyl group such as
methyl, ethyl, etc. This will be rendered more clear to persons skilled in the art
by the following diagram.
If the above formula of phenyl rosinduline be taken as an example of an induline,
then members of the new class of dyestuffs or colouring matters are obtained by
suitably substituting the phenyl groups A and B by alkyl-groups. Thus for
instance the group A can be substituted by methyl ethyl etc. while the phenyl
group B remains.
Having now indicated the chemical nature of the new class of dyestuffs or
colouring matters I next describe ways in which they may be prepared. As afore-
said they are derived from the so-called eurhodines and their analogues. Under
this name numbers of bodies have been described in chemical literature (see Witt
Berichte der Deutschen Chemischen Gesellschaft 19, 441, 1720; Journal of the
Chemical Society 49, 391; 50, 473, 889 Fischer & Hepp Berichte der Deutschen
Chemischen Gesellschaft 23, 845; Journal of the Chemical Society 58, 80-
Kehrmann Berichte der Deutschen Chemischen Gesellschaft 23, 2451 Journal of the
Chemical Society 58, 1266 Kehrmann & Messinger Berichte der Deutschen
Chemischen Gesellschaft, 24, 584 2167 Journal of the Chemical Society 60, 746
1213).
The process of preparing the new dyestuffs or colouring matters from the
eurhodines varies to a certain extent with the eurhodine used. Thus to prepare the
new basic dyestuff's or colouring matters from the eurhodine C₁,H₁₂N, (obtainable
3

page_text: from an ortho azo compound of para toluidine and alpha-naphthylamine) the
eurhodine is first melted with aniline and aniline salt and an intermediate product
(phenyl-eurhodine) is formed, which by subsequent alkylation is converted into the
new dyestuff or colouring matter. But if the eurhodině used as the initial material
had already been phenylated or alkylated the melting operation with aniline might
have been omitted.
Further just as the introduction of the phenyl group into the finished eurhodine
can be evaded, so also the alkylation hereinbefore described as the final operation
in obtaining the new dyestuffs or colouring matters can be performed indirectly at
an early stage of the process by preparing an eurhodine such as can be obtained, as
my foreign correspondents have discovered, from an ortho-azo-compound of an
alkyl-para-toluidine. The alkylated eurhodine thus obtained is then itself a dye-
stuff or colouring matter belonging to the new class. The new dyestuffs or colouring
matters obtained by proceeding as above explained are basic but all such of them
as contain a phenyl group can be sulphonated to valuable acid dyes which dye most
even shades. The said sulpho acids can be obtained by the direct action of sul-
phuric acid on the finished basic dye or colouring matter. To further illustrate the
nature of the invention I give the following examples of the production of certain
of the new dyestuffs or colouring-matters, but I do not bind myself to details as
considerable variations can be made in many respects, further in operating with
different eurhodines different treatment is often necessary as hereinbefore explained.
The parts are by weight.
EXAMPLE 1.
PREPARATION OF A PHENYL-EURHODINE.
Mix together about ten parts of the above mentioned eurhodine C₁,H₁3N3 in
the form of hydrochloric acid salt, about five parts of aniline hydrochlorate and
about twenty parts of aniline, and heat the mixture in an oil bath for about two
hours at a temperature of about one hundred and fifty to one hundred and sixty
degrees centigrade or until no appreciable quantity of unchanged eurhodine is con-
tained in the melt. This can be ascertained by drawing samples from time to time
and testing for the eurhodine taking advantage of its ready solubility in dilute
hydrochloric acid.
Pour the melt into water, add excess of caustic soda, and drive off the unused
aniline with steam. A yellow body remains behind consisting of crude phenyl-
eurhodine which can be crystallized, and so purified from an alcoholic phenol solution.
When pure this new body melts at a temperature of about two hundred and thirty
degrees centigrade, and is scarcely soluble in boiling water, coutaining a little acid
whilst in concentrated sulphuric acid it dissolves with a green colour.
The proportions of aniline and aniline salt and the temperature given in the
above example can be varied within wide limits without changing the nature of the
reaction.
EXAMPLE 2.
PREPARATION OF AN INDULINE OF THE NEW CLASS FROM PHENYL
EURHODINE.
Mix together about ten parts of phenyl eurhodine (obtained as above described
or in any other way) with about five parts of methyl-iodide and fifty parts of
methyl-alcohol or wood spirit, in a closed vessel capable of withstanding pressure.
Heat the mixture to a temerature of about one hundred and sixty to one hundred

page_text: the amount of unchanged phenyleurhodine can be recognized in test portions of the
melt. These tests can be made as follows:-Withdraw a sample of the melt boil
for a few minutes with an excess of caustic soda solution to decompose the hydro-
iodate, precipitate the bases by adding water, filter and wash with water, and then
boil the residue with dilute hydrochloric acid, in which the new induline is very
readily soluble, while the phenyl eurhodine as above mentioned is scarcely soluble
at all. To work up the entire product, add an excess of caustic soda, then distil
off the wood-spirit and after washing with water dissolve the residual base in hot
water adding sufficient hydrochloric acid; filter, precipitate the base with alkali,
wash and dry. To further purify recrystallize, if desired from benzene. This
compound when pure has its melting point at about two hundred and ten degrees
centigrade and by analysis is shewn to possess the composition which may be
represented by the formula C24 H1N3. On stirring the base with twice its weight
of dilute hydrochloric acid containing about five per cent, real acid (HCI) a semi-
solid mass of the soluble hydrochlorate results, which on drying is obtained as a
red brown crystalline mass with a dull sheen. Cotton mordanted with tannin and
silk are dyed red by this compound.
PREPARATION OF A PHENYL EURHODINE.
Mix about ten parts of the above mentioned eurhodol C₁,H₁₂N₂O (Witt,
Berichte der Deutschen Chemischen Gesellschaft 19, 441 et seq.) with about ten
parts of aniline salt and twenty parts of aniline and heat the mixture to a
temperature of about one hundred and fifty to one hundred and sixty degrees
centigrade for about two hours, or until no increase in the purity of the shade of
green obtained on dissolving a test portion of the melt in concentrated sulphuric
acid can be noticed in successive samples. Saturate the melt with caustic soda
solution and drive off the excess of aniline with steam. The phenyl-eurhodine
remains behind and is treated as described in Example 2.
JAAMILE
PREPARATION Of a sulpho acid of the indulINE C₂, H₁, N..
3'
Dissolve about ten parts of the induline base or a similar quantity of its
hydrochlorate in about forty parts of concentrated sulphuric acid (containing about
ninety-five per cent. real acid H₂SO) and heat the mixture on the boiling water
bath until a sample precipitated with water and washed dissolves completely in
dilute caustic soda. This point being reached pour the whole mixture into about
two hundred parts of ice-water, the sulpho acid separates out and is collected,
washed with water, pressed and dried.
This sulpho acid is almost insoluble even in koiling water and is used in the
manufacture of the more soluble sulpho-acid.

page_text: hydrochlorate or of the above described almost insoluble sulpho acid in about forty
parts of fuming sulphuric acid containing about twenty three per cent. of free
anhydride (SO3). Keep the acid cool during mixing and subsequently raise the
temperature to about twenty five to thirty degrees centigrade and stir till a sample
precipitated and washed with cold water dissolves completely in hot water. Pour
the whole product into about two hundred parts of ice water collect the precipitated
dye, press and redissolve the press cakes in hot water, adding ammonia. Precipitate
the dye with common salt solution, filter when cold press and dry.
The red brown crystalline powder, thus obtained dissolves readily in hot water
but not so readily in cold water and on adding an acid to a solution the free sulpho
acid is precipitated in bright shining crystalline form.
This dye fixes itself on wool from the acid bath giving very even shades of bright
red which are considerably yellower than those obtained with azo-carmine described
in the Specification of Letters Patent 1525989.
Dated this 27th day of February 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements relating to the Manufacture of a New Class of Basic
Dyestuffs or Colouring Matters and of Sulpho-acids thereof, and
of Materials and Intermediate Products relating thereto.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex 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 manner the
same is to be performed to be particularly described and ascertained in and by the
following statement :-
This invention relates principally to the manufacture of a new class of basic
dyestuffs or colouring matters which are derived from certain of the so called
eurhodines and the analogous eurhodols and which in their chemical constitution
closely resemble the indulines. They may indeed be regarded as indulines in which
one or more than one phenyl- (or substituted phenyl-) group is or are replaced by
hydrogen or by an alkyl-group such as methyl, ethyl or the like. The nature of
this substitution will be rendered clear by the following diagram and description.
In this diagram and the references to it I have used (simply as being a more
rational nomenclature) "Alpha" and "Beta" in place respectively of the "B"
and "A" used in my Provisional Specification.

page_text: If the above formula of phenyl- rosinduline be taken as an example of an induline,
then the constitution of the members of the new class of dyestuffs or colouring
matters is obtained by suitably substituting the phenyl groups beta and alpha by
alkyl-groups in the following manner namely the group beta can be substituted by
methyl, ethyl or the like while the phenyl-group alpha remains.
Having now indicated the chemical nature of the new class of dyestuffs or
colouring matters to which this invention relates I next describe ways in which
they may be prepared and from this the nature of this invention and the manner
in which it may be carried into effect will be made clear. As aforesaid the said
dye stuff's or colouring matters are derived from the so-called eurhodines and the
analogous eurhodols. Under this name numbers of bodies have been described in
chemical literature. (See, Witt, Berichte der Deutschen Chemischen Gesell-
schaft, 19, 441, 1720; Journal of the Chemical Society 49, 391; 50 473, 889 ;-
Fischer and Hepp, Berichte der Deutschen Chemischen Gesellschaft 23, 845;-
Journal of the Chemical Society 58, 80;-Kehrmann, Berichte der Deutschen
Chemischen Gesellschaft, 23, 2451;Journal of the Chemical Society 58, 1266 ;-
Kehrmann & Messinger, Berichte der Deutschen Chemischen Gesellschaft 24, 584,
2167;Journal of the Chemical Society 60, 746, 1213.)
The process of preparing the new dyestuffs or colouring-matters from the
eurhodines varies to a certain extent with the eurhodine used. Thus to prepare
the new basic dyestuffs or colouring matters from the homoeurhodine C₁,H,N,
(obtainable from an ortho-azo- compound of para-toluidine and alpha-naphthyl-
amine) the eurhodine is first melted with aniline and aniline salt (see Example 1)
and an intermediate product-(phenyl-homo-eurhodine) is formed, which by subse-
quent alkylation (see Example 2) is converted into the new dyestuff or colouring-
matter. But if the eurhodine used as the initial material had already been
phenylated or alkylated the melting operation with aniline can be omitted.
Further, just as the direct introduction of the phenyl-group into the finished
eurhodine can be avoided, so also the alkylation hereinbefore described as the final
operation in obtaining the new dyestuffs or colouring-matters can be performed
indirectly at an early stage of the process. The production of an induline of the
new class avoiding the aniline melt for the introduction of the phenyl-group and
also of the alkyl-group as above mentioned is described in Example 4.
. The new dyestuffs or colouring matters obtained by proceeding as above
explained are basic, but such of them as contain a phenyl-group can be sulphonated
to valuable acid dyes, which dye most even shades. The said sulpho-acids can be
obtained by the direct action of sulphuric acid on the finished basic dyestuff or
colouring matter.
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
certain of the new dyestuffs or colouring-matters, but I do not bind myself to the
precise details hereinafter given as considerable variations can be made in many
respects; further in operating with different eurhodines different treatment is often
necessary as hereinbefore indicated.
EXAMPLE 1.
PREPARATION OF A PHENYL-HOMO EURHODINE.

page_text: aniline with steam. A yellow body remains behind consisting of crude phenyl-
homo eurhodine which can be crystallized, and so purified from an alcoholic phenol
solution. When pure this new body melts at a temperature of about two hundred
and thirty degrees centrigrade and is scarcely soluble in boiling water, containing
a little acid, whilst in concentrated sulphuric acid it dissolves with a green colour.
The proportions of aniline and aniline salt and the temperature given in the
above example can be varied within wide limits without changing the nature of the
reaction.
PREPARATION OF AN INDULINE (C2, 19N3) OF THE NEW CLASS
PHENYL-HOMO EURHODINE.
"Mix together about ten parts of phenyl-homo eurhodine (obtained as described
under Example 1 or in any other way) with about five parts of methyl-iodide and
fifty parts of methyl-alcohol or wood spirit, in a closed vessel capable of with-
standing pressure. Heat the mixture to a temperature of about one hundred and
sixty to one hundred and seventy degrees centigrade, for about two hours, or until
no further decrease in the amount of unchanged phenyl-homo-eurhodine is
observed in test portions of the melt. These tests can be made as follows:-
Withdraw a sample of the melt, boil for a few minutes with an excess of caustic
soda solution, to decompose the hydro-iodate, precipitate the bases by adding
water, filter and wash with water and then boil the residue with dilute hydrochloric
acid, in which the new induline is very readily soluble while the phenyl-homo-
eurhodine as above mentioned is scarcely soluble at all.
To work up the entire product, add an excess of caustic soda, then distil off the
wood-spirit and after washing with water dissolve the residual base in hot water
adding sufficient hydrochloric acid; filter precipitate the base with alkali, wash and
dry. To further purify recrystallize if desired from benzene. This compound
when pure has its melting point at about two hundred and ten degrees centigrade
and by analysis is shewn to possess the composition which may be represented by
the formula C2H₁, N. On stirring the base with twice its weight of dilute
hydrochloric acid containing about five per cent. real acid, (HCl) a semi-solid mass
of the soluble hydrochlorate results, which on drying is obtained as a red-brown
crystalline mass with a dull sheen; cotton mordanted with tannin and also silk are
dyed red by this compound.
PREPARATION OF THE SAME INDULINE OF THE NEW CLASS (C2H₁, N3) FROM
THE HOMO-EURHODOL CH₁₂N₂O. PREPARATION OF
EURHODINE.
PHENYL-HOMO
Mix about ten parts of the above mentioned homo-eurhodol C₁7H₁₂NO (Witt,
Berichte der Deutschen Chemischen Gesellschaft 19, 441, et seq.) with about
ten parts of aniline salt and twenty parts of aniline and heat the mixture to a
temperature of about one hundred and fifty to one hundred and sixty degrees
centigrade for about two hours, or until no increase in the purity of the shade of
green obtained on dissolving a test portion of the melt in concentrated sulphuric
acid is observed in successive samples. Saturate the melt with caustic soda solution
and drive off the excess of aniline with steam. The phenyl-homo eurhodine remains
behind and is treated as described in Example 2.

page_text: PREPARATION OF A SULPHO-ACID READILY SOLUBLE IN WATER DERIVED
FROM THE NEW INDULINE CH₁, N3.
Dissolve about ten parts of the induline base or a similar quantity of its hydro-
chlorate or of the above described almost insoluble sulpho acid in about forty parts
of fuming sulphuric acid containing about twenty three per cent. of the free
anhydride (SO3). Keep the acid cool during mixing and subsequently raise the
temperature to about twenty five to thirty degrees centigrade and stir till a sample
precipitated and washed with cold water dissolves completely in hot water.
the whole product in about two hundred parts of ice water, collect the precipitated
dye, press, and redissolve the press cakes in hot water, adding ammonia. Precipitate
the dye with common salt solution, filter when cold, press and dry.
Pour
The red-brown crystalline powder thus obtained dissolves readily in hot water,
but not so readily in cold water; and on adding au acid to a solution the free:
sulpho-acid is precipitated in bright shining crystalline form.

page_text: This dye fixes itself on wool from the acid bath giving very even shades of
bright red which are considerably yellower than those obtained with azo-carmine
(described in the Specification of Letters Patent 1525989.
By sulphonating more energetically than is above described sulpho acids are
obtained which are readily soluble in cold water.
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 a new phenyl-homo-eurhodine by treating the eurho-
dine C₁,H3N, or the analogous eurhodol with aniline and aniline hydrochlorate
substantially as hereinbefore described.
13
2. The manufacture of an induline of the new class by alkylating the phenyl-
homo-eurhodine obtainable as herein described and claimed in the preceding claiming
clause substantially as hereinbefore described.
.
3. The manufacture of an induline of the new class by first preparing a new
phenyl-eurhodine substantially as herein described and claimed in the first claiming
clause and then alkylating it substantially as hereinbefore described.
4. The manufacture of the induline referred to in the second and third claiming
clauses by the combination of hydroxy-naphtha-quinone-anil and mono-methyl-
ortho-toluylene-diamine, thereby suitably introducing the phenyl and alkyl group
simultaneously with the formation of the eurhodine all substantially as herein-
before described.
5. The manufacture of a monosulpho acid of an induline of the new class by
treating the induline referred to in the second third and fourth claiming clauses
with concentrated sulphuric acid, substantially as herein before described.
6. The manufacture of a sulpho acid soluble in water by treating the basic
indulines of the new class herein before described or the salts or almost insoluble
monosulpho acids thereof with fuming sulphuric acid all substantially as herein-
before described.
7. The manufacture of a homologous phenyl-eurhodine, of a homologous induline
of the new class and of sulpho-acids thereof by treating a homologous curhodine
by the processes hereinbefore described and claimed in the foregoing first second
third fifth and sixth claiming clauses all substantially as herein before set forth.
8. As new articles of manufacture the indulines of the new class hereinbefore
described and the sulpho acids thereof hereinbefore described.
Dated this 97th day of March 1893
J. H. JOHNSON & Co.

page_text: Date of Application, 27th May, 1892
Complete Specification Left, 27th Mar., 1893-Accepted, 29th Apr., 1893
PROVISIONAL SPECIFICATION.
Improvements relating to the Manufacture of Sulpho-acids of a New
Class of Basic Dye-stuffs or Colouring Matters, and of Materials
and Intermediate Products relating thereto.
.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention which has been communi-
cated to me from abroad by the Badische Aniline and Soda Fabrik of Ludwigshafen
on Rhine in the Empire of Germany to be as follows:-
This invention relates principally to the manufacture of sulpho acids of a new
class of basic dyestuffs or colouring matters which latter are derived from the so
called eurhodines and their analogues and which in their chemical constitution
closely resembles the indulines. The said basic dyestuffs or colouring matters
may indeed be regarded as indulines in which one or more phenyl- (or substituted
phenyl-) group is replaced by hydrogen or by an alkyl-group such as methyl
ethyl &c. This will be rendered more clear to persons skilled in the art by the
following diagram.
If the above formula of phenyl-rosinduline be taken as an example of an induline,
15 then members of the new class of dyestuffs or colouring matters are obtained by
suitably substituting the phenyl groups A and B by alkyl groups. Thus for
instance the group A can be substituted by methyl ethyl &c. while the phenyl-
group B remains.

page_text: 4
As aforesaid the new colouring matters or dyestuffs are derived from the so called
eurhodines and their analogues. Under this name numbers of bodies have been
described in chemical literature. (See Witt Berichte der Deutschen Chemischen
Gesellschaft 19, 441, 1720; Journal of the Chemical Society 49, 391; 50, 473, 889,
Fischer & Hepp Berichte der Deutschen Chemischen Gesellschaft 23, 845; Journal
of the Chemical Society 58, 80; Kehrmann, Berichte der Deutschen Chemischen
Gesellschaft 23, 2451; Journal of the Chemical Society 58, 1266 Kehrmann &
Messinger, Berichte der Deutschen Chemischen Gesellschaft, 24, 584, 2167; Journal
of the Chemical Society 60, 746, 1213).
The process of preparing the new dyestuffs or colouring matters from the
eurhodiues varies with the eurhodine used. Methods of preparing certain of the
basic dyestuffs or colouring matters are described in the Specifications of applica-
tions for Patents Nos. 101382, 1013849 and 1013809.
Now such of the basic dyestuffs or colouring matters as contain a phenyl-group
can be sulphonated to valuable acid dyestuffs or colouring matters, which yield
most even shades. And not only can the sulpho acids be obtained by the direct
action of sulphuric acid on the finished basic dyestuff or colouring matter (as is
more particularly described in the Specifications of applications for Patents
Nos. 10138 and 10138092) but by the use of suitable sulphonated materials in the
preparation of the eurhodines sulphonated eurhodines result which on alkylation
either directly or indirectly give sulpho-acids of the basic dyestuffs or colouring
matters. Thus by the interaction of beta-naphthoquinone-anil sulpho acid on
ortho-diamines a sulpho-phenyl eurhodine is obtained which on alkylation gives
directly a member of the new class of dyestuffs or colouring matters in the form
of sulpho acid.
Dated this 27th day of February 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, W.C., Agents.

page_text: COMPLETE SPECIFICATION (AMENDED).
Improvements relating to the Manufacture of Sulpho-acids of a New
Class of Basic Dyestuffs or Colouring Matters, and of Materials
and Intermediate Products relating thereto.
"
I, JAMES YATE JOHNSON, of 47 Lincolns Inn Fields in the County of
Middlesex, 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 manner the
same is to be performed to be particularly described and ascertained in and by the
following statement :-
This invention relates principally to the manufacture of sulpho-acids of a new
class of basic dyestuffs or colouring matters which latter are derived from certain
of the so-called eurhodines and the analogous eurhodols and which in their chemical
constitution closely resemble the indulines. The said basic dyestuffs or colouring
matters may indeed be regarded as indulines in which one or more than one phenyl-
(or substituted phenyl-) group is or are replaced by hydrogen or by an alkyl-group
such as methyl, ethyl or the like. The nature of this substitution will be rendered
clear by the following diagram and description.
39
"
In this diagram and the references to it I have used simply as being a more
rational nomenclature “Alpha" and "Beta" in place respectively of the "B
and "A" used in my Provisional Specification.
If the above formula of phenyl-rosinduline be taken as an example of an induline,
then the constitution of the members of the new class of dyestuffs or colouring
matters is obtained by suitably substituting the phenyl-groups beta and alpha by
alkyl groups in the following manner namely the group beta can be substituted by
methyl, ethyl or the like while the phenyl-group alpha remains.
As aforesaid the new colouring matters or dyestuffs are derived from the so-called
eurhodines and analogous eurhodols. Under this name numbers of bodies have been
described in chemical literature. (See Witt, Berichte der Deutschen Chemischen
Gesellschaft, 19, 441, 1720; Journal of the Chemical Society 49, 391; 50, 473, 889;
Fischer & Hepp, Berichte der Deutschen Chemischen Gesellschaft 23, 845; Journal
of the Chemical Society 58, 80; Kehrmann, Berichte der Deutschen Chemischen
Gesellschaft, 23, 2451; Journal of the Chemical Society 58, 1266; Kehrmann &

page_text: Messinger, Berichte der Deutschen Chemischen Gesellschaft 24, 584, 2167 ; Journal
of the Chemical Society 60, 746, 1213.)
The process of preparing the new dyestuffs or colouring matters from the
eurhodines varies with the eurhodines used. Methods of preparing certain of the
basic dyestuffs or colouring matters are described in the Specifications of applications
for Patents Nos. 10138, 10.138 and 10138 of 1892.
Now such of the basic dyestuffs or colouring matters as contain a phenyl-group
at alpha can be sulphonated to valuable acid dyestuffs or colouring matters, some
of which yield most even shades. And not only can the sulpho-acid be obtained
by the direct action of sulphuric acid on the finished basic dyestuff or colouring
mattér (as is more particularly described in the Specifications of the applications
for Patents Nos. 10138% and 10138492) but by the use of suitable sulphonated
materials in the preparation of the eurhodines, sulphonated eurhodines result, which
on alkylation either directly or indirectly give sulpho acids. of the basic dye-stuffs
or colouring matters. Thus by the inter-action of beta-naphthoquinone-anil sulpho
acid (see Example 1), on ortho-diamines a sulpho-phenyl-eurhodine is obtained (see
Example 2), which on alkylation gives directly a member of the new class of dye-
stuffs or colouring matters in the form of sulpho-acid (see Example 3). For an
instance of this case with indirect alkylation by the use of alkylated materials see
Example 4.
The following examples illustrate the nature of the invention and the manner in
which it can be carried into practical effect, but considerable variations can be
made therein without departing from this invention.
A NEW
PREPARATION OF HYDROXY-NAPHTHOQUINONE-ANIL-SULPHO-ACID.
MATERIAL FOR USE IN THE MANUFACTURE OF THE NEW CLASS OF
COLOURING MATTERS.
Dissolve about ten parts beta-naphtho-quinone in about two hundred and fifty
parts of hot alcohol; add a solution of about ten parts of sodium sulphanilate in
about twenty five parts water. Stir for about twelve hours filter and press. The
red product so obtained consists of the sodium salt of hydroxy-naphtho-quinone-
anil-sulpho-acid. To prepare the free acid dissolve this in about three hundred
parts of boiling water add sufficient acetic acid to make the solution strongly acid
and filter. The free acid crystallizes from the filtrate on adding about one
hundred parts of saturated salt solution collect on the filter press and dry.
PREPARATION OF A SULPHO-PHENYL EURHODINE (ALPHA-PARA-SULPHO-
BENZOL-EURHODINE).
Dissolve about thirty five parts of the sodium salt of hydroxy-naphthoquinone-
anil-sulpho acid in about nine hundred parts of hot water, and run into the
solution about eleven parts of ortho-phenylene diamine dissolved in about one
hundred parts of acetic acid (containing about thirty per cent. real acid C₂HO₂).
Heat the mixture for about four hours on the boiling water-bath. The desired
condensation product, which may be called a sulpho-phenyl-eurhodine, (or alpha-
para-sulpho-benzol-eurhodine) separates out in the crystalline form, while the
solution which was originally of a deep-red colour becomes almost colourless. To
purify wash the product well with hot water and dissolve in boiling dilute soda
solution and precipitate the sodium salt with common salt. The said sodium salt
is obtained in a crystalline condition.
If an acid be added to its solutions the
free acid is precipitated as a red precipitate.

page_text: ALKYLATION OF THE
SULPHO-PHENYL
EURHODINE. PREPARATION OF
ALPHA-PARA-SULPHO-BENZOL-BETA-METHYL EURHODINE.
Mix together about five parts of the sodium salt of sulpho-phenyl-eurhodine
(alpha-para-sulpho-benzol-eurhodine) (obtained as described in the preceding
Example 2 or in any other way) with about fifty parts wood-spirit (methyl-alcohol)
and about five parts of methyl-iodide. And heat the mixture for about two hours
at a temperature of about one hundred and fifty to one hundred and seventy degrees
centigrade whereby a pressure of about thirty to thirty one atmospheres should be
developed. The end of the reaction can be recognised as follows:-Take tests
from time to time and work up (in the manner hereinafter described) the crystal-
line portion of the product which separates from the alcoholic solution.
When no
increase in the quantity of sulpho-acid insoluble in dilute caustic soda can be
observed, the operation may be regarded as ended; further the mother liquor in
this case should no longer shew a yellow colour due to the presence of the
immethylated body.
Work up the whole product as follows; pour off the red methyl-alcoholic mother
liquor from the crystalline product, wash with alcohol and dry. The body so
obtained will as a rule be pure enough for ordinary purposes. It can be further
purified thus-Dissolve in a large quantity of boiling water adding sufficient
caustic soda solution. A deep red solution of the sodium salt is obtained which is
precipitated in the form of glittering crystals by adding an excess of the alkali.
Filter dissolve again in boiling water and by the addition of a mineral acid
precipitate the free sulpho-acid of alpha-phenyl-beta-methyl-eurhodine.
PREPARATION OF THE MONO-SULPHO-ACID OF ALPHA-PHENYL-BETA-METHYL-
HOMO-EURHODINE.
Dissolve about four and one fifth parts of mono-methyl-ortho-toluylene-diamine
in about forty-two parts of acetic acid (30 % C₂HO₂) as above and stir about ten
parts of the hydroxy-naphthoquinone-anil-sulpho-acid into this solution. Maintain
the temperature of the mixture at about fifty to sixty degrees centigrade for about
seven hours or until no increase in the quantity of induline mono-sulpho acid
formed is observed on washing a test portion, free from acetic acid, and stirring
with weak ammoniacal water. The said sulpho acid is, in the form of its ammonia
salt, difficultly soluble in cold water. Dilute the entire product of the reaction with
much water, filter, and wash with water. Mix the residue well with about one
hundred parts of water so as to form a thin paste add ammonia-in-such quantity
that a strong excess is present. A bye product is dissolved while the ammonia
salt of the induline sulpho acid remains undissolved. Filter and wash with very
weak ammoniacal water. Convert the pure salt so obtained into the acid by treating
with a mineral acid, wash, press and dry.
CONVERSION OF THE MONO-SULPHO ACIDS OF THE INDULINES OF THE NEW
CLASS INTO SULPHO ACIDS READILY SOLUBLE IN WATER.
Dissolve about ten parts of the almost insoluble sulpho acid obtained as described
in the preceding Examples 3 and 4 or in any other way in about forty or fifty
parts of fuming sulphuric acid containing about twenty three per cent. of free
anhydride (SO). Keep the acid cool during mixing and subsequently, stir till a
sample precipitated and washed with cold water dissolves completely in hot water.

page_text: Pour the whole product into about two to three hundred parts of ice water collect
the precipitated dye, press and redissolve the press cakes in hot water, adding
aminonia. Precipitate the dye with common salt solution, filter when cold, press
and dry.
The red brown crystalline powder thus obtained dissolves readily in hot water but
not so readily in cold water and on adding an acid to a solution the free sulpho acid
is precipitated in bright shining crystalline form.
This dye fixes itself on wool from the acid bath giving very even shades.
By-sulphonating more energetically than-is-above-described-sulpho-neids-are
obtained which are readily soluble in cold water.
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) The manufacture of hydroxy-naphtho-quinone-anil-sulpho-acid a new
material for use in the manufacture of the new class of colouring-matters by the
condensation of beta-naphthoquinone with sulphanilic acid substantially as herein-
before described.
(2) The manufacture of a sulpho-phenyl-curhodine (alpha-para-sulpho-benzol-
eurhodine) by the condensation of hydroxy-naphtho-quinone-anil-sulpho acid with
ortho-phenylene-diamine substantially as hereinbefore described.
(3) The manufacture of a mono-sulpho acid of an induline of the new class
(alpha-para-sulpho-benzol-beta-methyl-eurhodine) by the alkylation of the sulpho-
phenyl-eurhodine hereinbefore described and claimed in the second claiming clause
substantially as herein before described.
(4) The manufacture of a mono-sulpho acid of phenyl-methyl-homo-eurhodine
(alpha-para-sulpho-benzol-beta-methyl-homo-eurhodine) by the condensation of
hydroxy-naphthoquinone-anil-sulpho acid with mono-methyl-ortho-toluylene-
diamine substantially as hereinbefore described.
(5) The manufacture of new sulpho-acids of the new class by sulphonating the
mono-sulpho acids herein described and claimed in the third and fourth claiming
clauses by treatment with fuming sulphuric acid as hereinbefore described.
(6) As Dew articles of manufacture, hydroxy-naphtho-quinone-anil-sulpho
acid, alpha-para-sulpho-benzol-eurhodine, alpha-para-sulpho-benzol-beta-methyl-
eurhodine, alpha-para-sulpho-benzol-beta-methyl-homo-eurhodine, and the disulpho-
acids corresponding to the two last named mono-sulpho-acids all such as can be
obtained substantially as hereinbefore described.
T: 07h day of Manah 10G2
J. H. JOHNSON & Co.,
Agents.

page_text: Date of Application, 27th May, 1892
Complete Specification Left; 27th Mar., 1893-Accepted, 29th Apr.,
1893
PROVISIONAL SPECIFICATION.
Improvements relating to the Manufacture of a New Class of Basic
Dye-stuffs or Colouring Matters, and of Materials and Inter-
mediate Products relating thereto.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention which has been com-
municated to me from abroad by The Badische Aniline and Soda Fabrik of
Ludwigshafen on Rhine in the Empire of Germany to be as follows:-
This invention relates principally to the manufacture of a new class of basic
dyestuffs or colouring matters which are derived from the so-called eurhodines
and their analogues and which in their chemical constitution closely resemble the
indulines. They may indeed be regarded as indulines in which one or more
phenyl (or substituted phenyl) group is replaced by hydrogen or by an alkyl-group
such as methyl, ethyl &c. This will be rendered more clear to persons skilled in
the art by the following diagram
"
If the above formula of phenyl rosinduline be taken as an example of an induline
then members of the new class of dye-stuffs or colouring matters are obtained by
suitably substituting the phenyl groups A and B by alkyl groups. Thus for
instance instead of the group B an alkyl-group or hydrogen may be introduced
while an alkyl-group occupies the place of the group A.
Having now indicated the chemical nature of the new class of dyestuffs or
colouring matters I next describe ways in which they may be prepared. As
aforesaid they are derived from the so called eurhodines and their analogues.
Under this name numbers of bodies have been described in chemical literature
(see Witt Berichte der Deutschen Chemischen Gesellschaft 19, 441, 1720;
Journal of the Chemical Society 49, 391; 50, 473, 889. Fischer and Hepp
Berichte der Deutschen Chemischen Gesellschaft 23, 845 Journal of the Chemical
Society 58, 80-Kehrmann Berichte der Deutschen Chemischen Gesellschaft 23,
2451;
Journal of the Chemical Society 58, 1266; Kehrmann & Messinger, Berichte
der Deutschen Chemischen Gesellschaft 24, 584, 2167; Journal of the Chemical
Society 60, 746, 1213).
The process of preparing the new dyestuffs or colouring matters from the
eurhodines varies to a certain extent with the eurhodine used. Thus by using
certain alkyl-naphthyl amines in the manufacture of eurhodine, alkyl-eurhodines
CD 017

page_text: are obtained which on further alkylation give dyestuffs on colouring matters of the
new class.
Further the alkylation hereinbefore described as the final operation in obtaining
the new dyestuffs or colouring matters can be performed indirectly at an early stage
of the process by preparing an eurhodine such as can be obtained, as my foreign
correspondents have discovered from an ortho azo compound of an alkyl para-
toluidine. The alkylated eurhodine thus obtained is then itself a dyestuff or
colouring matter belonging to the new class.
The new dyestuff's or colouring matters obtained by proceeding as above
explained are basic.
Dated this 27th der of Wohnuary 1902
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents.
COMPLETE SPECIFICATION.
Improvements relating to the Manufacture of a New Class of Basic
Dye-stuffs or Colouring Matters, and of Materials and Inter-
mediate Products relating thereto.
1 JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex 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 manner the
same is to be performed to be particularly described and ascertained in and by the
following statement :-
This invention relates principally to the manufacture of a new class of basic dye-
stuffs or colouring matters which are derived from certain of the so-called
eurhodines and the analogous eurhodols. and which in their chemical constitution
closely resemble the indulines. They may indeed be regarded as indulines in which
one or more than one phenyl (or substituted phenyl) group is, or are, replaced by
hydrogen, or by an alkyl-group such as methyl, ethyl, or the like. The nature of
this substitution will be rendered clear by the following diagram and description.
In this diagram and the references to it I have used (simply as being a more
rational nomenclature) "Alpha" and "Beta" in place, respectively, of the "B"
and "A" used in my Provisional Specification.
If the above formula of phenyl-rosinduline be taken as an example of an induliné, 35
then the constitution of the members of the new class of dyestuffs, or colouring-
matters, is obtained by suitably substituting the phenyl groups beta and alpha by

page_text: alkyl groups in the following manner: namely, instead of the group alpha an alkyl
group or hydrogen can be introduced, while an alkyl group occupies the place of
the group beta.
Having now, by these instances, indicated the chemical nature of the new class of
dyestuffs, or colouring matters, I will hereinafter describe ways in which they may
be prepared according to this invention. As aforesaid they are derived from certain
so-called eurhodines and eurhodols. Under this name a large number of bodies has
been described in chemical literature (see Wilt, Berichte der Deutschen Chemischen
Gesellschaft 19, 441, 1720; Journal of the Chemical Society 49, 391, 50, 473, 889;
Fischer & Hepp, Berichte der Deutschen Chemischen Gesellschaft, 23, 845; Journal
of the Chemical Society 58, 80; Kehrmann, Berichte der Deutschen Chemischen
Gesellschaft 23, 2451; Journal of the Chemical Society 58, 1266; Kehrmann &
Messinger, Berichte der Deutschen Chemischen Gesellschaft 24, 584, 2167; Journal
of the Chemical Society 60, 7+6, 1213).
The process of preparing the new dye-stuffs or colouring matters from the
eurhodines may vary with the eurhodine used and the groups to be introduced or
substituted. Thus by using certain alkyl-naphthyl amines in the manufacture of
eurhodines, alkyl-eurhodines are obtained (see Example 1), which on further
alkylation (see Example 2) give dyestuffs or colouring matters of the new class.
Further the alkylation hereinbefore described as the final operation in obtaining
the new dyestuffs or colouring matters can be performed indirectly at an early stage
of the process by preparing an eurhodine such as can be obtained, as my foreign
correspondents have discovered, from an ortho-azo-compound of an alkyl-para-
toluidine (see Example 3).
The alkylated eurhodine thus obtained is then itself a dyestuff or colouring matter
belonging to the new class. The new dyestuffs or colouring matters obtained
by proceeding as above explained are basic.
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, but I do not
limit myself to the precise details thereof.
The preparation of an induline of the new class called alpha-beta-dimethyl-
homo-eurhodine where instead of the group alpha an alkyl group has been
introduced while an alkyl group occupies the place of group beta is described
in the following Examples 1 and 2.
Example 3 affords an instance of a dye of the new class-beta-methyl-homo-
eurhodine-where instead of the group alpha, hydrogen has been introduced while
an alkyl group occupies the place of the group beta.
PREPARATION OF
ALPHA-METHYL HOMO-EURHODINE. AN INTERMEDIATE
PRODUCT IN THE PRODUCTION OF THE NEW CLASS OF
MATTERS.
COLOURING
Dissolve about ten parts of mono-methyl-alpha-naphthylamine hydro-chlorate
in about fifteen parts phenol by heating on the water bath to a temperature of
about ninety degrees centigrade and add about ten parts of an amido-azo-com-
pound of para-toluidine to this hot solution. After a short time the temperature
rises spontaneously to about one hundred and sixty to one hundred and seventy
degrees centigrade in consequence of the reaction setting in. As soon as the
temperature has sunk again to about one hundred degrees centigrade mix the
entire product with dilute caustic soda to remove the phenol and wash with water
the raw product which separates out. To purify boil it with dilute bydrochloric
acid containing about five per cent. real acid and filter; from the filtered solution
the alpha-methyl-homo-eurhodine is precipitated in the form of its hydrochlorate
by adding one fifth of its volume of strong hydrochloric acid (containing thirty
per cent, real acid HCl) filter and press. Dissolve the residue in water, filter,

page_text: EXAMPLE 2.
PREPARATION OF A DYE OF THE NEW CLASS BY FURTHER ALKYLATING
ALPHA-METHYL-HOMO-EURHODINE.
Mix together about ten parts of alpha-methyl-homo-eurhodine, about five and
half parts méthyliodide and about fifty parts of wood spirit and heat the mixture
in a vessel capable of withstanding pressure for about two hours at a temperature
of about one hundred and fifty degrees centigrade or until the following test
shews that no further conversion of alpha-methyl-homo-eurhodine into the new
colouring-matter is taking place. To ascertain this take test portions of the
mixture and convert them into the base as hereinafter described dissolve in water
containing hydrochloric acid and add ammonia. The precipitate, if any, will
consist of unchanged alpha-methyl-homo-eurhodine. When no further decrease
in the quantity hereof is observed allow the mixture to cool, filter, and boil the
hydroiodate of the dye remaining in the filter with about sixty parts of alcohol
and six parts of soda-lye. (Containing about thirty five per cent. Na OH.) The
base so formed goes into solution but after a short time separates out in the
crystalline form. Filter while still warm, press and dry. The new dye so obtained
yields orange-red shades both on cotton mordanted with tannin and on silk.
Heat together about ten parts of the azo dye obtained by combining diazo-
sulphanilic-acid and mono-methyl paratoluidine 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 alpha-naphthylamine hydrochlorate. 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
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. The colouring matter can then be precipitated from the
solution with hydrochloric acid, press and dry. The hydrochlorate so obtained is
readily soluble in water and dyes bright yellowish red shades on cotton mordanted
with tannin and on silk.
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 alpha-methyl-homo-eurhodine a new intermediate product
in the manufacture of the indulines of the new class by heating together mono-
methyl-alpha-naphthylamine hydrochlorate and an amido azo-compound of para-
toluidine in the presence of a suitable solvent substantially as hereinbefore
described.

page_text: 2. The manufacture of an induline of the new class by further alkylating alpha-
methyl-homo-eurhodine substantially as hereinbefore described.
3. The manufacture of beta-methyl-homo-eurhodine a new basic dyestuff of the
new class by heating together the azo-dye from diazo-sulphanilic acid and mono-
methyl-para-toluidine with alpha-naphthylamine hydro-chlorate in the presence of
a suitable diluent substantially as hereinbefore described.
4. As new articles of manufacture the indulines of the new class namely alpha-
methyl-homo-eurhodine, alpha-beta-methyl-homo-eurhodine and beta-methyl-homo-
eurhodine all such as can be obtained substantially as hereinbefore described.
Dated this 27th day of March 1893.
J. H. JOHNSON & Co.,
Agents.

page_text: [The decision of the Chief Examiner, acting on behalf of the Comptroller, of the
30th day of August 1893, allowed, under Section 18 of the Patents, &c. Act, 1883,
an Amendment of this Specification.]
Date of Application, 27th May, 1892
Complete Specification Left, 27th Mar.; 1893-Accepted, 20th May, 1893
PROVISIONAL SPECIFICATION.
The Manufacture of a New Class of Basic Dyestuffs for Colouring
Matters and of Sulpho Acids thereof, and of Materials or
Intermediate Products relating thereto.
I JAMES YATE JOHNSON, of 47 Lincolns Inn Fields, in the County of
Middlesex, Gentleman, do hereby declare the nature of this invention (which has
been commimicated to me from abroad by The Badische Anilin and Soda Fabrik,
| of Ludwigshafen on Rhine, in the Empire of Germany,) to be as follows :—
This invention relates principally to the manufacture of a new class of basic
dyestuffs or colouring matters which are derived from the so-called eurhodines and
their analogues and which in their chemical constitution closely resemble the
indulines. They may indeed be regarded as indulines in which one or more phenyl
(or substituted phenyl) group is 'replaced by hydrogen or by an alkyl group such
as methyl, ethyl &c. This will be rendered more clear to persons skilled in the
art by the following diagram-
If the above formula of phenyl-rosinduline be taken as an example of an
induline, then members of the new class of dyestuffs or colouring matters are
obtained by suitably substituting the phenyl-groups A and B by alkyl-groups.
Thus for instance the group A can be substituted by methyl, ethyl, &c. while the
phenyl-group B remains, or again instead of the group B, an alkyl-group or
hydrogen may be introduced while an alkyl group occupies the place of the
group A.
Having now by these instances indicated the chemical nature of the new class of
dyestuffs or colouring matters I next describe ways in which they may be pre-
pared. As aforesaid they are derived from the so-called curhodines and their

page_text: analogues. Under this name numbers of bodies have been described in chemical
literature [see Witt, Berichte der Deutschen Chemischen Gesellschaft 19, 441,
1720;Journal of the Chemical Society 49, 391: 50, 473, 889;-Fischer & Hepp,
Berichte der Deutschen Chemischen Gesellschaft 23, 845,-Journal of the
Chemical Society 58, 80;-Kehrmann, Berichte der Deutchen Chemischen
Gesellschaft, 23, 2451,-Journal of the Chemical Society, 58, 1266, Kehrmann
& Messinger, Berichte der Deutschen Chemischen Gesellschaft 24, 584, 2167,
Journal of the Chemical Society 60, 746, 1213].
The process of preparing the new dyestuffs or coloring matters from the
eurhodines varies to a certain extent with the eurhodine used. Thus to prepare
the new basic dyestuffs or coloring matters from the eurhodine C₁,H13N3 (obtain-
able from an ortho-azo-compound of para-toluidine and alpha-naphthylamine) the
eurhodine is first melted with aniline and aniline salt and an intermediate product,
(phenyl-eurhodine) is formed, which, by subsequent alkylation, is converted into
the new dyestuff or colouring matter. But if the eurhodine used as the initial
material had already been phenylated or alkylated the melting operation with
aniline might have been omitted. Thus by using certain alkyl-naphthylamines in
the manufacture of eurhodine, alkyleurhodines are obtained, which on further
alkylation give dyestuff's or coloring matters of the new class.
Further just as the introduction of the phenyl-group into the finished eurhodine
can be evaded, so also the alkylation hereinbefore described as the final operation
in obtaining the new dyestuffs or colouring matters can be performed indirectly at
an early stage of the process by preparing an eurhodine such as can be obtained,
as my foreign correspondents have discovered from an ortho-azo compound of an
alkyl para-toluidine. The alkylated eurhodine thus obtained is then itself a dyestuff
or coloring matter belonging to the new class.
The new dyestuffs or colouring matters obtained by proceeding as above
explained are basic, but such of them as contain a phenyl-group can be sulphonated
to valuable acid dyestuffs or colouring matters which yield most even shades. And
not only can the sulpho acids be obtained by the direct action of sulphuric acid on
the finished basic dyestuff or colouring matter but by the use of suitable sulphonated
materials in the preparation of the eurhodines, sulphonated eurhodines result which
on alkylation either directly or indirectly give sulpho-acids of the basic dyestuff's
or colouring matters. Thus by the interaction of beta-naphthoquinone-anil-sulpho-
acid on orthodiamines a sulpho-phenyl-eurhodine is obtained which on alkylation
gives directly a member of the new class of dyestuffs or colouring matters in the
form of sulpho acid.
To further illustrate the nature of the invention I give the following examples
of the production of certain of the new dyestuffs or colouring matters but I do not
bind myself to details as considerable variations can be made in many respects
further in operating with different eurhodines different treatment is often necessary
as hereinbefore explained. The parts are by weight.
PREPARATION OF A PHENYL EURHODINE.
Mix together about ten parts of the above mentioned eurhodine C₁,H,,N, in the
form of hydrochloric acid salt, about five parts of aniline hydrochlorate and about
twenty parts of aniline, and heat the mixture in an oilbath for about two hours at a
temperature of about one hundred and fifty, to one hundred and sixty, degrees centi-
grade, or until no appreciable quantity of unchanged eurhodine is contained in the
melt. This can be ascertained by drawing samples from time to time and testing

page_text: for the eurhodine taking advantage of its ready solubility in dilute hydrochloric
acid.
Pour the melt into water, add excess of caustic soda, and drive off the unused
aniline with steam. A yellow body remains behind consisting of crude phenyl
eurhodine which can be crystallized, and so purified from an alcoholic phenol
solution. When pure this new body melts at a temperature of about two hundred
and thirty degrees centigrade, and is scarcely soluble in boiling water containing a
little acid whilst in concentrated sulphuric acid it dissolves with a green color.
The proportions of aniline and aniline salt and the temperature given in the
above example can be varied within wide limits without changing the nature of the
reaction.
TRETARATION OF AN INDULINE OF THE NEW CLASS FROM PHENYL-
EURHODINE.
Mix together about ten parts of phenyl-eurhodine (obtained as above described
or in any other way) with about five parts of methyl-iodide and fifty parts of
methyl alcohol or wood spirit in a closed vessel capable of withstanding pressure.
Heat the mixture to a temperature of about one hundred and sixty to one hundred
and seventy degrees centigrade, for about two hours, or until no further decrease
in the amount of unchanged phenyl eurhodine can be recognized in test portions of
the melt. These tests can be made as follows:-Withdraw a sample of the melt,
boil for a few minutes, with an excess of caustic soda-solution, to decompose the
hydro-iodate, precipitate the bases by adding water, filter and wash with water and
then boil the residue with dilute hydrochloric acid, in which the new induline is
very readily soluble, while the phenyl-eurhodine as above mentioned is scarcely
soluble at all. To work up the entire product add an excess of caustic soda, then
distil off the wood spirit and after washing with water dissolve the residual base in
hot water adding sufficient hydro-chloric acid; filter, precipitate the base with
alkali, wash and dry. To further purify recrystallize if desired from benzene.
This compound when pure has its melting point at about two hundred and ten
degrees centigrade and by analysis is shewn to possess the composition which may
be represented by the formula C24H,N On stirring the base with twice its
weight of dilute hydrochloric acid, containing about five per cent. real acid HCl,
a semi-solid mass of the soluble hydro-chlorate results, which, on drying, is obtained
as a red-brown crystalline mass with a dull sheen cotton mordanted with tannin
and silk are dyed red by this compound.
PREPARATION OF A PHENYL EURIODINE.
Mix about ten parts of the above mentioned eurhodol C₁,H₁₂N₂O (Witt Berichte
der Deutschen Chemischen Gesellschaft 19. 441 et seq. with about ten parts of
aniline salt, and twenty parts of aniline, and heat the mixture to a temperature of
about one hundred and fifty to one hundred and sixty degrees centigrade for about
two hours, or until no increase in the purity of the shade of green obtained on
dissolving a test portion of the melt in concentrated sulphuric acid can be noticed
in successive samples, saturate the melt with caustic soda solution and drive off the
excess of aniline with steam. The phenyl-eurhodine remains behind and is treated
as described in Example 2.

page_text: EXAMPLE 4.
PREPARATION OF A SULPHO ACID OF THE INDULINE C₂, H₁, N.
Dissolve about ten parts of the induline base or a similar quantity of its hydro-
chlorate in about forty parts of concentrated sulphuric acid (containing about
ninety five per cent. real acid H₂SO) and heat the mixture on the boiling water
bath until a sample, precipitated with water and washed, dissolves completely in
dilute caustic soda. This point being reached pour the whole mixture into about
two hundred parts of ice water, the sulpho-acid separates out and is collected,
washed with water, pressed, and dried. This sulpho acid is almost insoluble even
in boiling water and is used in the manufacture of the more soluble sulpho acid.
PREPARATION OF A SULPHO-ACID READILY SOLUBLE IN HOT WATER DERIVED
FROM THE NEW INDULINE CH¸¸Ñ¸.
Dissolve about ten parts of the induline base, or a similar quantity of its hydro-
chlorate, or of the above described almost insoluble sulpho-acid, in about forty
parts of fuming sulphuric acid containing about twenty three per cent. of free
anhydride (SO). Keep the acid cool during mixing and subsequently raise the
temperature to about twenty five to thirty degrees centigrade and stir till a sample
precipitated and washed with cold water dissolves completely in hot water. Pour
the whole product into about two hundred parts of ice water collect the precipitated
dye, press and redissolve the press cakes in hot water adding ammonia. Precipate
the dye with common salt.solution, filter when cold press and dry.
•
The red brown crystalline powder thus obtained dissolves readily in hot water
but not so readily in cold water and on adding an acid to a solution the free sulpho-
acid is precipitated in bright shining crystalline form.
This dye fixes itself on wool from the acid bath giving very even shades of
bright red which are considerably yellower than those obtained with azo-carmine
(described in the Specification of Letters Patent 1525989).
Dated this 27th day of May 1805
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION (AMENDED).
The Manufacture of a New Class of Basic Dyestuffs or Colouring
Matters and of Sulpho Acids thereof, and of Materials or
Intermediate Products relating thereto.
1 JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
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 manner the
same is to be performed to be particularly described and ascertained in and by the
following statement
-
This invention relates principally to the manufacture of a new class of basic
dyestuffs or colouring matters which are derived from certain of the so-called
eurhodines and the analogous eurhodols and which in their chemical constitution
closely resemble the indulines. They may indeed be regarded as indulines in which

page_text: one or more than one phenyl- (or substituted phenyl-) group is or are replaced by
hydrogen or by an alkyl-group such as methyl, ethyl or the like. The nature of
this substitution will be rendered clear by the aid of the diagram and explanation
following.
In this diagram and the references to it I have used (simply as being a more
rational nomenclature) "Alpha" and "Beta" in place respectively of the "B"
and "A" used in my Provisional Specification.
If the above formula of phenyl-rosinduline be taken as an example of an induline,
then the constitution of the members of the new class of dyestuffs or colouring
matters is obtained by suitably substituting the phenyl groups beta and alpha by
alkyl groups in the following manner namely; the group beta can be substituted
by methyl, ethyl, or the like, while the phenyl group alpha remains or instead of
the group alpha an alkyl-group or hydrogen may be introduced while an alkyl group
occupies the place of the group beta; in all cases the phenyl group beta must be
replaced by alkyl.
New indulines where the group beta is replaced by methyl while the phenyl-
group alpha remains are hereinafter described being the basic dyes of the new class
obtained according to the Examples 1 and 2, 3, 4 and 11.
The preparation of an induline of the new class called alpha-beta-dimethyl-
homo-eurhodine where instead of the group alpha an alkyl-group has been
introduced while an alkyl-group occupies the place of group beta is described in
the Examples 12 and 13.
Example 14 affords an instance of a dye of the new class (viz. beta-methyl-
homo-eurhodine) where instead of the group alpha hydrogen has been introduced
while an alkyl-group occupies the place of the group beta.
-
Having now by these instances indicated the chemical nature of the new class of
dyestuffs or colouring matters, I next describe ways in which they may be prepared.
As aforesaid they are derived from certain so-called eurhodines and eurhodols.
Under this name a large number of bodies has been described in chemical literature
[see Witt, Berichte der Deutschen Chemischen Gesellschaft, 19, 441, 1720 ;-
Journal of the Chemical Society 49, 391, 50, 473, 889; Fischer & Hepp,
Berichte der Deutschen Chemischen Gesellschaft 25, 845; Journal of the Chemical
Society 58, 80,- Kehrmann, Berichte der Deutschen Chemischen Gesellschaft,
23, 2451;Journal of the Chemical Society 58, 1266; Kehrmann & Messinger,
Berichte der Deutschen Chemischen, Gesellschaft, 24, 584, 2167;-Journal of the
Chemical Society 60, 746, 1213].
The process of preparing the new dyestuffs or colouring matters from the
eurhodiues may vary with the eurhodine used and the groups to be introduced or
substituted. Thus to prepare a new basic dyestuff or colouring matter of the new

page_text: 13
class from the homo-eurhodine C₁7 H₁ N3 (obtainable from an ortho-azo-compound
of para-toluidine and alpha-naphthylamine) the homo-eurhodine is first melted with
aniline and aniline salt and an intermediate product (phenyl-homo-eurhodine)-is
formed (Example 1) which by subsequent alkylation (Example 2) is converted
into the new dyestuff or colouring matter. But if the eurhodine used as initial
material had already been phenylated or alkylated the melting operation with
aniline can be omitted. Thus by using certain alkyl-naphthylamines in the
manufacture of enrhodine, alkyl-eurhodines are obtained (see Example 12) which
on further alkylation (see Example 13) give dyestuffs or colouring matters of the
new class.
Further, just as the direct introduction of the phenyl group into the finished
eurhodine can be avoided, so also the alkylation hereinbefore described as the final
operation in obtaining the new dyestuff's or colouring matters can be performed
indirectly at an early stage of the process by preparing an eurhodine such as can
be obtained, as my foreign correspondents have discovered, from an ortho-azo
compound of an alkyl-para-toluidine. (See Example 14 and for an analogous case,
Example 4.)
The alkylated eurhodine thus obtained is then itself a dyestuff or colouring-
matter belonging to the new class.
The new dyestuffs or colouring matters obtained by proceeding as above explained
are basic, but such of them as contain a phenyl-group at alpha can be sulphonated
to form valuable acid colouring matters or dyestuffs, some of which yield most even
shades. And not only can the sulpho-acids be obtained by the direct action of
sulphuric acid on the finished basic colouring matter or dyestuff (Examples 5 and 10)
but by the use of suitable sulphonated materials in the preparation of the
eurhodines,, sulphonated eurhodines result (see Example 7) which on alkylation
either directly (see Example 8) or indirectly (see Example 9) give sulpho
acids of the basic colouring-matters. Thus by the interaction of beta-hydroxy-
naphthoquinone-anil-sulpho-acid (see Example 6) on ortho-diamines a sulpho-
phenyl eurhodine (see Example 7) is obtained which on alkylation gives directly a
member of the new class of colouring matters in the form of sulpho acid (see
Example 8). In Example 9 instead of using an ortho-diamine as in Example 7 an
alkylated-ortho-diamine is used whereby the direct alkylation of the finished
eurhodine is avoided.
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 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 A PHENYL-HOMO-EURHODINE (AN INTERMEDIATE PRODUCT
IN THE MANUFACTURE OF THE NEW CLASS OF DYESTUFFS).
Mix together about ten parts of the eurhodine C₁,H,N, in the form of
hydrochloric acid salt, about five parts of aniline hydrochlorate, and about twenty
parts of aniline, and heat the mixture in an oil bath for about two hours at a
temperature of about one hundred and fifty, to one hundred and sixty degrees
centigrade, or until no appreciable quantity of unchanged eurhodine, is contained
in the melt. This can be ascertained by withdrawing samples from time to time
and testing for the eurhodine taking advantage for the purpose of its ready
solubility in dilute hydrochloric acid.
Pour the melt into water, add excess of caustic soda, and drive off the unused
aniline with steam. A yellow body remains behind consisting of crude phenyl-
homo-eurhodine which can be crystallized, and so purified from an alcoholic phenol
solution. When n pure this new body melts at a temperature of about two hundred

page_text: 1
EXAMPLE 2.
PREPARATION OF AN INDULINE OF THE NEW CLASS FROM PHENYL-HOMO-
EURHODINE.
Mix together about ten parts of phenyl-homo-eurhodine (obtained as described
in Example 1 or in any other way) with about five parts of methyl-iodide and
fifty parts of methyl-alcohol or wood spirit, in a closed vessel capable of with-
standing pressure. Heat the mixture to a temperature of about one hundred
and sixty to one hundred and seventy degrees centigrade, for about two hours, or
until no further decrease in the amount of unchanged phenyl-homo-eurhodine is
observed in test' portions of the melt.. These tests can be made as follows:
Withdraw a sample of the melt boil for a few minutes with an excess of caustic
soda-solution to decompose the hydro-iodate, precipitate the bases by adding.
water, filter and wash with water, and then boil the residue with dilute hydrochloric
acid, in which the new induline is very readily soluble, while the phenyl-homo
eurhodine, as above mentioned, is scarcely soluble at all. To work up the entire
product, add an excess of caustic soda, then distil off the wood-spirit and after
washing with water dissolve the residual base in hot water, adding sufficient hydro-
chloric acid filter, precipitate the base with alkali, wash and dry. To further
purity recrystallize if desired from benzene. This compound when pure has its
melting point at about two hundred and ten degrees centigrade and by analysis is
shewn to possess
the composition, which may be represented by the
formula C₂HN3
24
On stirring the base with twice its weight of dilute hydrochloric acid containing
about five per cent. real acid (HCI) a semi-solid mass of the soluble hydrochlorate
results, which on drying is obtained as a red-brown crystalline mass with a dull
sheen. Cotton mordanted with tannin and also silk are dyed red by this
PREPARATION OF. THE SAME PHENYL-HOMO-EURHODINE AS DESCRIBED IN
EXAMPLE 1 FROM THE ANALOGOUS HOMO-EURHODOL.
12-
Mix about ten parts of the above mentioned homo-eurhodol C₁H₁₂N₂O (Witt,
Berichte der Deutschen Chemischen Gesellschaft 19, 441 et seq.) with about
ten parts of aniline salt and twenty parts of aniline and heat the mixture to a
temperature of about one hundred and fifty to one hundred and sixty degrees centi-
grade for about two hours, or until no increase in the purity of the shade of
green obtained on dissolving a test portion of the melt in concentrated sulphuric
acid is noticed in successive samples. Saturate the milk with caustic soda solution
and drive off the excess of aniline by means of steam. The phenyl-homo eurhodine
remains behind and is treated as described in Example 2 in order to obtain the
basic colouring matter of the new class.
PREPARATION OF THE SAME NEW INDULINE BY THE USE OF HYDROXY-
NAPHTHO-QUINONE-ANIL AND MONO-METHYL-ORTHO-TOLUYLENEDIAMINE.
Stir together about ten parts of hydroxy-naphtho-quinone-anil with
0 about three hundred parts of acetic acid (containing about thirty per cent.

page_text: real acid C₂HO₂). To the mixture add about six parts of mono-methyl-ortho-
toluylene diamine (obtained by the reduction of mono-methyl-dinitro-
toluidine CH, NO, NHCH) in about one hundred parts of acetic acid
1
(30% CHO, as above).
Heat the mixture on the water-bath for about four hours, or until on working
up test portions in the manner hereinafter described no increase in the quantity
of induline formed is noticed. This point being reached dilute the product of
the reaction with twice its volume of water filter and precipitate the .induline from
the deep red solution so obtained by adding an alkali. To purify, dissolve the
precipitate in dilute acetic acid (containing one per cent. real acid) filter and
precipitate with an alkali.
PREPARATION OF
A DIFFICULTLY SOLUBLE
MONO-SULPHO-ACID
OF
THE
INDULINE CH₁, N3 BY DIRECT SULPHONATION.
Dissolve about ten parts of the induline base or a similar quantity of its hydro-
chlorate in about forty parts of concentrated sulphuric acid (containing about
ninety five per cent. real acid H,SO, and heat the mixture on the boiling water-
bath until a sample, precipitated with water, and washed, dissolves completely in
dilute caustic soda. This point being reached pour the whole mixture into about
two hundred parts of ice water, the sulpho acid separates out and is collected,
washed with water, pressed and dried. This sulpho acid is almost insoluble even
in boiling water and is used in the manufacture of the more soluble sulpho-acid.
A NEW
PREPARATION OF HYDROXY-NAPHTHO-QUINONE ANIL SULPHO-ACID.
IN THE MANUFACTURE OF
MATERIAL FOR USE
CLASS
THE NEW
COLOURING MATTERS.
OF
Dissolve about ten parts of beta-naphthoquinone in about two hundred and fifty
parts of hot alcohol; add a solution of about ten parts of sodium sulphanilate in about
twenty five parts of water. Stir for about twelve hours filter and press. The
red product so obtained consists of the sodium salt of hydroxy-naphtho-quinone-anil-
sulpho acid. To prepare the free acid dissolve this in about three hundred parts
of boiling water add sufficient acetic acid to make the solution strongly acid and
filter. The free acid crystallizes from the filtrate on adding about one hundred
parts of saturated salt solution. Collect on the filter press and dry.
PREPARATION OF A SULPHO
PHENYL-EURHODINE (ALPHA-PARA-SULPHO-
BENZOL-EURHODINE).
Dissolve about thirty five parts of the sodium salt of hydroxy-naphtho-quinone-
anil-sulpho-acid in about nine hundred parts of hot water, and run into the solution
about eleven parts of ortho-phenylene diamine dissolved in about one hundred
parts of acetic-acid (containing about thirty per cent. real acid C,HO₂). Heat
the mixture for about four hours on the boiling water bath. The desired con-
densation product, which may be called a sulpho-phenyl-eurhodine-(or alpha-para-
sulpho-benzol-eurhodine), separates out in the crystalline form, while the solution,
which was originally of a deep-red colour, becomes almost colourless. To purify
wash the product well with hot water and dissolve in boiling dilute soda solution
and precipitate the sodium salt with common salt. The said sodium salt is obtained

page_text: ALKYLATION OF THE SULPHO-PHENYL-EURHODINE.
PREPARATION OF ALPHA-
PARA-SULPHO-BENZOL-BETA-METHYL-EURHODINE.
Mix together about five parts of the sodium salt of sulpho-phenyl-eurhodine
(alpha-para-sulpho-benzol-eurhodine obtained as described in Example 7 or in any
other way) with about fifty parts wood-spirit (methyl alcohol) and about five
parts of methyl iodide and heat the mixture for about two hours at a temperature
of about one hundred and fifty to one hundred and seventy degrees centigrade
whereby a pressure of about thirty to thirty one atmospheres should be developed.
The end of the reaction can be recognized as follows:-Take tests from time to
time and work up (in the manner hereinafter described) the crystalline portion of
the product which separates from the alcoholic solution. When no increase in the
quantity of sulpho acid insoluble in dilute caustic soda is observed, the operation.
may be regarded as ended, further the mother liquor in this case should no longer
shew a yellow colour, due to the presence of the unmethylated body.
Work up the whole product as follows:-Pour off the red methyl-alcoholic
mother liquor from the crystalline product wash with alcohol, and dry. The
body so obtained will, as a rule, be pure enough for ordinary purposes but it
can be further purified thus:-Dissolve it in a large quantity of boiling water
adding sufficient caustic soda solution. A deep red solution of the sodium salt is
obtained which is precipitated in the form of glittering crystals by adding an
excess of the alkali. Filter, dissolve again in boiling water, and, by the addition
of a mineral acid, precipitate the free sulpho-acid of alpha-phenyl-beta-methyl-
eurhodine.
PREPARATION OF A MONO-SULPHO-ACID OF THE NEW CLASS OF COLOURING
MATTERS BY THE USE OF SUITABLY SULPHONATED AND ALKYLATED
INITIAL MATERIALS.
Dissolve about four and one fifth parts of mono-methyl-ortho-toluylene-diamine
in about forty two parts of acetic acid (30% C,H,O2) as above and stir about
ten parts of the hydroxy-naphtho-quinone anil-sulpho acid into this solution.
Maintain the temperature of the mixture for about seven hours at about fifty to
sixty degrees centigrade or until no increase in the quantity of induline mono-
sulpho acid formed can be observed by washing a test portion free from acetic acid
and stirring with weak ammoniacal water. The said sulpho acid in the form of its
ammonia salt, is difficultly soluble in cold water. Dilute the entire product of the
reaction with much water, filter, and wash with water. Well mix the residue
with about one hundred parts of water so as to form a thin paste, and add ammonia
in such quantity, that a strong excess is present. A bye-product is dissolved while
the ammonia salt of the induline sulpho acid remains undissolved. Filter and
wash with very weak ammoniacal water. Convert the pure salt so obtained into
the acid by treating with a mineral acid, wash, press and dry.

page_text: acid containing about twenty three per cent. of free anhydride (SO3). Keep the
acid cool during mixing and subsequently raise the temperature to about twenty-
five to thirty degrees centigrade and stir till a sample precipitated and washed with
cold water dissolves completely in hot water. Pour the whole product into about
two hundred parts of ice water, collect the precipitated dye, press, and redissolve
the press cakes in hot water, adding ammonia. Precipitate the dye with common
salt solution, filter when cold, press and dry. By sulphonating more energetically
than is above described sulpho acids are obtained which are readily soluble in
cold water. This however does not apply to such mono-sulpho acid as is described in
Example 9.
The red-brown crystalline powder thus obtained dissolves readily in hot water,
but not so readily in cold water, and, on adding an acid to a solution thereof, the
free sulpho-acid is precipitated in bright shining crystalline form.
This dye fixes itself on wool from the acid bath giving very even shades of bright
red which are considerably yellower than those obtained with azo carmine (described
in the Specification of Letters Patent 1525989).
EXAMPLE 11.
•
PREPARATION OF A HOMOLOGOUS INDULINE AND ITS SULPHO ACIDS.
3
In a similar manner to that described in the above examples homologous colouring
matters of the new class can be obtained by applying the same processes to homologous
initial materials. Thus for instance by melting the eurhodine C₁H₁₁N (Berichte
der Deutschen Chemischen Gesellschaft 23 485 and 2452) with aniline and aniline
hydrochlorate in the manner described in the preceding Example 1 a new homo-
logous phenyl-eurhodine is obtained. Also the same phenyl-eurhodine results on
treating the analogous eurhodol C16H1N2O (Berichte der Deutschen Chemischen
Gesellschaft 23 2453) precisely in the manner described in the foregoing
Example 3. Further this phenyl-eurhodine can be alkylated to yield a dyestuff
of the new class in the manner described in the foregoing Example 2. This same
new dyestuff can be obtained by the process described in Example 4 as applied
to the lower homologous diamine. Again, this basic colouring matter can be
sulphonated to yield new sulpho acids in the manner described in the foregoing
Examples 5 and 10.
PREPARATION OF ALPHA-METHYL-HOMO-EURHODINE. AN INTERMEDIATE
PRODUCT IN THE PRODUCTION OF THE NEW CLASS OF COLOURING
MATTERS.
Dissolve about ten parts of mono-methyl-alpha-naphthylamine hydrochlorate in
about 15 parts of phenol by heating on the water bath to a temperature of
about ninety degrees centigrade and add to this hot solution about ten parts of an
amido azo compound of para-toluidine. After a short time the temperature rises
spontaneously to about one hundred and sixty to one hundred and seventy degrees
centigrade in consequence of the reaction setting in. As soon as the temperature
has sunk again to about one hundred degrees centigrade mix the entire product
with dilute caustic soda to remove the phenol and wash with water the raw product
which separates out. To purify boil it with dilute hydrochloric acid containing
about five per cent. real acid and filter. From the filtered solution the alpha-
methyl-homo-eurhodine is precipitated in the form of its hydrochlorate by adding
one fifth of its volume of strong hydrochloric acid (containing thirty per cent. real
acid HCl) filter and press. Dissolve the residue in water, filter, and precipitate
the cold solution with ammonia. Stir the voluminous precipitate with about five
hundred parts of cold dilute acetic acid (containing one per cent. real acid). Filter
the red solution obtained and boil. The alpha-methyl-homo-eurhodine separates
almost completely out in the form of yellow needles.

page_text: PREPARATION OF A DYE OF THE NEW CLASS BY FURTHER ALKYLATING
ALPHA-METHYL-HOMO-EURHODINE.
Mix together about ten parts of alpha-methyl-homo eurhodine, about five and
half parts of methyliodide and about fifty parts of wood spirit and heat the mixture
in a vessel (capable of withstanding pressure) for about two hours at a temperature
of about one hundred and fifty degrees centigrade or until the following test shews
that no further conversion of alpha-methyl-homo-eurhodine into the new colouring
matter takes place. To ascertain this take test portions of the mixture and convert
them into the base, as hereinafter described; dissolve this in water containing hydro-
chloric acid, and add ammonia. The precipitate if any will consist of unchanged
alpha-methyl-homo-eurhodine. When no further decrease in the quantity hereof
is noticed allow the mixture to cool. Filter and boil the hydroiodate of the dye
which remains on the filter with about sixty parts of alcohol and six parts of soda-
lye (containing about thirty five per cent. NaOH). The base so formed goes into
solution but after a short time separates out in the crystalline form, filter while
still warm, press and dry. The new dye so obtained yields orange red shades both
on cotton mordanted with tannin and on silk.
Heat together about ten parts of the azo dye obtained by combining diazo-
sulphanilic-acid and mono-methyl-paratoluidine 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 alpha-naphthylamine hydrochlorate. 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. Separate 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 dye stuff from the filtered 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.
The colouring matter can then be precipitated from the solution with hydro-
chloric acid; press and dry. The hydrochlorate so obtained is readily soluble
in water and dyes bright yellowish red shades on cotton mordanted with tannin
and on silk.
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 the new class of induline dyestuffs or colouring matters
of the constitution or nature hereinbefore described and more particularly defined
by the aid of the foregoing diagram.
(2.) The manufacture of sulpho acids of such of the indulines of the new class as
contain a phenyl group at alpha in the diagram either by direct sulphonation of the
said indulines or by the use of sulphonated materials substantially as hereinbefore
described.

page_text: (3.) The manufacture of the phenyl-eurhodines and sulpho-phenyl-eurhodines
such as contain a phenyl group at alpha of the diagram, substantially as herein-
before described.
J. H. JOHNSON & Co.,
Agents.