Improvements in the Manufacture of the Red Basic Naphthalene Colouring Matter which Yields Azocarmine on Sulphonation.
Year: 1892

page_text: Date of Application, 21st Mar., 1892
Complete Specification Left, 6th Dec., 1892-Accepted, 14th Jan., 1893
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of the Red Basic Naphthalene
Colouring Matter which Yields Azocarmine on Sulphonation.
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 Anilin & Soda Fabrik of Ludwig-
shafen on Rhine in the Empire of Germany) to be as follows:-
In the Specification of Letters Patent No. 15259 of 1888 granted to me, there is
described the production of a red basic colouring-matter and its conversion into new
sulpho-acids one of which is widely used in the dyeing industry under the name of
azo-carmine. This basic colouring-matter (which was then called rosinduline but
which has since received the name phenylrosinduline; see Journal of the Chemical
Society vol. 58 page 909 and Annalen der Chemie, vol. 256 page 235) was obtained
by melting certain naphthalene derivatives with aniline and aniline salt. These
naphthalene derivatives, belong to the following groups of compounds, viz., bromo-
nitroso- and azo-derivatives of naphthylamine or naphthol, and quinone-derivatives
of naphthalene.
In the Specification of Letters Patent No. 6875 of 1890 granted to me, there is
described the production of sulpho-acids of phenyl-rosinduline by an analogous
treatment of suitable sulphonated naphthalene derivatives and inter alia by treat-
ment of certain nitro-derivatives e.g. di-nitro-alpha-naphthol sulpho-acid (known in
commerce as naphthol yellow S,) with aniline and aniline salt.
of
The present invention relates to the discovery that the simplest nitro-derivative
naphthalene-alpha-nitro-naphthalene- on melting with aniline and analine salt in
a manner similar to that described in the above mentioned Specifications, yields
phenyl-rosinduline, which can be used in the manufacture of the sulpho-acids
described in the Specifications No. 15259 of 1888 and No. 19167 of 1890.
To further illustrate the nature of the invention, I give by way of example the
following directions for the production of phenyl-rosinduline from nitro-naphthalene.
The parts are by weight.
Mix together about seventy parts of nitro-naphthalene, one hundred and eighty
parts of aniline salt (hydrochloride of aniline) and sixty parts of aniline, and heat
the mixture in an enamelled pot furnished with a stirrer and mounted in an oil
bath. The mixture melts completely at about one hundred and thirty degrees
centigrade. After reaching this point raise the temperature slowly and stir
continuously. The reaction begins when the temperature reaches about one
hundred and fifty to one hundred and sixty degrees centigrade and proceeds
continuously at this temperature, but it can be more rapidly effected by raising the
temperature to about one hundred and eighty to one hundred and ninety degrees
centigrade. Maintain this heat for about fifteen hours or until no further production
of the colouring matter appears to take place. This can be best judged by taking
samples and working them up to obtain monosulpho acid, by extracting the aniline
and treating with concentrated sulphuric acid.
When the melting operation is ended pour the whole product into a mixture of
about five hundred parts of water and about one hundred and fifty parts of hydro-
chloric acid (containing about thirty two per cent. real acid HCI) and boil the
mixture, dilute with about five hundred parts of water and filter; the residue is
washed by stirring thoroughly with about five hundred parts of water and again
filtered, and the residual phenyl-rosinduline is dried at about fifty degrees
centigrade.
The colouring matter so obtained is pure enough for use in the manufacture of

page_text: the practically insoluble mono-sulpho acid of phenyl rosinduline, and of the soluble
sulpho acids thereof described in the Specifications No. 15259 of 1888 (including
azocarmine) and No. 19167 of 1890 and their production can be effected in the
manner described in the said Specifications.
Dated this 21st day of March 189
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of the Red Basic Naphthalene
Colouring Matter which Yields Azocarmine on Sulphonation.
I JAMES YATE JOHNSON of No. 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 & 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. 15259 of 1888 granted to me, there is
described the production of a red basic colouring matter and its conversion into
new sulpho-acids one of which is widely used in the dyeing industry under the name
of azocarmine. This basic colouring matter (which was then called rosinduline
but which has since received the name phenylrosinduline; see Journal of the
Chemical Society vol. 58 page 909 and Annalen der Chemie vol. 256 page 235)
was obtained by melting certain naphthalene derivatives with aniline and aniline
salt. These naphthalene derivatives, belong to the following groups of compounds,
viz.-bromo-nitroso- and azo derivatives of naphthylamine or naphthol, and quinone
derivatives of naphthalene.
In the Specification of Letters Patent No. 6875 of 1890 granted to me,
there is described the production of sulpho-acids of phenyl-rosinduline by an
analogous treatment of suitable sulphonated naphthalene derivatives and inter alia
by treatment of certain nitro-derivatives, e.g. di-nitro-alpha-naphthol-sulpho-acid
(known in commerce as naphthol yellow S,) with aniline and aniline salt.
The present invention relates to the discovery that the simplest nitro-derivative
of naphthalene, (alpha-nitro-naphthalene) on melting with aniline and aniline salt
in a manner similar to that described in the above mentioned Specifications, yields
phenyl-rosinduline, which can be used in the manufacture of the sulpho-acids
described in the Specifications No. 15259 of 1888 and No. 19167 of 1890.
To further illustrate the nature of this invention and the manner in which it may
be carried into practical effect I give by way of example the following directions
for the production of phenylrosinduline from alpha-nitro-naphthalene. The parts
are by weight.
Mix together about seventy parts of alpha nitronaphthalene, one hundred and
eighty parts of aniline salt (hydrochloride of aniline) and sixty parts of aniline, and
heat the mixture in an enamelled pot furnished with a stirrer and mounted in an oil
bath. The mixture melts completely at about one hundred and thirty degrees
centigrade. After reaching this point raise the temperature slowly and stir
continuously. The reaction begins when the temperature reaches about one hundred
and fifty to one hundred and sixty degrees centigrade and proceeds continuously at
this temperature but it can be more rapidly effected by raising the temperature to
from about one hundred and eighty to one hundred and ninety degrees centigrade.
Maintain this heat for about fifteen hours or until no further production of the
colouring matter appears to take place. This can be best judged by taking samples
and working them up to obtain mono-sulpho-acid by extracting the aniline and
treating with concentrated sulphuric acid.
When the melting operation is ended, pour the whole product into a mixture of

page_text: about five hundred parts of water and about one hundred and fifty parts of hydro-
chloric acid (containing about thirty two per cent. of real acid HCI) and boil the
mixture and dilute with about five hundred parts of water and filter. The residue
is washed by stirring thoroughly with about five hundred parts of water and
again filtered and the residual phenyl-rosinduline is dried at about fifty degrees
centigrade.
The colouring matter so obtained is pure enough for use in the. manufacture of
the practically insoluble mono-sulpho-acid of phenyl-rosinduline and of the soluble
sulpho acids of phenyl-rosinduline described in the Specifications No. 15259 of 1888
(including azocarmine) and No. 19167 of 1890 and the production of the said acids
can be effected in the manner described in the said Specifications.
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 :-
First. The manufacture of the aforesaid red basic naphthalene colouring matter
by treating alpha-nitro-naphthalene with aniline and aniline salt.
Second. The manufacture of the aforesaid red basic naphthalene colouring matter
by treating alpha-nitro-naphthalene with aniline and aniline salt as described under
the foregoing example.
Dated this 5th day of Decembou. 2000.
J. H. JOHNSON & Co.,
Agents.