Improvements in the Manufacture of Yellow Basic Colouring- matters.
Year: 1898

page_text: Date of Application, 12th Oct., 1898
Complete Specification Left, 11th July, 1899-Accepted, 12th Aug., 1899
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Yellow Basic Colouring-
matters.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the German Empire) to be as follows:
In the Specification of Letters Patent No. 14920 of 1897 granted to me
on a communication from my foreign correspondents there is described the
manufacture of colouring matters resembling phosphines by the condensa-
tion of para-amido-benzaldehyde or its substitution products substituted in
the amido group with the alphyl derivative of meta-toluylene-diamine.
The present invention consists of a new or improved process for the pro-
duction of the same, or similar colouring-matters, from the same initial materials
and consists mainly in carrying out the condensation of the para-amido-ben-
zaldehyde or its equivalent, with the alphyl-meta-toluylene-diamine in the
presence of ferric chloride and it is preferred to work in alcoholic solution.
From theoretical considerations, the reaction is described in the aforesaid
Specification of Letters Patent No. 14920 of 1897 might be expected to lead
to the leuco products of dyes of the phosphine class, but instead of that, the
dyes themselves are obtained. It appears probable that this takes place at the
expense of a reduction of some of the materials present, involving the occurrence
of some bye re-actions, and it is found by experiment that bye reactions, resulting
in the formation of pitchy products to take place. By working according to
the present invention I believe that in the presence of ferric chloride, the
oxidising agent, requisite for the production of the colouring matters themselves,
is provided, without the occurrence of any bye re-actions being necessary, and
the dyes are obtained in much larger quantity from the same quantity of initial
material, for the waste due to the bye-re-actions is largely avoided.
The following examples will serve to illustrate further the nature of this inven-
tion which is however not confined to these examples. Parts are by weight.
EXAMPLE 1.
Dissolve about fifty-five parts of phenyl-meta-toluylene-diamine-hydrochlorate in
160 parts of hot alcohol, and add to the solution a mixture of about 24 parts
para-amido-benzaldehyde and 50 parts of crystallised ferric chloride. Boil the
mixture for about six hours in a vessel furnished with an inverted condenser,
then distil off the alcohol and extract the residue with about 2000 parts of
hot water, whilst stirring thoroughly. Filter the solution so obtained.
The colouring-matter may be separated from the solution in various ways.
For instance, add to the hot filtrate about 55 parts of nitric acid (containing
about 62 per cent. of real nitric acid, HNO3). Allow to stand for about 24 hours.

page_text: The colouring-matter separates out as a heavy yellow-red powder. Filter press
and dry at a low temperature, say about 40 to 50 degrees Centigrade.
EXAMPLE 2.
Dissolve about 275 parts of phenyl-meta-toluylene-diamine-hydrochlorate in
60 parts of hot alcohol. Boil the solution and add, gradually, a mixture of about
15 parts of di-methyl-para-amido-benzaldehyde, dissolved in 40 parts of alcohol
and 25 parts of ferric chloride, also dissolved in 40 parts of alcohol. Boil the
entire mixture for about five hours, distil off the alcohol, and extract the residue
with about 4000 parts of boiling water. Allow to cool, and to stand for several
hours, filter from any precipitated impurity, add about 25 parts of hydrochloric
acid, (containing about 30 per cent. HCl) and 540 parts of a solution of sodium
nitrate (containing about 42 per cent. by weight of this salt). Allow the mix-
ture to stand for about ten hours, whilst keeping it cool with ice. A voluminous
red crystalline mass fills the liquid. "Filter, press, and dry at about 40 to
50 degrees Centigrade.
Dated this 12th day of October 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Yellow Basic Colouring-
matters.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the German Empire) 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. 14920 of 1897 granted to me
for an invention communicated to me by my present foreign correspondents there is
described the manufacture of colouring-matters resembling phosphines by the con-
densation of para-amido-benzaldehyde, or its substitution products substituted in
the amido-group with the alphyl derivative of meta-toluylene-diamine.
The present invention consists of a new, or improved, process for the pro-
duction of the same, or similar, colouring-matters, from the same initial materials,
and consists mainly in carrying out the condensation of the para-amido-ben-
zaldehyde, or its equivalent, with the alphyl-meta-toluylene-diamine, in the
presence of ferric chloride, and it is preferred to work in alcoholic solution.
From theoretical considerations the reaction, as described in the aforesaid
Specification of Letters Patent No. 14920, of 1897, might be expected to lead
to the leuco-products of dyes of the phosphine class, but, instead of that, the
dyes themselves are obtained. It appears probable that this takes place at the
expense of a reduction of some of the materials present, involving the occurrence
of some bye-reactions, and it is found by experiment that bye-reactions, resulting
in the formation of pitchy products, do take place. By working according to
the present invention I believe that in the presence of ferric chloride, the
oxidising agent, requisite for the production of colouring-matters themselves,
is provided, without the occurrence of any bye-reactions being necessary, and
the dyes are obtained in much larger quantity from the same quantity of
initial material, for the waste due to the bye-reactions is largely avoided.

page_text: The following examples will serve to illustrate the nature of the invention
and the manner in which it can be carried into practical effect, but the invention
is not confined to the examples. The parts are by weight;-
EXAMPLE 1.
Dissolve about 55 parts of phenyl-meta-toluylene-diamine-hydrochlorate in
160 parts of hot alcohol, and add to the solution a mixture of about 24 parts
para-amido-benzaldehyde and 50 parts of crystallised ferric chloride. Boil the
mixture for about six hours in a vessel furnished with an inverted condenser,
then distil off the alcohol and extract the residue with about 2000 parts of
hot water, whilst stirring thoroughly. Filter the solution so obtained.
The colouring-matter may be separated from the solution in various ways.
For instance, add to the hot filtrate about 55 parts of nitric acid, (containing
about 62 per cent. of real nitric acid HNO,). Allow to stand for about 24 hours.
The colouring-matter separates out as a heavy yellow-red powder. Filter, press
and dry at a low temperature, say about 40 to 50 degrees Centigrade.
EXAMPLE 2.
Dissolve about 275 parts of phenyl-meta-toluylene-diamine-hydrochlorate in
60 parts of hot alcohol. Boil the solution and add gradually a mixture of about
15 parts of dimethyl-para-amido-benzaldehyde, dissolved in 40 parts of alcohol
and 25 parts of ferric chloride, also dissolved in 40 parts of alcohol. Boil the
entire mixture for about five hours, distil off the alcohol, and extract the residue
with about 4000 parts of boiling water. Allow to cool, and to stand for several
hours, filter from any precipitated impurity, add about 25 parts of hydrochloric
acid, (containing about 30 per cent. H Cl) and 540 parts of a solution of sodium
nitrate, (containing about 421 per cent, by weight of this salt). Allow the mix-
ture to stand for about ten hours, whilst keeping it cool with ice. A voluminous
red crystalline mass fills the liquid. Filter, press and dry at about 40 to
50 degrees Centigrade.
Having now particularly described and ascertained the nature of the said
invention, and in what manner the same is to be performed, I declare that what
1 claim is:―
1. The manufacture of yellow basic colouring-matters by effecting the con-
densation of para-amido-benzaldehyde, or its substitution products, substituted
in the amido group, with an alphyl-derivative of meta-toluylene-diamine in the
presence of ferric chloride substantially as hereinbefore described.
2. The manufacture of yellow basic colouring-matters by effecting the con-
densation of para-amido-benzaldehyde, or its substitution products, substituted in
the amido-group, with an alphyl-derivative of meta-toluylene-diamine, in alcoholic
solution and in the presence of ferric chloride, substantially as hereinbefore
described.
3. The manufacture of yellow basic colouring-matters, substantially as herein-
before described in each of the foregoing examples.
Dated this 11th day at T.... 1900
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.