The Manufacture and Production of New Dyes of the Rosaniline Series, and of New Materials therefor.
Year: 1891

page_text: Date of Application, 2nd July, 1891
Complete Specification Left, 25th Mar., 1892-Accepted, 30th Apr., 1892
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Dyes of the Rosaniline
Series, and of New Materials therefor.
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 mc from abroad by The Badische Anilin &
Soda Fabrik of Ludwigshafen on Rhine in the Empire of Germany to be as
follows:-
:-
It is known that meta-hydroxy-diphenyl-amine can be obtained by the interaction
of aniline and resorcinol and that meta-hydroxy-phenyl-para-tolyl-amine can be
obtained by a similar reaction between para toluidine and resorcinol (see Berichte
der deutschen Chemischen Gesellschaft 16, 2786. Journal für practische Chemie
N.F. 33, 209; Journ. Chem. Soc. 46, 591; 50, 455). Analogous compounds can be
obtained by the condensation of resorcinol with other amido-compounds such as,
for instance meta-xylidine, and in other ways.
The present invention is based upon the discovery that many such compounds,
that is to say neta-hydroxy-amido compounds substituted in the amido group give
alkyl ethers and these new ethers yield, by condensation with tetra-alkyl-diamido-
benzophenone, a series of new basic dyes of the rosaniline series, which can be
used either as basic dyestuff's, or can, by sulphonation, be converted into more
soluble acid dyes of very valuable properties.
To illustrate the nature of the invention I.give directions for
(1) The production of the methyl ether of meta-hydroxy-phenyl-para-tolyl-
amine.
(2) The condensation of this body with tetra methyl-diamido benzophenone to
produce a blue basic dyestuff.
(3) The conversion of this basic dye by sulphonation into an acid dyestuff.
These directions are given merely as examples the details of which can be
considerably varied and instead of the metahydroxy-phenyl-para-tolyl-amine many
analogous compounds can be employed in a similar manner. By parts I mean
parts by weight.
EXAMPLE 1. PREPARATION OF
META-METHOXY-PHENYL-PARATOLYLAMINE
Mix together about one hundred parts of meta-hydroxy-phenyl-para-tolylamine,
about twenty parts of solid caustic soda, about four hundred parts of methylalcohol
and about forty parts of methyl chloride, and heat the mixture in an autoclave (or
like vessel capable of withstanding pressure) for about twenty four hours at a
temperature of about one hundred and fifteen to one hundred and twenty degrees
centigrade. Distil off the methyl-alcohol from the resulting product and wash the
residue first with dilute caustic soda solution and then with water, and finally dry
at a temperature of about one hundred degrees centigrade. In this way the
desired ether is obtained in a condition sufficiently pure for use in the manufacture
of dyestuffs. It is a thick oil which can be distilled at a temperature of about
three hundred and sixty degrees centigrade and which, on standing for a long
time, solidifies to a lightly coloured crystalline mass. This can be recrystallized
from benzene and then has a melting point of about sixty eight degrees
centigrade.
In an analogous manner other alkyl-ethers of meta-hydroxy-phenyl-para-tolyl-

page_text: amme call DE ODRETTen, and
GITC Cifiers
ՆԵՂ
amido-compounds.
EXAMPLE 2. THE
PRODUCTION OF
ار
BLUE
BASIC DYESTUFF BY THE
WITHI THE
CONDENSATION OF TETRA-METHYL-DIAMIDO-BENZOPHENONE
META-METHOXY-PHENYL-PARA-TOLYLAMINE.
The manner of effecting this condensation resembles that described in the
Specifications of Letters Patent Nos. 4850 and 5033 of the year 1884. Phosphor
oxychloride is preferably used as the condensation agent, but phosphorous
chloride, phosgene and similar halogen compounds can be employed.
about
Mix about twenty two parts of meta-methoxy-phenyl-para-tolylamine,
twenty seven parts of tetra-methyl-diamido benzophenone and about thirty five
parts of phosphorous oxychloride with about eight parts of toluene (which acts as
a diluent) and heat the mixture on the water bath in a vessel provided with a
stirrer. Heat the water-bath to boiling and stir the mixture for half an hour at
this temperature. The melt, which assumes a metallic sheen, is poured, in small
portions at a time, into a solution of common salt and is boiled therewith and is
then extracted with toluene or heavy oil. The residual colouring matter is then
dried at a temperature of about sixty degrees centigrade and finally reduced to
powder.
The dye thus obtained is a dark powder with a metallic sheen slightly soluble
in water but more readily soluble in alcohol. It yields violet-blue shades on wool
and on cotton mordanted with tannin.
Instead of the substituted meta-hydroxy-amido-ether used in the above example
equivalent quantities of analogous bodies can be employed. Also instead of
tetramethyl-diamido-benzophenone other alkyl-compounds can be used.
EXAMPLE 3. PREPARATION OF A NEW SULPHO-ACID.
Fuming sulphuric acid is preferably used for sulphonating the basic dyes.
obtained as above described, but equivalent compounds can be used.
The:
temperature of the sulphonation must be varied according to the strength of the
acid used. The following method gives good results.
Grind together about thirty parts of the basic-colouring matter obtained as
described under Example 2, and thirty parts of anhydrous sodium sulphate, and
slowly add this mixture to about one hundred and fifty parts of fuming sulphuric
acid containing about twenty four per cent. of sulphuric anhydride (SO). The
acid must be well cooled and during the addition the temperature should be kept
below about ten degrees centigrade. Continue stirring for a few hours until a
sample is completely soluble in alkali, then pour the whole into ice water and add
sufficient caustic soda to nearly neutralize the solution. Precipitate the dyestuff
with sodium sulphate, filter and dry. The dyestuff thus obtained is soluble in
water and dyes wool from the boiling acid bath a violet-blue colour.
In a similar manner the analogous basic colouring matters, obtainable as herein-
before indicated can be converted into soluble sulpho acids.
Dated this 2nd day of July 1891.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.

page_text: COMPLETE SPECIFICATION.
The Manufacture and Production of New Dyes of the Rosaniline
Series, and of New Materials therefor.
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 communi-
cated to me from abroad by The Badische Anilin and Soda Fabrik of Ludwig-
shafen 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:
It is known that meta hydroxy-phenyl para-tolylamine can be obtained by the
interaction of para-toluidine and resorcinol; and that in the same way. neta-
hydroxy-phenyl-ortho-tolylamine has been prepared from ortho-toluidine (see
Journal für practische Chemie [N.F.] 33, 209; 34, 70, and Journal of the
Chemical Society 50, 455 and 942), and the analogous compound meta-hydroxy-
phenyl-meta-xylylamine can be obtained similarly by the condensation of resorcinol
with meta-xylidine.
The present invention is based upon the discovery of my foreign correspondents,
that the above mentioned meta-hydroxy-amido-compounds substituted in the
amido group give alkyl ethers, and these new alkyl-ethers yield by condensation
with tetra-alkyl-diamido-benzophenone, a series of new basic dyes of the rosaniline
series, which can be used either as basic dyestuffs, or which can, by sulphonation,
be converted into more soluble acid dyes of very valuable properties.
The alkyl-compounds which are practically of greatest importance, are the ethyl-
and methyl-compounds though others can be used as will be readily understood by
chemists.
To further illustrate and describe the invention and the manner in which it can
be carried into practical effect, I give directions for-
(1). The production of the methyl ether of meta-hydroxy-phenyl-paratolylamine ;.
(2). The condensation of this body with tetramethyl-diamido-benzophenone to
produce a violet-blue basic dyestuff;
(3). The conversion of this basic dyestuff by sulphonation into an acid dyestuff.
These directions are given as examples the details of which can be con-
siderably varied and instead of the meta-hydroxy-phenyl-para-tolyl-amine other
analogous compounds as herein set forth can be employed in a similar manner.
The parts are by weight.
EXAMPLE 1. PREPARATION OF META-METHOXY-PHENYL-PARA-TOLYLAMINE.
Mix together about one hundred parts of meta-hydroxy-phenyl-para-tolylamine,
about twenty parts of solid caustic soda, about four hundred parts of methyl-alcohol
and about forty parts of methyl-chloride, and heat the mixture in an autoclave, or
like vessel capable of withstanding pressure for about twenty four hours at a
temperature of about one hundred and fifteen, to one hundred and twenty, degrees
centigrade. Distil off the methyl-alcohol from the resulting product and wash the
residue first with dilute caustic soda solution and then with water, and finally dry
at a temperature of about one hundred degrees centigrade. In this way the desired
ether (meta-methoxy-phenyl-para-tolylamine) is obtained in a condition sufficiently
pure for use in the manufacture of dyestuffs. It is a thick oil which can be distilled
at a temperature of about three hundred and sixty degrees centigrade, but is liable
to decomposition at this temperature and is therefore preferably distilled in vacuo.
On standing for a long time it solidifies to a slightly coloured crystalline mass
This can be recrystallized from benzene and then has a inelting point of about sixty
eight degrees centigrade.
In an analogous manner the ethyl-ethers of meta-hydroxy-phenyl-para-tolyl-

page_text: amine can be obtained and also the ethyl-and methyl-ethers of the other substituted
meta-hydroxy-amido-compounds, hereinbefore mentioned, viz. :
meta-methoxy-phenyl-ortho-tolylamine
meta-ethoxy-phenyl-ortho-tolylamine
EXAMPLE 2. THE PRODUCTION
OF A VIOLET-BLUE BASIC DYESTUFF BY
THE CONDENSATION OF TETRAMETHYL-DIAMIDO-BENZO-PHENONE WITH
THE META-METHOXY-PHENYL-PARA-TOLYLAMINE.
The manner of effecting this condensation resembles that described in the Speci-
fications of Letters Patent Nos. 4850 and 5038 of the year 1884. Phosphorus-
oxychloride is preferably used as the condensation agent but the other phosphorus
chlorides, phosgene and similar halogen compounds can be employed. Mix about
twenty two parts of meta-methoxy-phenyl-para-tolylamine, about twenty seven
parts of tetramethyldiamido-benzo-phenone and about thirty five parts of phosphorus
oxychloride with about eight parts of toluene (which acts as a diluent) and heat the
mixture on the water bath in a vessel provided with a stirrer.
Heat the water-
bath to boiling and stir the mixture for half an hour at this temperature. The melt
which assumes a metallic sheen is poured into a solution of common salt and is
boiled therewith and is then extracted with toluene or heavy oil. The residual
colouring matter is then dried at a temperature of about sixty degrees centigrade
and is afterwards reduced to powder.
The dye thus obtained is a dark powder (with a metallic sheen) slightly soluble
in water but more readily soluble in alcohol. It yields violet-blue shades on wool
and on cotton mordanted with tannin.
Instead of the substituted meta-hydroxy-amido-ether used in the above example
equivalent quantities of the analogous bodies obtained from the other meta-hydroxy-
amido-compounds hereinbefore mentioned can be employed. Also instead of
tetramethyl-diamido-benzophenone the tetra-ethyl-compound can be used.
EXAMPLE 3. PREPARATION OF A NEW SULPHO-ACID.
Fuming sulphuric acid is preferably used for sulphonating the basic dyes obtained
as above described, but equivalent compounds can be employed. The temperature
of the sulphonation must be varied according to the strength of the acid used. The
following method gives good results.
Grind together about thirty parts of the basic coloring-matter obtained as
described under Example 2 and about thirty parts of anhydrous sodium sulphate,
and slowly add this mixture to about one hundred and fifty parts of fuming
sulphuric acid containing about twenty-four per cent. of sulphuric anhydride (SO3).
The acid must be well cooled and during the addition the temperature should be
kept below about ten degrees centigrade. Continue stirring for a few hours until
a sample is completely soluble in alkali, then pour the whole into ice water and
add sufficient caustic soda to nearly neutralise the solution. Precipitate the dye-
stuff with sodium sulphate, filter and dry. The dyestuff thus obtained is soluble
in water and dyes wool from the boiling acid bath a violet-blue colour.
In a similar manner the analogous basic colouring matters obtainable as herein-
before described can be converted into soluble sulpho-acids.
I am aware that the process herein described under Example 2 is as applied to
other materials already patented in the Letters Patent Nos. 4850 and 5038 of the
year 1884 granted to John Henry Johnson and I under this present application
make no general claim to this process but only to its use as applied to the materials
herein before referred to being within the scope of this present invention.

page_text: 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 process for the manufacture of new materials for the preparation of dyes
namely the alkyl ethers (and especially the ethyl- and methyl-ethers) of the sub-
stituted meta-hydroxy-amido compounds hereinbefore mentioned, all substantially
as herein before described.
2. As new articles of manufacture, the new materials for the manufacture of dyes,.
being the ethyl- and methyl-ethers of the substituted meta-hydroxy-amido-
compounds hereinbefore mentioned, viz. :
meta-methoxy-phenyl-para-tolylamine
meta-ethoxy-phenyl-para-tolylamine
meta-methoxy-phenyl-ortho-tolylamine
meta-ethoxy-phenyl-ortho-tolylamine
meta-methoxy-phenyl-meta-xylylamine
meta-ethoxy-phenyl-meta-xylylamine,
all such as can be obtained substantially as hereinbefore described.
3. The process for the manufacture of basic dyes of the rosaniline series which.
consists in preparing an alkyl-ether of a substituted meta-hydroxy-amido-compound
hereinbefore mentioned and claimed in the 1st and 2nd claiming clauses and then
condensing it with either tetra-methyl-diamido-benzophenone or tetra-ethyl-diamido-.
benzophenone substantially as hereinbefore described.
4. As new articles of manufacture, the basic dyes of the rosaniline series, such as.
can be obtained by the process hereinbefore described and claimed in the 3rd
claiming clause.
5. The manufacture of new acid dyes of the rosaniline series by first preparing
one of the basic dyes, hereinbefore described, and claimed in the 3rd and 4th
claiming clauses and then converting it by sulphonation into a soluble sulpho-acid,.
substantially as herein before described.
6. As new articles of manufacture the acid dyes of the rosaniline series such as
can be obtained by the process hereinbetore described and claimed in the 5th claiming
clause.
7. The manufacture of materials for use in the production of dyes substantially
as herein described under Example 1.
8. The manufacture of basic dyes of the rosaniline series substantially as herein.
described under Example 2.
9. The manufacture of acid dyes of the rosaniiine series substantially as herein.
described under Example 3.
Dated this 25th day of March 1892.
J. H. JOHNSON & Co.,
Agents.