The Manufacture of New Basic Colouring Matters of the Auramine Class and of New Materials for use therein.
Year: 1892

page_text: Date of Application, 1st June, 1892
Complete Specification Left. 21st Feb. 1893-Accepted 1st Apr. 1893
PROVISIONAL SPECIFICATION.
The Manufacture of New Basic Colouring Matters of the Auramine
Class and of New Materials for use therein.
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 com-
municated to me from abroad by The Badische Anilin and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany to be as follows
In the Specification of Letters Patent No. 5512 of 1884 granted to John Henry
Johnson there is described the production of the yellow basic dye known as
auramine. Up to the present time auramine is the only yellow basic colouring
matter of the diphenyl-methane-series which has been successfully introduced into
the dyeing trade. The present invention relates to a new auramine which dyes
greener (that is less orange) shades of yellow than does the aforesaid auramine
which is of great importance as all attempts to obtain a basic dye of this class
yielding such shades of yellow have hitherto failed.
The initial material for the production of the new auramine is the hitherto
unknown dimethyl-diamido-di-orthotolyl-methane which can be obtained by the
condensation of monomethyl-orthotoluidine with formaldehyde. This new di-tolyl-
methane derivative is converted into the new colouring matter by treatment_simul-
taneously with sulphur and ammonia, or by some equivalent treatment. Instead
of starting from the methane derivative, the new auramine can be obtained from
the corresponding ketone, thio-ketone, hydrol or thio-hydrol.
The nature of the invention is further illustrated by the following directions for
carrying into practical effect which I give by way of example only as the
details can be considerably varied without departing from the nature of the
invention. The parts are by weight.
EXAMPLE 1.-PREPARATION OF DIMETHYL-DIAMIDO-DIORTHOTOLYL-
METHANE.
Mix together one molecular proportion of formaldehyde (in the form of say, a
forty per cent. solution) with two molecular proportions of mono-methyl-ortho-toluidine
and whilst the mixture is kept cold pass thereinto one molecular proportion of
hydrochloric acid gas.
The mono-methyl-ortho-toluidine need not be pure as a mixture thereof with
dimethyl-ortho-toluidine may be employed, provided that the quantity of the
mixture taken be such as to contain the required quantity of mono-methyl-ortho-
toluidine. Heat the product obtained for ten hours on the water-bath. Dilute
with water add soda till alkaline, and distil off any unaltered methyl-toluidine with
steam. The mass remaining behind solidifies on standing sometime in the cold,
and can be purified by crystallization from alcohol or petroleum spirit. When
pure the new base melts at a temperature of about 86 to 87 degrees centigrade.
The mixture which is heated on the water bath, can also be obtained in a manner
slightly different from that described, namely by mixing one molecular proportion
of formaldehyde with one molecular proportion of hydrochlorate of mono-methyl-
ortho-toluidine and one molecular proportion of free mono-methyl-ortho-toluidine
the further treatment being as herein before described. If in the above example
mono-ethyl-ortho-toluidine be used analogous results are obtained.
EXAMPLE 2.-PREPARATION OF THE NEW AURAMINE DYE.

page_text: diamido di-ortho-tolyl-methane (obtained as above described or in any other way)
and about six and a half parts sulphur with a suitable diluent; say, for instance, a
mixture of two hundred and forty parts of common salt and fourteen parts of
ammonium chloride. Heat the mixture in a closed vessel provided with a stirrer
and standing in an oil bath which is maintained at a temperature of about one
hundred and seventy five degrees centigrade. Pass in (under slight pressure) a
stream of dry ammonia gas and continue this treatment for about seven or eight
hours when the reaction will be ended. Allow to cool, extract the brown crystalline
melt with cold water, to get rid of the common salt and ammonium chloride, and
dissolve the residue in water having a temperature of about eighty degrees centi-
grade filter the solution and precipitate the dye with common salt. Collect in the
usual way.
The new dye fixes itself on cotton mordanted with tannin and tartar-emetic,
giving a very pure shade of yellow with a slight greenish tinge.
If in Example 2 the corresponding ethyl derivative of diamido-diortho-tolyl-
methane be taken analogous results are obtained.
Dated this 1st day of June 1899
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture of New Basic Colouring Matters of the Auramine
Class and of New Materials for use therein.
I JAMES YATE JOHNSON of No. 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 :-
In the Specification of Letters Patent No. 5512 of 1884 granted to John Henry
Johnson there is described the production of the yellow basic dye known as
auramine.
Prior to the present invention auramine was the only yellow basic colouring
matter of the diphenylmethane series which had been successfully introduced into
the dyeing trade. The present invention relates to a new auramine which dyes
greener (that is less orange) shades of yellow than does the aforesaid auramine,
which is of great importance, as all attempts to obtain a basic dye of this class
yielding such shades of yellow have hitherto failed.
As initial material for the production of the new auramine is the hitherto
unknown dimethyl-diamido-diorthotolylmethane which can be obtained by the
condensation of monomethyl orthotoluidine with formaldehyde. This new di tolyl
methane derivative is converted into the new colouring matter by treatment
simultaneously with sulphur and ammonia, or by some equivalent treatment.
The nature of the invention is further illustrated by the following directions for
carrying it into practical effect which I give by way of example only, as the details
can be considerably varied without departing from the nature of the invention; the
parts are by weight.

page_text: pure as a mixture thereof with dimethyl-ortho-toluidine may be employed, provided
that the quantity of the mixture taken be such as to contain the required quantity
of mono-methyl-ortho-toluidine. Heat the obtained product for ten hours on the
water bath. Dilute with water, add soda till alkaline, and distil off any unaltered
methyl-toluidine with steam. The mass remaining behind solidifies on standing
some time in the cold and can be purified by crystallization from alcohol or petroleum
spirit. When pure the new base melts at a temperature of about 86 to 87 degrees
centigrade.
The mixture which is heated on the water bath can also be obtained in a manner
slightly different from that described, namely by mixing one molecular proportion
of formaldehyde with one molecular proportion of hydrochlorate of mono-methyl-
ortho-toluidine and one molecular proportion of free mono-methyl-ortho-toluidine,
the further treatment being as hereinbefore described. If in the above example
mono-ethyl-ortho-toluidine (or the lower homologue mono-methyl-aniline) be used
analogous results are obtained.
EXAMPLE 2.-PREPARATION OF THE NEW AURAMINE DYE.
Mix together about twenty-five and a half parts of symmetrical dimethyl-diamido-
di-ortho-tolyl-methane (obtained as above described or in any other way) and about
six and a half parts sulphur with a suitable diluent, say, for instance a mixture of
two hundred and forty parts of common salt and fourteen parts of ammonium
chloride. Heat the mixture in a closed vessel provided with a stirrer and standing
in an oil bath which is maintained at a temperature of about one hundred and
seventy-five degrees centigrade. Pass in (under slight pressure) a stream of dry
ammonia gas and continue this treatment for about seven or eight hours when the
reaction will be ended. Allow to cool, extract the brown crystalline melt with cold
water to get rid of the common salt and ammonium chloride, and dissolve the
residue in water having a temperature of about eighty degrees centigrade filter the
solution and precipitate the dye with common salt. Collect in the usual way.
The new dye fixes itself on cotton mordanted with tannin and tartar-emetic giving
a very pure shade of yellow with a slight greenish tinge.
If in Example 2 the corresponding ethyl derivative of diamido-diortho-
tolylmethane (or the homologue dimethyl-diamido-diphenylmethane) be taken
analogous results are obtained.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be perforined, I declare that what I
claim is:-
:-
1. The manufacture of new basic colouring matters of the auramine clase by the
treatment of di-methyl-diamido-diortho-tolyl-methane (or its equivalents as herein-
before mentioned) simultaneously with sulphur and ammonia substantially as
hereinbefore described.
2. The manufacture of new materials for the manufacture of new basic colouring
matters of the auramine class by treating mono-methyl-ortho-toluidine, (or its
equivalents as herein before stated) with formaldehyde substantially as herein before
described.
3. The manufacture of di-methyl-diamido-diortho-tolyl-methane by the conden-
sation of formaldehyde with mono-methyl-ortho-toluidine as herein before described
under Example 1.
4. The manufacture of a new auramine dye by the simultaneous action of sulphur
and ammonia on dimethyl-diortho-tolyl-methane as hereinbefore described under
Example II.
5. As new articles of manufacture products consisting of the new basic colouring

page_text: matters and the new materials for use in the manufacture thereof such as can be
obtained as hereinbefore described.
ليمم
T1
1000
J. H. JOHNSON & Co.,
Agents.