The Manufacture and Production and Application of New Colouring Matters or Dyes from Naphthalene.
Year: 1893

page_text: Date of Application, 5th June, 1893
Complete Specification Left, 4th Apr., 1894-Accepted, 28th Apr., 1894
PROVISIONAL SPECIFICATION.
The Manufacture and Production and Application of New Colouring
Matters or Dyes from Naphthalene.
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 communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows:-
It is well known that on nitrating naphthalene in such a way that two nitro
groups enter the molecule, a mixture containing two isomeric di-nitro-naphthalenes
is obtained, namely the so-called 1.4' and 1-1' dinitro naphthalenes.
The present invention relates to the production of new dyestuffs which are
obtained by the treatment of the said dinitro-naphthalenes (either singly or in
admixture) with certain reducing agents, as hereinafter explained and further
to methods of using the said dyes.
Already in the early years of the coal tar colour industry unsuccessful attempts
were made to produce useful dyes from the mixture of these nitro-compounds
although such had been obtained from nitro-benzene. Thus in 1861 Troost
experimented on the action of alkaline reducing agents on the said dinitro-
naphthalenes with a view to the foundation of a practical manufacture, but neither
he nor Roussin, Carey Lea, Kopp and other chemists who made experiments with
a similar object attained any useful result, and all experiments of this kind were
abandoned and for over thirty years nothing more has been published with reference
to the solution of this problem.
In the meantime one constituent of the above mentioned mixture namely the
so-called 14 or alpha-dinitro-naphthalene has come into use in large quantities in
the manufacture of naphthazarine, (see Specification of Letters Patent No. 7833
of 1887) of 1-4 naphthalene-diamine and of other bodies. No useful application
however has been discovered for the 1-1' dinitro-compound, and this consequently
constitutes a valueless and troublesome bye-product in the above manufactures.
Now my foreign correspondents have discovered processes for the production of
very valuable new dyes from this hitherto useless bye-product and also dyeing
processes or methods by means of which these new dyes can be applied in the arts
in the manufacture of black cotton goods resisting the action of light acids
and soap.
The statements published by Troost as to the methods he adopted and the
products he obtained are scanty and in part incorrect. He describes his initial
material as pure dinitro-naphthalene but gives the method used for its preparation,
and from this it can be seen that it was the mixture of dinitro-naphthalenes that he
used. From this mixture he obtained red, violet and blue colours by the action of
a large variety of alkaline reducing agents. My foreign correspondents have not
succeeded in obtaining products agreeing in their properties with those described by
Troost either from the mixture of dinitro-naphthalenes or from the separated
dinitro-bodies but by lengthy investigation and experiments my foreign corre-
spondents have discovered that the nature of the reaction and of the products
formed varies according to the reducing agent used, the conditions of the treatment,
and the relative quantities of the reagents employed.

page_text: New and valuable dyes which differ from one another can for instance be
obtained by the following treatments :-
A. On reducing 1-11 dinitro-naphthalene with grape sugar in a boiling alkaline
solution a dark coloured solution is gradually obtained. A violet precipitate
possessing a metallic lustre separates out, and can be purified by the aid of alcohol.
Certain specimens of dye obtained in this way possess the characteristics of being
insoluble in soda solution but soluble in sulphuric acid giving a blue solution
possessing a strong green fluorescence. This dye (hereinafter called dye A) can
best be applied by producing it on the vegetable fibre by the reaction above
described. Black to violet-black shades are obtained.
B. If the alkaline sulphides be used as reducing agents the nature of the result
closely depends upon the conditions observed. Thus if the 1.1' dinitro-naphthalene
be treated with a rather dilute solution of sodium sulphide taking to one molecular
proportion of the dinitro-body say about from three to five or more molecular
proportions of the alkaline sulphide, and if the treatment be effected at the boiling.
temperature then after acidification with a mineral acid and boiling for some time
a dye (hereinafter called dye B) is obtained. This dye B is insoluble in carbonate
of soda, though the product obtained, as a rule, contains some dye soluble in this
solution. It can be purified to a certain extent by extracting with soda solution.
Certain specimens of the dye when dry constitute a dark powder with copper
coloured sheen and are practically insoluble in concentrated sulphuric acid. This
dye can be fixed upon cotton by the aid of a new special dyeing process consisting
in treating the dye with grape sugar or similar reagents in the boiling strong (10%)
alkaline dye bath in the presence of the goods to be dyed. A dead-black colour
can be obtained possessing a very high degree of fastness against the action of light
acids and soap.
C. If a more concentrated solution of sodium sulphide be allowed to react in the
cold on the 11 dinitro-naphthalene and taking less of the alkaline sulphide than
above described under B (say about from two to four molecular proportions to one
molecular proportion of the dinitro-body) and the solution be acidified in the cold
with acetic acid or a dilute mineral acid then a dye soluble in soda solution
(hereinafter called dye C) is precipitated. It contains as a rule an admixture of
dye B but differs from this and from dye A in being soluble in hot soda solution.
A sample of this dye dissolved in cold concentrated sulphuric acid gives a dirty
green solution.
It can be fixed upon cotton in a manner similar to dye B with or
without the addition of grape sugar and gives beautiful shades of black.
If the 11 dinitro-naphthalene be treated with cold and more dilute alkaline
sulphide solution then dye A can also be obtained side by side with dyes B and C.
The differences between the dyes A B and C as shewn by a comparison of
certain samples thereof can be readily seen from the following table of properties ;
but these may be affected in some cases by the presence of unchanged dinitro-
naphthalene or of the other dyes in each case.

page_text: bluish-black
green black
coppery lustre
blue-black with me-
insoluble
tallic lustre
violet solution espe-
cially on boiling
Although in the above instances and in the following examples I refer particularly
to the 11 dinitro-naphthalene, still in practically manufacturing it is not necessary
to purify and isolate this dinitro-body as if desired a mixture thereof with the
aforesaid 14 dinitro-naphthalene can be used. In this the properties of the
product obtained are affected by the somewhat similar compounds obtained from
the 1.41 compound but the products obtained can be practically applied in the
same way.
The following examples of the manner in which the new dyes can be obtained
will serve to further illustrate the nature of the invention, but these are merely
typical methods of production and great variations can be made without departing
from the nature of the invention.
The parts are by weight.

page_text: Add about ten parts of 11' dinitro-naphthalene in a finely divided state to about
five hundred parts of twenty per cent. soda solution. Boil the mixture and add in
small portions at a time about thirty parts of grape sugar. A solution forms
which usually passes in colour from greenish to violet or brown, and from the
solution an insoluble violet body with a metallic lustre separates out. Continue
boiling for say about one hour or until on testing the mixture, no dinitro-naphtha-
lene is found to be present, filter and wash the precipitate. The colouring
matter can be purified with the aid of benzene, alcohol and the like. Instead of
the soda other alkaline carbonates or caustic alkalies can be used. In addition to
the properties tabulated above, dye A is characterized by dissolving in cold aniline
giving a red solution which turns violet on heating.
As aforesaid this dye can best be usefully applied by producing it as above
described but in the presence of the fibre to be dyed whereby it is generated in or
on the fibre
Mix together about fifty parts of the 11' dinitro-naphthalene and about six
thousand parts of water, boil the mixture and add about two hundred parts of
sodium sulphide (Na2S + 9 A,). Boil for about half an hour or until no dinitro-
naphthalene remains unchanged. Filter add to the violet solution obtained about
five hundred parts of hydrochloric acid (containing about 30 per cent. real acid),
boil two hours longer, filter and wash. The main product is insoluble in soda
solution but usually contains some dye C which can if desired be extracted by
means of soda which can be done for example by boiling the whole product with
about five thousand parts of a ten per cent. soda solution. This dye is preferably
prepared and used in the form of paste and is applied to vegetable fibre by the aid
of the new dyeing process hereinbefore mentioned consisting in preparing a dye-vat
by the use of a reducing agent such as grape sugar and a strongly alkaline
salution
PRODUCTION OF DYE C (SOLUBLE IN HOT SODA SOLUTION).
Mix together about fifty parts of 111 dinitro-naphthalene, about one hundred
and sixty parts of water and about one hundred and sixty five parts of sodium
suphide (NaS + 9 A,). Stir the mixture cold for about five hours or until no
unchanged dinitro-naphthalene remains, then dilute with about five hundred parts
of water, filter and acidify cold with about three hundred parts of acetic acid;
filter and wash. The product so obtained is in the main soluble in hot soda
solution, but usually contains some dye B from which it can readily be purified if
desired which can be done for example by dissolving the product in about five
thousand parts of hot soda solution (containing 10 per cent. Na2CO3); filter and
precipitate with hydrochloric acid; filter and wash and preserve as paste. This
dye can be used in the same way as dye B with or without the addition of grape
sugar and mixtures of dyes B and C however obtained, can be used in the manner
described without separation from each other.
Dated this 5th day of June 1893.
J. H. JOHNSON & Co.,
Agents.

page_text: The Manufacture and Production and Application of New Colouring
Matters or Dyes from Naphthalene.
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 Gerinany) and in what manner the
same is to be performed to be particularly described and ascertained in and by
the following statement:-
It is well known that on nitrating naphthalene in such a way that two nitro
groups enter the molecule, a mixture containing two isomeric di-nitro-naphthalenes
is obtained, namely the so called 1-4 and 1-1 dinitro-naphthalenes.
The present invention relates to the production of new black dyestuffs which are
obtained by the treatment of the said dinitro-naphthalenes (either singly or in
admixture) under suitable conditions with certain reducing agents as hereinafter
explained, and further to methods of using the said dyes.
Already in the early years of the coal-tar colour industry unsuccessful attempts
were made to produce useful dyes from the mixture of these nitro-compounds
although such had been obtained from nitro-benzene.
Thus in 1861 Troost experimented on the action of alkaline reducing agents on
the said dinitro-naphthalenes with a view to the foundation of a practical manu-
facture, but neither he nor Roussin, Carey-Lea, Kopp, and other chemists, who
made experiments with a similar object attained any useful result, and all experiments
of this kind were abandoned and for over thirty years nothing more has been
published with reference to the solution of this problem.
In the meantime one constituent of the above-mentioned mixture, namely the
so called 14 or alpha-dinitro-naphthalene, has come into use in large quantities in
the manufacture of naphthazarine (see Specification of Letters Patent No. 7833
of 1887), of 1.41 naphthalene-diamine and of other bodies. No useful application
however has been discovered for the 111 dinitro-compound and this consequently
has hitherto constituted a valueless and troublesome bye-product in the above
manufactures.
Now my foreign correspondents have discovered process for the production of
very valuable new black dyes from this hitherto useless bye-product and also dyeing
processes or methods by means of which these new dyes can be applied in the arts
in the manufacture of black cotton, linen and jute goods and the like resisting the
action of light, acids and soap.
The statements published by Troost as to the methods he adopted and the
products he obtained are scanty and in part incorrect. He describes his initial
material as 66
pure dinitro-naphthalene but gives the method used for its
preparation and from this it can be seen that it was the mixture of dinitro-naphtha-
lenes that he used. From this mixture he obtained red, violet and blue colours by
the action of a large variety of alkaline reducing agents, but the products are
incapable of any practical application. By a lengthy investigation and experiments
my foreign correspondents have discovered that the nature of the reaction and of
the products formed varies according to the reducing agent used, the conditions of
the treatment, and the relative quantities of the reagents employed.
New and valuable black dyes, which differ from one another, and from the
products described by Troost, can for instance be obtained by the following
treatments :-
A. On reducing 11' dinitro-naphthalene with grape sugar in a boiling alkaline
solution a dark coloured solution is gradually obtained. A violet precipitate

page_text: possessing a metallic lustre separates out, and can be purified by the aid of alcohol.
Certain specimens of dye obtained in this way possess the characteristics, of being
insoluble in soda solution, but soluble in sulphuric acid giving a blue solution
possessing a strong green fluorescense. This dye (hereinafter called dye A) can
best be applied usefully by producing it on the vegetable fibre by the reaction
above described. Black to violet-black shades are obtained.
B. If the alkaline sulphides be used as reducing agents the nature of the result closely
depends upon the conditions observed. Thus if the 1.11 dinitro naphthalene be treated
with a rather dilute solution of sodium sulphide, taking, to one molecular proportion
of the dinitro-body, say, about from three to five, or more, molecular proportions of
the alkaline sulphide, and if the treatment be effected at the boiling temperature,
then, after acidification with a mineral acid and boiling for some time, a dye
(hereinafter called dye B) is obtained. This dye B is insoluble in carbonate of
soda, though the product obtained, as a rule, contains some dye soluble in this
solution. It can be purified to a certain extent by extracting with soda solution,
but such purification is superfluous in practical working. Certain specimens of the
dye when dry have been observed to constitute a dark powder with copper coloured
sheen and to be practically insoluble in concentrated sulphuric acid. This purified
dye can be fixed upon cotton, linen, jute and the like by the aid of a new special
dyeing process consisting in treating the dye in a strongly alkaline bath containing
up to 25 per cent. of soda Na,CO, with the addition of grape sugar or similar
reagents. If the product be a mixture of the dyes B & C the same process for
fixing it on the fibre can be used but it is unnecessary to add grape sugar. A dead-
black colour can be obtained possessing a very high degree of fastness against the
action of light, acids and soap.
C. If a more concentrated solution of sodium sulphide be allowed to react in
the cold on the 1-11 dinitro-naphthalene and taking less of the alkaline sulphide
than above described under B (say about from two to four molecular proportions
to one molecular proportion of the dinitro body) and the solution be acidified in
the cold with acetic acid or a dilute mineral acid then a dye soluble in soda solution
(hereinafter called dye C) is precipitated. It contains, as a rule, an admixture of
dye B, but differs from this and from dye A in being soluble in hot soda solution.
A sample of this dye dissolved in cold concentrated sulphuric acid yields a dirty
green solution.
It can be fixed upon cotton, linen, jute and the like in a manner
similar to dye B with or without the addition of grape sugar and gives beautiful
shades of black.
If the 11 dinitro-naphthalene be treated with cold and more dilute alkaline
sulphide solution then dye A can also be obtained side by side with dyes B and C.
These differences between the dyes A, B and C as shewn by a comparison of
certain samples thereof can be readily seen from the following table of properties;
but these may be affected in some cases by the presence of unchanged dinitro-
naphthalene or of the other dyes in each case.

page_text: bluish-black
green-black
coppery lustre
blue-black with.
metallic lustre
nsoluble
violet
solution.
especially
boiling
lmost insoluble bluish-violet solu-.
Although, in the above instances, and in the following examples, I refer
particularly to the 1·1' dinitro-naphthalene, still in practically manufacturing it.
is not necessary to purify and isolate the dinitro-body, as if desired a mixture
thereof with the aforesaid 1-4 dinitro-naphthalene can be used. In this the
properties of the product obtained are affected by the somewhat similar compounds
obtained from the 14' compound but the products obtained can be practically
applied in the same way;
The following examples of the manner in which the new dyes can be obtained
will serve to further illustrate the nature of the invention and the manner in which
it can be carried into practical effect, but these are merely typical methods of
production and great variations can be made without departing from the nature of
the invention. The parts are by weight.

page_text: Add about ten parts of the 1·11 dinitro-naphthalene in a finely divided state to
about five hundred parts of twenty per cent. soda solution. Boil the mixture and
add in small portions at a time about thirty parts of grape sugar. A solution
forms which usually passes in colour from greenish to violet or brown, and from
the solution an insoluble violet body with a metallic lustre separates out. Continue
boiling for say about one hour or until on testing the mixture no dinitro-naphtha-
lene is found to be present, filter and wash the precipitate. The colouring matter
can be purified with the aid of benzene, alcohol and the like. Instead of the
soda, other alkaline carbonates or caustic alkalies can be used. In addition to the
properties tabulated above dye A is characterized by dissolving in cold aniline
giving a red solution which turns violet on heating.
.
As aforesaid this dye can best be usefully applied by producing it as above
described but in the presence of the fibre to be dyed whereby it is generated in,
Ar An
the Ch
Mix together about fifty parts of the 1-11 dinitronaphthalene about one hundred
and sixty parts of water and about one hundred and sixty five parts of sodium
sulphide (Na2S+ 9 Ag). Stir the mixture cold for about five hours or until no
unchanged dinitro-naphthalene remains, then dilute with about five hundred parts
of water, filter and acidify cold with about three hundred parts of acetic acid,
filter and wash. The product so obtained is in the main soluble in hot soda
solution, but usually contains some dye B from which it can readily be purified
if desired which purification can be effected for example by dissolving the product
in about five thousand parts of hot soda solution (containing ten per cent. Na2CO3)
and filtering and precipitating with hydrochloric acid; filter and wash and preserve
as paste. This dye can be used in the same way as dye B with or without the

page_text: addition of grape sugar and mixtures of dyes B and C, however obtained, can be-
used in the manner described without separation from each other.
If desired the dyes B and C, can be produced on the fibre, by printing or
padding the goods with an intimate mixture of 1·11 dinitro naphthalene, sodium
sulphide and a suitable thickening mixture. The colour is produced by drying at
about fifty degrees then steaming, passing through a weak hydrochloric acid bath,
and washing with soap.
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 the new colouring matters dyeing cotton black herein-
before described by treating 1.11 dinitro-naphthalene or mixtures thereof with 1.4'
dinitro-naphthalene with the reducing agents hereinbefore mentioned substantially
in the proportions and under the conditions hereinbefore set forth.
2. The production of the colouring-matters herein before described and claimed!
on or in the presence of the fibre substantially as hereinbefore set forth.
3. The application of the dyes obtained substantially in the manner herein-
before set forth in the dyeing of cotton, linen and jute by using a strongly
alkaline dyebath containing up to about twenty five per cent. of soda Na,CO, with
or without the addition of a reducing agent such as grape-sugar.
4. The manufacture of new colouring matters substantially in the manner
herein before described in the examples.
5. As articles of manufacture the new dyes hereinbefore described such as can.
be obtained substantially as hereinbefore set forth.
Dated the 3rd day of April 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, Agents..